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WO2013028307A1 - Dérivés de terpènes hydrocarbonés - Google Patents

Dérivés de terpènes hydrocarbonés Download PDF

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Publication number
WO2013028307A1
WO2013028307A1 PCT/US2012/048203 US2012048203W WO2013028307A1 WO 2013028307 A1 WO2013028307 A1 WO 2013028307A1 US 2012048203 W US2012048203 W US 2012048203W WO 2013028307 A1 WO2013028307 A1 WO 2013028307A1
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WIPO (PCT)
Prior art keywords
diels
alder
substituted
farnesene
adduct
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Ceased
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PCT/US2012/048203
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English (en)
Inventor
Frank X. Woolard
Derek James Mcphee
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Amyris Inc
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Amyris Inc
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Publication of WO2013028307A1 publication Critical patent/WO2013028307A1/fr
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
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    • C07C47/32—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings with a six-membered ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/16—Quinones the quinoid structure being part of a condensed ring system containing three rings
    • C07C50/20—Quinones the quinoid structure being part of a condensed ring system containing three rings with unsaturation outside the ring system
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    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • C10M2207/0225—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/08—Aldehydes; Ketones
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1253—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C10M2207/1273—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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    • C10M2207/28—Esters
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Definitions

  • This application relates to derivatives of hydrocarbon terpenes comprising at least one conjugated diene moiety (e.g. , myrcene or farnesene), methods of making the derivatives, and the use of the derivatives in various applications such as use as oils, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents, or reactive diluents for use in making oligomers or polymers.
  • conjugated diene moiety e.g. , myrcene or farnesene
  • Conjugated terpenes such as myrcene and the sesquiterpene ⁇ -farnesene can be synthesized via biological routes.
  • myrcene and ⁇ -farnesene can be produced in high yield from modified yeast, as described in U.S. Patent Nos. 7,399,323 and 7,659,097, each of which is incorporated herein by reference in its entirety, as if put forth fully below.
  • oils, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or monomers, cross-linking agents or reactive diluents for use in making oligomers or polymers that are made at least in part from renewable carbon sources such as sugars and biomass, other than conventional oleochemicals derived from petroleum-based carbon sources.
  • Diels-Alder adducts between a hydrocarbon terpene comprising a conjugated diene (e.g., myrcene, ⁇ -farnesene, or a-farnesene) and a dienophile and derivatives of such adducts, methods of making the adducts, methods for derivatizing the adducts, and to the use of the adducts and their derivatives as oils, solvents, lubricants, additives or base oils for lubricant
  • described herein are compounds comprising a Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile.
  • the compounds can be adapted for use, for example, as additives to modify at least one physical property of one or more polymers, or as monomers, cross-linking agents, or reactive diluents for making one or more polymers, or as lubricants or components of a lubricant formulations, or as oils, solvents, or surfactants.
  • the hydrocarbon terpene is ⁇ -farnesene.
  • the dienophile is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, fumaric acid, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl or dialkyl maleates, monoalkyl or dialkyl fumarates, monoalkyl or dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, monoalkyl or dialkyl acetylene di
  • azidocarboxylates acetylene dicarboxylic acid, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, sulfur dioxide, vinyl sulfonates, vinyl sulfonates, vinyl sulfoxides, naphthoquinones, phosphorus trihalide, and combinations thereof.
  • the Diels-Alder adduct is chemically modified, e.g., by oxidizing the adduct, reducing the adduct, and/or by reacting the adduct with one or more reactants.
  • a Diels-Alder adduct or its derivative is hydrogenated.
  • a Diels-Alder adduct is hydrogenated before chemical modification, and in some cases, a Diels-Alder adduct is hydrogenated after chemical modification.
  • the Diels-Alder adduct is physically blended with a polymer. In some variations, the Diels-Alder adduct is chemically reacted with a polymer.
  • the Diels-Alder adducts and their derivatives as described herein may be used to modify any suitable type of polymer.
  • a Diels-Alder adduct or its derivative is used to modify a condensation polymer.
  • a Diels-Alder adduct or its derivative is used to modify a thermoplastic.
  • a Diels-Alder adduct or its derivative is used to modify a thermoset.
  • a Diels-Alder adduct or its derivative is used as a monomer, cross- linking agent, or reactive diluent to make a polymer.
  • a Diels-Alder adduct or its derivative may be used to make an alkyd resin.
  • a Diels-Alder adduct or its derivative as described herein may be used to make a polyester.
  • a Diels-Alder adduct or its derivative as described herein may be used to make a polyamide.
  • a Diels-Alder adduct or its derivative as described herein may be used to make a lubricant, a base oil, or a component of a lubricant formulation.
  • a dienophile used to make a Diels-Alder adduct that has utility in a lubricant application is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, fumaric acid, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl or dialkyl maleates, monoalkyl or dialkyl fumarates, monoalkyl or dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinna
  • the adduct or its derivative is adapted for use as a viscosity index improver in a lubricant composition. In some variations, the adduct or its derivative is adapted for use as a base oil in a lubricant composition. In some variations, the adduct or its derivative is adapted for use as a pour point modifier in a lubricant composition. In some variations, the adduct or its derivative is adapted for use as a cutting oil.
  • the hydrocarbon terpenes (e.g., ⁇ -farnesene) or the Diels-Alder adducts derived from the hydrocarbon terpenes comprise at least one epoxy group. In some variations, the hydrocarbon terpenes (e.g., ⁇ -farnesene) or the Diels-Alder adducts comprise one epoxy group. In some variations, the hydrocarbon terpenes (e.g., ⁇ -farnesene) or the Diels-Alder adducts comprise two epoxy groups.
  • the hydrocarbon terpenes e.g., ⁇ -farnesene
  • the Diels-Alder adducts comprise more than two epoxy groups.
  • the epoxidized hydrocarbon terpenes and/or the epoxidized Diels-Alder adducts are adapted for use as monomers or as cross-linking agents, or as curing agents to make a polymer.
  • at least one epoxy group may be hydrolyzed.
  • a Diels-Alder adduct or its derivative as described herein may be used to make a surfactant.
  • the surfactants derived from the Diels-Alder adducts may be nonionic in some variations.
  • the Diels-Alder adduct may be an alcohol (e.g., a primary alcohol), or a polyol (e.g., a diol).
  • a nonionic surfactant is an alkoxylated alcohol (which may be a primary alcohol or end-capped with a terminal group such as a methyl group).
  • a nonionic surfactant comprises at least one glucoside group, at least one glucamide group, at least one amine group, or at least one alkanolamide group.
  • the Diels-Alder adducts are adapted for use as anionic surfactants.
  • a Diels-Alder adduct may comprise a carboxylate salt, a sulfonate salt, a sulfate salt, or a phosphate salt.
  • the Diels-Alder adducts are adapted for use as cationic surfactants.
  • a Diels-Alder adduct may comprises a quaternary ammonium ion.
  • the Diels-Alder adducts may be adapted for use as zwitterionic surfactants.
  • a Diels- Alder adduct may comprise an amine-oxide group, or may be a betaine.
  • the surfactants are derived from Diels-Alder adducts comprising alcohol or aldehyde functionality.
  • the surfactants are derived by reacting a Diels-Alder adduct comprising at least one alcohol group with an alkylene oxide such as ethylene oxide and/or propylene oxide.
  • a Diels-Alder adduct or its derivative as described herein may be used to make a solvent.
  • the hydrocarbon terpene used to make the Diels-Alder adduct is ⁇ -farnesene.
  • the hydrophobicity and/or hydrophilicity of the solvent may be tuned by selection of the hydrocarbon terpene and the dienophile, as well as by subsequent chemical modification of the Diels- Alder adduct.
  • the solvent is a reactive solvent that undergoes a chemical reaction with one or more co-solvents or with one or more solutes.
  • the hydrocarbon terpene used to make the Diels-Alder adduct is derived from a simple sugar by a microorganism.
  • ⁇ -farnesene that is derived from a simple sugar by a microorganism is used to make the Diels-Alder adduct.
  • At least about 25%, at least about 30%, at least about 40%, at least about 50%), at least about 60%, at least about 70%, at least about 80%, at least about 90%, or about 100%) of the carbon atoms in the Diels-Alder adducts are derived from readily renewable, non-petroleum carbon sources, such as a sugar or biomass.
  • FIGURE 1 shows weight loss with heat aging for Example 22, Comparative Examples
  • FIGURE 2 shows toughness for Examples 21 and 22, Comparative Examples CE 4-CE
  • FIGURE 3 shows Young's modulus for Examples 21 and 22 and Comparative Examples
  • CE 4-CE 9 measured according to ASTM D638 using a pull rate of 50mm/min.
  • FIGURE 4 shows engineering strain (%> elongation) at failure for Examples 21 and 22,
  • FIGURE 5 shows displacement at break for Examples 21 and 22, Comparative Examples
  • FIGURE 6 shows load at break for Examples 21 and 22, Comparative Examples CE 4-
  • FIGURE 7 shows stress at break for Examples 21 and 22, Comparative Examples CE 4-
  • FIGURE 8 shows energy to yield point for Examples 21 and 22, Comparative Examples
  • FIGURE 9 shows l B NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7- dienyl)cyclohex-4-ene-l,2-dicarboxylate of Example 30.
  • FIGURE 10 shows l H NMR spectrum of dimethyl 4-(4,8-dimethylnonyl)cyclohexane-
  • FIGURE 11 shows l H NMR spectrum of (4-(4,8-dimethylnonyl)cyclohexane-l ,2- diyl)dimethanol of Example 32.
  • FIGURE 12A and FIGURE 12B show 13 C NMR spectra of (4-(4,8- dimethylnonyl)cyclohexane-l,2-diyl)dimethanol of Example 32.
  • FIGURE 13 shows l H NMR spectrum of a mixture of (E)-3-(4,8-dimethylnona-3,7- dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3- enecarbaldehyde of Example 33.
  • FIGURE 14A and 14B show GC/MS spectra of a mixture of (E)-3-(4,8-dimethylnona-
  • FIGURE 15 shows l H NMR spectrum of a mixture of (3-(4,8- dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol of Example 34.
  • FIGURES 16A-16C show l B NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-pentaethylene glycol of Example 35.
  • FIGURES 16D-16F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-pentaethylene glycol of Example 35.
  • FIGURES 17A-17C show l B NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-decaethylene glycol of Example 36.
  • FIGURES 17D-17F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-decaethylene glycol of Example 36.
  • FIGURES 18A-18C show l B NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentadecaethylene glycol and 1 -(4,8-dimethyl-nonyl)-cyclohexane-4-pentadecaethylene glycol of Example 37.
  • FIGURES 18D-18F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentadecaethylene glycol and 1 -(4,8-dimethyl-nonyl)-cyclohexane-4-pentadecaethylene glycol of Example 37.
  • FIGURES 19A-19C show l B NMR spectra of l-(4,8-dimethyl-nonyl)-cyclohexane-3,4- bis(methyl-pentaethylene glycol) of Example 38.
  • FIGURES 19D-19F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 38.
  • FIGURES 20A-20C show l B NMR spectra of 1 -(4,8-dimethyl-nonyl)-cyclohexane-3,4- bis(methyl-decaethylene glycol) of Example 39.
  • FIGURES 20D-20F show 13 C NMR spectra of a mixture of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 39.
  • FIGURES 21A-21C show l B NMR spectra of l-(4,8-dimethyl-nonyl)-cyclohexane-3,4- bis(methyl-decapentaethylene glycol) of Example 40.
  • FIGURES 21D-21F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 40.
  • FIGURE 22 shows correlation of durometer hardness A with Hansen solubility parameters using durometer hardness A values from Table 64 and Hansen solubility parameters from Table 5.
  • FIGURE 23 shows correlation of durometer hardness A with tensile properties for data shown in Table 64.
  • FIGURE 24 shows DMA results for Example 78.
  • FIGURE 25A shows a plot of surface tension (mN/m) vs. logi 0 (surfactant concentration in ppm) for the surfactant of Example 37.
  • FIGURE 25B shows a plot of surface tension (mN/m) vs. logi 0 (surfactant concentration in ppm) for the surfactant of Example 38.
  • FIGURE 25C shows a plot of surface tension (mN/m) vs. logi 0 (surfactant concentration in ppm) for the surfactant of Example 39.
  • FIGURE 25D shows a plot of surface tension (mN/m) vs. logio(surfactant concentration in ppm) for the surfactant of Example 40.
  • R R L +k*(R u -R L ), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent or 100 percent.
  • k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent or 100 percent.
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
  • Terpene as used herein is a compound that is capable of being derived from isopentyl pyrophosphate (IPP) or dimethylallyl pyrophosphate (DMAPP), and the term terpene encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes and polyterpenes.
  • a hydrocarbon terpene contains only hydrogen and carbon atoms and no heteroatoms such as oxygen, and in some embodiments has the general formula (C 5 H 8 ) n , where n is 1 or greater.
  • conjugated terpene or “conjugated hydrocarbon terpene” as used herein refers to a hydrocarbon terpene comprising at least one conjugated diene moiety, but is not part of an aromatic ring.
  • a conjugated hydrocarbon termpene may contain a conjugated diene at a terminal position (e.g., myrcene, farnesene) or the conjugated diene may be at an internal position (e.g., isodehydrosqualene or isosqualane precursor I or II).
  • conjugated diene moiety of a conjugated terpene may have any stereochemistry ⁇ e.g., cis or trans) and may be part of a longer conjugated segment of a terpene, e.g., the conjugated diene moiety may be part of a conjugated triene moiety.
  • hydrocarbon terpenes as used herein also encompasses monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene but have either fewer or additional hydrogen atoms than the corresponding terpene, e.g., terpenoids having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenoids having 2 additional, 4 additional or 6 additional hydrogen atoms than the corresponding terpene.
  • conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, ⁇ -ocimene, a-farnesene, ⁇ -farnesene, ⁇ -springene, geranylfarnesene, neophytadiene, d,y-phyta-l,3-diene, ira3 ⁇ 4y-phyta-l,3-diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.
  • Terpenes or isoprenoid compounds are a large and varied class of organic molecules that can be produced by a wide variety of plants and some insects.
  • terpenes or isoprenoid compounds can also be made from organic compounds such as sugars by microorganisms, including bioengineered microorganisms. Because terpenes or isoprenoid compounds can be obtained from various renewable carbon sources, they are useful monomers for making eco-friendly and renewable chemicals.
  • the conjugated hydrocarbon terpenes as described herein are derived from microorganisms using a renewable carbon source, such as a sugar or biomass that can be replenished in a matter of months or a few years unlike fossil fuels.
  • Myrcene refers to a compound having the following structure:
  • Optimene refers to a-ocimene, ⁇ -ocimene or a mixture thereof.
  • a-ocimene refers to a compound having the following formula:
  • ⁇ -ocimene refers to a compound having the following formula:
  • Frnesene refers to a-farnesene, ⁇ -farnesene or a mixture thereof.
  • a-Farnesene refers to a compound having the following structure:
  • a-farnesene comprises a substantially pure stereoisomer of a-farnesene.
  • a-farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers.
  • the amount of each of the stereoisomers in an a-farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.%) to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.% to about 95 wt.%), from about 10 wt.% to about 90 wt.% or from about 20 wt.% to about 80 wt.%, based on the total weight of the a-farnesene mixture of stereoisomers.
  • ⁇ -farnesene refers to a compound having the following structure:
  • ⁇ -farnesene comprises a substantially pure stereoisomer of ⁇ -farnesene.
  • substantially pure ⁇ -farnesene refers to compositions comprising at least 80%, at least 90%, at least 95%, at least 97%, at least 98% or at least 99% ⁇ - farnesene by weight, based on total weight of the farnesene.
  • ⁇ -farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers.
  • the amount of each of the stereoisomers in a ⁇ -farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.% to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.%) to about 95 wt.%, from about 10 wt.% to about 90 wt.%, or from about 20 wt.% to about 80 wt.%), based on the total weight of the ⁇ -farnesene mixture of stereoisomers.
  • ⁇ -springene or “springene” refers to a compound having the following structure:
  • Neophytadiene refers to a compound having the following structure:
  • rra3 ⁇ 4y-phyta-l,3-diene refers to a compound having the following structure:
  • Q,y-phyta-l,3-diene refers to a compound having the following structure:
  • Isodehydrosqualene refers to a compound having the following structure:
  • 2,6,11,17,21 -pentaene refers to a compound having the following structure:
  • 2,6, 10, 14, 17,21 -pentaene refers to a compound having the following structure:
  • Frnesol refers to a compound having the following structure:
  • Neolidol refers to a compound having the following structure:
  • Farnesol or nerolidol may be converted into a-farnesene or ⁇ -farnesene, or a combination thereof by dehydration with a dehydrating agent or an acid catalyst.
  • a dehydrating agent or an acid catalyst Any suitable dehydrating agent or acid catalyst that can convert an alcohol into an alkene may be used.
  • suitable dehydrating agents or acid catalysts include phosphoryl chloride, anhydrous zinc chloride, phosphoric acid, and sulfuric acid.
  • a "polymer” refers to any kind of synthetic or natural oligomer or polymer having two or more repeat units, including thermoplastics, thermosets, elastomers, polymer blends, polymer composites, synthetic rubbers, and natural rubbers.
  • a synthetic oligomer or polymer can be prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term “polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as “interpolymer.”
  • Interpolymer refers to a polymer prepared by the polymerization of at least two different types of monomers.
  • the generic term “interpolymer” includes the term “copolymer” (which generally refers to a polymer prepared from two different monomers) as well as the term “terpolymer” (which generally refers to a polymer prepared from three different types of monomers). Interpolymer also encompasses polymers made by polymerizing four or more types of monomers.
  • Hydrocarbyl refers to a group containing one or more carbon atom backbones and hydrogen atoms, and the group may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups known to one of skill in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic, or any combination thereof. Aliphatic segments may be straight or branched. Aliphatic and cycloaliphatic groups may include one or more double and/or triple carbon-carbon bonds.
  • hydrocarbyl groups include alkyl, alkenyl, alkynyl, aryl, cyclalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic moieties and noncyclic portions.
  • the hydrocarbyl group is a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted Ci-C 30 hydrocarbyl group (e.g., Ci-C 2 o alkyl, C 1 -C 20 alkenyl, C 1 -C 20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl).
  • Alkyl refers to a group having the general formula C n H 2n+ i derived from a saturated, straight chain or branched aliphatic hydrocarbon, where n is an integer. In certain embodiments, n is from 1 to about 30, from 1 to about 20, or from 1 to about 10.
  • Non- limiting examples of alkyl groups include CpCg alkyl groups such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2-methylbutyl, 3- methylbutyl, 2,2,-dimethylpropyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-butyl, isobutyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl and isodecyl.
  • CpCg alkyl groups such as methyl,
  • An alkyl group may be unsubstituted, or may be substituted.
  • the alkyl group is straight chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons.
  • the alkyl group is branched having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons.
  • Cycloaliphatic encompasses "cycloalkyl” and "cycloalkenyl.” Cycloaliphatic groups may be monocyclic or polycyclic. A cycloaliphatic group can be unsubstituted or substituted with one or more suitable substituents.
  • Cycloalkyl refers to a saturated carbocyclic mono- or bicyclic (fused or bridged) ring of 3-12 (e.g., 5-12) carbon atoms.
  • Non-limiting examples of cycloalkyl include C 3 -C 8 cycloalkyl groups, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups and saturated cyclic and bicyclic terpenes. Cycloalkyl groups may be unsubstituted or substituted.
  • Cycloalkenyl refers to a non-aromatic carbocyclic mono- or bicyclic ring of 3 to 12
  • cycloalkenyl include C3-C8 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and unsaturated cyclic and bicyclic terpenes. Cycloalkenyl groups may be unsubstituted or substituted.
  • Aryl refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom.
  • Non-limiting examples of the aryl group include phenyl, naphthyl, benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl.
  • An aryl group can be unsubstituted or substituted with one or more suitable substituents.
  • the aryl group can be monocyclic or polycyclic. In some embodiments, the aryl group contains at least 6, 7, 8, 9, or 10 carbon atoms.
  • one or more dashed bonds in a structure independently represents a bond that may or may not be present.
  • the dashed bond in the structure indicates a bond that may be present to result in a double bond, or may not be present to result in a single bond.
  • Isoprenoid and “isoprenoid compound” are used interchangeably herein and refer to a compound derivable from isopentenyl diphosphate.
  • a substituted group or compound refers to a group or compound in which at least one hydrogen atom is replaced with a substituent chemical moiety.
  • a substituent chemical moiety may be any suitable substituent that imparts desired properties to the compound or group.
  • substituents include halo, alkyl, heteroalkyl, alkenyl, alkynyl, aryl, heteroayrl, hydroxyl, alkoxyl, amino, nitro, thiol, thioether, imine, cyano, amido, phosphonato, phosphine, carbosyl, thiocarbonyl, sulfonyl, sulfonamide, carbonyl, formyl, carbonyloxy, oxo, haloalkyl (e.g.
  • carbocyclic cycloalkyl (which may be monocyclic, or fused or non-fused polycyclic) such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or a heterocycloalkyl (which may be monocyclic, or fused or nonfused polycyclic such as pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl or thiazinyl), carbocyclic or heterocyclic, monocyclic or fused or nonfused polycyclic aryl (e.g.
  • detergent refers to an agent or composition that is useful for cleaning surfaces or articles.
  • a detergent may lift or remove soil, food, oil, grease and the like from a surface (e.g., fabric or a hard surface) and/or disperse or solubilize particles in a medium (e.g., disperse or suspend oil particles in an aqueous solution).
  • a detergent can be in any form such as liquid, paste, gel or solid (e.g., powder, a granular solid, a bar or tablet).
  • the conjugated terpenes disclosed herein may be obtained from any suitable source.
  • the conjugated terpene is obtained from naturally occurring plants or marine species.
  • farnesene can be obtained or derived from naturally occurring terpenes that can be produced by a variety of plants, such as Copaifera langsdorfii, conifers, and spurges; or by insects, such as swallowtail butterflies, leaf beetles, termites, or pine sawflies; and marine organisms, such as algae, sponges, corals, mollusks, and fish.
  • Terpene oils can also be obtained from conifers and spurges.
  • Conifers belong to the plant division Pinophya or Coniferae and are generally cone-bearing seed plants with vascular tissue. Conifers may be trees or shrubs. Non-limiting examples of suitable conifers include cedar, cypress, douglas fir, fir, juniper, kauris, larch, pine, redwood, spruce and yew.
  • Spurges also known as Euphorbia, are a diverse worldwide genus of plants belonging to the spurge family (euphorbiaceae). Farnesene is a sesquiterpene, a member of the terpene family, and can be derived or isolated from terpene oils for use as described herein.
  • a conjugated terpene is derived from a fossil fuel (petroleum or coal), for example, by fractional distillation of petroleum or coal tar.
  • a conjugated terpene is made by chemical synthesis.
  • suitable chemical synthesis of farnesene includes dehydrating nerolidol with phosphoryl chloride in pyridine as described in the article by Anet E.F.L.J., "Synthesis of ( ⁇ , ⁇ )- ⁇ -, and (Z)-P-farnesene, Aust. J. Chem. 23(10), 2101-2108, which is incorporated herein by reference in its entirety.
  • a conjugated terpene is obtained using genetically modified organisms that are grown using renewable carbon sources (e.g., sugar cane).
  • a conjugated terpene is prepared by contacting a cell capable of making a conjugated terpene with a suitable carbon source under conditions suitable for making a conjugated terpene.
  • suitable carbon source e.g., sugar cane
  • Non-limiting examples conjugated terpenes obtained using genetically modified organisms are provided in U.S. Pat. No. 7,399,323, U.S. Pat. Publ. Nos. 2008/0274523 and 2009/0137014, and International Patent
  • any carbon source that can be converted into one or more isoprenoid compounds can be used herein.
  • the carbon source is a fermentable carbon source (e.g., sugars), a nonfermentable carbon source or a combination thereof.
  • a non-fermentable carbon source is a carbon source that cannot be converted by an organism into ethanol.
  • suitable non-fermentable carbon sources include acetate, glycerol, lactate and ethanol.
  • the sugar can be any sugar known to one of skill in the art.
  • the sugar is a monosaccharide, disaccharide, polysaccharide or a combination thereof.
  • the sugar is a simple sugar (a monosaccharide or a disaccharide).
  • suitable monosaccharides include glucose, galactose, mannose, fructose, ribose and combinations thereof.
  • suitable disaccharides include sucrose, lactose, maltose, trehalose, cellobiose, and combinations thereof.
  • the sugar is sucrose.
  • the carbon source is a polysaccharide.
  • suitable polysaccharides include starch, glycogen, cellulose, chitin, and combinations thereof.
  • the sugar suitable for making a conjugated terpene can be obtained from a variety of crops or sources.
  • suitable crops or sources include sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potato, sweet potato, cassava, sunflower, fruit, molasses, whey, skim milk, corn, stover, grain, wheat, wood, paper, straw, cotton, cellulose waste, and other biomass.
  • suitable crops or sources include sugar cane, sugar beet and corn.
  • the sugar source is cane juice or molasses.
  • a conjugated terpene can be prepared in a facility capable of biological manufacture of isoprenoids.
  • the facility may comprise any structure useful for preparing C i5 isoprenoids (e.g., a-farnesene, ⁇ -farnesene, nerolidol or farnesol) using a microorganism capable of making the Ci 5 isoprenoids with a suitable carbon source under conditions suitable for making the Ci 5 isoprenoids.
  • the biological facility comprises a cell culture comprising a desired isoprenoid (e.g., a Cio, a Ci 5 , a C 20 , or a C25 isoprenoid) in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%, based on the total weight of the cell culture.
  • the biological facility comprises a fermentor comprising one or more cells capable of generating a desired isoprenoid. Any fermentor that can provide for cells or bacteria a stable and optimal environment in which they can grow or reproduce may be used herein.
  • the fermentor comprises a culture comprising one or more cells capable of generating a desired isoprenoid (e.g., a C w , a Ci 5 , a C 2 o, or a C25 isoprenoid).
  • a desired isoprenoid e.g., a C w , a Ci 5 , a C 2 o, or a C25 isoprenoid.
  • the fermentor comprises a cell culture capable of biologically manufacturing farnesyl pyrophosphate (FPP).
  • FPP farnesyl pyrophosphate
  • IPP isopentenyl diphosphate
  • the fermentor comprises a cell culture comprising a desired isoprenoid (e.g., a C 10 , a Ci 5 , a C 20 , or a C25 isoprenoid) in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%, based on the total weight of the cell culture.
  • a desired isoprenoid e.g., a C 10 , a Ci 5 , a C 20 , or a C25 isoprenoid
  • the facility may further comprise any structure capable of manufacturing a chemical derivative from the desired isoprenoid (e.g., a C 10 , a Ci 5 , a C 20 , or a C25 isoprenoid).
  • a facility comprises a reactor for dehydrating nerolidol or farnesol to a-farnesene or ⁇ - farnesene or a combination thereof.
  • a facility comprises a reactor for dehydrating linalool to myrcene or ocimene or a combination thereof. Any reactor that can be used to convert an alcohol into an alkene under conditions known to skilled artisans may be used.
  • the reactor comprises a dehydrating catalyst.
  • Described herein are Diels-Alder adducts of conjugated terpenes and a dienophile, and derivatives of such Diels-Alder adducts.
  • Diels-Alder reaction between a conjugated terpene and a dienophile a [2 ⁇ + 4 ⁇ ] cycloaddition reaction between the conjugated diene moiety of the conjugated terpene and the dienophile occurs.
  • the stereochemistry of the resulting compounds can be reliably predicted using orbital symmetry rules.
  • the hydrocarbon terpene is selected to have a stereochemistry amenable to Diels-Alder reactions. That is, the conjugated diene is able to adopt an s-cis conformer.
  • the double bonds exist in an s-cis conformation or conformational rotation around the single bond between the double bonds so that an s-cis conformation of the diene is adoptable.
  • the s-trans conformer population is in rapid equilibrium with s-cis conformers. In some cases, steric effects due to substituents on the conjugated diene may impede a Diels-Alder reaction.
  • the hydrocarbon terpene and a dienophile in a Diels-Alder reaction may each demonstrate stereoisomerism.
  • Stereoisomerism of the reactants is preserved in the Diels-Alder adduct, and the relative orientation of the substituents on the reactants is preserved in the Diels-Alder adduct.
  • fumaric acid and fumaric acid esters exist as trans -isomers, so if a fumaric acid ester is used a dienophile, the carboxylate groups in the Diels-Alder adduct have a 1 ,2-anti- (also referred to as trans-) orientation relative to each other.
  • the carboxylate groups (or anhydride) of maleic anhydride, maleic acid, and maleic acid esters (maleates) have a cis- orientation, so that the carboxylate groups in the Diels-Alder adduct have a ⁇ ,2-syn- (also referred to as cis-) orientation relative to each other.
  • a Diels-Alder reaction between a conjugated terpene and a dienophile is thermally driven, without the need for a catalyst.
  • a Diels-Alder reaction occurs at a temperature in a range from about 50 °C to about 100 °C, or from about 50 °C to about 130 °C.
  • a catalyst is used, e.g., to increase reaction rate, to increase reactivity of weak dienophiles or sterically hindered reactants, or to increase selectivity of certain adducts or isomers.
  • a Lewis acid may be used in some variations.
  • a Diels- Alder reaction is run without solvent.
  • reaction conditions e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere are selected so that formation of dimers, higher oligomers and/or polymers of the conjugated terpene is suppressed or minimized.
  • Reaction conditions e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere may be selected so that formation of dimers, higher oligomers and/or polymers of the diene is suppressed or minimized.
  • the reaction conditions e.g., temperature, catalyst (if present), solvent (if present), reactant purities, reactant concentrations, reaction times, reaction atmosphere and/or reaction pressure are selected to produce a desired adduct or isomer.
  • trans- ⁇ -farnesene [(6E)-7,1 l-dimethyl-3-methylidenedodeca-l,6,10-triene] is selected to be reacted with a suitable dienophile to form Diels-Alder adducts described herein.
  • a variety of electron deficient dienophiles may effectively undergo the Diels-Alder reaction with conjugated terpenes to produce cyclic compounds that have utility as described herein. Any dienophile that can undergo the Diels-Alder reaction with one or more dienes may be used herein. Some non-limiting examples of suitable dienophiles are disclosed in Fringuelli et al., titled “The Diels- Alder Reaction: Selected Practical Methods " 1 st edition, John Wiley & Sons, Ltd., New York, pages 3- 5 (2002), which is incorporated herein. Other non-limiting examples of dienophiles are provided in Section D below.
  • Any conjugated terpene described herein or otherwise known may undergo Diels- Alder reaction with a dienophile to provide a Diels-Alder adduct having utility as described herein.
  • Some non-limiting examples of conjugated terpenes that may be used to make the Diels-Alder adducts are provided in Section E below and include myrcene, ocimene, a-farnesene, ⁇ -farnesene, ⁇ -springene, geranylfamesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.
  • Some non- limiting examples of Diels-Alder adducts are provided in Section G below. D) Dienophiles
  • the dienophile used herein can be any dienophile that undergoes a Diels-Alder reaction with a diene on the conjugated hydrocarbon terpene to form the corresponding cyclic compound.
  • the dienophile has formula (I), (II) or (III):
  • each of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C 1 -C30 hydrocarbyl group (e.g., C 1 -C 2 0 alkyl, C 1 -C 2 0 alkenyl, C 1 -C 20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl), hydroxyalkyl (e.g., -CH 2 OH), aminoalkyl (e.g., -CH 2 NH 2 ), carboxylalkyl (e.g., -CH 2 C0 2 H), thioalkyl (e.g., -CH 2 SH), epoxyalkyl (e.g., glycidyl), hydroxyaryl, aminoaryl, carboxylaryl, thioaryl, hydroxyl,
  • R 25 , R 26 , R 27 and R 28 is independently H, hydrocarbyl, hydroxyalkyl, aminoalkyl, carboxylalkyl, thioalkyl, epoxyalkyl, hydroxyaryl, aminoaryl, carboxylaryl, thioaryl, hydroxyl, amino, halo, cyano, nitro or acyl, or R 25 and R 26 together or R 27 and R 28 together form a benzo ring or a substituted or
  • each of m, n and k is independently an integer from 1 to 20 or from 1 to 12, with the proviso that at least one of R 11 , R 12 , R 13 and R 14 is not H, and the proviso that at least one of R 15 and R 16 is not H, and the proviso that at least one of R 17 and R 18 is not H.
  • a dienophile has formula (Al), (A2), (A3), (A4), (A5), (A6), or
  • QA 1 may be O, S, or NRA 19 ; each of QA 2 , QA 3 and QA 4 may independently be a halo substituent (e.g., chloro or bromo), NRA 20 RA 21 or ORA 22 ; QA 5 may be a halo substituent (e.g., chloro or bromo), a cyano group or ORA 23 ; and each of RA 1 , RA 2 , RA 3 , RA 4 , RA 5 , RA 6 , RA 7 , RA 8 , RA 9 , RA 10 , RA 11 , RA 12 , RA 13 , RA 14 , RA 15 , RA 16 , RA 17 , RA 18 , RA 19 , RA 20 , RA 21 , RA 22 and RA 23 is independently H, C 1 -C 20 alkyl
  • the dienophile comprises an unsaturated carbon-carbon bond with one or more electron withdrawing groups attached to a carbon of the unsaturated bond.
  • electron withdrawing groups that may be attached to an unsaturated carbon-carbon bond in a dienophile include: one or more substituted carbonyl groups such as one or more ester groups represented as -COOR, one or more aldehyde groups represented as -CHO, one or more ketone groups represented as -COR, one or more carboxyl groups represented as -COOH, one or more amide groups represented as - CONRR', one or more imide groups represented as -CONRCOR', one or more aryloxycarbonyl groups such as a phenoxycarbonyl group, one or more carbonyloxycarbonyl groups, or a one or more carbonyliminocarbonyl groups, wherein each of R and R' is independently H or any Ci-C 30 aliphatic, aromatic, linear, branched, cyclic or
  • the dienophile comprises sulfur dioxide, or a sulfone SO 2 RR', where R and R' may independently be any Ci-C 30 hydrocarbyl group.
  • Suitable dienophiles that can form Diels-Alder adducts with conjugated terpenes (e.g., farnesene or myrcene) include acrylate esters, vinyl ketones, monoalkyl or dialkyl maleates, maleic anhydride, maleimides and substituted maleimides, acetylene dicarboxylic acids and their monoesters or diesters, and quinones.
  • dienophiles that can react with a conjugated terpene (e.g., farnesene or myrcene) to produce a compound useful as described herein include dienophiles in groups (A)-(Y) below:
  • (G) monoalkyl or dialkyl maleates or monoalkyl or dialkyl fumarates e.g., linear or branched, cyclic or acyclic, C 1 -C30 dialkyl maleates or dialkyl fumarates such as dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, di-n-propyl maleate, di-n-propyl fumarate, di-isopropyl maleate, diisopropyl fumarate, di-n-butyl maleate, di-n-butyl fumarate, diisobutyl maleate, di(isobutyl) fumarate, di-tert-butyl maleate, di-tert-butyl fumarate, di-n-pentyl maleate, di-n-pentyl fumarate, diisopentyl maleate, diisopentyl fumarate, di-n-hexyl maleate, di
  • (H) monoalkyl or dialkyl itaconates e.g., linear or branched, cyclic or acyclic, Ci-C 30 dialkyl itaconates such as dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, diisopropyl itaconate, di-n-butyl itaconate, diisobutyl itaconate, di-tert-butyl itaconate, di-n-pentyl itaconate, diisopentyl itaconate, di-n- hexyl itaconate, bis(2-ethylhexyl) itaconate, diisohexyl itaconate, di-n-heptyl itaconate, diisoheptyl itaconate, di-n-octyl itaconate, diisooctyl itaconate, di-n-nonyl itacon
  • acrylic acid esters e.g., linear or branched, cyclic or acyclic, Ci-C 30 alkyl acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isohexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, isoheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, 2-
  • methacrylic acid esters e.g., linear or branched, cyclic or acyclic, C 1 -C30 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, isoheptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl me
  • (M)hydroxyalkyl acrylates e.g., 2-hydroxymethyl acrylate and 2 -hydroxy ethyl acrylate
  • (N) carboxyalkyl acrylates e.g., 2-carboxy ethyl acrylate
  • dialkylamino)alkyl acrylates e.g., 2-(diethylamino)ethyl acrylate
  • (P) monoalkyl and dialkyl acetylene dicarboxylates e.g., linear or branched, cyclic or acyclic, C 1 -C30 dialkyl acetylene dicarboxylates such as dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, di-n-propyl acetylene dicarboxylate, diisopropyl acetylene dicarboxylate, di-n- butyl acetylene dicarboxylate, diisobutyl) acetylene dicarboxylate, di(tert-butyl) acetylene dicarboxylate, di-n-pentyl acetylene dicarboxylate, diisopentyl acetylene dicarboxylate, di-n-hexyl acetylene dicarboxylate, bis(2-ethylhexyl)
  • an alkyl propiolate e.g., an alkyl propiolate incorporating any C 1 -C 20 alkyl group such as methyl propiolate, ethyl propiolate, or butyl propiolate
  • an alkyl 2-butynoate e.g., an alkyl 2-pentynoate, an alkyl 2-hexynoate, 2-butynoic acid, and 2-pentynoic acid
  • an alkyl 2-butynoate e.g., an alkyl 2-butynoate incorporating any C 1 -C 20 alkyl group such as methyl 2-butynoate, ethyl 2-butynoate, propyl 2-butynoate, or propyl 2-butynoate
  • an alkyl 2-pentynoate e.g., an alkyl 2-pentynoate incorporating any C 1 -C 20 alkyl group such as methyl 2-penty
  • (Q) vinyl ketones e.g., linear or branched, cyclic or acyclic, aliphatic or aromatic, C 1 -C30 vinyl ketones, such as methyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, n-butyl vinyl ketone, isobutyl vinyl ketone, tert-butyl vinyl ketone, n-pentyl vinyl ketone, n-hexyl vinyl ketone, 2-ethylhexyl vinyl ketone, n-heptyl vinyl ketone, n-octyl vinyl ketone, n-nonyl vinyl ketone, n-decyl vinyl ketone, n-undecyl vinyl ketone, n-dodecyl vinyl ketone, n-tridecyl vinyl ketone, n-tetradecyl vinyl ketone, n-penta
  • maleamides, fumaramides, maleimide and substituted maleimides e.g., maleic acid diamide, or C r C 30 alkyl or aryl N- or ⁇ , ⁇ '- substituted maleamides such as N-methyl maleamide, N-ethyl maleamide, N-n-butyl maleamide, ⁇ , ⁇ '-dimethyl maleamide, ⁇ , ⁇ '-methyl ethyl maleamide, or N,N'-tetramethyl maleamide; fumaramide, or Ci-C 30 alkyl or aryl N- or ⁇ , ⁇ '- substituted fumaramides such as N-methyl fumaramide, N-isopropyl fumaramide, ⁇ , ⁇ '-diethyl fumaramide, N,N'-di-n-butyl fumaramide, ⁇ , ⁇ '- tetraethyl fumaramide; linear or branched, cyclic or acyclic, C 1 -C30 alkyl or aryl
  • (S) dialkyl azidocarboxylates e.g. linear or branched, cyclic or acyclic, Ci-C 30 dialkyl
  • azidocarboxylates such as dimethyl azidocarboxylate, and diethyl azidocarboxylate
  • the conjugated hydrocarbon terpene used herein can be any conjugated hydrocarbon terpene having a diene group that undergoes a Diels-Alder reaction with a dienophile to form the corresponding cyclic compound.
  • the conjugated hydrocarbon terpene has formula (IV):
  • each of RB 1 , RB 2 , RB 3 and RB 4 is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted Ci-C 30 hydrocarbyl group, with the proviso that at least one of RB 1 , RB 2 , RB and RB 4 is not hydrogen.
  • the hydrocarbon terpene is selected to have a stereochemistry amenable to Diels-Alder reactions, That is, the conjugated diene is able to adopt an s-cis conformer.
  • Diels-Alder cycloaddition reaction the double bonds exist in an s-cis conformation or conformational rotation around the single bond between the double bonds so that an s-cis conformation of the diene is adoptable.
  • the s-trans conformer population is in rapid equilibrium with s-cis conformers.
  • hydrocarbon terpenes having terminal conjugated diene groups are selected, i.e., hydrocarbon terpenes in which RB 1 , RB 2 , and RB 3 are each H, but RB 4 is not H.
  • RB 1 is H
  • RB 2 , RB 3 and RB 4 are not H.
  • ⁇ B 1 and RB 2 are H, but RB 3 and RB 4 are not H.
  • the conjugated hydrocarbon terpene has formula (IV) where each of RB 1 , RB 3 and RB 4 is independently H; and RB 2 has formula (V):
  • the conjugated hydrocarbon terpene has formula (AI):
  • n 1, 2, 3 or 4.
  • the conjugated hydrocarbon terpene is myrcene which has formula (AI) where n is 1. In some embodiments, the conjugated hydrocarbon terpene is ⁇ -farnesene which has formula (AI) where n is 2. In certain embodiments, the conjugated hydrocarbon terpene is ⁇ - springene which has formula (AI) where n is 3. In some embodiments, the conjugated hydrocarbon terpene is geranylfarnesene which has formula (AI) where n is 4.
  • the conjugated hydrocarbon terpene has formula (IV) where each of RB 3 and RB 4 is H; RB 2 is methyl; and RB 1 has formula (VI): (VI), wherein m is 1, 2, 3 or 4.
  • the dashed bond in formula (VI) represents a bond that may be present to result in a double bond, or may not be present to result in a single bond.
  • the conjugated hydrocarbon terpene has formula (All):
  • m 1, 2, 3 or 4.
  • the conjugated hydrocarbon terpene is ⁇ -ocimene which has formula (All) where m is 1. In some embodiments, the conjugated hydrocarbon terpene is a-farnesene which has formula (All) where m is 2.
  • the conjugated hydrocarbon terpene that can react with a dienophile disclosed herein is isodehydrosqualene.
  • the conjugated hydrocarbon terpene is isosqualane precursor I.
  • the hydrocarbon terpene is isosqualane precursor II.
  • Diels-Alder adducts can be prepared by reacting a dienophile disclosed herein with one or more conjugated hydrocarbon terpene under suitable Diels-Alder reaction conditions with or without the presence of a catalyst.
  • the hydrocarbon terpene and a dienophile in a Diels-Alder reaction may each demonstrate stereoisomerism. Stereoisomerism of the reactants is preserved in the Diels-Alder adduct, and the relative orientation of the substituents on the reacts is preserved in the Diels-Alder adduct.
  • fumaric acid and fumaric acid esters exist as trans-isomers, so if a fumaric acid ester is used as a dienophile, the carboxylate groups in the Diels-Alder adduct have a 1 ,2-anti- (also referred to as trans-) orientation relative to each other.
  • the carboxylate groups (or anhydride) of maleic anhydride, maleic acid, and maleic acid esters (maleates) have a cis- orientation, so that the carboxylate groups in the Diels-Alder adduct have a 1 ,2-syn- (also referred to as a cis-) orientation relative to each other.
  • a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (I) to provide the Diels-Alder adduct having formula (VIIA) or (VIIB) or a mixture thereof:
  • the Diels-Alder adduct of formula (VIIA) and (VIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIA') and (VIIB') respectively:
  • RB 1 , RB 2 , RB 3 , RB 4 , R 11 , R 12 , R 13 and R 14 are as defined herein.
  • a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (II) to provide the Diels-Alder adduct having formula (VIIIA) or (VIIIB) or a mixture thereof:
  • the Diels-Alder adduct of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB”), respectively.
  • the Diels-Alder adduct of formula (VIIIA) and (VIIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIIA') and (VIIIB') respectively:
  • the Diels-Alder adduct of formula (VIIIA) and (VIIIB) or of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB"), respectively: (VIIIA"), or (VIIIB”),
  • RB 1 , RB 2 , RB 3 , RB 4 , R 15 and R 1 1 6 6 are as defined herein.
  • a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (III) to provide the Diels-Alder adduct having formula (IXA) or (IXB) or a mixture thereof:
  • RB 1 , RB 2 , RB 3 , RB 4 , R 17 and R 18 are as defined herein.
  • the Diels-Alder adduct of formula (IXA) and (IXB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula ( ⁇ ') and ( ⁇ ') respectively:
  • RB 1 , RB 2 , RB 3 , RB 4 , R 17 and R 18 are as defined herein.
  • each of RB 1 , RB 3 and RB 4 of the adduct of formula (VILA) is adduct of formula (VILA)
  • n 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4. [00116] In some embodiments, RB having formula (X) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XI):
  • n 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.
  • RB 2 having formula (X) in the adducts disclosed herein can be epoxidized by any epoxidation reaction known to a skilled artisan to form the corresponding epoxy group having formula (XII):
  • n 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.
  • m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4.
  • RB 1 having formula (XIII) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XLV): wherein m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4. [00120] In some embodiments, RB having formula (XIII) in the adducts disclosed herein can be epoxidized by any epoxidation reaction known to a skilled artisan to form the corresponding epoxy group having formula (XV):
  • m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4.
  • the Diels-Alder adduct between a conjugated hydrocarbon terpene and a dienophile is represented by formula (Bl):
  • RB 1 , RB 2 , RB 3 and RB 4 represent the substituents of the conjugated diene of the conjugated terpene and may each independently be H or a Ci-C 30 saturated or unsaturated, cyclic or acyclic, hydrocarbyl group, with the proviso that one of RB 1 , RB 2 , RB 3 and RB 4 is not hydrogen.
  • QB 1 and QB 2 represent the residue of the dienophile directly following the Diels-Alder reaction.
  • QB 1 and QB 2 represent the residue following Diels-Alder reaction that has undergone subsequent chemical modification.
  • a 6-membered ring adduct is formed by the Diels-Alder reaction.
  • the Diels-Alder adduct formed comprises a 5-membered ring so that QB 1 and QB 2 are the same.
  • Each of the dashed bonds in formula (Bl) independently represents a bond that may be present to result in a double bond, or may not be present to result in a single bond.
  • the Diels-Alder adduct is derived form a dienophile containing a double bond and therefore, the bond between QB 1 and QB 2 is single and the bond between RB 2 and RB 3 is double.
  • the Diels-Alder adduct is derived form a dienophile containing a triple bond, and therefore, the bond between QB 1 and QB 2 is double and the bond between RB 2 and RB 3 is double. In some embodiments, the Diels-Alder adduct is derived form a dienophile containing a double bond and is hydrogenated to saturate the double bond between RB 2 and RB 3 to form a single bond.
  • the Diels-Alder adduct is hydrogenated to saturate all or some of the unsaturated bonds in the ring and/or in one or more of the RB 1 , RB 2 , RB 3 , RB 4 , QB 1 and QB 2 groups.
  • a cyclohexenyl ring may be oxidized to form a cyclohexadienyl ring.
  • a cyclohexenyl or a cyclohexadienyl ring may be oxidized so that the ring is aromatic.
  • the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (AI) and a dienoph herein and the adduct has formula
  • the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 2.
  • the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 1.
  • the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (All) and a dienophile disclosed herein and the adduct has formula
  • the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 2.
  • the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 1.
  • Table 1 shows RB 1 , RB 2 , RB 3 and RB 4 for exemplary conjugated terpenes, where dashed lines indicate unsaturated olefinic bonds originating from the conjugated terpene that may in some embodiments be completely or partially hydrogenated prior to or subsequent to the Diels-Alder reaction.
  • Table 2 shows QB 1 and QB 2 for some exemplary dienophiles.
  • isomers may be formed in which RB 1 is reversed with RB 4 , RB 2 is reversed with RB 3 , and/or QB 1 is reversed with QB 2 .
  • the Diels-Alder adduct having formula (Bl) may include any combination of RB 1 , RB 2 , RB 3 and RB 4 shown in Table 1 with any combination of QB 1 and QB 2 shown in Table 2.
  • RB 1 , RB 2 , RB 3 and RB 4 are as defined herein, and RB 1 , RB 2 , RB 3' , and RB 4' are defined as RB 1 , RB 2 , RB 3 and RB 4 .
  • Table 1 Some exemplary conjugated terpenes for making Diels-Alder adducts having formula (Bl).
  • a Diels-Alder adduct is formed in which two conjugated terpene molecules react with a single dienophile (e.g., a dienophile comprising an acetylenic moiety).
  • a single dienophile e.g., a dienophile comprising an acetylenic moiety.
  • Some non- limiting examples are shown as entries 11, 12, 13, 14, 16 and 17 in Table 2. It should be noted that the two conjugated terpenes that react with a single dienophile may be the same or different.
  • conjugated terpenes may react with a single dienophile: 2 myrcene; 2 a- farnesene; 2 ⁇ -farnesene; 1 a-farnesene and 1 ⁇ -farnesene; 1 myrcene and 1 a-farnesene, 1 myrcene and 1 ⁇ -farnesene.
  • a Diels-Alder adduct is formed in which one conjugated terpene molecule (e.g., myrcene, ⁇ -farnesene, or ⁇ -farnesene) and one substituted or unsubstituted conjugated diene molecules (e.g., 1,3 -butadiene) is reacted with a single dienophile (e.g., a dienophile comprising an acetylenic moiety).
  • one conjugated terpene molecule e.g., myrcene, ⁇ -farnesene, or ⁇ -farnesene
  • one substituted or unsubstituted conjugated diene molecules e.g., 1,3 -butadiene
  • oligomers e.g., dimers and trimers
  • Diels-Alder adducts between oligomers e.g., dimers and trimers
  • oligomers e.g., dimers and trimers
  • ⁇ -farnesene can be dimerized (e.g., to form isodehydrosqualene, isosqualane precursor I or isosqualane precursor II), trimerized, or oligomerized as described in U.S. Patent Application No. 13/ US 13/112,991, filed May 20, 2011, and U.S. Patent Application No. 12/552278, filed Sept. 1, 2009, or to form cyclic dimers, as described in U.S. Patent Nos.
  • the dimers, trimers and oligomers so formed may contain a conjugated diene, which can undergo Diels- Alder reaction with a dienophile.
  • a Diels-Alder adduct between one or more conjugated terpenes and a dienophile as described herein may be chemically modified following the Diels-Alder reaction.
  • the chemical modifications may be selected to tune the applicability to the modified Diels-Alder reaction for use as oils, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • any one of or any suitable combination of the following chemical modifications in any suitable order may be made to a Diels-Alder adduct: i) an alkoxycarbonyl group may be reduced to a hydroxymethyl or methyl group; ii) one or more ester groups may be hydrolyzed to a carboxylic acid or a salt thereof; iii) one or more carboxyl groups may be decarboxylated to a hydrogen; iv) an anhydride group may be opened to yield the dicarboxylic acid compound or a salt thereof; v) an anhydride group may be opened with an amine to produce a compound having a carboxylic acid group and an amide group on adjacent carbons; vi) reduction of amides to amines; vii) opening of anhydrides with hydrogen peroxide; viii) one or more ester groups on a Diels Alder adduct may undergo
  • transesterification with an alcohol e.g. a methyl ester may undergo transesterification with a C 8 or longer primary alcohol
  • a formyl group may be reduced to a methyloyl group
  • x) a hydroxyl substituent may be alkoxylated to form an alkoxylated substituent (e.g., ethoxylated or propoxylated)
  • xi) one or more double bonds originating from the conjugated terpene can be oxidized (e.g., epoxidized);
  • xii) one or more double bonds originating from the conjugated terpene may be halogenated;
  • xiii) a hydroxyl or ester group may undergo a condensation reaction;
  • xiv) a hydroxyl group or amide group may undergo a condensation reaction;
  • xv) a hydroxyl group or ester group may be sulfated;
  • xvi) an alcohol may be converted to an alky
  • a Diels-Alder adduct between a conjugated terpene and a dienophile as described herein is hydrogenated so as to completely or partially hydrogenate aliphatic portions of the Diels-Alder adduct.
  • Such hydrogenated Diels-Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo-oxidative stability in use.
  • a ring formed in the Diels-Alder adduct is oxidized.
  • a cyclohexenyl ring may be oxidized to a cyclohexadienyl ring or to an aromatic 6-membered ring, or a cyclohexadienyl ring may be oxidized to an aromatic 6-membered ring.
  • At least one carbon-carbon double bond remains in the aliphatic tail originating from the conjugated terpene in the Diels-Alder adduct.
  • the unsaturated tail provides a reactive site that may have a variety of functions.
  • the unsaturated tail may be oxidized as described in more detail herein, may provide scavenging functionality, may provide a site for oligomerization or polymerization, and/or may provide a site for cross-linking into a matrix.
  • the unsaturated bond may undergo oxidation, e.g., to form a polyol.
  • Table 3 illustrates some non-limiting examples of chemical modifications of Diels-Alder adducts between conjugated terpenes and dienophiles.
  • Diels-Alder adduct as described herein is oxidized (e.g., epoxidized).
  • oxidized (e.g., epoxidized) hydrocarbon terpene derivatives may be useful in a variety of applications.
  • oxidized farnesene derivatives may exhibit increased compatibility or solubility with relatively polar polymers or solvents.
  • an epoxidized farnesene derivative may be useful as a reactive diluent in a resin and/or as a cross-linking agent. Any suitable oxidation technique known to oxidize carbon- carbon double bonds may be used.
  • any suitable oxidant such as peroxides, peracetic acid, meta chloroperoxybenzoic acid, enzymes, or peroxide complexes such as urea-peroxide complexes (e.g., Novozyme-435TM urea-peroxide complex) may be used.
  • the oxidation (e.g., epoxidation) conditions are adjusted to oxidize only one carbon-carbon double bond, e.g., one carbon- carbon double bond that originated in the conjugated terpene starting material.
  • the oxidation (e.g., epoxidation) conditions are adjusted to oxidize two carbon-carbon double bonds, e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, oxidation (e.g., epoxidation) conditions are adjusted to oxidize three or more carbon- carbon double bonds, e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, oxidation (e.g. , epoxidation) conditions are adjusted to oxidize substantially all carbon-carbon double bonds originating in the conjugated terpene starting material.
  • a molar ratio of oxidan conjugated terpene may be lower than the number of unsaturated carbon-carbon bonds to produce compositions in which not all carbon-carbon double bonds are oxidized (e.g., epoxidized).
  • a molar ratio of oxidant:conjugated terpene may be about 5: 1 or less for farnesene- based compounds, such as about 5: 1, 4: 1, 3: 1, 2: 1, 1 : 1 or 0.5: 1.
  • Alcohols and polyols may be derived from epoxidized hydrocarbon terpene Diels-Alder adducts using any known technique that allows for reaction of epoxy groups to form hydroxyl groups. For example, an epoxy group can be reduced to form a single hydroxyl group, or an epoxy group can be hydrolyzed to form two hydroxyl groups. In some varaitions, the hydroxyl groups may be subsequently acetylated to form a compound that may have use as described herein.
  • the alcohols and diols disclosed herein have utility as solvents, emollients (e.g., cosmetics), or surfactants.
  • Diels-Alder adduct as described herein is halogenated, e.g., with chlorine where one chlorine atom is added to each double bond using a reagent such as HC1, or where two chlorine atoms are added to each double bond using a reagent such as chlorine gas.
  • a reagent such as HC1
  • chlorine gas such as chlorine gas
  • Such chloride containing hydrocarbon conjugated terpene derivatives may for example exhibit increased compatibility or solubility with relatively polar polymers or solvents.
  • the reaction conditions are adjusted such only one carbon- carbon double bond is chlorinated, e.g. , one carbon-carbon double bond that originated in the conjugated terpene starting material.
  • reaction conditions are adjusted so that two carbon- carbon double bonds are halogenated (e.g., chlorinated), e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material.
  • reaction conditions are adjusted such that three or more carbon-carbon double bonds are halogenated (e.g., chlorinated), e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material.
  • substantially all carbon-carbon double bonds originating from the conjugated terpene are halogenated (e.g., chlorinated).
  • Diels-Alder adducts made using ⁇ -farnesene or a-farnesene as the conjugated hydrocarbon terpene. It should be understood that analogs of these examples of Diels-Alder adducts are contemplated in which conjugated terpenes other than a-farnesene or ⁇ -farnesene are used.
  • a Diels-Alder adduct is formed between ⁇ -farnesene and acrylic
  • An oil, solvent, lubricant, additive or base oil for a lubricant formulation, a surfactant, a plasticizer, or a monomer, cross-linking agent or reactive diluent for use in making oligomers or polymers may be derived from a Diels-Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester. Diels-Alder adducts formed between ⁇ -farnesene and an acrylate ester can be represented by formula (H-IA), (H-IB), and/or an isomer thereof, or a mixture thereof:
  • R 1 may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g., Ci-C 30 hydrocarbyl.
  • R 1 is an aliphatic Ci-C 30 substituent.
  • R 1 is a linear saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., Ci, C2, C3, C4, C 5 , C , C7, Cg, C9, Cio, C11, C12, Ci 3 , Ci 4 , Ci 5 , C ⁇ , Cn, Qg, C19, C20 or C21-C30
  • Ci-C 30 hydrocarbyl or a branched saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., C C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , Cg, C 9 , Cio, Cn, C12, Ci3, CM, C15, C l6 , Cn, Cig, C l9 , C 20 or C 2 i-C 30 hydrocarbyl).
  • R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethyl
  • R 1 is an aromatic substituent, e.g., comprising a phenyl or benzyl group.
  • R 1 may comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride.
  • R 1 may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group.
  • R 1 is a polyol substituent, e.g., including 2, 3 or 4 hydroxyl groups.
  • R 1 is a saturated or unsaturated C 8 -C 30 fatty acid or a saturated or unsaturated C 8 -C 30 fatty alcohol, e.g., R 1 is cetyl, oleyl or stearyl.
  • R 1 is a Ci-C 30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • R 1 is selected to increase the compatibility of the Diels-Alder adduct with an oil, a component of a formulation, or with a selected host polymer.
  • the host polymer is relatively polar such as PVC
  • R 1 may be selected to be a relatively short linear or branched aliphatic hydrocarbon chain (e.g., a linear or branched Q-C4 hydrocarbyl), and/or R 1 may be substituted with or include one or more polar moieties (e.g., R 1 may be a Ci-C 30 aliphatic hydrocarbon that includes one or more hydroxyl, carboxyl, amino, epoxy, or chloro substituents, or R 1 may include a carbonyl group or an ether group).
  • R 1 may be selected to increase solubility in water, or to increase solubility in electrolyte solutions.
  • the Diels-Alder adduct is nonionic and R 1 comprises one or more hydroxyl s such that the adduct is a primary alcohol, an amino group, a primary alcohol including an alkoxylate chain, an alkyl-capped alkoxylate, an amide, an ethanolamide, or one or more glucose groups.
  • the Diels-Alder adduct is anionic, e.g., R 1 may comprise a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt.
  • the Diels-Alder adduct is cationic, e.g., R 1 may comprise a quaternary amine. In some variations, the Diels- Alder adduct is zwitterionic, e.g., R 1 may comprise an amine oxide.
  • a Diels-Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IA) and (HIB) in any relative amount may be used, e.g. , a mixture comprising a ratio of formula (H-IA): formula (H-IB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20: 80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95 :5, 99: 1 , or 99.9:0.1 by weight, by mole, or by volume.
  • the ratio of formula (H-IA): formula (H-IB) is from about 0. 1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5 :95 to about 95 :5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.
  • a Diels-Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester is hydrogenated, prior to use, to form a compound having formula (H-IC), or (H-ID) or an corner thereof, or a combination thereof:
  • R 2 may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g. , C 1 -C 30 .
  • R 2 is an aliphatic Ci-C 3 o Substituent.
  • R 2 is a linear saturated or unsaturated C 1 -C 30 hydrocarbyl group (e.g.
  • Ci Ci, C 2 , C 3 , C 4 , C5, Ce, C7, Cs, C9, Cio, C 11 , C 12 , Ci3, CM, Ci 5 , Ci6, Ci 7 , Ci8, Ci9, C 2 0 or C 21 -C30 hydrocarbyl), or a branched saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g. , C C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , Ci 0 , C 11 , C 12 , Ci 3 , CM, Ci 5 , Ci 6 , On, Cig, Ci 9 , C 20 or C 21 -C 30 hydrocarbyl).
  • R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n- nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-
  • R 2 is an aromatic group, e.g., comprising a phenyl or benzyl group.
  • R 2 may comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride.
  • R 2 may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or polyalkoxylate, a hydroxyl group, an amide group, or an amine group.
  • R 2 is a saturated or unsaturated C8-C30 fatty acid or a saturated or unsaturated C8-C30 fatty alcohol, e.g., R 2 is cetyl, oleyl or stearyl.
  • R 2 is a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g. , one or more internal double bonds and/or a terminal double bond.
  • R 2 includes a polyol substituent, e.g., including 2, 3, or 4 hydroxy groups.
  • R 2 is selected to increase the compatibility of the Diels-Alder adduct with an oil or a host polymer to be modified, to increase solubility in water, or to increase solubility in electrolyte solutions.
  • the Diels-Alder adduct is nonionic, e.g., R 2 may be selected so that the adduct is a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, a glucoside, or a glucamide.
  • the surfactant is anionic, e.g., R 2 may comprise a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt.
  • Diels-Alder adduct is cationic, e.g., R 2 may comprise a quaternary amine.
  • the Diels-Alder adduct is zwitterionic, e.g., R 2 may comprise an amine oxide.
  • compounds of formula (H-IC) may be derived from compounds of formula (H-IA), and compounds of formula (H-ID) may be derived from compounds of formula (H- IB) by hydrogenation.
  • hydrogenation occurs so that R 2 is the same as R 1 .
  • some degree of hydrogenation occurs in the R 1 group so that R 2 is not the same as R 1 .
  • compounds of formulae (H-IC) and (H-ID) are derived using additional chemical modification of a hydrogenated Diels-Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester, so that R 2 is not the same as R 1 .
  • a mixture of compounds of formulae (H-IC) and (H-ID) in any relative amounts may be used in the applications described herein, e.g., a mixture comprising a ratio of formula (H-IC): formula (H-ID) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume.
  • the ratio of formula (H-IC): formula (H-ID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a possible Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester may have formula (H-IE), formula (H-IF), or an isomer thereof, or a mixture thereof:
  • R 1 is as described in relation to formula (H-IA) and (H-IB).
  • a Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IE) and (H-IF) in any relative amount, e.g., a mixture comprising a ratio of formula (H-IE): formula (H-IF) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume.
  • the ratio of formula (H-IE): formula (H-IF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a compound having formula (H-IA), (H-IB), (H-IC), (H-ID), (H-IE), (H-IF), (H-IG) and (H-IH) or a derivative thereof may have use as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • R 3 and R 3 are each independently H or a straight or branched chain, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted substituents or hydrocarbyl, e.g. Ci-C 30 .
  • R 3 and R 3 are the same. In other embodiments, R 3 and R 3 are different.
  • each of R 3 and R 3 is independently a linear saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., Ci, C2, C3, C 4 , C 5 , C , C 7 , Cg, C 9 , C10, Cn, C12, C13, CI 4 , CI 5 , Ci , Cn, Qg, C19, C20 or C21-C30 hydrocarbyl ), or a branched saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., C C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , Cg, C 9 , Cio, Cn, C12, C , CM, C15, C i6 , Cn, Cig, C19, C 20 or C21-C30 hydrocarbyl).
  • a linear saturated or unsaturated Ci-C 30 hydrocarbyl group e.g., Ci, C2, C3, C 4 , C 5 , C ,
  • each of R 3 and R 3 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, 2-prop
  • each of R 3 and R 3 is independently an aromatic group, e.g., comprsing a phenyl or benzyl group.
  • each of R 3 and R 3 may independently comprise one or more heteroatoms, e.g. , oxygen, phosphorus, sulfur, nitrogen or chloride.
  • each of R 3 and R 3 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or polyalkoxylate, a hydroxyl group, an amine, an amide, or one or more glucose groups.
  • each of R 3 and R 3 may independently include a polyol substituent, e.g., each of R 3 and R 3 may independently include 2, 3 or 4 hydroxy groups.
  • each of R 3 and R 3 is independently a saturated or unsaturated C 8 -C 3 o fatty acid or a saturated or unsaturated C8-C30 fatty alcohol, e.g., each of R 3 and R 3 may independently be cetyl, oleyl or stearyl.
  • each of R 3 and R 3 is independently a C 1 -C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • the carboxylate substituents on the adduct have a 1 ,2-syn- orientation relative to each other originating form the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1,2-anti- orientation of the carboxylate substituents relative to each other on the adduct is desired, a dialkyl fumarate may be used as dienophile instead of a dialkyl maleate.
  • each of R 3 and R 3 is independently selected to increase compatibility with an oil or a host polymer to be modified. In some cases, R 3 and R 3 are independently selected to increase solubility in water or in an electrolyte solution.
  • each of R 3 and R 3 may independently be selected to be a relatively short linear or branched aliphatic hydrocarbyl (e.g., a linear or branched Q-C4 hydrocarbyl group), or each of R 3 and R 3 may independently be substituted with or include one or more polar moieties (e.g., each of R 3 and R 3 is independently Ci-C 30 aliphatic hydrocarbyl that includes one or more hydroxyl, carboxyl, amino, epoxy, or chloro substituents, each of R 3 and R 3 may independently include a carbonyl group, or each of R 3 and R 3 may independently include an ether group).
  • the Diels-Alder adduct is nonionic, e.g., the adduct comprises a primary alcohol (a monoalcohol or a diol), an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, or a glucoside.
  • the Diels-Alder adduct is anionic, e.g., one or both of R 3 and R 3 comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt.
  • the Diels-Alder adduct is cationic, e.g., one or both of R 3 and R 3 comprises a quaternary amine. In some variations, the Diels- Alder adduct is zwitterionic, e.g., one or both of R 3 and R 3 comprises an amine oxide. In some variations, one of R 3 and R 3 is a carboxylic acid salt and the other of R 3 and R 3 is an ammonium ion.
  • a compound having formula (H-IIA) is obtained by derivatizing a
  • Diels-Alder adduct between ⁇ -farnesene and a dienophile For example, a compound having formula (H- IIA) may be obtained by making a Diels-Alder adduct between ⁇ -farnesene and maleic anhydride, hydrolysis of the farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques.
  • H-IIB hydrogenated adduct having formula (H-IIB): where each of R 4 and R 4 is independently H or a straight or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituents, e.g. C 1 -C30.
  • R 4 and R 4 are the same. In other embodiments, R 4 and R 4 are different.
  • each of R 4 and R 4 is independently a linear saturated or unsaturated C 1 -C30 hydrocarbyl group (e.g. , Ci, C 2 , C3, C4, C 5 , Ce, C 7 , Cg, C 9 , Cio, C11, C12, Co, CM, Ci5, Ci6, Ci?, Ci8, Ci9, C 20 or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C 1 -C30 hydrocarbyl group (e.g.
  • Ci Ci, C 2 , C3, C4, C 5 , Ce, C 7 , Cg, C9, Cio, Cn, C 12 , Ci3, CM, Ci 5 , Ci6, Cn, Cig, Ci9, C 2 0 or C 21 -C30 hydrocarbyl).
  • each of R 4 and R 4 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylunde
  • each of R 4 and R 4 comprises an aromatic group (e.g., one or both of R 4 and R 4 may comprise a phenyl group or one or both of R 4 and R 4 may be a benzyl group).
  • each of R 4 and R 4 may independently comprise one or more heteroatoms, e.g. , oxygen, phosphorus, sulfur, nitrogen or chloride.
  • each of R 4 and R 4' may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a polyalkoxylate, a hydroxyl group, an amide group, an amine group, or one or more glucose groups.
  • each of R 4 and R 4 may independently include a polyol substituent, e.g. , each of R 4 and R 4' may independently include 2, 3 or 4 hydroxyl groups.
  • each of R 4 and/or R 4 is independently a saturated or unsaturated Cg-C 3 o fatty acid or a saturated or unsaturated Cg-C 3 o fatty alcohol, e.g. , each of R 4 and R 4 may independently be cetyl, oleyl or stearyl.
  • each of R 4 and R 4 is independently a C 1 -C 30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIA).
  • R 3 and R 3 are not affected by the hydrogenation so that R 4 is the same as R 3 and R 4 is the same asR 3 .
  • R 3 and R 3 are at least partially hydrogenated so that R 4 and R 4 are not the same as R 3 and R 3 .
  • compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIB) with further chemical modification, e.g. , to chemically modify R 3 and/or R 3 to form R 4 and/or R 4 respectively.
  • compounds having formula (H-IIB) are obtained by making a Diels-Alder adduct between ⁇ -farnesene and maleic anhydride, hydrogenating the adduct, and hydrolysis of the hydrogenated farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques.
  • (H-IIB) is derived by hydrogenating (H-IIA) made using a maleate dienophile
  • the carboxylate groups on (H-IIB) have a 1 ,2-syn- orientation relative to each other originating from the cis- orientatin of the carboxylate substituents on the maleate dienophile
  • (H-IIB) is derived by hydrogenating (H-IIA) made by using a fumarate dienophile
  • the carboxylate groups on (H-IIB) have a 1 ,2-anti- orientation relative to each other originating from the trans- orientation of the carboxylate substituents on the fumarate dienophile.
  • each of R 4 and R 4 is independently selected to increase compatibility with an oil or host polymer to be modified.
  • R 4 and R 4' are independently selected to increase solubility in water or in an electrolyte solution.
  • the host resin is a relatively polar substance
  • each of R 4 and R 4 may independently be selected to be a relatively short linear or branched aliphatic hydrocarbyl chain (e.g., a linear or branched C 1 -C4 hydrocarbyl), or each of R 4 and R 4 may independently be substituted with or include one or more polar moieties (e.g., each of R 4 and R 4 may independently be a Ci-C 30 aliphatic hydrocarbyl that includes one or more hydroxy, carboxy, amino, epoxy, or chloro substituents, each of R 4 and R 4 may independently include a carbonyl group, or each of R 4 and R 4' may independently include an ether group).
  • the Diels-Alder adduct is nonionic, e.g., the adduct comprises a primary alcohol (a monoalcohol or a diol), an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, or a glucoside.
  • the Diels- Alder adduct is anionic, e.g., one or both of R 4 and R 4 comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt.
  • the Diels-Alder adduct is cationic, e.g., one or both of R 4 and R 4 comprises a quaternary amine. In some variations, the Diels-Alder adduct is zwitterionic, e.g., one or both of R 4 and R 4 comprises an amine oxide. In some variations, one of R 3 and R 3 is a carboxylic acid salt and the other of R 4 and R 4 is an ammonium ion.
  • a Diels-Alder adduct between a-farnesene and a dialkyl maleate, , or maleic acid, or a dialkyl fumarate or fumaric acid has utility the applications described herein, the adduct having formula (H-IIC)
  • R3 and R3' are as described in relation to formula (H-IIA).
  • the carboxylate substituents on the adduct (H-IIC) have a 1 ,2-syn- orientation relative to each other originating form the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile.
  • a dialkyl fumarate may be used as dienophile instead of a dialkyl maleate.
  • Compounds having formula (H-IID) may be made by hydrogenating compounds of formula (H-IIC), or by any suitable reduction reaction:
  • Compounds of formulae (H-IIA), (H-IIB), (H-IIC) and (H-IID) may be useful in applications utilizing diesters.
  • compounds of formula (H-IIA), (H-IIB), (H-IIC) and (H-IID) or a derivative thereof may have use as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • maleic anhydride is used as a dienophile in a Diels-Alder reaction with farnesene.
  • a reaction product with ⁇ -farnesene is shown as compound (H-IIIA):
  • Compound (H-IIIC) can be hydrogenated to form Compound (H-IIID).
  • the anhydride compounds (H-IIIA), (H-IIIB), (H-IIIC) and (H-IIID) may have use in any application in which an anhydride is used.
  • the anhydride compounds (H- IIIA), (H-IIIB), (H-IIIC) and (H-IIID) or derivatives thereof may be used to make oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • the anhydride compounds disclosed herein may be use to make polyesters or co-polymers with one or more polyols such as diols and triols.
  • Additional compounds disclosed herein are compounds (H-IVA), (H-IVB), (H-IVC) and
  • Compounds (H-IVA), (H-IVB), (H-IVC) and (H-IVD) can be made by any suitable method.
  • a Diels-Alder adduct between ⁇ -farnesene and maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g. , using lithium aluminum hydride) to form Compound (H-IVA).
  • Compound (H-IVB) may be made by hydrogenating Compound (H-IVA), or alternatively by reducing Compound (H-IIIB) using known techniques.
  • a Diels-Alder adduct between a-farnesene, maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g., using lithium aluminum hydride) to form Compound (H-IVC).
  • Compound (H-IVD) may be made by hydrogenating Compound (H-IVC), or alternatively by reducing a compound having formula (H-IIID) using known techniques.
  • the diols of formulae (H-IVA), (H-IVB), (H-IVC) and (H-IVD) may be used in place of any diol.
  • the diol of formula (H-IVA), (H-IVB), (H-IVC) or (H-IVD) or a derivative thereof may be used to make an ester or a diester as a plasticizer or as a cross-linking agent or reactive diluent.
  • the diols disclosed herein may be use as monomers or comonomers for making polyesters, co-polyesters, polyurethanes, polycarbonates and the like.
  • the diols disclosed herein may be used as surfactants, or may be treated with one or more alkylene oxides to make a surfactant.
  • the alcohols and diols disclosed herein have utility as solvents, in cosmetics, or in surfactant formulations (e.g, in personal care formulations such as emollients, shampoos, cleansers, certain cosmetics, and the like; in emulsions; or in detergents and other cleaning formulations).
  • the diols disclosed herein may be used as is in applications or may be treated, alkoxylated, or otherwised derivatized.
  • R 5 and R 5 may independently be H, a Ci-C 30 saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubsubstituted aromatic group.
  • each of R 5 and R 5 may independently be a linear saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., C C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C u , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , Ci9, C 2 o or C 21 -C 30 hydrocarbyl), or a branched saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., Ci, C 2 , C3, C4, C5, C , C7, C%, C9, Cio, Cu, C12, Ci3, CM, C15, Ci , Cn, Cis, C19, C 2 0 or C 21 -C30
  • a linear saturated or unsaturated Ci-C 30 hydrocarbyl group e.g., C C 2 , C 3 , C 4 , C 5 , C
  • each of R 5 and R 5 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3- ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl,
  • each of R 5 and R 5 independently comprises an aromatic group, e.g., a phenyl group or a benzyl group. In some cases, R 5 or R 5 is a benzyl group. In some embodiments, each of R 5 and R 5 may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R 5 and R 5 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group. In some embodiments, each of R 5 and R 5 is independently a C 1 -C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • Compounds of formula (H-VA) may be obtained as a Diels-Alder reaction product between ⁇ -farnesene and a maleimide.
  • Compounds of formula (H-VC) may be obtained as a Diels-Alder adduct between a-farnesene and a maleimide.
  • the Diels-Alder adduct may be subsequently chemically modified to incorporate a desired functionality into the adduct.
  • a compound having formula (H-VB) may be derived by hydrogenating a compound having formula (H-VA).
  • a compound having formula (H-VD) may be derived by
  • a compound having formula (H-VC) is obtained by hydrogenating a compound having formula (H-VA), with additional chemical modification.
  • a compound having formula (H-VD) is obtained by hydrogenating a compound having formula (H-VC), with additional chemical modification.
  • the maleimide compounds of formulae (H-VA), (H-VB), (H-VC) and (H-VD) may be used in any application utilizing a maleimide.
  • compounds of formulae (H-VA), (H-VB), (H-VC) and (H-VD) or derivatives thereof have utility as oils, solvents, surfactants, additives for plastics or other resins, or monomers, cross-linking agents, curing agents or reactive diluents.
  • fumaronitrile, CN ? undergoes a Diels-Alder reaction with ⁇ -farnesene or a-farnesene.
  • the reaction product between ⁇ -farnesene and fumaronitrile is Compound (H-VIA) and the proposed reaction product between ⁇ -farnesene and fumaronitrile is Compound (H-VIB):
  • the cyano groups in the Diels-Alder adducts have a trans- orientation relative to each other oroiginating from the trans- orientation of the fumaronitrile.
  • Compounds having formula (H-VIA) and (H-VIB) or derivatives thereof may be used to make surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers or polymer composition. In some variations, compounds (H-VIA) and (H-VIB) are hydrogenated.
  • nitrile groups on compounds (H-VIA) and (H- VIB) may undergo hydrolysis under acid or base to form the dicaboxamide or dicarboxylic acid using known techniques.
  • compounds having structure (H-VIC) or (H-VID) may be derived from compound (H-VIA) using hydrolysis:
  • an unsaturated aldehyde is used as a dienophile in a Diels-Alder reaction with farnesene.
  • Some unsaturated aldehydes have the formula , where R may be
  • R is Ci-C 30 alkyl examples of unsaturated aldehydes include acrolein, 0 , and crotonaldehyde, .
  • the reaction product between ⁇ -farnesene and acrolein may be Compound (H-VIIA) or (H-VIIB) or a mixture thereof in which Compound (H-VIIA) and Compound (H-VIIB) are present in any relative amounts, e.g., a mixture comprising a ratio of Compound (H-VIIA): Compound (H-VIIB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99:1, or 99.9:0.1 by weight or by volume.
  • the ratio of Compound (H-VIIA): Compound (H-VIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • the ratio of Compound (H-VIIC) Compound (H-VIID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • the ratio of Compound (H-VIIE): Compound (H-VIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • the ratio of Compound (H-VIIG): Compound (H-VIIH) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • H-VIID H-VIID
  • H-VIIE H-VIIE
  • H-VIIF H-VIIG
  • H-VIIH ompounds having formula (H-VIIA), (H-VIIB), (H- VIIC), (H-VIID), (H-VIIE), (H-VIIF), (H-VIIG), or (H-VIIH) may be hydrogenated, and alcohols derived from the aldehydes.
  • itaconic anhydride , itaconic acid, , or a
  • dialkyl itaconate s is used as a dienophile in a Diels-Alder reaction with ⁇ -farnesene or a- farnesene, where R is any suitable hydrocarbyl group, e.g., a Ci-C 30 hydrocarbyl group.
  • Non-limiting examples of dialkyl itaconates that may be used include dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-sec -butyl itaconate, di-tert-butyl itaconate, bis(cyclohexylmethyl) itaconate, dicyclohexyl itaconate, di-isopropyl methyl itaconate, di-n-pentyl itaconate, di-n-hexyl itaconate, di-n-heptyl itaconate, di-n-octyl itaconate, di-n-nonyl itaconate and di-n-decyl itaconate.
  • reaction product between ⁇ -farnesene and itaconic acid or a dialkyl itaconate is illustrated by formulae (H-VIIIA) and (H-VIIIB) where R is H or any suitable hydrocarbyl group, e.g., a C1-C30 hydrocarbyl group , where the reaction product may have formula (H-VIIIA) or (H-VIIIB), or a mixture thereof in which formula (H-VIIIA) and formula (H-VIIIB) are present in any relative amounts, e.g., a ratio of formula (H-VIIIA): formula (H-VIIIB) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 by weight, by mole, or by volume.
  • R is H or any suitable hydrocarbyl group, e.
  • the ratio of formula (H-VIIIA): formula (H-VIIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a ratio of Compound (H-VHTE): Compound (H-VIIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20
  • the ratio of Compound (H-VIIIE): Compound (H-VIIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • (H-VIIIE), (H-VIIIF) may be hydrogenated to form Compounds (H-
  • a-farnesene may undergo Diels-Alder reaction with itaconic anhydride, itaconic acid or a dialkyl itaconate.
  • itaconic anhydride for example, possible reaction products between a- farnesene and itaconic anhydride are shown as Compounds (H-VIIIJ) and (H-VIIIK).
  • the reaction product may be Compound (H-VIIIJ) or (H-VIIIK) or a mixture thereof, where Compounds (H-VIIIJ) and (H-VIIIK) are present in any relative amounts, e.g., a ratio Compound (H-VIIIJ): Compound (H- VIIIK) of 0.1 :99.9, 1:99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 by weight or by volume.
  • the ratio of Compound (H-VIIIJ): Compound (H-VIIIK) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • Compounds (H-VIIIL) and (H-VIIIM) may be obtained by hydrogenating Compounds (H-VIIIJ) and (H-VIIIK) respectively, or by any suitable route.
  • the anhydride compounds of formulae (H-VIIIA), (H-VIIIB), (H-VIIIC) and (H-VIIID), and Compounds (H-VIIIE), (H-VIIIF), (H-VIIIG), (H-VIIIH), (H-VIIIJ), (H-VIIIK), (H-VIIIL) and (H- VIIIM) may be used in any application utilizing an anhydride.
  • the anhydride compounds of formulae (H-VIIIA), (H-VIIIB), (H-VIIIC) and (H-VIIID), and Compounds (H-VIIIE), (H-VIIIF), (H-VIIIG), (H-VIIIH), (H-VIIIJ), (H-VIIIK), (H-VIIIL) and (H-VIIIM), and derivatives thereof may have utility as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • the anhydride compounds disclosed herein can be used as monomers or co-monomers to make polyesters or co-polyesters with polyols such as diols and triols.
  • R or R' may be selected to increase compatibility of the adduct with a host polymer or an oil to be modified, or to increase solubility in water or in an electrolyte solution.
  • the anhydride functionality may be opened up using known techniques to form a diacid, which may be used as is, or further derivatized.
  • acetylene dicarboxylic acid H0 2 C ⁇ or ace tylene
  • R can be H or any suitable hydrocarbyl group (e.g., C 1 -C30 hydrocarbyl), is used as a dienophile in a Diels- Alder reaction with farnesene.
  • a reaction product between ⁇ -farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXA) and (H-IXB), where the reaction product may be represented by Compound (H- IXA) or (H-IXB), or a mixture thereof, in which Compound (H-IXA) and Compound (H-IXB) are present in any relative amounts, e.g., a ratio of Compound (H-IXA): Compound (H-IXB) of
  • the ratio of Compound (H-IXA): Compound (H-IXB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a reaction product between a-farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXC) and (H-IXD), where the reaction product may be represented by Compound (H- IXC) or (H-IXD), or a mixture thereof, in which Compound (H-IXC) and Compound (H-IXD) are present in any relative amounts, e.g., a ratio of Compound (H-IXC): Compound (H-IXD) of 0.001:99.999, 0.01 :99:99, 0.1 :99.9, 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight or by volume.
  • the ratio of Compound (H-IXC):Compound (H-IXD) is from about 0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.
  • a reaction product between ⁇ -farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXE) and (H-IXF),where the reaction product may be represented by formula (H-IXE) or (H-IXF), or a mixture thereof, in which formula (H-IXE) and formula (H-IXF) are present in any relative amounts, e.g., a ratio of formula (H-IXE): formula (H-IXF) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1 , 99.9:0.1 , 99.99:0.01 , 99.999:0.001 by weight or by volume.
  • the ratio of formula (H- IXE):formula (H-IXF) is from about 0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.
  • each of R 6 and R 6 is independently H, a Ci-C 30 saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group.
  • each of R 6 and R 6 may independently be a linear saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., C b C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C u , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 or C 2 i-C 30 hydrocarbyl), or a branched saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., C C 2 , C 3 , C4, C5, Ce, C7, Cs, C9, Cio, Cu, C12, Ci 3 , C14, C15, Ci6, Cn, Cis, C19, C 2 o or C 2 i-C 3 o hydrocarbyl).
  • a linear saturated or unsaturated Ci-C 30 hydrocarbyl group e.g., C b C 2 ,
  • each of R 6 and R 6 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, methyl
  • each of R 6 and R 6 is independently aromatic (e.g., one or both of R 6 and R 6 may comprise phenyl or benzyl groups). In some cases, R 6 and/or R 6 is a benzyl group. In some embodiments, each of R 6 and R 6 may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen, or chloride. In some embodiments, each of R 6 and R 6 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy, or a hydroxyl group. In some embodiments, each of R 6 and R 6 is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • a reaction product between a-farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXG) and (H-IXH), where the reaction product may be represented by formula (H-IXG) or (H-IXH) or a mixture thereof, in which formula (H-IXG) and formula (H-IXH) are present in any relative amounts, e.g., a ratio of formula (H-IXG): formula (H-IXH) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of formula (H-IXG): formula (H-IXH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • R 6 and R 6 are as described in relation to formulae (H-IXE) and (H-IXF).
  • IXE), (H-IXF), (H-IXG), and (H-IXH) may be used in any application that utilizes an unsaturated carboxylic acid or unsaturated carboxylic acid ester.
  • Compounds (H-IXA) and (H-IXC), and Compounds of formulae (H-IXE) and (H-IXG) may be reacted with another conjugated terpene or conjugated diene.
  • Compounds (H-IXA), (H-IXB), (H-IXC) and (H-IXD) and Compounds of formulae (H-IXE), (H-IXF), (H-IXG) and (H-IXH) and derivatives thereof may have utility as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • an acetylene diamide or dicyanoacetylene is used as a dienophile with farnesene in a Diels-Alder reaction.
  • a reaction product between an acetylene diamide and ⁇ - farnesene is represented by formulae (H-XA) and (H-XB), where the reaction product may have formula (H-XA) or (H-XB), or a mixture thereof , in which formulae (H-XA) and (H-XB) may be present in any relative amounts, a ratio of formula (H-XA): formula (H-XB) of about 0.001 :99.999, 0.01:99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, or 99.999:0.001
  • the ratio of formula (H- XA):formula (H-XB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a reaction product between an acetylene diamide and a-farnesene is represented by formulae (H-XC) and H- (XD), where the reaction product may be formula (H-XC) or (H-XD), or a mixture thereof, in which formulae (H-XC) and (H-XD) may be present in any relative amounts, e.g., a ratio of formula (H-XC): formula (H-XD) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of formula (H-XC): formula (H-XD) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • reaction product may be Compound (H-XE) or (H-XF), or a mixture thereof, in which Compounds (H-XE) and (H-XF) may be present in any relative amounts, e.g., a ratio of Compound (H-XE) Compound (H-XF) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001by weight, by mole, or by volume.
  • a ratio of Compound (H-XE) Compound (H-XF) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:
  • the ratio of Compound (H-XE): Compound (H- XF) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a ratio of Compound (H-XG): Compound (H-XH) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5
  • the ratio of Compound (H-XG): Compound (H- XH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • dicyanoacetylene is derived from acetylene dicarboxylic acid, following by treatment with ammoniolysis, followed by dehydration with P 2 O 5 or the like. In some embodiments, dicyanoacetylene is derived from acetylene diamide, followed by dehydration with P 2 0 5 or the like.
  • a Diels-Alder adduct between ⁇ -farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make Compound (H-XE) or (H-XF) or a mixture thereof, or a Diels-Alder adduct between a-farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make Compound (H-XG) or (H-XH) or a mixture thereof.
  • XE), (H-XF), (H-XG) and (H-XH) may be used in any application that utilizes an unsaturated diamide or saturated dicyanoacetylene.
  • compounds of formula (H-XA) and (H-XC), and Compounds (H-XE) and (H-XG) may be reacted with another conjugated terpene or conjugated diene (e.g., 1,3-butadiene or a substituted 1,3 -butadiene).
  • conjugated terpene or conjugated diene e.g., 1,3-butadiene or a substituted 1,3 -butadiene.
  • Compounds of formula (H-XA), (H-XB), (H-XC) and (H-XD), and Compounds (H-XE), (H-XF), (H-XG) and (H-XH) and derivatives thereof may have utility as surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • a benzoquinone or a naphthoquinone is used as a dienophile.
  • Compound (H-XIA), (H-XIB) or (H-XIC) may be made as a Diels-Alder adduct between ⁇ - farnesene and 1 ,4-benzoquinone.
  • Compounds (H-XIA), (H-XIB) and (H-XIC) may be hydrogenated to form compounds (H-XID), (H-XIE) and (H-XIF) respectively.
  • only one of Compounds (H-XIA), (H-XIB) and (H-XIC) is produced during a Diels-Alder reaction.
  • the reaction conditions may be slowed or otherwise controlled to produce only Compound (H-XIA).
  • the reaction conditions may favor formation of a mixture of Compounds (H-XIB) and (H-XIC) in which Compounds (H-XIB) and (H-XIC) are present in any relative amounts, e.g., a ratio of Compound (H-XIB): Compound (H-XIC) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume.
  • a ratio of Compound (H-XIB): Compound (H-XIC) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:
  • the ratio of Compound (H-XIB): Compound (H-XIC) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. In some embodiments, all three of compounds (H-XIA), (H- XIB) and (H-XIC) are present.
  • Compound (H-XIA) may be oxidized to form a benzoquinone having structure (H-XIA' ):
  • Compounds (H-XIB) and/or (H-XIC) may be oxidized to form a benzoquinone having structures ( ⁇ - ⁇ ') and (H-XIC), respectively:
  • H-XIB Compounds (H-XIB) and/or (H-XIC) may be oxidized to form an anthraquinone having structures (H-XIB”) and (H-XIC”) respectively:
  • a-Famesene may also reacts with 1 ,4-benzoquinone or 1 ,2-benzoquinone in a Diels-
  • a possible reaction product between a-farnesene and 1 ,4-naphthoquinone is Compound
  • Compounds (H-XIA)-( H-XIS) may be completely or partially hydrogenated prior to use.
  • Compounds of formulae (H-XIA)-( H-XIS) may be used in any application that utilizes ketones or quinones.
  • Compounds (H- XIA)-( H-XIS) and derivatives thereof may have utility as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.
  • one or more unsaturated bonds of a conjugated hydrocarbon terpene may be oxidized (e.g., epoxidized).
  • oxidized e.g., epoxidized
  • mono-epoxides, di-epoxides, tri-epoxides, and tetra-epoxides derived from ⁇ -farnesene are Compounds (15a), (15b), (16), (17) and (18) as shown below:
  • one or more unsaturated bonds originating from the conjugated terpene in a Diels-Alder adduct is oxidized (e.g., epoxidized).
  • epoxidized Diels-Alder adduct having any of structures (H-XIIA)-( H-XIIF) may be formed.
  • one or more remaining double bonds of adducts (H-XIIA)-( H-XIIE) may be hydrogenated to the corresponding Compounds (H-XIIA')-( H-XIIE') as shown below:
  • each of R and R' independently represents H or any Ci-C 30 linear or branched, cyclic or acyclic, substituted or unsubstituted alkyl group, and R and R' may be the same or different.
  • each of R and R' independently represents a C 1 -C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or t-butyl.
  • each of R and R' independently represent n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl.
  • each of R and R' is independently substituted with one or more heteroatoms, e.g., oxygen, nitrogen, or chlorine. In one embodiment, each of R and R' is independently methyl.
  • a polyol may be derived from epoxidized Diels-Alder derivatives using known techniques.
  • any suitable Diels-Alder adduct described herein may be oxidized in a similar fashion.
  • Diels-Alder adducts in which unsaturated bonds on the hydrocarbon tail or cyclohexene ring that have been oxidized to form epoxy groups or hydroxyl groups, or derivatives thereof may have utility as oils, surfactants, plasticizers, or monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers.
  • the epoxidized Diels-Alder adducts disclosed herein can be used to prepare epoxy resins or varies epoxidized or epoxy- modified polymers.
  • one or more unsaturated bonds may be halogenated (e.g., chlorinated).
  • Halogenated Diels- Alder adducts or derivatives thereof may have utility as oils, surfactants, plasticizers, or monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers.
  • the Diels-Alder adducts and derivatives thereof as described herein have a variety of applications.
  • Non-limiting examples of applications which may employ Diels-Alder adducts described herein include: solvents, lubricants (e.g., ester-based lubricants, base oils for lubricants or lubricant additives); surfactants (e.g., nonionic, anionic, cationic, or zwitterionic); plasticizers; and monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers.
  • a “renewable carbon” source refers to a carbon source that is made from modern carbon that can be regenerated within a several months, years or decades rather than a carbon source derived from fossil fuels (e.g., petroleum) that takes typically a million years or more to regenerate.
  • the terms “renewable carbon” and “biobased carbon” are used interchangeably herein.
  • “Atmospheric carbon” refers to carbon atoms from carbon dioxide molecules that have been free in earth's atmosphere recently, in the most recent few decades.
  • renewable carbon content can be measured using any suitable method.
  • renewable carbon content can be measured according to ASTM D6866-11, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis,” published by ASTM International, which is incorporated herein by reference in its entirety.
  • Some carbon in atmospheric carbon dioxide is the radioactive 14 C isotope, having a half life of about 5730 years.
  • Atmospheric carbon dioxide is utilized by plants to make organic molecules.
  • the atmospheric 14 C becomes part of biologically produced substances.
  • the biologically produced organic molecules degrade to produce carbon dioxide into the atmosphere, no net increase of carbon in the atmosphere is produced as a result, which may control or diminish undesired climate effects that may result when molecules produced from fossil fuels degrade to produce carbon dioxide to increase carbon in the atmosphere.
  • Isotope fractionation occurs during physical processes and chemical reactions, and is accounted for during radiocarbon measurements. Isotope fractionation results in enrichment of one isotope over another isotope. Exemplary processes that can affect isotope fractionation include diffusion (e.g., thermal diffusion), evaporation, and condensation. In some chemical reactions, certain isotopes may exhibit different equilibrium behaviors than others. In some chemical reactions, kinetic effects may affect isotope ratios. In the carbon cycle of plants, isotope fractionation occurs. During photosynthesis, the relative amounts of different carbon isotopes that are consumed are 12 C> 13 C> 14 C, due to slower processing of heavier isotopes.
  • the international reference standard for isotope fractionation between 13 C and 12 C is PDB (Pee Dee Belemnite standard) or VPDB (Vienna Pee Dee Belemnite standard, replacement for depleted PDB standard).
  • 8 l3 C is the relative change of the 13 C/ 12 C ratio for a given sample from that of the VPDB standard.
  • Carbon isotopic ratios are reported on a scale defined by adopting a 8 13 C value of +0.00195 for NBS-19 limestone (RM 8544) relative to VPDB.
  • RM 8544 NBS-19 limestone
  • “New IUPAC guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data” Letter to the Editor, J. Res. Natl. Stand. Technol. 100, 285 (1995).
  • Most naturally occurring materials exhibit negative 8 l3 C values.
  • 5C 13 varies between -22 and -32 % 0
  • C 4 plants ⁇ C varies between -8 to -18 IQQ.
  • the C fractionation factor can be approximated as the square of the 13 C fractionation factor. See, e.g., M. Stuiver and S.W. Robinson, Earth and Planetary Science Letters, vol. 23, 87-90.
  • 14 C content of a sample can be measured using any suitable method.
  • 14 C content can be measured using Accelerator Mass Spectrometry (AMS), Isotope Ratio Mass Spectrometry (IRMS), Liquid Scintillation Counting (LSC), or a combination of two or more of the foregoing, using known instruments.
  • Activity refers to the number of decays measured per unit time and per unit mass units. To compare activity of a sample with that of a known reference material, isotope fractionation effects can be normalized.
  • a SN A s ⁇ [( 13 C/ 12 C)reference]/[( 13 C/ 12 C)sample] ⁇ 2 .
  • the factor 0.95 is used to correct the value to 1950 because by the late 1950s, 14 C in the atmosphere had artificially risen about 5% above natural values due to testing of thermonuclear weapons.
  • the AD 1950 standard had 100 pMC. Fresh plant material may exhibit a pMC value of about 107.5.
  • Biobased carbon content is determined by settingl00% biobased carbon equal to the pMC value of freshly grown plant material (such as corn), and pMC value of zero corresponds to a sample in which all of the carbon is derived from fossil fuel (e.g., petroleum).
  • a sample containing both modern carbon and carbon from fossil fuels will exhibit a biobased carbon content between 0 and 100%.
  • a sample that is more than several years old but containing all biobased carbon (such as wood from a mature tree trunk) will exhibit a pMC value to yield a biobased carbon content > 100%.
  • Renewable carbon content or biobased carbon content as used herein refers to fraction or percent modern carbon determined by measuring 14 C content, e.g., by any of Method A, Method B, or Method C as described in ASTM D6866-11 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis.” Counts from 14 C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% 14 C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% C indicates carbon originating entirely from modern sources. A measurement of >100% 14 C indicates the source of carbon has an age of more than several years.
  • any of the Diels-Alder adducts and derivatives thereof may be made from conjugated terpenes and/or dienophiles that have been derived from renewable carbon sources.
  • at least about 25%, at least about 30%, at least about 40%, at least about 50%, at least about 60%), at least about 70%, at least about 80%, at least about 90%, or about 100% of the carbon atoms in the Diels-Alder adducts or derivatives thereof originate from renewable carbon sources.
  • the conjugated hydrocarbon terpene (e.g., myrcene, ⁇ -farnesene, or a-farnesene) is made by genetically modified microorganisms using renewable carbon sources such as a sugar (e.g. , sugar cane).
  • a dienophile is at least partially derived from renewable carbon sources.
  • a dienophile may be derived from ethanol derived from plant sources, e.g. , a dienophile may be derived from renewable ethylene that is derived from renewable ethanol.
  • one or more chemicals used to modify the Diels-Alder adducts described herein may be at least partially derived from renewable carbon sources.
  • renewable alcohols or renewable glycols may be used to derivatize a Diels-Alder adduct as described herein.
  • the renewable carbon content of a Diels-Alder adduct or its derivatives is measured according to ASTM D6866-11, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," published by ASTM International, which is incorporated herein by reference in its entirety.
  • the properties of a Diels-Alder adduct between a conjugated terpene and a dienophile may be tuned, adjusted or modified to accomplish any one of or any combination of two or more of the following: modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule; modify compatibility with a desired oil; improve solubility in water (e.g., hard water or cold water) in use; improve solubility in electrolytes (e.g., builders); provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; increase thermal stability; undergo a reverse Diels-Alder reaction to produce desired species; modify molecular weight; modify viscosity, crystallinity, volatility at processing temperatures and/or at use temperatures; modify migration or leaching behavior in operiation; enable the adduct or a composition comprising the adduct to be suitable for use in food grade applications; enable the a
  • the Diels-Alder adducts described herein have a structure X CHT -
  • a DA -Y DP in which X CHT originates or derives from one or more conjugated hydrocarbon terpenes reacted with a dienophile, Y DP originates or derives from the dienophile, and A DA comprises one or more cyclic groups resulting from the Diels-Alder reaction between the dienophile and the one or more conjugated hydrocarbon terpenes.
  • one conjugated hydrocarbon terpene reacts with a dienophile so that the Diels-Alder adduct has structure X-A-Y, where X represents a tail originating from that conjugated terpene; A represents a cyclic structure (e.g., 6-membered ring); and Y originates from the dienophile.
  • two conjugated hydrocarbon terpenes undergo a Diels-Alder reaction with one dienophile so that the Diels-Alder adducts may
  • X CHT may refer to X, X 1 or X 2 ; and Y D p may refer to Y, Y 1 or Y 2 .
  • X CHT and/or Y DP may be selected or chemically modified to make the Diels-Alder adduct suitable for use in certain applications.
  • X CHT and/or Y DP may be selected or chemically modified to a Diels-Alder adduct to impart any one of or any combination of two or more of the following properties to the adduct: modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule, modify compatibility with a desired oil or polymer; improve solubility in water (e.g., hard water or cold water) in use; improve solubility in electrolytes (e.g., builders); provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; increase thermal stability; undergo a reverse Diels-Alder reaction to produce desired species; modify molecular weight; modify viscosity, crystallinity, volatility at processing temperatures and/or at use temperatures;
  • a Diels-Alder adduct it is desirable for a Diels-Alder adduct to include a nonpolar
  • Y D p may contain heteroatoms such as O, S, P or N, included in functional groups such as ester, keto, ether, acid, alcohol, amine, amide and thiol.
  • X CHT may be tuned or modified in a variety of ways.
  • X CHT in general includes methyl substituents originating from the conjugated terpene.
  • X CHT is an unsaturated hydrocarbon chain
  • X CHT is a saturated hydrocarbon chain
  • X CHT includes one or more nonionic oxygen groups (e.g., epoxy, hydroxy, or keto), and/or one or more nonionic halo substituents (e.g., chloro).
  • Hydrophobicity of X CHT may be decreased by using a shorter chain conjugated terpene and/or oxidizing or halogenating one or more of the unsaturated carbon bonds of X CHT -
  • Hydrophilicity of Y D p may be tuned or modified in a variety of ways.
  • a dienophile may be selected to vary the number of polar substituents resulting in the Diels-Alder adduct.
  • a dienophile may be selected that provides only one polar substituent to the cyclic group formed by the Diels-Alder reaction.
  • a dienophile may be selected that provides more than one (e.g., two) polar substituents to the cyclic group formed by the Diels-Alder reaction, e.g., a dienophile that is a diacid, a diester, or a di-cyano may be selected.
  • a dienophile may be selected or a Diels-Alder adduct may be modified so that Y DP includes one or more hydrocarbon chains, in which the length and degree of branching in the hydrocarbon chains is varied to tune hydrophobicity of the adduct.
  • a Diels-Alder adduct is alkoxylated (any number of ethylene oxide or propylene oxide segments are incorporated into the adduct) to tune hydrophobicity properties.
  • an N-oxide of a Diels-Alder adduct is formed.
  • a Diels-Alder adduct may be modified so as to form an anionic or cationic compound.
  • a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate, a phosphate, or an ammonium ion may be made.
  • Non-limiting examples of applications that may utilize the Diels-Alder adducts described herein having a polar end and a nonpolar end include: use as a plasticizer in which compatibility with a polar polymer host is required; use as a surfactant or as positive or negative surface tension modifier; use as an ester-containing base oil additive (e.g., antifriction agent, antiwear agent, or anticorrosion agent) or as an ester-containing base oil; or use as a monomers, cross-linker or reactive diluents for making oligomers and polymers.
  • a Diels-Alder adduct that is to be used as a plasticizer, surfactant, or solvent for a target substance is selected based on one or more measured or calculated solubility parameters of the Diels-Alder adduct and of the target substance.
  • a plasticizer for use in PVC may be selected to have solubility parameters close to that of PVC.
  • a solubility parameter is an empirical, calculated or semi-empirical numerical value that indicates relative solubility of a Diels-Alder adduct and a target substance.
  • any suitable solubility parameter or combination of parameters can be used to evaluate and quantify intermolecular interactions between the Diels-Alder adduct and the target substance to estimate or predict efficacy as a plasticizer, surfactant, or solvent.
  • intermolecular interactions that can be evaluated to incorporate into a solubility parameter include dispersion (van der Waals forces, related to polarizable electrons), dipole moment, hydrogen bonding, and orientation effects.
  • Any scheme or algorithm known in the art to calculate or measure solubility of a Diels-Alder adduct in a target substance can be used to arrive at a solubility parameter.
  • Hildebrand solubility parameters For example, Hildebrand solubility parameters, Hansen solubility parameters, UNIFAC semi-empirical calculations, or a combination thereof can be used to estimate solubility parameters for Diels-Alder/target substance combinations.
  • quantum mechanical chemical calculations e.g., COSMO-RS® software, available from COSMOlogic® GmbH & Co. KG
  • Hildebrand solubility parameters do not take into account hydrogen bonding, and may be more relevant for nonpolar systems than for polar systems.
  • Hansen solubility parameters include three different parameters: SD (dispersion), ⁇
  • ⁇ dipole moment
  • ⁇ hydrogen bonding
  • R a compatibility between a Diels-Alder adduct and a target substance
  • R a ⁇ 4[6D plas -6D host ] 2 +[6P p i as -6P host ] 2 +[6H plas -6H host ] 2 ⁇ 1,2
  • 8D host is the dispersion parameter for the host resin
  • 8D p i is the dispersion parameter for the plasticizer
  • ⁇ 3 ⁇ 408 ⁇ is the dipole parameter for the host resin
  • 8H host is the hydrogen bonding parameter for the host resin
  • 8H plas is the hydrogen bonding parameter for the plasticizer.
  • a smaller value for R a indicates a greater "likeness" or compatibility between a Diels-Alder adduct and a target substance.
  • a RED value approximately equal to or less than 1 for a particular Diels-Alder adduct/target substance combination indicates that combination is compatible, which will result in a desired effective interaction (e.g., plasticization or solvency).
  • a RED value greater than 1 for a particular Diels-Alder/target substance combination indicates an incompatible combination, such that the Diels-Alder adduct is unlikely to be sufficiently compatible with the target substance to provide the desired effect (e.g., effective plasticization or effective solvency).
  • the parameters ⁇ , ⁇ , ⁇ for the host resin and the plasticizers can be calculated, measured or estimated in any suitable manner or retrieved from existing databases.
  • Hansen solubility parameters for a substance are determined from empirical solubility data for that substance in about 20 to 30 known solvents.
  • One software package that uses Hansen Solubility parameters to evaluate suitability of particular plasticizers for a desired application is HSPiP, available at www.hansen-solubility.com.
  • the HSPiP package has the capability to read a data table containing chemical name and structure encoded as a SMILES string, and to automatically calculate the HSP of the chemical using the so-called Y-MB fragment-based method. Like all automatic techniques for estimating molecular properties, the results need to be checked for values that may be numerical artifacts. This method is used to calculate those compounds that are not included in the HSP database.
  • ⁇ , ⁇ or ⁇ for a substance is obtained from Hansen, C. M., Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton, FL, 1999, Hansen, C. M., Hansen Solubility Parameters: A User's Handbook, Second Ed., CRC Press, Boca Raton, FL, 2007, or Hansen Solubility Parameters in Practice, eBook/software, 1st Ed.2008, 2nd Ed. 2009, with Prof. Stephen Abbott and Dr. Hiroshi Yamamoto available from www.hansen-solubility.com, each of which is incorporated herein by reference in its entirety.
  • a set of solvents is selected to sufficiently characterize solubility or swellability of a substance in a host resin of choice.
  • Hansen solubility parameters for a substance are determined by mathematical modeling of the substance.
  • mathematical modeling comprises
  • Y-MB Yamamoto molecular breaking model
  • Stefanis-Panayiotou 2008 model
  • a Diels-Alder adduct may be modified so as to form an anionic or cationic compound.
  • a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate may be formed (e.g., using standard sulfation techniques such as S0 3 /oleum sulfation), a phosphate or phosphite may be formed, or an ammonium ion may be made.
  • Cationic Diels- Alder adducts e.g., ammonium ions such as quaternary ammonium ions
  • anionic Diels-Alder adducts e.g., sulfates or phosphates
  • surfactants such as soaps, detergents, wetting agents, dispersants, emulsifiers, foaming agents, antistatic agents, corrosion inhibitors and antimicrobials.
  • Certain anionic surfactants derived from Diels-Alder adducts may be useful in detergents, soaps, builders and other cleaning agents, emulsifiers and the like.
  • Certain cationic surfactants derived from the Diels-Alder adducts described herein may have use in personal care products.
  • ammonium ions e.g., quaternary ammonium ions
  • Ammonium ions e.g., quaternary ammonium ions
  • N-oxides formed from the Diels-Alder adducts described herein may have use as surfactants, e.g., for use in personal care products (e.g., shampoos, conditioners, and the like).
  • a Diels-Alder adduct may include a reactive site by which the adduct may be reacted with another component of a composition to incorporate the adduct.
  • a Diels-Alder adduct may be a monomer to be reacted with itself to form an oligomer (e.g., a dimer, trimer, tetramer, etc.) or a homopolymer, or co-polymerized with another monomer to form an oligomer or polymer.
  • X CHT is a reactive site.
  • Y DP is a reactive site.
  • both X CHT and Y DP are reactive sites.
  • Oligomerization and polymerization can proceed by any known route, e.g., using free radical polymerization, anionic polymerization, cationic polymerization, condensation polymerization, polymerization using metallocene or Ziegler Natta catalysts, or hydrovinylation.
  • At least one olefinic bond on X CHT is left unsaturated, and the one or more unsaturated bonds is used to polymerize the adduct with another like molecule to form a homopolymer or with a co-monomer to form a copolymer.
  • an unsaturated bond on a X CHT serves as a cross-linking site.
  • at least one olefinic bond on X CHT is epoxidized or halogenated, and the epoxy moiety or halogenated site is used to polymerize the adduct with another like molecule to form a homopolymer or with a co-monomer to form a copolymer.
  • At least olefinic bond is oxidized to form a hydroxyl group, which can be coupled with another like molecule, or coupled with a co-monomer.
  • at least one olefin bond on the X CHT is halogenated, which can serve as a reactive site to couple with another like molecule or a co- monomer.
  • Y D p contains one or more hydroxy, cyano, ester, epoxy, amine, amide, anhydride, or olefinic bonds that can serve as reactive sites to couple to another like molecule, or to a co- monomer.
  • Y D p includes a reactive site that can be used to make an oligomer or polymer.
  • Y D p includes a reactive site that can be used to cross-link between polymer chains.
  • both X CHT and Y D p include one or more reactive sites that can be used to make an oligomer or polymer.
  • both X CHT and Y D p include one or more reactive sites that can be used to cross-link between polymer chains.
  • X CHT and/or Y DP are modified so as to increase thermo-oxidative stability of the adduct.
  • the thermal stability requirements are application dependent, but in some embodiments, thermal stability may be tuned or modified to withstand transient processing temperature (e.g., melt mixing, extruding, molding, soldering, heat treatments, annealing, and the like) and long term use steady state and thermal excursion requirements. As stated above, olefinic bonds may be partially or completely saturated to increase thermal stability.
  • the dienophile may be selected or chemically modified so that the final Diels-Alder adduct does not contain functional groups (e.g., nitrogen containing groups and certain oxygen containing groups) that are susceptible to oxidation in the anticipated processing or use conditions.
  • functional groups e.g., nitrogen containing groups and certain oxygen containing groups
  • a Diels-Alder adduct may formed which subsequently undergoes a reverse Diels-Alder reaction to produce a desired species using known techniques.
  • the molecular weight of a Diels-Alder adduct may be tuned or modified to make the adduct appropriate for certain applications. For example, if the adduct is to be used as plasticizer dispersed into a polymer, the molecular weight of the adduct may be increased to reduce the amount of migration within the polymer or out of the polymer.
  • the molecular weight of the adduct may be increased by any one of or any combination of the following: reacting two hydrocarbon terpenes with a dienophile, forming dimers or other oligomers, either between like molecules or between different molecules, or by selecting a conjugated terpene with a larger molecular weight, or by functionalizing the adduct with one or more longer hydrocarbon chains, or by alkoxylating the adduct (e.g., ethoxylating or propoxylating).
  • Volatility of a Diels-Alder adduct may be tuned or modified to make the adduct more or less volatile in certain applications.
  • the Diels- Alder adduct may be functionalized to increase molecular weight and/or increase intermolecular interactions between adduct molecules.
  • the Diels-Alder adduct may be functionalized to increase molecular weight and/or intermolecular interactions between the adduct and its solvent (which may be a liquid or solid).
  • Oils and/or plastics derived from or containing Diels-Alder adducts may be adapted for use in food grade applications, cosmetic applications, or in medical grade applications. Toxicity and biodegradability of the oils and/or plastics incorporating the adducts may be tested according to country- based regulations, local regulations, and/or standards-based tests, and according to anticipated uses (e.g., regulations for substances to come into contact with food to be ingested, substances to be used in food processing equipment, substances to come into contact with the human body, substances to be ingested, or substances to be implanted in the human body).
  • Diels-Alder adducts may be functionalized to tune or modify absorption by the adduct of a desired portion of the electromagnetic spectrum (e.g., infrared, visible or ultraviolet).
  • a Diels-Alder adduct may include one or more conjugated rings so that it absorbs the UV or visible light.
  • Such adducts may function as dyes, UV absorbers or sensitizers.
  • absorption of the infrared radiation of an adduct may be adjusted, e.g., by tuning the concentration and nature of various infrared absorbing moieties.
  • the Diels-Alder adducts are reactive diluents or solvents that chemically react with one or more co-solvents or solutes, e.g., by cross-linking, by condensation, by addition, or by transesterification.
  • farnesene as such e.g., ⁇ - farnesene
  • a Diels-Alder adduct as described herein is used as a reactive diluent, e.g., for an alkyd resin, a polyester, a polyurethane, or any other suitable type of resin that may be used as a coating.
  • a Diels-Alder adduct between ⁇ -farnesene and a dienophile is used in any one or more than one of the applications.
  • Diels-Alder adducts between a-farnesene and dienophiles are used.
  • Diels-Alder adducts between myrcene and dienophile are used in the applications.
  • the solvents, surfactants, lubricants, plasticizers, monomers, cross-linking agents, curing agents, and reactive diluents may be made from conjugated hydrocarbon terpenes that are not farnesene or myrcene.
  • the conjugated terpene used to make a Diels-Alder adduct useful in the applications described herein may for example be any of the C 10 -C30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.
  • Diels-Alder adducts described herein or derivatives thereof may be designed as lubricants or as components in lubricant compositions.
  • monoesters or diester Diels-Alder adducts as described herein have utility as base oils or as additives for lubricant compositions.
  • Monoesters and diesters have relatively high dipole moments, causing intermolecular forces to be increased, which may decrease vapor pressure, decrease volatility, and/or increase flash point. These properties may make an ester containing Diels-Alder adduct described herein advantageous for a variety of applications.
  • the polarity of the ester-containing Diels-Alder adduct may increase their compatibility with other polar molecules, which increase their utility as solvents and dispersants for additives and the like.
  • Esters tend to solubilize or disperse oil degradation by-products which may be deposited as sludge in a motor or other lubricated machinery, so that the use of ester-containing Diels- Alder adducts in lubricants may result in increased lubricant lifetime, increased lubricity, and/or improved additive solubility.
  • Monoester or diester-containing Diels-Alder adducts may in some instances exhibit relative stability against oxidative and thermal breakdown, but have high biodegradability.
  • ester-containing Diels-Alder adducts that are hygroscopic are not used in applications in which moisture is present or generated.
  • a conjugated terpene e.g., myrcene, ⁇ -farnesene or a-farnesene
  • the adduct is hydrogenated to form a saturated adduct
  • the saturated adduct is esterified with a polyol (e.g., pentaerythritol, neopentyl glycol, and the like) to obtain a high boiling point ester that is expected to exhibit high viscosity and low pour point due to the methyl-branched hydrocarbon chain originating from the hydrocarbon terpene.
  • a polyol e.g., pentaerythritol, neopentyl glycol, and the like
  • Monoester or diester-containing Diels-Alder adducts may exhibit increased lubricity in some applications, and may be useful as friction modifiers.
  • the polarity of the ester moiety may be attracted to metal oxide layers formed on metal surfaces, whereas the hydrocarbon tail of the Diels-Alder adduct is solubilized in an oil, which may increase the adducts' utility as boundary lubricants and friction modifiers.
  • a monoester or diester-containing Diels-Alder adduct is used in place of all or a portion of a vegetable oil or petroleum-derived monoester, diester (e.g., an adipate), phthalate, dimerate, or trimellitate in a base oil or in a lubricant composition.
  • a monoester or diester containing Diels-Alder adduct as described herein is used as a metalworking fluid.
  • a monoesters or diester containing Diels- Alder adduct as described herein is used as a friction modifier in a lubricant composition.
  • the conjugated terpene and/or alkyl substituent on the ester moiety or moieties that are used to make an ester-containing Diels-Alder adduct are selected to adjust a pour point of a base oil or lubricant formulation comprising the adduct.
  • longer chains may be selected to increase pour point, and shorter or more branched chains may be selected to decrease pour point.
  • Diester or mono-ester containing Diels-Alder adducts may be used in place of adipate diesters in some embodiments.
  • diester or monoester containing Diels-Alder adducts are used in combination with a polyalphaolefin (PAO).
  • PAO polyalphaolefin
  • diester or monoester containing Diels-Alder adducts are used in combination with PAOs or mineral oils in compressor oils, gear oils, transmission oils, crankcase oils, or hydraulic fluids.
  • diester or monoester containing Diels-Alder adducts are used as base oil where biodegradability is desired or low sludge formation is desired (e.g., used as lubricants for textile machines or ovens).
  • the Diels-Alder adducts disclosed herein can be used as base oils or additives in lubricant compositions. In some embodiments, the Diels-Alder adducts disclosed herein are used as additives in lubricant compositions comprising a base oil and optionally other additives.
  • Diels-Alder adducts suitable as base oils or additives in lubricant compositions can be prepared by Diels-Alder reaction between ⁇ -farnesene and a dienophile, wherein the dienophile is selected from monoalkyl or dialkyl maleates, monoalkyl or dialkyl fumarates, monoalkyl or dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, maleamide or substituted maleamides, fumaramide and substituted fumaramides, maleimide and substituted maleimides, 1 ,4-benzoquinone and substituted 1 ,4- benzoquinones, 1 ,2-benzoquinone, substituted 1 ,2-benzoquinones, and combinations thereof.
  • the dienophile is selected from monoalky
  • any base oil known to a person of ordinary skill in the art can be used for preparing the lubricant compositions comprising one or more Diels-Alder adducts disclosed herein.
  • the base oils suitable for preparing lubricant compositions have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapters 1 and 2 (1996), incorporated herein by reference.
  • the lubricant composition may comprise from about 70 to 99 wt% of the base oil, based on the total weight of the lubricant composition.
  • the lubricant composition comprises from about 80 to 98 wt% of the base oil, based on the total weight of the lubricant composition.
  • the base oil comprises any of the base stocks in Groups I-V as specified in the American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (i.e., API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils), which is incorporated herein by reference.
  • the API guideline defines a base stock as a lubricant component that may be manufactured using a variety of different processes.
  • Groups I, II and III base stocks are mineral oils, each with specific ranges of the amount of saturates, sulfur content and viscosity index.
  • Group IV base stocks are polyalphaolefins (PAO).
  • Group V base stocks include all other base stocks not included in Group I, II, III, or IV.
  • the base oil comprises a combination of the base stocks in Groups I-V.
  • the base oil comprises a natural oil, a synthetic oil or a combination thereof.
  • suitable natural oils include animal oils (e.g., lard oil), vegetable oils, (e.g., corn oil, castor oil, and peanut oil), oils derived from coal or shale, mineral oils (e.g., liquid petroleum oils and solvent treated or acid-treated mineral oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types) and combinations thereof.
  • Non-limiting examples of suitable synthetic lubricating oils include poly-alpha-olefins, alkylated aromatics, polybutenes, aliphatic diesters, polyol esters, polyalkylene glycols, phosphate esters and combinations thereof.
  • the base oil comprises hydrocarbon oils such as polyolefins
  • polybutylenes e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, polyhexene, polyoctene, polydecene, and the like
  • alkylbenzenes e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes, and the like
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls, and the like
  • alkylated diphenyl ethers alkylated diphenyl sulfides
  • derivatives, isomers, analogs, homologs and combinations thereof e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, polyhexene, polyoctene, polydecen
  • the base oil comprises a poly-alpha-olefin (PAO).
  • PAO poly-alpha-olefin
  • the poly-alpha-olefins may be derived from an alpha-olefin having from about 2 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms.
  • suitable poly- alpha-olefins include those derived from octene, decene, mixtures thereof, and the like.
  • These poly- alpha-olefins may have a viscosity from about 2 to about 15, or from about 3 to about 12, or from about 4 to about 8 centistokes at 100°C.
  • the poly-alpha-olefins may be used together with other base oils such as mineral oils.
  • the base oil comprises a polyalkylene glycol or a polyalkylene glycol derivative, where the terminal hydroxyl groups of the polyalkylene glycol may be modified by esterification, etherification, acetylation and the like.
  • suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof.
  • suitable polyalkylene glycol derivatives include ethers of
  • polyalkylene glycols e.g., methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.
  • mono- and polycarboxylic esters of polyalkylene glycols and combinations thereof.
  • the polyalkylene glycol or polyalkylene glycol derivative may be used together with other base oils such as poly-alpha-olefins and mineral oils.
  • the base oil comprises any of the esters of dicarboxylic acids
  • phthalic acid e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, and the like
  • alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, and the like.
  • Non-limiting examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the like.
  • the base oil comprises a hydrocarbon prepared by the Fischer-
  • Fischer-Tropsch process prepares hydrocarbons from gases containing hydrogen and carbon monoxide using a Fischer-Tropsch catalyst. These hydrocarbons may require further processing in order to be useful as base oils. For example, the hydrocarbons may be dewaxed, hydroisomerized, and/or hydrocracked using processes known to a person of ordinary skill in the art.
  • the base oil comprises a refined, unrefined, or rere fined oil.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Non-limiting examples of unrefined oils include shale oils obtained directly from retorting operations, petroleum oils obtained directly from primary distillation, and ester oils obtained directly from an esterification process and used without further treatment.
  • Refined oils are similar to the unrefined oils except the former have been further treated by one or more purification processes to improve one or more properties. Many such purification processes are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like.
  • Rerefined oils are obtained by applying to refined oils processes similar to those used to obtain refined oils.
  • Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally treated by processes directed to removal of spent additives and oil breakdown products.
  • the lubricant composition may further comprise at least an additive or a modifier (hereinafter designated as "additive") that can impart or improve any desirable property of the lubricant composition.
  • additive any additive known to a person of ordinary skill in the art may be used in the lubricant compositions disclosed herein. Some suitable additives have been described in Mortier et al., “Chemistry and Technology of Lubricants 2nd Edition, London, Springer, (1996); and Leslie R.
  • the additive can be selected from the group consisting of detergents, dispersants, friction modifiers, pour point depressants, demulsifiers, anti- foams, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, and combinations thereof.
  • concentration of each of the additives in the lubricant composition when used, can range from about 0.001 to about 20 wt%, from about 0.01 to about 10 wt% or from about 0.1 to about 5 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a detergent that can control varnish, ring zone deposits, and rust by keeping insoluble particles in colloidal suspension and in some cases, by neutralizing acids.
  • Any detergent known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates and combinations thereof.
  • the metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate detergents.
  • suitable metals include alkali metals, alkaline metals and transition metals.
  • the metal is Ca, Mg, Ba, K, Na, Li or the like.
  • the amount of the detergent may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a dispersant that can prevent sludge, varnish, and other deposits by keeping particles suspended in a colloidal state.
  • a dispersant that can prevent sludge, varnish, and other deposits by keeping particles suspended in a colloidal state.
  • Any dispersant known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable dispersants include succinimides, succiamides, benzylamines, succinate esters, succinate ester-amides, Mannich type dispersants, phosphorus-containing dispersants, boron-containing dispersants and combinations thereof.
  • the amount of the dispersant may vary from about 0.01 to about 10 wt%, from about 0.05 to about 7 wt%, or from about 0.1 to about 4 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a friction modifier that can lower the friction between moving parts.
  • Any friction modifier known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable friction modifiers include fatty carboxylic acids; derivatives ⁇ e.g., esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives ⁇ e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-alkyl substituted amides and combinations thereof.
  • the friction modifier is selected from the group consisting of aliphatic amines, ethoxylated aliphatic amines, aliphatic carboxylic acid amides, ethoxylated aliphatic ether amines, aliphatic carboxylic acids, glycerol esters, aliphatic carboxylic ester-amides, fatty imidazolines, fatty tertiary amines, wherein the aliphatic or fatty group contains more than about eight carbon atoms so as to render the compound suitably oil soluble.
  • the friction modifier comprises an aliphatic substituted succinimide formed by reacting an aliphatic succinic acid or anhydride with ammonia or a primary amine.
  • the amount of the friction modifier may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a pour point depressant that can lower the pour point of the lubricant composition.
  • a pour point depressant Any pour point depressant known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable pour point depressants include polymethacrylates, polyacrylates, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphthalene and combinations thereof.
  • the pour point depressant comprises an ethylene -vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, polyalkyl styrene or the like.
  • the amount of the pour point depressant may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a demulsifier that can promote oil-water separation in lubricant compositions that are exposed to water or steam. Any demulsifier known by a person of ordinary skill in the art may be used in the lubricant composition.
  • demulsifiers include anionic surfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids and combinations thereof.
  • the amount of the demulsifier may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise an anti-foam that can break up foams in oils. Any anti-foam known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable anti-foams include silicone oils or
  • the anti-foam comprises glycerol monostearate, polyglycol palmitate, a trialkyl monothiophosphate, an ester of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate.
  • the amount of the anti-foam may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a corrosion inhibitor that can reduce corrosion.
  • Any corrosion inhibitor known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable corrosion inhibitor include half esters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosines and combinations thereof.
  • the amount of the corrosion inhibitor may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition.
  • Some suitable corrosion inhibitors have been described in Mortier et al., "Chemistry and Technology of Lubricants 2nd Edition, London, Springer, Chapter 6, pages 193-196 (1996), which is incorporated herein by reference.
  • the lubricant composition disclosed herein may comprise an anti-wear agent that can reduce friction and excessive wear.
  • Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphate, metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamate, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof.
  • the amount of the anti-wear agent may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise an extreme pressure (EP) agent that can prevent sliding metal surfaces from seizing under conditions of extreme pressure.
  • EP extreme pressure
  • Any extreme pressure agent known by a person of ordinary skill in the art may be used in the lubricant composition.
  • the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads.
  • Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alpha-olefin,
  • the amount of the extreme pressure agent may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise an antioxidant that can reduce or prevent the oxidation of the base oil.
  • Any antioxidant known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable antioxidants include amine- based antioxidants ⁇ e.g., alkyl diphenylamines, phenyl-a- naphthylamine, alkyl or aralkyl substituted phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like), phenolic antioxidants ⁇ e.g., 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert- butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis
  • the amount of the antioxidant may vary from about 0.01 to about 10 wt %, from about 0.05 to about 5%, or from about 0.1 to about 3%, based on the total weight of the lubricant composition.
  • the lubricant composition disclosed herein may comprise a rust inhibitor that can inhibit the corrosion of ferrous metal surfaces.
  • Any rust inhibitor known by a person of ordinary skill in the art may be used in the lubricant composition.
  • suitable rust inhibitors include oil- soluble monocarboxylic acids ⁇ e.g., 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid and the like), oil-soluble polycarboxylic acids (e.g., those produced from tall oil fatty acids, oleic acid, linoleic acid and the like), alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms (e.g., tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecen
  • the additives may be in the form of an additive concentrate having more than one additive.
  • the additive concentrate may comprise a suitable diluent, most preferably a hydrocarbon oil of suitable viscosity.
  • a suitable diluent can be selected from the group consisting of natural oils (e.g., mineral oils), synthetic oils and combinations thereof.
  • the mineral oils include paraffin-based oils, naphthenic-based oils, asphaltic-based oils and combinations thereof.
  • Non-limiting examples of the synthetic base oils include polyolefin oils (especially hydrogenated alpha-olefin oligomers), alkylated aromatic, polyalkylene oxides, aromatic ethers, and carboxylate esters (especially diester oils) and combinations thereof.
  • the diluent is a light hydrocarbon oil, both natural or synthetic.
  • the diluent oil can have a viscosity in the range of 13 to 35 centistokes at 40°C.
  • the lubricant composition disclosed herein may be suitable for use as motor oils (or engine oils or crankcase oils), transmission fluids, gear oils, power steering fluids, shock absorber fluids, brake fluids, hydraulic fluids and/or greases.
  • the lubricant composition disclosed herein is a motor oil.
  • a motor oil composition may be used to lubricate all major moving parts in any reciprocating internal combustion engine, reciprocating compressors and in steam engines of crankcase design. In automotive applications, the motor oil composition may also be used to cool hot engine parts, keep the engine free of rust and deposits, and seal the rings and valves against leakage of combustion gases.
  • the motor oil composition may comprise a base oil and the Diels-Alder adduct disclosed herein.
  • the motor oil composition may further comprise at least an additive.
  • the motor oil composition further comprises a pour point depressant, a detergent, a dispersant, an anti-wear, an antioxidant, a friction modifier, a rust inhibitor, or a combination thereof.
  • the lubricant composition disclosed herein is a gear oil for either automotive or industrial applications.
  • the gear oil composition may be used to lubricate gears, rear axles, automotive transmissions, final drive axles, accessories in agricultural and construction equipment, gear housings and enclosed chain drives.
  • the gear oil composition may comprise a base oil and the Diels-Alder adduct disclosed herein.
  • the gear oil composition may further comprise at least an additive.
  • the gear oil composition further comprises an anti-wear, an extreme pressure agent, a rust inhibitor, or a combination thereof.
  • the lubricant composition disclosed herein is a transmission fluid.
  • the transmission fluid composition may be used in either automatic transmission or manual transmission to reduce transmission losses.
  • the transmission fluid composition may comprise a base oil and the Diels-Alder adduct disclosed herein.
  • the transmission fluid composition may further comprise at least an additive.
  • the transmission fluid composition further comprises a friction modifier, a detergent, a dispersant, an antioxidant, an anti-wear agent, an extreme pressure agent, a pour point depressant, an anti-foam, a corrosion inhibitor or a combination thereof.
  • the lubricant composition disclosed herein is a grease used in various applications where extended lubrication is required and where oil would not be retained, e.g., on a vertical shaft.
  • the grease composition may comprise a base oil, the Diels-Alder adduct disclosed herein and a thickener.
  • the grease composition further comprise a complexing agent, an antioxidant, an anti-wear agent, an extreme pressure agent, an anti-foam, a corrosion inhibitor or a mixture thereof.
  • the thickener is a soap formed by reacting a metal hydroxide (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide and the like) with a fat, a fatty acid, or an ester.
  • a metal hydroxide e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide and the like
  • the type of soap used depends on the grease properties desired.
  • the thickener may be a non-soap thickener selected from the group consisting of clays, silica gels, carbon black, various synthetic organic materials and combinations thereof.
  • the thickener comprises a combination of soaps and non-soap thickeners.
  • the lubricant compositions disclosed herein can be prepared by any method known to a person of ordinary skill in the art for making lubricating oils.
  • the base oil can be blended or mixed with the Diels-Alder adduct disclosed herein and optionally at least an additive.
  • the Diels-Alder adduct disclosed herein and the optional additives may be added to the base oil individually or simultaneously.
  • the Diels-Alder adduct disclosed herein and the optional additives are added to the base oil individually in one or more additions and the additions may be in any order.
  • the Diels-Alder adduct disclosed herein and the additives are added to the base oil simultaneously, optionally in the form of an additive concentrate.
  • the solubilizing of the Diels-Alder adduct disclosed herein or any solid additives in the base oil may be assisted by heating the mixture to a temperature between about 25 and about 200°C, from about 50 and about 150°C or from about 75 and about 125°C.
  • Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients.
  • the blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., Ross double planetary mixers and Collette planetary mixers), a homogenizer (e.g., Gaulin homogeneizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art.
  • a blender e.g., Ross double planetary mixers and Collette planetary mixers
  • a homogenizer e.g., Gaulin homogeneizers and Rannie homogenizers
  • a mill e.g., colloid mill, ball mill and sand mill
  • Viscosity index refers to viscosity index as measured according to
  • the Diels-Alder adducts can be formulated for use in the following lubricant applications described below.
  • Diels-Alder adducts comprising ester functionality and having low volatility, high viscosity index, clean burning, and high lubricity may be used in automotive applications.
  • a PAO is blended with a Diels-Alder adduct comprising ester functionality (e.g., a diester), with the ester present at about 5%-50%, 5%-40%, 5%-30%, 5%-20%, or 5%-10% to make a lubricant useful in automotive applications.
  • a Diels-Alder adduct comprising a nonpolar hydrocarbon chain and a polar group as described herein may be used as a friction modifier.
  • a Diels- Alder adduct comprising one or two ester groups and/or one or two amide groups may be used as a friction modifier.
  • a Diels-Alder adduct comprising one or two ester groups and/or one or two amide groups may be used in combination with one or more organometallic compounds as a friction modifier.
  • suitable organometallic compounds include oil-soluble titanium compounds, oil-soluble organo-molybdenum compounds (e.g., molybdenum dithiocarbamate) and oil-soluble organo-tungsten compounds.
  • a Diels-Alder adduct as described herein may be used in a two stroke oil, e.g., to replace mineral oil as lubricant component of a conventional two stroke oil.
  • Use of Diels-Alder adducts comprising one or more ester groups may provide increased lubricity because of polar groups interaction with metal.
  • use of Diels-Alder adducts containing one or more ester groups in a lubricant formulation may remove or reduce a need to use brightstock.
  • a two stroke oil may be formulated with a Diels-Alder described herein without use of a solvent.
  • the Diels-Alder adducts may be used as metal working fluids in a variety of applications, such as steel rolling, aluminum drawing and cutting oils.
  • a metal working fluid may perform a variety of functions, including emulsification, metal complexing agent, solubilizing sludge and the like, and adding lubricity between the metal and a working tool.
  • An ester-containing Diels-Alder adduct may be used as a metal working fluid in some variations.
  • a carboxyl group containing Diels-Alder adduct may be used as a metal working fluid in some variations.
  • a Diels-Alder adduct between a conjugated terpene (e.g., farnesene) and itaconic acid derived from renewable sources is used as a metal working fluid.
  • an ester-containing Diels-Alder adduct may be used as an additive in a metal working fluid, e.g., where the Diels-Alder adduct is present at about 5%-50%, about 5%-40%, about 5%- 30%, about 5%-20%, or about 5%-10%.
  • the ester-containing Diels-Alder adducts may be selected to function as boundary lubricants, as friction modifiers, and to demonstrate sufficient wetting ability to penetrate between tool and work piece.
  • ester-containing Diels-Alder adducts may be used as quench fluids.
  • Other suitable applications for the Diels-Alder adducts include in air compressors and refrigerants, to lubricate and reduce friction between moving parts, function at oil seal at rings, screws, and the like, and to cool bearings and points of friction.
  • a Diels-Alder adduct e.g., an ester-containing Diels-Alder adduct
  • Base oil for grease In some variations, an ester-containing Diels-Alder adduct is used as an ester as a base oil for grease.
  • Drilling fluid In some variations, a Diels-Alder adduct (e.g., an ester-containing Diels-
  • Alder adduct is used as a base fluid added to drilling mud, where the Diels-Alder adduct functions to cool and lubricate the drill bit and to bring cuttings to the surface. Diels-Alder adducts that do not contain aromatic groups may be used to lower accumulation of undesired aromatic species during drilling.
  • Dielectric fluid Dielectric fluid.
  • a Diels-Alder adduct e.g., an ester-containing diels-Alder adduct
  • Diels-Alder adduct may be used to replace some or all mineral oil in a dielectric fluid in transformers, capacitors, and the like. Select Diels-Alder adducts may demonstrate resistance to discharge and high permittivity, and low moisture content.
  • Non-limiting examples of ester-containing lubricants are provided in Examples 41-47.
  • Example 48 One non-limiting example of a Diels-Alder adduct between b-farnesene and 1 ,4-benzoquinone is provided in Example 48.
  • lubricants and lubricant additives may be made from conjugated hydrocarbon terpenes that are not farnesene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a lubricant or lubricant additive is myrcene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a lubricant or lubricant additive is not myrcene or farnesene, and may for example be any of the Cio-C 30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.
  • the Diels-Alder adducts disclosed herein comprising one or more functional groups, such as one or more anhydride groups or two or more epoxy groups, may be used as comonomers for making addition polymers (e.g., epoxy resins) or a condensation polymer (e.g., polyesters or polyamides).
  • addition polymers e.g., epoxy resins
  • condensation polymer e.g., polyesters or polyamides
  • the Diels-Alder adduct having formula (J-XVA) or (J-XVB):
  • n 1 , 2, 3 or 4
  • diols can be used to react with a diol to form a polyester or with a diamine to form a polyamide or with a dithiol to form a polythioester.
  • suitable diols include 2,2'-bi-7-naphtol, 1,4- dihydroxybenzene, 1,3 dihydroxybenzene, 10,10 bis(4 hydroxyphenyl)anthrone, 4,4'-sulfonyldiphenol, bisphenol, 4,4' (9 fluorenylidene)diphenol, 1,10-decanediol, 1,5-pentanediol, diethylene glycol, 4,4' -(9- fluorenylidene)-bis(2-phenoxyethanol), bis(2 hydroxyethyl) terephthalate, bis[4 (2- hydroxyethoxy)phenyl] sulfone, hydroquinone-bis (2-hydroxyethyl)ether, and bis(2 -hydroxyethyl
  • Non- limiting examples of suitable diamine include diaminoarenes such as 1 ,4- phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone, and diaminoalkanes such as 1 ,2-ethanediamine and 1 ,4-butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino- 2(4),8-dimethyldibenzothiophene 5,5-dioxide.
  • diaminoarenes such as 1 ,4- phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone
  • diaminoalkanes such as 1 ,2-ethanediamine and 1 ,4-butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamin
  • Non-limiting examples of suitable dithiol include 3,6- dioxa-l,8-octanedithiol, erythro-l,4-dimercapto-2,3-butanediol, ( ⁇ )-threo-l,4-dimercapto-2,3-butanediol, 4,4'-thiobisbenzenethiol, 1,4 benzenedithiol, 1,3-benzenedithiol, sulfonyl-bis(benzenethiol), 2,5 dimecapto 1,3,4 thiadiazole, 1 ,2-ethanedithiol, 1,3-propanedithiol, 1 ,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol.
  • the Diels-Alder adduct having formula (J-XVIA) or (J-XVIB):
  • n 1, 2, 3 or 4; and R 11 , R 12 , R 13 and R 14 are as defined herein, can be used to react with a diamine to form an epoxy resin.
  • suitable diamine include diaminoarenes such as 1 ,4- phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone, and diaminoalkanes such as 1 ,2-ethanediamine and 1 ,4-butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino- 2(4),8-dimethyldibenzothiophene 5,5-dioxide.
  • the Diels-Alder adduct as described herein comprises one or more functional groups suitable for making an addition polymer or a condensation polymer such as a polyester or a polyamide.
  • X CHT and/or Y DP may be functionalized with one or more hydroxy groups and/or ester groups that are used to make a polyester.
  • a Diels-Alder adduct as described herein is used to make an alkyd polymer, without the need for adding in an additional oil because X CHT may provide sufficient oily properties.
  • X CHT and/or Y DP may be functionalized with one or more hydroxyl groups and/or amide groups to make a polyamide.
  • a Diels-Alder adduct between ⁇ -farnesene and a dienophile is a monomer that undergoes co-polymerization with one or more co-monomers to make a polymer.
  • the nature of the polymerization reaction and type and relative amounts of one or more co-monomers may be selected to tune one or more physical properties of the resulting polymer. For example, polymerization conditions favorable to the formation of block copolymers may be selected in one instance, and polymerization conditions favorable to the formation of random copolymers may be selected in another instance.
  • a conjugated terpene Diels-Alder adduct replaces an acid anhydride, a carboxylic acid, an amine, and/or a polyol in a polymerization reaction, e.g., in a condensation polymerization reaction.
  • a ⁇ -farnesene Diels-Alder adduct can replace an acid anhydride, a carboxylic acid and/or a polyol to make a polyester, or a ⁇ -farnesene Diels-Alder adduct can replace an acid anhydride, a carboxylic acid, or an amine to make a polyamide.
  • a Diels-Alder adduct that includes an anhydride moieity is used as a monomer that undergoes a condensation reaction with a polyol to make an unsaturated polyester resin, or an alkyd resin.
  • unsaturated polyester resins or alkyd resins are useful as coatings.
  • one or more fatty acids may be co-reacted with the polyol and the anhydride-containing adduct to make an alkyd resin.
  • the aliphatic tail originating from the hydrocarbon terpene may provide sufficient long chain hydrocarbon functionality to the resulting resin so a fatty acid is not used.
  • the polyol used to make an alkyd resin is glycerine.
  • a Diels-Alder adduct that includes an anhydride moiety is useful as a paper sizing agent, e.g., for cellulose-containing papers.
  • the hydrophilic head of the Diels-Alder adduct may interact with cellulose fibers to provide cohesion, and the hydrophobic tail originating from the conjugated terpene may provide printability and water resistance.
  • the hydrocarbon terpene used in such applications may in some paper sizing applications be ⁇ -farnesene or a-farnesene. However, other conjugated hydrocarbon terpenes described herein or otherwise known may be used.
  • any of the anhydride -containing adducts described herein may be used for paper sizing applications, e.g., maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides.
  • Diels-Alder adducts described herein have utility as cross-linking agents, curing agents, or as reactive diluents for resins.
  • the cross-linking agents, curing agents comprise epoxidized farnesene, epoxidized dimers of farnesene, epoxidized oligomers of farnesene, epoxidized Diels-Alder adducts of farnesene, and epoxidized Diels-Alder adducts of conjugated terpenes other than farnesene.
  • epoxidized farnesene or epoxidized Diels-Alder adducts of farnesene have utility as UV-cured cross-linking agents or curing agents.
  • epoxidized farnesene or epoxidized derivatives of farnesene have utility as multifunctional cross linking agents, e.g., comprising reactive sites that can undergo addition reactions, and reactive sites that can undergo hydrogen abstraction and subsequent cross-linking.
  • the polymers derived from the Diels-Alder adducts disclosed herein can be used to prepare useful polymer compositions for various applications.
  • the polymer compositions comprise the polymer derived from the Diels-Alder adducts and optionally one or more additives.
  • the compositions disclosed herein comprise at least one additive for the purposes of improving and/or controlling the processibility, appearance, physical, chemical, and/or mechanical properties of the polymer compositions.
  • the compositions do not comprise an additive.
  • Any plastics additive known to a person of ordinary skill in the art may be used in the compositions disclosed herein.
  • suitable additives include plasticizers, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, fillers, tackifier, flow aids, coupling agents, crosslinking agents, surfactants, solvents, and combinations thereof.
  • the additive is plasticizer, such as a mineral oil, liquid polybutene or a combination thereof.
  • the total amount of the additives can range from about greater than 0 to about 80%, from about 0.001 % to about 70%, from about 0.01 % to about 60%, from about 0.1 % to about 50%, from about 1 % to about 40%>, or from about 10 % to about 50%> of the total weight of the polymer composition.
  • the amount of each of the additives can range from about greater than 0 to about 25%, from about 0.001 % to about 20%, from about 0.01 % to about 15%, from about 0.1 % to about 10%, from about 0.1 % to about 5%>, or from about 0.1 % to about 2.5%> of the total weight of the polymer composition.
  • the compositions disclosed herein can comprise a wax, such as a petroleum wax, a low molecular weight polyethylene or polypropylene, a synthetic wax, a polyolefin wax, a beeswax, a vegetable wax, a soy wax, a palm wax, a candle wax or an ethylene/a-olefin interpolymer having a melting point of greater than 25 °C.
  • the wax is a low molecular weight polyethylene or polypropylene having a number average molecular weight of about 400 to about 6,000 g/mole.
  • the wax can be present in the range from about 10% to about 50%> or 20%> to about 40%> by weight of the total composition.
  • the compositions disclosed herein can comprise a plasticizer.
  • a plasticizer is a chemical that can increase the flexibility and lower the glass transition temperature of polymers. Any plasticizer known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of plasticizers include mineral oils, abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates, difuran diesters, fluorine -containing plasticizers, hydroxybenzoic acid esters, isocyanate adducts, multi-ring aromatic compounds, natural product derivatives, nitriles, siloxane-based plasticizers, tar-based products, thioesters and combinations thereof.
  • the amount of the plasticizer in the polymer composition can be from greater than 0 to about 15 wt.%, from about 0.5 wt.% to about 10 wt.%), or from about 1 wt.% to about 5 wt.% of the total weight of the polymer composition.
  • compositions disclosed herein optionally comprise an antioxidant that can prevent the oxidation of polymer components and organic additives in the polymer compositions. Any antioxidant known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of suitable antioxidants include aromatic or hindered amines such as alkyl diphenylamines, phenyl-a- naphthylamine, alkyl or aralkyl substituted phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like; phenols such as 2,6-di-t-butyl-4-methylphenol; l,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'- hydroxybenzyl)benzene; tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane ⁇ e.g., IRGANOXTM 1010, from Ciba Geigy, New York); acryloyl modified phenols; octadecyl-3,5
  • the amount of the antioxidant in the polymer composition can be from about greater than 0 to about 5 wt.%, from about 0.0001 to about 2.5 wt.%, from about 0.001 wt.% to about 1 wt.%, or from about 0.001 wt.% to about 0.5 wt.%) of the total weight of the polymer composition.
  • compositions disclosed herein optionally comprise an UV stabilizer that may prevent or reduce the degradation of the polymer compositions by UV radiations.
  • an UV stabilizer Any UV stabilizer known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • suitable UV stabilizers include
  • the amount of the UV stabilizer in the polymer composition can be from about greater than 0 to about 5 wt.%, from about 0.01 wt.% to about 3 wt.%, from about 0.1 wt.% to about 2 wt.%, or from about 0.1 wt.% to about 1 wt.% of the total weight of the polymer composition.
  • compositions disclosed herein optionally comprise a colorant or pigment that can change the look of the polymer compositions to human eyes. Any colorant or pigment known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of suitable colorants or pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo and monoazo compounds, arylamides, benzimidazolones, BONA lakes, diketopyrrolo-pyrroles, dioxazines, disazo compounds, diarylide compounds, flavanthrones, indanthrones, isoindolinones, isoindolines, metal complexes, monoazo salts, naphthols, ⁇ -naphthols, naphthol AS, naphthol lakes, perylenes, perinones,
  • inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo and monoazo compounds, arylamides, benzimid
  • the amount of the colorant or pigment in the polymer composition can be from about greater than 0 to about 10 wt.%), from about 0.1 wt.% to about 5 wt.%, or from about 0.25 wt.% to about 2 wt.% of the total weight of the polymer composition.
  • compositions disclosed herein can comprise a filler which can be used to adjust, inter alia, volume, weight, costs, and/or technical performance. Any filler known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina trihydrate, glass microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof.
  • the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fiber, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fiber or a mixture thereof.
  • the amount of the filler in the polymer composition can be from about greater than 0 to about 80 wt.%, from about 0.1 wt.% to about 60 wt.%), from about 0.5 wt.% to about 40 wt.%, from about 1 wt.% to about 30 wt.%, or from about 10 wt.%) to about 40 wt.% of the total weight of the polymer composition.
  • the polymer compositions disclosed herein may be crosslinked, partially or completely.
  • the polymer compositions disclosed herein comprise a cross- linking agent that can be used to effect the cross-linking of the polymer compositions, thereby increasing their modulus and stiffness, among other things.
  • An advantage of a polymer composition is that crosslinking can occur in its side chains instead of the polymer backbone like other polymers such as polyisoprene and polybutadiene. Any cross-linking agent known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of suitable crosslinking agents include organic peroxides ⁇ e.g., alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, and cyclic peroxides) and silanes ⁇ e.g.,
  • the amount of the cross-linking agent in the polymer composition can be from about greater than 0 to about 20 wt.%, from about 0.1 wt.% to about 15 wt.%, or from about 1 wt.% to about 10 wt.% of the total weight of the polymer composition.
  • the cross-linking of the polymer compositions can also be initiated by any radiation means known in the art, including, but not limited to, electron-beam irradiation, beta irradiation, gamma irradiation, corona irradiation, and UV radiation with or without cross-linking catalyst.
  • any radiation means known in the art including, but not limited to, electron-beam irradiation, beta irradiation, gamma irradiation, corona irradiation, and UV radiation with or without cross-linking catalyst.
  • U.S. Patent Application No. 10/086,057 published as US2002/0132923 Al
  • U.S. Patent No. 6,803,014 disclose electron-beam irradiation methods that can be used in embodiments of the invention.
  • Diels-Alder adducts described herein function as cross-linking agents or as curing agents in polymer systems.
  • any of the Diels-Alder adducts containing one or more epoxy groups, hydroxyl groups, acid groups, and/or unsaturated double bonds may function as cross-linking agents, e.g., in epoxy and/or polyester coatings, or in structural materials requiring crosslinking for increased mechanical strength or solvent resistance.
  • Any of the Diels-Alder adducts described herein containing one or more epoxy groups may function as an epoxy curing agent, or as a UV curing agent.
  • a Diels-Alder adduct used as a UV curing agent may be used with or without a photosensitizer. As described herein, it is possible to tune UV absorption of Diels-Alder adducts by increasing conjugation, which may allow the Diels-Alder adducts to be used as a UV curing agent without a photosensitizer in some applications.
  • an unsaturated Diels-Alder adduct containing epoxy groups may have utility as a multi-functional cross-linker in UV cured cationic epoxy systems in which the unsaturated ethylenic bonds are reactive and the epoxy groups are reactive and able to crosslink with acids, amines, and the like.
  • a polyol formed from a Diels-Alder adduct as described herein may be used as a cross-linker and/or monomer in a polymer resin (e.g., a polyurethane or polyester).
  • a polyol formed from a Diels-Alder adduct may be used in polymer formulations to enhance hardness, mechanical performance, and/or increase solvent resistance.
  • an unsaturated Diels-Alder adduct formed between a conjugated hydrocarbon terpene (e.g., famesene) and an acrylate ester may be used as a renewable starch bioplastic modifier.
  • the ester function on the Diels-Alder adduct may react with hydroxyl groups in starch, and unsaturated ethylenic bonds on the adduct may react with other unsaturated monomers.
  • monomers, cross-linking agents, curing agents, and reactive diluents may be made from conjugated hydrocarbon terpenes that are not famesene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a monomer, cross-linking agent, or reactive diluent is myrcene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a monomer, cross-linking agent, or reactive diluent is not myrcene or famesene, and may for example be any of the Cio-C 30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.
  • a Diels-Alder adduct (which includes any Diels-Alder adduct that has undergo post-Diels-Alder reaction modification) between a conjugated terpene and a dienophile is incorporated into a polymer to plasticize the polymer.
  • the conjugated terpene is ⁇ -famesene. In some embodiments, the conjugated terpene is a-famesene.
  • the dienophile is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, fumaramide and substituted fumaramide
  • a plasticizer as used herein refers to a compound that can be added to a host polymer
  • thermoplastics thermosets, or elastomers
  • polymer blends polymer composites, synthetic rubbers, natural rubbers, or other resins (individually and collectively referred to "resin” or “resins” herein) to lower glass transition temperature or melt temperature, increase flexibility, increase toughness, increase elasticity, decrease rigidity, improve low temperature brittleness, and/or improve processibility of the host polymer.
  • a plasticizer may act to modify any one of or any combination of glass transition temperature, melt temperature, tensile properties (e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus), flexural properties, impact resistance, extrudability, flexibility, processability, workability, stretchability, and improve a low temperature brittleness or low temperature strength.
  • tensile properties e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus
  • flexural properties impact resistance, extrudability, flexibility, processability, workability, stretchability, and improve a low temperature brittleness or low temperature strength.
  • a plasticizer acts to lower glass transition temperature of the host resin.
  • a plasticizer increases toughness, increases impact resistance, increases % elongation at break, decreases Young's modulus, increases displacement at break, increases load at break, increases processability, increases flexibility, improves low temperature brittleness, or any combination of two or more of the foregoing.
  • Polymer compositions are disclosed herein that comprise one or more plasticizers described herein in a host resin, wherein the plasticizer is present in an effective amount to modify one or more of the glass transition temperature, elasticity, toughness, elongation at break, displacement at break, load at break, energy to yield, impact resistance, flexibility, processability, or low temperature brittleness.
  • the host resin is PVC, a polycarbonate, a polyurethane, a nitrile polymer (such as acrylonitrile butadiene styrene (ABS)), an acrylate polymer, a polystyrene, a polyester, a polyamide, a polyimide, a polyvinyl acetal, a cellulose polymer, a polyolefin, a natural rubber, a synthetic rubber, a copolymers of any of the foregoing, a polymer blend of any of the foregoing, or a polymer composite of any of the foregoing.
  • polymer compositions comprise one or more additives in addition to one or more plasticizers described herein, e.g., an antioxidant, a flame retardant, a processing aid, an inorganic filler, or a colorant.
  • the polymer to be plasticized can be a vinyl polymer or copolymer, a non- vinyl polymer or copolymer, or a combination thereof.
  • vinyl polymers and copolymers are disclosed in Malcolm P. Stevens, "Polymer Chemistry, an Introduction " Third Edition, Oxford University Press, pp. 17-21 and 167-279 (1999), which is incorporated herein by reference.
  • polymer include polyolefms, polyurethanes, polyesters, polyamides, styrenic polymers, phenolic resins, polyacrylates, polymethacrylates and combinations thereof. If PVC is used as the host polymer resin, any suitable grade of PVC can be used, to be selected by intended application.
  • a rigid grade or a flexible grade of PVC may be used.
  • a flexible grade of PVC is used.
  • a grade of PVC suitable for making bottles is used.
  • a grade of PVC suitable for making thin films is used.
  • a grade of PVC suitable for making blown films is used.
  • a grade of PVC suitable for extrusion is used.
  • a grade of PVC suitable for coating wire is used.
  • a host resin comprises a chlorinated PVC (CPVC).
  • CPVC chlorinated PVC
  • one or more solubility parameters e.g., Hansen solubility parameters
  • PVC may be plasticized using one or more plasticizers described herein to decrease rigidity, increase flexibility, improve processibility, increase toughness, improve low temperature brittleness, and the like.
  • the polymer comprises a polyolefin (e.g., polyethylene, polypropylene, an ethylene/a-olefm interpolymer, a copolymer of ethylene and propylene, and a copolymer of ethylene and vinyl acetate (EVA)), polyurethane, polyester, polyamide, styrenic polymer (e.g., polystyrene, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene) and the like), phenolic resin, polyacrylate, polymethacrylate or a combination thereof.
  • a polyolefin e.g., polyethylene, polypropylene, an ethylene/a-olefm interpolymer, a copolymer of ethylene and propylene, and a copolymer of ethylene and vinyl acetate (EVA)
  • EVA ethylene and vinyl acetate
  • polyurethane
  • the polymer is polyethylene, polypropylene, polystyrene, a copolymer of ethylene and vinyl acetate, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene) or a combination thereof.
  • the host resin comprises a polyolefin.
  • polyolefins that may be plasticized with plasticizers described herein include polyethylene,
  • polypropylene an ethylene/a-olefm interpolymer, a copolymer of ethylene and propylene, a copolymer of ethylene and vinyl acetate (EVA), a polyfarnesene, a polyfarnesane, an interpolymer of farnesene such as a copolymer of farnesene and a styrene), or hydrogenated versions farnesene interpolymers.
  • EVA ethylene and vinyl acetate
  • Nonlimiting examples of farnesene interpolymers are disclosed in U.S. Pat. Publ. 2010/0056714, which is incorporated by reference herein in its entirety.
  • one or more solubility parameters e.g., Hansen solubility parameters
  • Hansen solubility parameters may be useful in determining a suitable plasticizer for a given polyolefin host resin.
  • the host resin comprises a styrenic polymer.
  • styrenic polymers that may be plasticized with plasticizers described herein include polystyrene, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene), poly(styrene- isoprene-styrene, poly(styrene-butadiene-isoprene-styrene and the like.
  • one or more solubility parameters e.g., Hansen solubility parameters
  • Hansen solubility parameters may be useful in determining a suitable plasticizer for a given styrenic host resin.
  • the host resin comprises a polyester or a copolymer comprising a polyester.
  • a polyester that may be plasticized with one or more plasticizers described herein may be aromatic, aliphatic, or aliphatic-aromatic interpolymers.
  • a linear saturated aromatic polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) is plasticized with one or more plasticizers described herein.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • an aliphatic-aromatic terpolyester e.g., poly(butylene terephthalate -co-succinate-co-adipate
  • plasticizers described herein is plasticized with one or more plasticizers described herein.
  • an aliphatic polyester or copolyester such as a lactic-acid based polyester, a polycaprolactone, a polyesteramide, or a polyhydroxyalkanoate (e.g., poly(hydroxybutyrate- co-hydroxyvalerate) may be plasticized with one or more plasticizers described herein.
  • the polymer is a biodegradable polyester such as poly(lactic acid) or an interpolymer of lactic acid, a polycaprolactone, a polyesteramide, a polyhydroxyalkanoate, or an aliphatic-aromoatic terpolyester.
  • aliphatic lactic acid-based polyesters that may be plasticized with plasticizers described herein include poly(lactic acid) (PLA); interpolymers between lactic acid and an aliphatic hydroxycarboxylic acid; aliphatic polyesters comprising
  • polyesters comprising an aliphatic polyvalent carboxylic acid unit, an aliphatic polyvalent alcohol unit, and a lactic acid unit; and mixtures or blends of the foregoing.
  • polyesters that may be plasticized with certain plasticizers described herein are described in U.S. Patent No. 6,544,607, which is incorporated herein by reference.
  • Lactic acid used in poly(lactic acid) and interpolymers of lactic acid can be produced in any manner known in the art, e.g., by chemical synthesis, or by fermentation of a sugar source from lactobacillus, and the term lactic acid encompasses both D-lactic acid and L-lactic acid.
  • Poly(lactic acid) or interpolymers of lactic acid can be made using enantiomeric monomers D-lactic acid and/or L-lactic acid by known methods.
  • Poly(lactic acid) may be poly(L-lactic acid) (solely composed of L-lactic acid), poly(D-lactic acid) (solely composed of D-lactic acid), poly(DL-lactic acid), composed of both D-lactic acid and L-lactic acid in varying proportions, e.g., a molar ratio of D-Lactic acid:L-Lactic acid of about 100:1, 50:1, 10:1, 5:1, 2:1, 1:1, 1 :2, 1:5, 1 :10, 1 :50, or 1 :100.
  • PLA and interpolymers of lactic acid are affected by relative amounts of the D- and L- forms.
  • poly(L-lactic acid) may exhibit a higher degree of crystallinity than copolymers of L-lactic acid and D- lactic acid, or copolymers of L-lactic acid with other non-lactic acid monomers.
  • one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid and another aliphatic hydroxycarboyxlic acid, such as glycolic acid, 3- hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6- hydroxycaproic acid, and the like.
  • Any relative proportions of lactic acid and another aliphatic hydroxycarboxylic acid may be used in the plasticized interpolymers, e.g., lactic acid: aliphatic hydroxycarboxylic acid molar ratio of about 1 :10, 1 :5, 1 :2, 1:1, 2:1, 5:1 or 10:1.
  • one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid and a saccharide, such as cellulose, cellulose acetate, cellulose nitrate, methyl cellulose, ethyl cellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cupro-ammonoium rayon, cuprofan, bemberg, hemicellulose, starch, acropectin, dextrin, dextran, glycogen, pectin, chitin, chitonsan, gum Arabic, cyamoposis gum , locust bean gum, acacia gum, and mixtures or blends thereof, or derivatives thereof.
  • a saccharide such as cellulose, cellulose acetate, cellulose nitrate, methyl cellulose, ethyl cellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cupro-ammonoium rayon,
  • lactic acid and a saccharide may be used in the plasticized interpolymers, e.g., lactic acid: saccharide molar ratio of about 1 : 10, 1 :5, 1 :2, 1 : 1, 2: 1, 5: 1 or 10: 1.
  • one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid, an aliphatic polyvalent carboxylic acid (e.g., oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof), and an aliphatic polyvalent alcohol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3 -butanediol, 1,4- butanediol, 3-methyl-l,5-pentanediol, 1 ,6-hexandediol, 1 ,0-nonanediol, neopentyl glycol, tetramethylene glycol, 1 ,4-cyclohe
  • lactic acid, aliphatic polyvalent carboxylic acid, and aliphatic polyvalent alcohol may be used, e.g., molar ratio of lactic acid: acid: alcohol of about 1 : 1 : 1, 2: 1 : 1, 3: 1 : 1, 4: 1 : 1, 5:1 :1, 10: 1 :1, 1 :2:2, 1 :3:3, 1 :4:4, 1 :5:5, 1 : 10: 10:, 10:2: 1, 5:2: 1, 2:2: 1, 10: 1 :2, 5: 1 :2, 2: 1 :2.
  • Any suitable plasticizer may be selected to plasticize a polyester such as a lactic-acid based polyester as described above.
  • alcohols e.g., monoalcohols, diols or other polyols
  • esters e.g., monoesters or diesters
  • one or more solubility parameters e.g., Hansen solubility parameters
  • PLA or interpolymers of lactic acid may be plasticized using one or more plasticizers described herein to decrease rigidity and increase flexibility.
  • plasticized PLA or interpolymers of lactic acid may be sufficiently plasticized to attain a flexibility making it suitable for use in applications traditionally using polyethylene, polypropylene, soft polyvinyl chlorides, and the like.
  • a variety of useful articles may be formed from plasticized polyesters (e.g., lactic acid based polyesters such as PLA) as described herein, e.g., trays, cups, plates, bottles, films, cutlery, toys, storage containers, tools, and the like.
  • plasticized polyesters e.g., lactic acid based polyesters such as PLA
  • the adduct may be incorporated into the polymer using any suitable method.
  • the adduct may be mechanically mixed with the polymer (e.g., melt blended).
  • the adduct may be co-dissolved with the polymer in a solution, and solvent cast.
  • the adduct may be chemically reacted with the host polymer to incorporate into the matrix, e.g., by cross-linking, transesterification, or the like.
  • ingredients i.e., the adduct, the polymer and optional additives
  • suitable blending methods include melt blending, solvent blending, extruding, and the like.
  • the ingredients are melt blended by a method as described by
  • the ingredients are processed using solvent blending. First, the ingredients are dissolved in a suitable solvent and the mixture is then mixed or blended. Next, the solvent is removed.
  • physical blending devices that can provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing can be used in preparing homogenous blends.
  • Both batch and continuous methods of physical blending can be used.
  • Non- limiting examples of batch methods include those methods using BRABENDER ® mixing equipments (e.g., BRABENDER PREP CENTER ® , available from C. W. Brabender Instruments, Inc., Southhackensack, N.J.) or BANBURY ® internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment.
  • Non-limiting examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding.
  • the additives can be added into an extruder through a feed hopper or feed throat during the extrusion of the farnesene interpolymer, the optional polymer or the foam.
  • the mixing or blending of polymers by extrusion has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, NY, pages 322-334 (1986), which is incorporated herein by reference.
  • plasticizers serve various functional roles when compounded with thermoplastics including making them more flexible, durable, tough, extrudable and moldable. When plasticizers are selected for such functional roles they are incorporated with the thermoplastic at levels anywhere from about 5 phr to about 60 phr either depending upon the mechanical or geometric properties needed of the finished article or composition or depending upon the properties needed for their fabrication.
  • a plasticizer's ability to modify the stress-strain properties of a thermoplastic is generally related to the mutual solubility of the plasticizer and thermoplastic where, in general, the greater the mutual solubility then the more effective the modification.
  • plasticizer-thermoplastic compositions are formulated with additional ingredients for various purposes including facilitating compounding, facilitating later stage processing or fabrication, and providing additional functional features in the final plasticized article or composition.
  • additional ingredients include acid scavengers, radical scavengers, flow viscosity improvers, UV absorbers, fire retardants, and colorants.
  • plasticizers when incorporated in high levels, typically in the 50-100 phr range, can modify thermoplastics to give fluid compositions known as plastisols which are compositions of sufficiently low viscosity that may be applied to the surfaces of solid or porous articles, such as metals, plastics, and textiles for example, by various coating means including spray, dip, knife over drum and gravure. Such coated articles may sometimes be finished in a subsequent step in order to cure the composition or to remove some or all of the plasticizer.
  • plasticizer candidates based on farnesene, farnesene oligomers, and their derivitives and examples of these molecules are disclosed in Table 5.
  • One reason why these plasticizers are especially advantageous over existing plasticizers is because between about 50- 100% of their carbon atoms can be derived from renewable resources.
  • plasticizers described herein may be compounded with the thermoplastic, along with any additional additives, to give useful compositions including compositions suitable for shaping or forming, by extrusion or compression molding for example, into useful articles and useful plastisol compositions.
  • the amount of plasticizer used in a polymer composition to impart the desired physical or mechanical properties to the plasticized resin may be affected by a number of factors, including the compatibility between the resin and the plasticizer, the effectiveness of the plasticizer, migration of the plasticizer within and/or out of the host resin, the intended use for the plasticized resin, processing conditions, and any applicable industry standards.
  • a plasticizer disclosed herein is added to a resin in an amount sufficient to impart desired physical or mechanical properties to the plasticized resin.
  • plasticizer is used to impart desired physical or mechanical properties to the plasticized resin, where wt% is based on the total weight of the plasticized resin.
  • the amount of plasticizer in a plasticized resin is about 30wt% or less, e.g. about 30wt%, 20wt%, 10wt% or 5wt%, based on total weight of the plasticized resin.
  • a plasticizer may be either a liquid or a solid at ambient temperature.
  • the plasticizer exhibits sufficient thermal stability at temperatures at which the resin will be processed, including temperatures used for melt-mixing, extrusion, injection molding, compression molding calendaring, laminating, blown film processing, and the like.
  • the plasticizer exhibits sufficiently low volatility at typical resin processing temperatures so as to allow melt mixing, extrusion, injection molding, compression molding, calendaring, laminating, blown film processing, and the like.
  • a plasticizer used to plasticize PVC may exhibit sufficient thermal stability and sufficiently low volatility to allow polymer processing at temperatures in a range from 170°C-210°C.
  • a plasticizer is solid at ambient temperature, in some variations, the plasticizer has a softening temperature that allows melt mixing with the polymer to be plasticized, e.g., if used to plasticize PVC, a solid plasticizer may have a softening temperature appropriate for melt mixing at temperatures in a range from 170°C-210°C.
  • a plasticizer may be incorporated into the resin and interact with the resin in any suitable manner to impart the desired physical or mechanical properties to the plasticized resin.
  • the plasticizer is at least partially miscible in the host resin.
  • a portion of the plasticizer is compatible with the resin.
  • the plasticized resin is not completely homogeneous in composition, such that domains rich in resin or domains rich in plasticizer are formed.
  • the plasticized resin shows evidence of phase separation between the resin and the plasticizer.
  • a plasticizer for a target resin is selected based on one or more measured or calculated solubility parameters of plasticizer and of the target resin.
  • a measured or calculated Hansen solubility parameter may be used to select a plasticizer for use in a target resin, e.g., a PVC, as illustrated in Table 5.
  • a plasticizer for use in PVC may be selected to have a solubility parameter close to that of PVC.
  • plasticizer characteristics that can affect diffusion include polarity of the plasticizer, polarity of the resin, plasticizer interaction with or compatibility with the resin, plasticizer molecular weight, and viscosity of the resin and/or plasticizer under use conditions.
  • a plasticizer may comprise a Diels Alder adduct between a conjugated terpene (e.g., farnesene) and a dienophile as described herein; or a derivative of such a Diels- Alder adduct as described herein, in which one or more carbon-carbon double bonds has been oxidized (e.g., epoxidized).
  • oxidized (e.g., epoxidized) farnesene derivatives may be useful as plasticizers in relatively polar host resins such as PVC. Any suitable oxidation technique known to oxidize carbon- carbon double bonds may be used.
  • any suitable oxidant such as peroxides, peracetic acid, meta chloroperoxybenzoic acid, enzymes, or peroxide complexes such as urea-peroxide complexes (e.g., Novozyme-435TM urea-peroxide complex) may be used.
  • the oxidation (e.g., epoxidation) conditions are adjusted to oxidize only one carbon-carbon double bond, e.g., one carbon- carbon double bond that originated in the ⁇ -farnesene starting material.
  • the oxidation (e.g., epoxidation) conditions are adjusted to oxidize two carbon-carbon double bonds, e.g., two carbon- carbon double bonds that originated in the ⁇ -farnesene starting material. In some variations, oxidation (e.g., epoxidation) conditions are adjusted to oxidize three or more carbon-carbon double bonds, e.g., three or more carbon-carbon double bonds that originated in the ⁇ -farnesene starting material. In some variations, oxidation (e.g., epoxidation) conditions are adjusted to oxidize substantially all carbon-carbon double bonds originating in the ⁇ -farnesene starting material.
  • a molar ratio of oxidant: farnesene may be lowered (e.g., lower than about 5: 1, such as about 4: 1, 3: 1, 2: 1, 1 : 1 or 0.5: 1 to produce compositions in which fewer carbon-carbon double bonds are oxidized (e.g., epoxidized).
  • a plasticizer may comprise a Diels Alder adduct between a conjugated terpene (e.g., farnesene) and a dienophile as described herein; or a derivative of such a Diels- Alder adduct as described herein, in which one or more carbon-carbon double bonds is halogenated, e.g., where one chlorine atom is added to each double bond using a reagent such as HC1, or where two chlorine atoms are added to each double bond using a reagent such as chlorine gas.
  • a reagent such as HC1
  • a reagent such as chlorine gas
  • reaction conditions are adjusted such only one carbon-carbon double bond is halogenated, e.g., one carbon-carbon double bond that originated in the conjugated terpene starting material. In some variations, the reaction conditions are adjusted so two carbon-carbon double bonds are halogenated, e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some variations, reaction conditions are adjusted such that three or more carbon-carbon double bonds are halogenated, e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene (e.g., farnesene) starting material. In some variations, substantially all carbon-carbon double bonds originating from the conjugated hydrocarbon terpene are halogenated. In certain variations, such halogenated derivatives of a Diels-Alder adduct of a conjugated terpene may have use as a plasticizers for PVC.
  • Hydroxy versions of epoxidized Diels-Alder adducts may be prepared using any known technique that allows for reaction of epoxy groups to form hydroxyl groups.
  • an epoxy group can be reduced to form a single hydroxy group, or an epoxy group can be hydrolyzed to form two hydroxy groups.
  • the hydroxyl groups may be subsequently acetylated to form a compound that may have use as a plasticizer, e.g., for PVC.
  • a Diels-Alder adduct to be used as a plasticizer may be tuned to increase compatibility with a host resin.
  • a plasticizer disclosed herein comprises a Diels Alder adduct of ⁇ -farnesene and a dienophile in which the aliphatic portion of the Diels Alder adduct originating from the ⁇ -farnesene and/or one or more substituents of the Diels Alder adduct originating from the dienophile have been selected or modified to increase compatibility with the host resin.
  • the aliphatic portion of the adduct may be oxidized (e.g., epoxidized) or chlorinated across one or more carbon-carbon double bonds and/or one or more substituents of the adduct originating from the dienophile may be selected or modified to include one or more polar moieties (e.g., one or more hydroxyl, ester, ether, epoxy, carboxy, amino, and/or chloro groups) to increase compatibility with polar host resins.
  • polar moieties e.g., one or more hydroxyl, ester, ether, epoxy, carboxy, amino, and/or chloro groups
  • Such nonpolar substituents may include one or more relatively long (e.g., C6-C 20 , or C6-C30) aliphatic substituents, which may be introduced into the Diels Alder adduct via the dienophile, or by subsequent modification of the Diels Alder adduct.
  • relatively long e.g., C6-C 20 , or C6-C30
  • a plasticizer disclosed herein comprises a Diels Alder adduct that has been hydrogenated so as to saturate the aliphatic portion of the Diels Alder adduct originating from the conjugated terpene (e.g., farnesene).
  • a hydrogenated Diels Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo-oxidative stability in use.
  • a hydrogenated Diels Alder adduct undergoes post-hydrogenation reaction, e.g., to modify one or more substituents originating in the dienophile. For example, one or more a carboxylic acid ester moieties remaining in the hydrogenated Diels Alder adduct may undergo transesterification, reduction, hydrolysis, and the like.
  • Any one of, or any combination of two or more of the compounds shown herein may have utility as a plasticizer. Any one of, or any combination of two or more of the examples illustrated in Table 5 herein may have utility as a plasticizer, e.g., for PVC.
  • a compound having utility as a plasticizer is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and acrylic acid or an acrylate ester.
  • Diels-Alder adducts formed when the hydrocarbon terpene is farnesene are given by formulae (H-IA), (H-IB), (H-IC), (H-ID), (H-IE), (H-IF), (H-IG) and (H-IH) as shown in Section H above.
  • plasticizers have formulae (H-IC) and/or (H-ID).
  • plasticizers have formulae (H-IG) and/or (H-IH).
  • H-IG Diels-Alder adduct produces more than one isomer
  • any one of the isomers may be present without significant amounts of other isomers may be used as a plasticizer, or any mixture of the isomers may be used, with the isomers present in any relative amounts.
  • any mixture comprising a ratio of 1,3- isomer: 1 ,4-isomer of about 0.1 :99.9, 5:95, 1 :99, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 may be used as a plasticizer.
  • a compound having utility as a plasticizer is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and a dialkyl maleate or a dialkyl fumarate.
  • Diels-Alder adducts produced when the hydrocarbon terpene is farnesene are given by formula (H-IIA), (H-IIB), (H- IIC) and (H-IID) as shown in Section H above.
  • plasticizers have formula (H-IIB).
  • plasticizers have formula (H-IID).
  • a plasticizer is, comprises, or is derived from a compound having formula (H-XIIA), ( ⁇ - ⁇ '), (H-XIIB), ( ⁇ - ⁇ '), (H-XIIC), (H-XIIC), (H-XIID), (H-XIID'), (H- XIIE), ( ⁇ - ⁇ '), or (H-XIIF).
  • a plasticizer is, comprises, or is derived from a compound having formula ( ⁇ - ⁇ '), ( ⁇ - ⁇ '), (H-XIIC), (H-XIID'), ( ⁇ - ⁇ '), or (H-XIIF).
  • a plasticizer is or comprises one of or a mixture of Compounds (J-
  • compound (J-3a) and/or (J-3b) may be useful as plasticizers in relatively low polarity host resins, e.g., in polyolefins, polystyrenes, synthetic rubbers, natural rubbers, or in copolymers thereof, or in polymer blends thereof, or in polymer composites thereof.
  • a plasticizer is or comprises compound (J-5):
  • a plasticizer is or comprises compound (J-9):
  • a plasticizer is or comprises compound (J-11):
  • a plasticizer is or comprises one of or a mixture of compounds (J-
  • a plasticizer is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and maleic anhydride.
  • a plasticizer is, comprises, or is derived from a compound having formula (H-IIIA), (H-IIIB), (H-IIIC), or (H-IIID) as shown in Section H above.
  • a plasticizer is, comprises, or is derived from a compound having formula (H-IIIB) or (H-IIID) as shown in Section H above.
  • a Diels-Alder adduct comprising one or more alcohol substituents is reacted with a fatty acid, succinic acid, or the like to make a plasticizer.
  • a Diels-Alder adduct comprising one or more carboxylic acid substituents is reacted with an isosorbide or a fatty alcohol to make a plasticizer.
  • a plasticizer derived from ⁇ -farnesene and isosorbide is shown as Example 47.
  • a plasticizer is or comprises one or more of compounds (J- 15a), (J-
  • a plasticizer is or comprises compound (J- 19):
  • a plasticizer comprises a dimer of ⁇ -farnesene (e.g., a cyclic or linear dimer as described in U.S. Pat. No. 7,691,792, which is incorporated by reference herein in its entirety) that has had one or more, or essentially all, of the carbon-carbon double bonds oxidized (e.g., epoxidized).
  • a ⁇ -farnesene derived plasticizer comprises one of or a mixture of two or more of compounds (J-21), (J-22), (J-23), and (J-24):
  • a plasticizer is or comprises compound (J-25):
  • multifunctional plasticizer molecules or multifunctional plasticizers having at least two functions when they are combined with thermoplastics where one of these functions relates to modifying the mechanical, geometric, or fluid flow properties of thermoplastics or articles made therefrom and where the other one or more functions may fulfill any beneficial purposes including charge dissipation, antithrombosis, heat stabilization, fire retardation, corrosion inhibition, flow viscosity improvement at relatively low plasticizer levels, radical scavenging, acid scavenging, oxygen scavenging, dye site creating, adhesion promoting, particularly of paints and coatings, blowing (to give foams and popcorns), and mold releasing.
  • One key advantage of the multifunctional plasticizers of the present invention is a cost savings relating to the use of fewer molecules in plasticizer-thermoplastic formulations.
  • a multifunctional plasticizer in addition to the plasticization function of a multifunctional plasticizer, its other one or more functions may provide a feature benefiting the fabrication of the composition or article or may provide a feature benefiting the final composition or article. In fact, the other one or more functions may provide a benefit both to fabrication and to the final composition or article.
  • a multifunctional plasticizer that provides an HC1 acid scavenging benefit is useful during the processing of PVC at elevated temperatures because it prevents degradation and the formation of color bodies during processing.
  • a multifunctional plasticizer that provides dye sites for anionic dyes for example is useful to the final article or composition because it improves its ability to be colored with dyes without containing pigment additives which often damage the mechanical properties of plasticized thermoplastics.
  • a multifunctional plasticizer that provides an anticorrosion benefit is useful both during and after processing because it keeps the processing equipment corrosion free and provides for corrsion protection to plasticized articles when they contact or contain metal parts such as nails and screws for example.
  • the multifunctional plasticizers may be compounded with the thermoplastic, along with any additional additives, to give useful compositions including compositions suitable for shaping or forming, by extrusion or compression molding for example, into useful articles and useful plastisol compositions. While it is the purpose of the plasticization function of a multifunctional plasticizer that it be directed toward affecting the bulk property of the thermoplastic article or composition, it should be recognized that in some application areas it is desirable that the other one or more functions of a multifunctional plasticizer be directed to the surface of the article or composition.
  • a multifunctional plasticizer that also functions as a antithrombolytic is present both in the bulk and entangled with the thermoplastic at the surface of the article or composition.
  • At least three methods for effecting migration of some of the multifunctional plasticizer towards the surface whilst maintaining a level of plasticizer in the bulk that is satisfactory for good plasticization employs a thermal treatment step.
  • Another method employs contact of the surface of said article with a liquid which promotes migration either by swelling, chemical potential, or diffusion gradient mechanisms.
  • a third method employs the use of small amount of a separate surfactant molecule that when added to the multifunctional plasticizer-thermoplastic composition effects surface migration.
  • a conjugated terpene e.g., ⁇ -farnesene
  • its oligomers to be advantageous precursors to multifunctional plasticizer molecules due to the ease of derivatization of its double bonds (in the case of farnesene, up to four of its double bonds) can be derivatized, and in some embodiments selectively derivatized, with groupings which give the derivative multiple functions.
  • groupings which give the derivative multiple functions.
  • the diene moiety of farnesene and certain oligomers can be easily made to enter into Diels- Alder reactions and the trisubstituted double bonds of farnesene can be easily made to enter into electrophilic and nucleophilic reactions.
  • these groupings give the derivative both plasticizing function and one or more aditional functions.
  • the farnesene molecule and its derivatives can be readily cyclized, bicylized, and tricylized to give useful
  • multifunctional plasticizers are disclosed in the examples of Table 5.
  • a plasticizer described herein (e.g., plasticizers in Table 5) is used to plasticize PVC to make a bottle cap.
  • a plasticizer provided herein may be mixed together in a 1 :4 weight ratio respectively in a blender for a suitable length of time (e.g., about 10 minutes) to give a divided composition.
  • an acid scavenger in a suitable amount e.g., about 1 phr
  • the divided composition may be blended for an additional time period (e.g., about 5 minutes).
  • the resulting composition may be kneaded for a suitable length of time in a suitable mixing apparatus (e.g., about 20 minutes under moderate energy using a Banbury batch mixer at about 200 degree blade temperature) to give a doughy composition.
  • a suitable mixing apparatus e.g., about 20 minutes under moderate energy using a Banbury batch mixer at about 200 degree blade temperature
  • a portion of the composition may be compression molded, e.g., into a 9x9x0.03" rectangular sheet using a Carver Press at a guage pressure of 10 tons and a mold temperature of about 230 degrees.
  • dog bone specimens may be cut from the molded sheet and its tensile properties measured using methods prescribed in ASTM D638. The specimens may give an average elongation at break of about 20%, 30%, 40%, 50%, 100%, 150%, 200%), 250%) or 300%.
  • a low-color molded article comprising PVC and a multifunctional plasticizer possessing acid scavenging function may be made by incorporating a plasticizer described herein with alkenyl chemical groupings into PVC by any method known in the art, but withought adding any separate acid scavenger ingredient giving a plasticized sheet or article with very low color.
  • a low-color molded article comprising PVC and a multifunctional plasticizer possessing acid scavenging function may be made by incorporating a plasticizer described herein with epoxy chemical groupings into PVC by any method known in the art, but without adding any separate acid scavenger ingredient giving a plasticized sheet or article with very low color.
  • a plasticizer described herein may be used to make a flexible safety hose having a charge dissipating fluid-contact surface.
  • a plasticizer described herein with an anhydride chemical grouping may be extruded in a continuous process into a hose geometry using any suitable method known in the art.
  • a screw extruder equipped with a tube die head may be used.
  • a conjugated terpene e.g., ⁇ -farnesene
  • its oligomers may be advantageous precursors to multifunctional plasticizer molecules due to the ease of derivatization of its double bonds (in the case of famesene, up to four of its double bonds) can be derivatized, and in some embodiments selectively derivatized, with groupings which give the derivative multiple functions.
  • the diene moiety of famesene and certain oligomers can undergo Diels- Alder reactions and the trisubstituted double bonds of famesene can undergo electrophilic and nucleophilic reactions.
  • these groupings may give the derivative (e.g., Diels- Alder adducts) both plasticizing function and one or more additional functions.
  • the famesene molecule and its derivatives e.g., Diels-Alder adducts
  • the plasticizer candidates of Table 5 are disclosed in the plasticizer candidates of Table 5.
  • a plasticizer may be altered in a processing step to give multifunctional properties.
  • anhydride groupings at the surface can be solvolyzed after extrusion in an alkaline water-alcohol quench bath to give a charge dissipating plasticized material.
  • such a charge dissipating plasticized material may safely eliminate charge buildup resulting from the streaming of fluids.
  • Table 5 and 6 and certain Examples provide non- limiting examples of Diels-Alder adducts that may be used as plasticizers in suitable polymer hosts.
  • Examples 24-26 provide non-limiting examples of epoxidized famesenes that may have utility as plasticizers, monomers in making oligomers or polymers, as cross-linking agents, curing agents, as reactive solvents or diluents, and the like.
  • plasticizers may be made from conjugated hydrocarbon terpenes that are not famesene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is myrcene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is not myrcene or famesene, and may for example be any of the C10-C30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.
  • a Diels-Alder adduct as described herein may be used as a nonionic surfactant.
  • the surfactants described herein include a hydrophilic portion that is soluble in water, including cold water in some variations, and a hydrophobic portion that can solubilize and efficiently remove oily soils (oil, fatty substance, grease, clay, and the like). Some of the surfactants described herein may demonstrate rapid water-oil interface kinetics so as to be able to effectively remove soil within a short wash time.
  • a Diels-Alder adduct may be modified so as to form an anionic or cationic compound that has utility as a surfactant.
  • a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate may be formed (e.g., using standard sulfation techniques such as SC oleum sulfation), a phosphate or phosphite may be formed, or an ammonium ion may be made.
  • Cationic Diels-Alder adducts e.g., ammonium ions such as quaternary ammonium ions
  • anionic Diels-Alder adducts e.g., sulfates or phosphates
  • surfactants such as soaps, detergents, wetting agents, dispersants, emulsifiers, foaming agents, antistatic agents, corrosion inhibitors, and antimicrobials.
  • Certain anionic surfactants derived from Diels-Alder adducts may be useful in detergents, soaps, builders and other cleaning agents, emulsifiers and the like.
  • Certain cationic surfactants derived from the Diels-Alder adducts described herein may have use in personal care products.
  • ammonium ions e.g., quaternary ammonium ions
  • Ammonium ions e.g., quaternary ammonium ions
  • N-oxides formed from the Diels-Alder adducts described herein may have use as surfactants, e.g., for use in personal care products (e.g., shampoos, conditioners, and the like).
  • anionic surfactants may be used at levels as high as about 30 to 40% of a detergent formulation.
  • Other important surfactants used in consumer products include amine oxides, cationic surfactants, zwitterionic surfactants, alkyl polyglycoside surfactants, soaps, and fabric softening cationic surfactants. These additional types of surfactants provide additional cleaning benefits over those provided by anionic surfactants, as well as enhanced foaming, enhanced skin mildness, and fabric softening.
  • the conjugated terpene and/or post-Diels-Alder reaction chemical modification may be selected to design surfactants that provide enhanced cold water cleaning performance, enhanced cleaning performance in general, and process and/or rheological advantages.
  • the Diels-Alder adducts described herein may be used to form cationic surfactants, zwitterionic surfactants, amine oxide surfactants, soaps and fatty acids, alkypolyglycoside surfactants, di-long-chain alkyl cationic surfactants and detergent products comprising them.
  • aldehydes or polyaldehydes are converted to alcohols or polyalcohols, respectively. In some variations, alcohols or polyalcohols are converted to functionalized or polyfunctionalized surfactants.
  • surfactants e.g., polyfunctionalized such as di-anionic
  • soil suspending capacity while reducing or minimizing tendency to crystallize or exhibit poor solubility.
  • a process is used which is tuned to create a polyalcohol (e.g., a di, a tri, or a tetraalcohol) in addition to or instead of a monoalcohol.
  • Surfactants may be formed from aldehyde-containing or alcohol-containing Diels-Alder adducts by way of any alcohol-to-surfactant or aldehyde-to-surfactant derivatization process known in the industry.
  • Fatty alcohols and aldehydes may be converted into additional surfactants such as cationic surfactants, zwitterionic surfactants, amine oxide surfactants, alkylpolyglycoside surfactants, soaps, fatty acids, and/or long-chain alkyl (e.g., di-long-chain alkyl) cationic surfactants.
  • Non-limiting examples of synthetic procedures for obtaining these materials from the parent alcohols or aldehydes may be found in the Kirk Othmer Encyclopedia of Chemical Technology or other suitable references.
  • Cationic surfactant, zwitterionic surfactants, amine oxide surfactants, alkylpolyglycoside surfactants, soaps, fatty acids may in some variations be combined with nonionic and/or anionic surfactants derived from alcohols.
  • an alcohol may be treated with an alkylene oxide such as ethylene oxide and/or propylene oxide to create an alkoxylated alcohol which may be used in or as a nonionic surfactant, or which optionally may undergo sulfation to create an anionic surfactant.
  • cationic surfactants may be derived from aldehydes or alcohols described herein.
  • an alcohol or aldehyde may be converted to a tertiary amine vi direct amination via reaction with secondary amines such as monoethanol amine to provide a methyl, hydroxyethyl tertiary amine or via reaction with dimethyl amine to provide a dimethyl tertiary amine.
  • Direct amination may occur in the presence of the reactant amine at about 230°C and 0.1-0.5 MPa using copper chromite (from an alcohol) or a noble metal, copper chelate, or copper carboxylate catalyst from an aldehyde.
  • Tertiary amines may be converted to a hydroxyalkyl quat or trimethyl quat via reaction with methyl chloride or dimethyl sulfate.
  • Ester quats may be prepared by oxidation of alcohols or aldehydes using any suitable oxidizing agent (e.g., potassium permanganate, Jones reagent, etc.) to form a carboxylic acid, followed by esterification (or diesterification) of N-methyldiethanolamine with the carboxylic acid, followed by quatermization with methyl chloride or dimethyl sulfate.
  • an amine oxide is prepared from a tertiary amine by oxidizing the peroxide in water with a bicarbonate buffer.
  • Amine oxides may be used in formulations in which grease cleaning and/or foaming ability is desired.
  • a fabric softener component comprises a quat-containing Diel-Alder adduct. Ester quats (e.g., diester quats) and dialkyl quats may be used in fabric softeners.
  • Ester quats e.g., diester quats
  • dialkyl quats may be used in fabric softeners.
  • zwitterionic betaine surfactants tertiary amines may be reacted with a substituted or unsubstituted 1,3-sultone, e.g., in acetone. Zwitterionic surfactants may be useful in enhancing cold water performance and/or formulability.
  • Soaps and fatty acids are sometimes useful in laundry detergents as surfactants and/or as additives to provide mildness or other tactile or sensorial benefits.
  • a soap or fatty acid Diels-Alder adduct described herein provides a surfactant with increased solubility.
  • Fatty acids and soaps may be prepared via oxidation of aldehydes or alcohols using any suitable oxidizing agent, e.g., potassium permanganate, Jones regent, or any other technique known in the art.
  • Alkylpolyglycosides derived from the Diels-Alder adducts described herein may be useful for their mildness, foaming ability and/or cold temperature solubility.
  • an alkylpolyglycoside e.g., with 0, 1, 2, 3, or 4 repeat units
  • a Diels-Alder adduct containing an alcohol via acid-catalyzed reaction with a monosaccharide.
  • Non-limiting examples are provided in U.S. Pat. No. 4,950,743, which is incorporated herein by reference in its entirety.
  • detergent alcohols may be used in shampoos, laundry detergents, dishwashing detergents, and/or hard surface cleaners after being formulated into appropriate surfactant compositions.
  • detergents and hard surface cleaners may comprise additional polymers as washing substances, cleaning polymers (modified or unmodified polycarboxylates, ethoxylated amines and derivatives of each of the foregoing), builders, co-builders, complexing agents, bleaches, standardizers, graying inhibitors, dye transfer inhibitors, enzymes and/or fragrances.
  • Surfactants derived from the Diels-Alder adducts may be used in any suitable amount in a cleaning, fabric softening, or personal care product formulation.
  • a surfactant derived from a Diels-Alder adduct is present in an amount from about 0.05wt% to about 70wt%, or from about 0.1 wt% to about 40wt%, or from about 0.25wt% to about 10 wt% of a cleaning, fabric softening, or personal care product formulation.
  • nonionic surfactants described herein comprise alkoxylated Diels-
  • the nonionic surfactants described herein comprise 4,8-dimethylnonyl-substituted
  • the surfactants described herein are nonaromatic and are biodegradable. Some of the surfactants described here may exhibit low levels of foaming or may not foam detectably. In some embodiments, a nonionic surfactant described herein may function as a defoaming agent.
  • the nonionic surfactants described herein comprise a hydrophobic end and a hydrophilic end, each connected to the cyclic structure residue from the Diels-Alder reaction.
  • the hydrophobic end originates from the conjugated hydrocarbon terpene
  • the hydrophilic end originates from the dienophile.
  • the hydrophobicity and hydrophilicity of the Diels-Alder adducts can be tuned by selection of the conjugated hydrocarbon terpene, the dienophile, and by post-Diels-Alder reaction chemical modifications of the aliphatic tail originating from the terpene and/or chemical modifications of the portion of the molecule originating from the dienophile.
  • the hydrophobic end comprises at least one 4,8- dimethylnonyl substituent.
  • the hydrophilic end comprises an alkyl alcohol, or any hydrophilic group that can be derived from an alkyl alcohol.
  • the hydrophilic end comprises an alkoxyl chain comprising one or more types of alkoxyl repeat units.
  • the hydrophilic end can be represented as R 3 -0-R a ] k -H, wherein R 3 represents a linear or branched alkyl group (e.g., -CH2- or -CH(CH 3 )-) and R a i k includes an alkoxyl chain that comprises one or more types of alkoxyl repeat units R 1 O s wherein R 1 is a CpCio or C 1 -C4 linear or branched alkyl group.
  • R 3 represents a linear or branched alkyl group (e.g., -CH2- or -CH(CH 3 )-)
  • R a i k includes an alkoxyl chain that comprises one or more types of alkoxyl repeat units R 1 O s wherein R 1 is a CpCio or C 1 -C4 linear or branched alkyl group.
  • R 1 -CH 2 -
  • the alkoxyl chain in the hydrophilic end comprises more than one type of alkoxyl repeat unit such that R a[k can be represented by the formula: wherein R 1 and R 2 are each independently C 1 -C 10 or Q-C4 linear or branched alkyl groups, p represents
  • the differing alkoxyl units can be distributed in any pattern, e.g., as a continuous series or block of a first type of alkoxyl repeat unit separated by a continuous series or block of a second type of alkoxyl repeat unit, or repeat units of the first type of alkoxyl repeat unit may be randomly interspersed with repeat units of the second type.
  • a Diels Alder adduct that has utility as a nonionic surfactant can be obtained by reacting a conjugated hydrocarbon terpene (e.g., ⁇ -farnesene or a-farnesene) with any suitable dienophile that can be converted to an alcohol or diol.
  • a conjugated hydrocarbon terpene e.g., ⁇ -farnesene or a-farnesene
  • any suitable dienophile that can be converted to an alcohol or diol.
  • any substituted or unsubstituted ⁇ , ⁇ -unsaturated aldehyde such as:
  • R 1 , R 2 , and R 3 is independently, H, Ci-Cio alkyl, C 3 -C 6 cycloalkyl, aryl, substituted aryl, and the like; or the dienophile may be an acrylate or substituted acrylate such as:
  • R 1 is H or C r C 8 alkyl
  • R 2 , R 3 , and R 4 are, each independently, H, C r Ci 0 alkyl, C 3 -C 6 cycloalkyl, aryl, substituted aryl, and the like.
  • allylic alcohols may be used as a dienophile in a Diels-Alder reaction with a conjugated terpene such as ⁇ -farnesene or a-farnesene.
  • methyl vinyl ketones may be used in a Diels-Alder reaction with a conjugated terpene such as ⁇ -farnesene or a-farnesene.
  • the surfactants described herein comprise or are derived from alcohol
  • J-4-1 represents any one of, or any combination of the two isomers J-4-IA and J-4-IB shown below:
  • alcohol J-4-I includes both isomers, J-4-IA and J-4-IB.
  • alcohol J- 4-1 includes isomer J-4-IA, with only trace amounts or no detectable amount of isomer J-4-IB.
  • alcohol J-4-I includes isomer J-4-IB, with only trace amounts or no detectable amount of isomer J-4-IA.
  • alcohol J-4-I includes about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J-4-IA.
  • Alcohol J-4-I may include any ratio of isomer J-4-IA to isomer J-4-IB.
  • alcohol J-4-I includes a ratio of isomer J-4-IA to isomer J-4-IB of about 0.001:1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1 .
  • compound J-4-11 as shown below functions as a nonionic surfactant:
  • Compound J-4-11 represents any one of or any combination of the two isomers J-4-IIA and J-4-IIB as shown below:
  • compound J-4-11 includes both isomers, J-4-IIA and J-4-IIB.
  • compound J-4-11 includes isomer J-4-IIA, with only trace amounts or no detectable amount of isomer J-4-IIB.
  • compound J-4-11 includes isomer J-4-IIB, with only trace amounts or no detectable amount of isomer J-4-IIA.
  • compound J -4-II includes 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J -4-IIA.
  • Compound J -4-II may include any ratio of isomer J -4-IIA to isomer J -4-IIB.
  • compound J -4-II includes a ratio of isomer J -4-IIA to isomer J -4-IIB of about 0.001 :1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • surfactants contain alkoxy repeat units that are different than ethoxyl repeat units.
  • some surfactants include propoxyl repeat units in the hydrophilic end, rather than ethoxyl repeat units.
  • Some surfactants include both ethyoxyl and propoxyl repeat units.
  • surfactants are derived from alcohols described herein (e.g., J -4-1 J -4-V, J -
  • m is in the range 1 to 30. In some variations, m is in the range 5 to 25. In some variations of the surfactants, m is in the range 6 to 20. In some variations, m is in the range 6 to 12. In some variations, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, m is 9.
  • surfactants contain both ethoxy and propoxy repeat units, and have structures analogous to compound J -4-II, J -4-VI, J -4-VIIIA, J -4-VIIIB and J -4-X, with the following structure substituted for the ethoxy repeat units:
  • the ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units.
  • the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions.
  • p and q are independently in the range 1 to 30.
  • p and q are independently in the range 6 to 20.
  • p and q are independently in the range 5 to 25.
  • p and q are independently in the range 6 to 12.
  • p and q are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.
  • the sum (p+q) is in the range 1 to 30, or 6 to 20, or 5 to 25, or 6 to 12. In some variations, the sum (p+q) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.
  • compound J-4-III functions as a nonionic surfactant:
  • compound J-4-III includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer.
  • compound J -4-III includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer.
  • compound J -4-III includes a ratio of the 1,3- isomer to the 1,4- isomer of about 0.001 :1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • compound J -4-IV as shown below functions as a nonionic surfactant:
  • the ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units.
  • the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions.
  • compound J-4-IV includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer.
  • compound J -4-IV includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer.
  • compound J -4-IV includes a ratio of the 1,3- isomer to the 1 ,4- isomer of about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1,50:1, 100:1, 500:1, or 1000:1.
  • Isomers J-4-VA and J-4-VB can be present in any relative amount, e.g., alcohol J-4-V may consist of isomer J -4-VA with no detectable amount of isomer J-4-VB, or may consist of isomer J-4-VB with no detectable amount of isomer J-4-VA, or a ratio of isomer J -4-VA: J-4-VB may be about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • alcohol J -4-V can be formed by carrying out a Diels- Alder reaction of ⁇ -farnesene with acrolein in the presence of a methyl magnesium halide (e.g. methyl magnesium bromide) or the like.
  • a methyl magnesium halide e.g. methyl magnesium bromide
  • the alcohol J-4-V may be used as is in a formulation in some embodiments, or in other embodiments, the alcohol may be subsequently alkoxylated to form a surfactant.
  • alcohol J-4-V can be ethoxylated to form surfactant J-4-VI:
  • Isomers J-4-VIA and J-4-VIB can be present in any relative amount, e.g. surfactant J-4-VI may consist of isomer J-4-VIA with no detectable amount of isomer J-4-VIB, or may consist of isomer J-4-VIB with no detectable amount of isomer J-4-VIA, or a ratio of isomer J-4-VIA:J-4-VIB may be about 0.001 :1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • surfactant J-4-VI may consist of isomer J-4-VIA with no detectable amount of isomer J-4-VIB, or may consist of isomer J-4-VIB with no detectable amount of isomer J
  • the alcohols J-4-VIIA and J-4-VIIB may be used in a formulation as is in some embodiments, or in other embodiments, may be subsequently treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a mixture of surfactants J-4-VIIIA and J-4-VIIIB (where ethoxylation is shown as a model alkoxylation):
  • an alkylene oxide e.g., ethylene oxide and/or propylene oxide
  • the average number of ethoxyl repeat units y and y' for surfactants J-4-VIIIA and J-4-VIIIB, respectively, is independently in the range of 1 to 30, or 5 to 25, 6 to 20, or 6 to 12. That is, y and y' can each independently be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30.
  • nonionic surfactants comprise or are derived from diol J-4-IX:
  • the diol J-4-IX is used as is in a formulation, and in other embodiments, the diol may be treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a nonionic surfactant having formula J-4-X (where ethoxylation is shown as a model alkoxylation):
  • an alkylene oxide e.g., ethylene oxide and/or propylene oxide
  • n is in the range 1 to 30. In some variations, n is in the range 5 to 25. In some variations of the surfactants, n is in the range 6 to 20. In some variations n is in the range 6 to 12. In some variations, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, n is about 9. [00407] It should be understood that analogs of surfactants J-4-VI, J-4-VIIIA, J-4-VIIIB, and J-4-
  • X are contemplated, in which a different alkoxyl repeat unit is substituted in place of some of or all of the ethoxyl repeat units.
  • the alcohols J-4-V, J-4-VIIA, J-4-VIIB, and J-4-IX can be propoxylated instead of ethoxylated, or propoxylated and ethoxylated instead of ethoxylated.
  • the alcohols and surfactants described herein can be made by any suitable method now known or later developed by one skilled in the art.
  • the compounds and surfactants can be made by Diels Alder addition of a dienophile to the diene functionality of the conjugated terpene (e.g., ⁇ -farnesene).
  • suitable dienophiles that can be used to produce substituted aldehydes (e.g., 4,8-dimethyl-3,7-nonadienyl-substituted) include: substituted
  • ⁇ , ⁇ -unsaturated aldehydes such as: wherein R 1 , R 2 , and R 3 are, each independently, H, CpCio alkyl, C 3 -C 6 cycloalkyl, aryl, substituted aryl, and the like; and acrylates or substituted acrylates such as: wherein R 1 is H or CpCg alkyl, and R 2 , R 3 , and R 4 are, each independently, H, Ci-Cio alkyl, C3-C6 cycloalkyl, aryl, substituted aryl, and the like.
  • an allylic alcohol may be used as the dienophile in a Diels-Alder reaction with a conjugated terpene such as ⁇ -farnesene or a-farnesene.
  • Substituted aldehydes resulting from a Diels-Alder reaction can be reduced to form a substituted alcohol as described above. Any suitable reducing methods and conditions may be used.
  • the unsaturated aldehyde e.g., 4,8-dimethyl-3,7-nonadienyl-substituted aldehyde
  • an unsaturated alcohol e.g., 4,8-dimethyl-3,7-nonadienyl-substituted alcohol
  • the saturated alcohol e.g., 4,8-dimethylnonyl-substituted alcohol.
  • Example 28 One non- limiting example of such a method is shown in Example 28, in which the 4,8-dimethyl-3-7-nonadiene substituted aldehyde (28-2) is first reduced using sodium borohydride to form a 4,8-dimethyl-3,7- nonadienyl-substituted alcohol (28-3).
  • the 4,8-dimethyl-3,7-nonadienyl-substituted alcohol is then hydrogenated, e.g., using a palladium catalyst such as Pd/C, a platinum catalyst, or a commercial nickel- based catalyst in a fixed-bed reactor, to saturate double bonds to form a 4,8-dimethylnonyl-substituted alcohol (28-4), which corresponds to Compound J-4-I above).
  • a palladium catalyst such as Pd/C
  • platinum catalyst e.g., a platinum catalyst, or a commercial nickel- based catalyst in a fixed-bed reactor
  • the unsaturated aldehyde resulting from the Diels-Alder reaction is reduced to a saturated alcohol (e.g., 4,8-dimethylnonyl-substituted alcohol) in a single step, without forming an unsaturated alcohol intermediate.
  • a saturated alcohol e.g., 4,8-dimethylnonyl-substituted alcohol
  • a catalyst such as a ruthenium catalyst over carbon or a palladium catalyst over carbon can be used to reduce the 4,8-dimethyl-3,7-nonadienyl-substituted aldehyde (28-2) directly to a 4,8-dimethylnonyl-substituted alcohol (28-4).
  • An alcohol made by any of the methods described above can be further alkoxylated by any method now known or later side chain.
  • Any of the mono-alcohols or diols described herein may be reacted with an alkylene oxide (e.g., ethylene oxide as shown in Examples 28 and 35-37, or propylene oxide, or both ethylene oxide and propylene oxide) under standard industrial alkoxylation conditions (e.g. sodium hydride, potassium tert-butoxide, or any base having pK>about 16 or 17).
  • the reaction conditions e.g. time, temperature, pK, concentrations of reagents, solvents
  • the ratio of ethoxyl to propoxyl repeat units can be controlled by adjusting the ratio of ethylene oxide to propylene oxide during the alkoxylation reaction.
  • surfactants may be made from conjugated hydrocarbon terpenes that are not farnesene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a surfactant is myrcene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a surfactant is not myrcene or farnesene, and may for example be any of the Cio-C 30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.
  • the surfactants described herein are nonaromatic and are readily biodegradable.
  • the hydrocarbon terpene (e.g., ⁇ -farnesene or a-farnesene) feed used to make the surfactants described herein can be derived from renewable carbon sources.
  • the surfactants described herein can be used as nonionic surfactants.
  • anionic sulfate surfactants can be derived from the surfactants described herein using standard sulfation techniques (e.g. SOs/oleum sulfation) as is used for conventional alkyl ethoxylated sulfates.
  • the surfactants described herein can be formulated into a variety of compositions adapted to specific purposes.
  • formulations comprising the surfactants described herein can be designed as emulsifiers, solubilizers, wetting agents, dispersants, anti-foam agents, detergents (e.g., laundry detergents, dishwasher soaps and the like), industrial and household cleaning products (e.g., floor and other surface cleansers, bathroom cleansers, furniture cleansers, degreasers, and the like), fabric care products, oil recovery surfactants, and personal care products (e.g., cleansing bars and liquids, hair care products, moisturizers, dental care products, emollients, humectants and the like).
  • detergents e.g., laundry detergents, dishwasher soaps and the like
  • industrial and household cleaning products e.g., floor and other surface cleansers, bathroom cleansers, furniture cleansers, degreasers, and the like
  • fabric care products e.g., cleansing
  • formulations comprising the surfactants described herein can be adapted for certain applications.
  • laundry detergents comprising the surfactants described herein can be developed to remove soil under a variety of laundry conditions, such as varied cycle time (e.g., cycle times as short as 15-20 minutes to cycle times as long as multiple hours), varied water conditions (e.g., hot or cold water, hard or soft water), water level (e.g., high volume water wash as in conventional washing machines to low volume water wash as used in high efficiency washing machines), washing machine design (e.g., degree of agitation) and hand washing.
  • cycle time e.g., cycle times as short as 15-20 minutes to cycle times as long as multiple hours
  • varied water conditions e.g., hot or cold water, hard or soft water
  • water level e.g., high volume water wash as in conventional washing machines to low volume water wash as used in high efficiency washing machines
  • washing machine design e.g., degree of agitation
  • the formulations comprising the surfactants describe herein can optionally comprise additional components.
  • detergents comprising one or more surfactants described herein can additionally comprise any one of or any combination of builders, enzymes, polymer additives, and bleach.
  • detergents comprise one or more surfactants described herein and one or more builders, one or more enzymes, and one or polymer additives.
  • a builder, enzyme, polymer additive, or bleach, or any combination thereof that can be used in combination with the surfactants described herein can be selected from those builders, enzymes, polymer additives, bleaches, and combinations thereof that are known in the detergent industry.
  • the surfactant comprises at least about 5 wt.%, lOwt.%, 15%, 20wt.%, 25wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.% or 50 wt.% of the total detergent.
  • more than one surfactant is present, e.g. a nonionic surfactant as described herein, and one or more additional surfactants (e.g. one or more anionic surfactants).
  • formulations comprising the surfactants described herein comprise any one of or any combination of the following non-limiting examples of additives: corrosion inhibitors, thickeners, colorants, fragrances, stabilizers, antioxidants, odorants, additional surfactants, stabilizers, emollients or humectants.
  • a surfactant described herein can be present in a formulation in any suitable amount.
  • a surfactant described herein may be present in an amount in a range from about 0.01 wt.% to about 99.99 wt.%, about 0.1 wt.% to about 99.9 wt.%, about 1 wt.% to about 99 wt.%, about 5 wt.% to about 95 wt.%, about 10 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, from about 30 wt.% to about 70 wt.%, from about 40 wt.% to about 60 wt.% in a formulation, from about 1% wt.% to about 50%wt.%, from about 1% wt.% to about 40wt.%, from about 1 wt.% to about 30wt.%, from about 1 wt.% to about 20wt.%, from about 1 wt.% to about 10 wt.%, where wt.% refers
  • a surfactant described herein is present in an amount as small as about 1 wt.%, 0.5 wt.%, 0.1 wt.%, or even smaller, e.g. about 0.01 wt.% or 0.05 wt.%. In some formulations, a surfactant described here is present in an amount of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, 99.9, or 99.99 wt.%) of the total formulation. [00418] A compound, composition, or surfactant described herein is used as a substitute for a nonylphenol or alkoxylated nonylphenol in some formulations.
  • alcohol J-4-I, J-4-V, J-4- VIIA, J-4-VIIB, or J-4-IX as described above may be used as a substitute for a nonylphenol in some formulations.
  • compound J-4-II, J-4-VI, J-4-VIIIA, J-4-VIIIB, or J-4-X as described above e.g., with n being about 9 can be used as a substitute for an ethoxylated nonylphenol.
  • a composition or surfactant described herein as a substitute for a nonylphenol e.g.
  • composition or surfactant described herein can in some circumstances be used as a direct replacement for the nonylphenol, while in other circumstances, the amount of surfactant substituted for the nonylphenol may be different, or one or more additives (e.g. , an additional surfactant such as an anionic surfactant) may be used in combination with the surfactant described herein to substitute for the nonylphenol.
  • an additional surfactant such as an anionic surfactant
  • certain ones of the Diels-Alder adducts described herein have utility as a surfactant for rubber emulsion (e.g., styrene-butadiene rubber) polymerization.
  • a Diels-Alder adduct that comprises one or more carboxyl groups may be used as an aid in rubber emulsion polymerization.
  • HLB hydrophobic-lipophilic balance
  • HLB values range from about 0.5 to 19.5.
  • a low HLB indicates a nonionic surfactant that has high solubility in oil; a high HLB value indicates a nonionic surfactant that has high solubility in water or other polar solvents.
  • a surfactant having a HLB in a range from about 1 to about 3 may be used.
  • a surfactant having a HLB in a range from about 4 to about 6 may be used.
  • a surfactant having a HLB in a range from about 7 to about 10 may be used.
  • a surfactant or blend of surfacts having HLBs in a range from about 8 to about 16 may be used.
  • surfactants having HLBs in a range from about 13 to about 15 may be used.
  • surfactants or surfactant blends having HLBs of about 13 to about 18 may be used.
  • HLB value may be selected to lower or minimize the interfacial tension between an oil phase and a water phase.
  • HLB Hydrophile-Lipophile Balance
  • HLB values can be calculated for simple alcohol ethoxylates, or measured empirically for other types of nonionic surfactants. HLB is calculated as follows: (molecular weight due to ethoxylate units/molecular weight of molecule) x 100%/ 5. In operation, HLB values range from about 0.5 to 19.5. HLB values for a mixture of surfactants can be determined as a weighted average of the HLB value for each separate surfactant weighted by the amount of that surfactant in the mixture. In some circumstances, an oil supplier supplies an HLB value for a surfactant (or mixture of surfactants) to be used in applications with that oil (e.g., emulsification).
  • a Diels-Alder adduct surfactant as described herein having an HLB value in a range from 0-3 is insoluble in water or has limited solubility in water, and may have application as a defoaming agent.
  • a surfactant having a HLB in a range from about 1 to about 3 may be used.
  • a Diels-Alder adduct surfactant having an HLB value in a range from 3-6 is insoluble in water or has limited solubility in water, but is dispersible in water, and may have application in forming water-in-oil emulsions.
  • a Diels-Alder adduct surfactant having an HLB value in a range from 6-9 is dispersible in water, and may have application as a wetting agent, in forming water-in-oil emulsions, or in forming self-emulsifying oils.
  • a Diels-Alder adduct surfactant having an HLB value in a range from 8-10 is somewhat soluble in water, and may have application as a wetting agent.
  • a surfactant or blend of surfactants having HLBs in a range from about 8 to about 16 may be used.
  • a Diels-Alder adduct surfactant having an HLB value in a range from 10-13 is soluble in water, and may have application in forming oil-in-water emulsions, detergents, or cleaning products.
  • a Diels- Alder adduct surfactant having an HLB value in a range from 13-15 is soluble in water, and may have utility in forming oil-in-water emulsions, detergents, or cleaning products.
  • surfactants or surfactant blends having HLBs of about 13 to about 18 may be used.
  • a Diels-Alder adduct surfactant having an HLB value that is greater than equal to about 15 is soluble in water, and may have application as a solubilizer, detergent, or cleaning product.
  • the Diels-Alder adducts disclosed herein may be used as surfactants if they comprises one or more ionic groups or polar group.
  • the Diels-Alder adduct having formula (J-XVIIA) or (J-XVIIB):
  • each of Mi and M 2 is independently a monovalent cation such as Fr+, Cs+, Rb+, K+, Na+, Li+, Ag+, Au+, Cu+, NH4+, primary ammonium, secondary ammonium, tertiary ammonium, or quaternary ammonium, where Mi + and M 2 + may the same or different.
  • the Diels-Alder adducts of formulae (J-XVIIA) and (J-XVIIB may be used as surfactants since each of them comprises both a hydrophobic group and a hydrophilic group.
  • the surfactant compounds described herein are useful as solvents.
  • Hansen solubility parameters may be used. Hansen solubility parameters were calculated for a number of theoretical and synthesized solvents derived from myrcene or farnesene using HSPiP software program, available at www.hansen- solubility.com.
  • the Y-MB algorithm was used to calculate estimated HSP parameters 3D, ⁇ and ⁇ for Diels-Alder adducts that may be derived from ⁇ -farnesene or myrcene as described herein, and are shown in Table S.4. Hansen solubility parameters were also calculated for a number of commercial solvents (Table S.5). As used below, glu indicates a glucose unit.
  • a Diels-Alder adduct or derivative thereof as described herein has utility as an emollient and as a UV absorber (e.g., for a light stabilizing compound or sunscreen applications).
  • a compound that may exhibit properties as an emollient and be capable of absorbing UV light in a useful wavelength range is a Diels-Alder adduct between ⁇ -farnesene and a quinone (preparation provided in theExamples).
  • a Diels- Alder adduct between ⁇ -farnesene and a quinone may be oxidized to increase the degree of conjugation, thereby tuning the UV absorption to the red.
  • the solvents described herein can be compared with existing solvents and used to replace existing solvents in formulations, or in combination with existing solvents in formulations.
  • One method that can be used to identify potential applications for the solvents described herein is to plot ⁇ vs. ⁇ for hydrocarbon terpene derived solvent described herein as well as existing solvents, and identify existing solvents with having similar ( ⁇ , ⁇ ).
  • Described herein are compounds comprising a Diels-Alder adduct of a hydrocarbon terpene (e.g., ⁇ -farnesene, such as trans-P-farnesene) comprising a conjugated diene and a dienophile, wherein the Diels-Alder adduct is adapted for use as an additive for a polymer to modify at least one physical property of the polymer.
  • a hydrocarbon terpene e.g., ⁇ -farnesene, such as trans-P-farnesene
  • the dienophile may be any suitable dienophile, with non-limiting examples including maleic anhydride and substituted maleic anhydrides, fumaric acid, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates,
  • dialkylaminoalkyl acrylates dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, fumaramide and substituted fumaramides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl acetylene dicarboxylates, monoalkyl acetylene carboxylates, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, vinyl sulfinates, vinyl sulfonates, vinyl sulfoxides, sulfur dioxide, naphthoquinones, phosphorus trihalide, and combinations thereof.
  • the Diels-Alder adduct is chemically modified prior to being used as an additive for the polymer.
  • the Diels-Alder adducts may be incorporated into the polymer in any suitable manner to modify at least one physical property of the polymer.
  • the adduct may be physically blended with the polymer or chemically reacted with the polymer.
  • the polymer to be modified may be a thermoplastic, a thermoset or an elastomer.
  • the polymer to be modified is a condensation polymer.
  • a hydrogenated Diels-Alder adduct is used to modify at least one physical property of the polymer.
  • the Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile may be used as a monomer and polymerized to make a homopolymer, or reacted with one or more comonomers to make an interpolymer.
  • the dienophile may be any suitable dienophile, with non-limiting examples including maleic anhydride and substituted maleic anhydrides, fumaric acid, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates,

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Abstract

La présente invention concerne des dérivés de terpènes hydrocarbonés (par exemple, du myrcène ou du farnésène), des procédés de fabrication des dérivés et l'utilisation des dérivés sous la forme d'huiles, de solvants, de lubrifiants, d'additifs ou d'huiles de base pour des compositions lubrifiantes, des agents tensioactifs, des plastifiants, et/ou sous la forme de monomères, d'agents de réticulation, d'agents de durcissement ou de diluants réactifs devant être utilisés dans la fabrication d'oligomères ou de polymères.
PCT/US2012/048203 2011-08-24 2012-07-25 Dérivés de terpènes hydrocarbonés Ceased WO2013028307A1 (fr)

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CN105296059A (zh) * 2015-11-20 2016-02-03 石家庄金路润滑油有限公司 月桂烯基酯类化合物作为润滑油的应用及其制备方法
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WO2021110620A1 (fr) * 2019-12-04 2021-06-10 Henkel Ag & Co. Kgaa Agents tensioactifs
CN113302266A (zh) * 2019-01-17 2021-08-24 路博润公司 牵引流体

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US12187674B2 (en) 2011-04-13 2025-01-07 Amyris, Inc. Olefins and methods for making the same
US11802100B2 (en) 2011-04-13 2023-10-31 Amyris, Inc. Olefins and methods for making the same
US9862906B2 (en) 2011-04-13 2018-01-09 Amyris, Inc. Base oils and methods for making the same
US10294439B2 (en) 2011-04-13 2019-05-21 Amyris, Inc. Olefins and methods for making the same
WO2015077215A1 (fr) * 2013-11-19 2015-05-28 Georgia-Pacific Chemicals Llc Résines hydrocarbonées modifiées en tant que réducteurs de filtrat
EA033117B1 (ru) * 2013-11-19 2019-08-30 ДЖОРДЖИЯ-ПЭСИФИК КЕМИКАЛЗ ЭлЭлСи Способ обработки бурового раствора на масляной основе и способ обработки подземного формирования обработанным буровым раствором на масляной основе
US9732179B2 (en) 2015-06-23 2017-08-15 Fina Technology, Inc. Dilithium initiators
WO2016209953A1 (fr) * 2015-06-23 2016-12-29 Fina Technology, Inc. Initiateurs de dilithium
CN105296059A (zh) * 2015-11-20 2016-02-03 石家庄金路润滑油有限公司 月桂烯基酯类化合物作为润滑油的应用及其制备方法
EP3668957A4 (fr) * 2017-08-17 2021-06-02 University of Delaware Compositions à base de furane et leurs procédés de fabrication
CN113302266A (zh) * 2019-01-17 2021-08-24 路博润公司 牵引流体
CN113302266B (zh) * 2019-01-17 2023-02-24 路博润公司 牵引流体
WO2021110620A1 (fr) * 2019-12-04 2021-06-10 Henkel Ag & Co. Kgaa Agents tensioactifs

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