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WO2010011949A2 - Monomères de caprolactame et copolymères préparés à partir de ceux-ci - Google Patents

Monomères de caprolactame et copolymères préparés à partir de ceux-ci Download PDF

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Publication number
WO2010011949A2
WO2010011949A2 PCT/US2009/051724 US2009051724W WO2010011949A2 WO 2010011949 A2 WO2010011949 A2 WO 2010011949A2 US 2009051724 W US2009051724 W US 2009051724W WO 2010011949 A2 WO2010011949 A2 WO 2010011949A2
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WO
WIPO (PCT)
Prior art keywords
caprolactam
monomer
amino
diacid
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2009/051724
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English (en)
Other versions
WO2010011949A3 (fr
Inventor
Douglas A. Wicks
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Draths Corp
Original Assignee
Draths Corp
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Filing date
Publication date
Application filed by Draths Corp filed Critical Draths Corp
Publication of WO2010011949A2 publication Critical patent/WO2010011949A2/fr
Publication of WO2010011949A3 publication Critical patent/WO2010011949A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • Polyamides form a class of polymers which have been used for many years for numerous applications. Polyamides may be used alone or in combination with processing auxiliaries, polymeric alloying components, or mineral reinforcing materials (e.g. fillers or glass fibers) to produce materials with desirable properties. Polyamides are used in large quantities for the manufacture of fibers, plastics molded parts, films, and in technical applications such as hot- melt adhesives and auxiliary agents, (see, Vieweg, Muller; Kunststoff-Handbuch, Vol. Vl, pages 11 et seq. Carl-Hanser Verlag, Kunststoff, 1966).
  • polyamides have been produced from chemical feedstocks that are derived from oil.
  • industrially useful chemicals such as polyamides
  • renewable resources One such renewable starting material is biomass. It has been reported by Frost that biomass can be converted to ⁇ -amino- ⁇ -caprolactam by a combination of fermentation and chemical processes (see, U.S. Patent Publication No. 2007/149777). The resulting ⁇ -amino- ⁇ -caprolactam can serve as the basis for synthesizing industrially useful chemicals through appropriate chemical reaction and/or modification.
  • the invention relates to caprolactam monomers and to copolymers prepared from these monomers.
  • the caprolactam monomers are derived from ⁇ - amino- ⁇ -caprolactam, ⁇ -amino- ⁇ -caprolactam, or a mixture thereof.
  • the ⁇ -amino- ⁇ -caprolactam or ⁇ -amino- ⁇ -caprolactam is manufactured from a renewable starting material, for example, biomass (see, U.S. Patent Publication No. 2007/149777 (Frost)).
  • the invention relates to caprolactam monomers, for example, bis- ⁇ - amido- ⁇ -caprolactam monomers and bis- ⁇ -amido- ⁇ -caprolactam monomers.
  • the caprolactam monomers of the invention have the structure shown in structure I.
  • Ri is a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms.
  • the caprolactam monomer is a bis- ⁇ -amido- ⁇ -caprolactam monomer having the structure shown in structure IA.
  • R 1 is a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms.
  • the caprolatctam monomer is a bis- ⁇ -amido- ⁇ -caprolactam monomer having the structure shown in IB.
  • Ri is a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms.
  • the caprolactam monomer has the structure shown in IC.
  • R 1 is a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms.
  • the invention relates to crosslinked polyamide polymers prepared by the anionic copolymerization of a caprolactam monomer of the invention with a lactam monomer.
  • the lactam monomers having the structure shown in structure II.
  • m ranges from 1 to 13, more typically 3.
  • lactams examples include pyrrolidone, ⁇ -caprolactam, oenantholactam, caprylic lactam, lauric lactam, or mixtures thereof.
  • Preferred lactams include ⁇ -caprolactam and lauric lactam, or mixtures thereof.
  • the polymers of the invention expand the physical property space of known polyamides.
  • the R 1 group may be varied in order to affect the glass transition temperature (Tg), crystallinity, modulus, and hydrophobicity of the polyamide polymer, for example, as compared to Nylon 6 which is prepared from the polymerization of ⁇ -caprolactam.
  • bis- ⁇ -amido- ⁇ -caprolactam monomers of the invention are prepared by first preparing ⁇ -amino- ⁇ -caprolactam as shown in Reaction 1 , followed by conversion of ⁇ -amino- ⁇ -caprolactam to bis- ⁇ -amido- ⁇ -caprolactam as shown in Reaction 2.
  • bis- ⁇ -amido- ⁇ -caprolactam monomers of the invention are prepared by first preparing ⁇ -amino- ⁇ -caprolactam as shown in Reaction V, followed by conversion of ⁇ -amino- ⁇ -caprolactam to bis- ⁇ -amido- ⁇ -caprolactam as shown in Reaction 2'.
  • biomass can be used as the starting material. As shown in
  • Step 1 the biomass is first converted into lysine or ⁇ -lysine by a fermentation process. This is followed by the conversion of lysine or ⁇ -lysine into ⁇ -amino- ⁇ -caprolactam or ⁇ -amino- ⁇ - caprolactam, respectively (Reaction 1 ).
  • the conversion of biomass to ⁇ -amido- ⁇ - caprolactam is described, for example, in U.S. Patent Publication No. 2007/149777 (Frost).
  • the conversion of biomass to ⁇ -lysine is described, for example, in WO 07/101867 (Zelder et al.).
  • the ⁇ -amino- ⁇ -caprolactam can then be converted into bis- ⁇ -amido- ⁇ -caprolactam monomer by reacting 2 equivalents of ⁇ -amino- ⁇ -caprolactam with 1 equivalent of a diacid, diester, or diacid chloride. This reaction may be performed with an excess of the acid component followed by removal of any unreacted starting material. An example of this reaction is shown below.
  • R 1 a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms; and where X is Cl or OR 2 , where R 2 is hydrogen or an alkyl group.
  • ⁇ -amino- ⁇ -caprolactam is converted into bis- ⁇ -amido- ⁇ - caprolactam monomer by reacting 2 equivalents of ⁇ -amino- ⁇ -caprolactam with 1 equivalent of a diacid, diester, or diacid chloride. This reaction may be performed with an excess of the acid component followed by removal of any unreacted starting material. An example of this reaction is shown below.
  • R 1 a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms; and where X is Cl or OR 2 , where R 2 is hydrogen or an alkyl group.
  • reaction 2 is conducted with a mixture of ⁇ -amido- ⁇ - caprolactam and ⁇ -amino- ⁇ -caprolactam.
  • the resulting monomer comprises a composition including bis- ⁇ -amido- ⁇ -caprolactam, bis- ⁇ -amido- ⁇ -caprolactam, and the monomer shown in Structure IC. An example of this reaction is shown below.
  • Ri a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms; and where X is Cl or OR 2 , where R 2 is hydrogen or an alkyl group.
  • the reaction is typically conducted in the presence of a mild base to scavenge the evolved acid.
  • Examples of useful diacids include those containing about 5 to about 36 carbon atoms, more typically about 6 to about 12 carbon atoms.
  • Representative examples include adipic acid, pimelic acid, trimethyl adipic acid, octane diacid, azelaic acid, sebacic acid, dodecane diacid, heptadecane dicarboxylic acids (i.e., mixture of 1 , 8-heptadecane dicarboxylic acid and 1 , 9-heptadecane dicaboxylic acid), dimeric fatty acid (hydrogenated or unhydrogenated C36), and mixtures thereof.
  • Diacid chlorides of the listed diacids may also be used. Generally, adipic acid, azelaic acid, dodecane diacid, and dimeric fatty acids are preferred.
  • an aromatic dicarboxylic acid is also used.
  • examples include isophthalic acid or terephthalic acid.
  • the caprolactam monomers of the invention are copolymerized with one or more lactam monomers as described above to form a copolymer.
  • the copolymer may be a random or block copolymer.
  • the polymerizable composition comprises about 5 to about 50 mole percent of bis- ⁇ -amido- ⁇ - caprolactam monomers and about 50 to about 95 mole % ⁇ -caprolactam.
  • a second lactam monomer may also be included in the polymerizable composition, for example, in an amount up to about 20 mole %.
  • the copolymers of the invention are prepared by a ring opening polymerization.
  • ring opening polymerization techniques include hydrolytic polymerization (i.e., hydrolytic polycondensation polymerization) and anionic ring- opening polymerization.
  • Hydrolytic polymerization is most commonly used for the preparation of polyamides from lactams (e.g., polyamide 6 from ⁇ -caprolactam).
  • Anionic ring opening polymerization of a lactam to form a polyamide is particularly useful in the preparation of reaction injection molding (i.e., RIM) polyamides due to the short time required for the reaction, which makes it possible for the lactam to be polymerized in the mold.
  • the viscosity of the components typically ranges from about 50 to 10000 cps, more typically ranging from about 1000 to 3000 cps.
  • the temperature of the components typically ranges from about room temperature for urethanes to about 100 0 C to 150 0 C for lactams.
  • the mold temperature in the RIM process typically ranges from about 100 to about 220 C and the applied pressure ranges from about 1 to about 100 bar, more typically about 1 to about 30 bar. Examples of useful polymerization techniques include those reported in U.S. Patent
  • the starting monomer composition may be varied along with the chain terminating agent type and composition in order to provide a polymer having the desired properties and molecular weight.
  • chain terminating agents such as monofunctional carboxylic acids or amines (e.g., acetic acid, hexanoic acid, benzoic acid, stearic acid, hexylamine or cyclohexylamine) may be used in typical quantities during the hydrolytic polycondensation.
  • monomers containing reactive groups may be included for various after-treatments (e.g.
  • Copolymers prepared using the bis- ⁇ -amido- ⁇ -caprolactam monomers of the invention are useful in the manufacture of fibers and in engineering thermoplastic resins.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

Cette invention concerne des monomères de caprolactame et des copolymères préparés à partir de ces monomères. Dans de nombreux modes de réalisation, les monomères de caprolactame sont dérivés d'α-amino-ε-caprolactame, de β-amino-ε-caprolactame, ou d'un mélange de ceux-ci. Dans de nombreux modes de réalisation, l'α-amino-ε-caprolactame ou le β-amino-ε-caprolactame est préparé à partir d'un matériau de départ renouvelable, par exemple, biomasse (voir, publication du brevet U.S. No. 2007/149777 (Frost)). Dans certains modes de réalisation, l'invention concerne des monomères de caprolactame, par exemple, des monomères de bis-α-amido-ε-caprolactame et des monomères de bis-β-amido-ε-caprolactame. Dans de nombreux modes de réalisation, les monomères de caprolactame selon l'invention ont la structure illustrée sur la structure I, A étant indépendamment choisi parmi la formule (II), et R1 étant un groupe alkyle linéaire, alkyle ramifié, aryle, ou aralkyle contenant d'environ 3 à environ 34 atomes de  carbone.
PCT/US2009/051724 2008-07-24 2009-07-24 Monomères de caprolactame et copolymères préparés à partir de ceux-ci Ceased WO2010011949A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13585708P 2008-07-24 2008-07-24
US61/135,857 2008-07-24

Publications (2)

Publication Number Publication Date
WO2010011949A2 true WO2010011949A2 (fr) 2010-01-28
WO2010011949A3 WO2010011949A3 (fr) 2010-03-18

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Country Status (1)

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WO (1) WO2010011949A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011144602A1 (fr) * 2010-05-19 2011-11-24 Basf Se Polyamide à réticulation transversale

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE655708A (fr) * 1963-11-14 1965-05-13
US3651023A (en) * 1968-07-02 1972-03-21 Stamicarbon Preparation of polyamides with special properties

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011144602A1 (fr) * 2010-05-19 2011-11-24 Basf Se Polyamide à réticulation transversale

Also Published As

Publication number Publication date
WO2010011949A3 (fr) 2010-03-18

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