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WO2023000098A1 - Composés de polyisobutylène ramifiés - Google Patents

Composés de polyisobutylène ramifiés Download PDF

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WO2023000098A1
WO2023000098A1 PCT/CA2022/051126 CA2022051126W WO2023000098A1 WO 2023000098 A1 WO2023000098 A1 WO 2023000098A1 CA 2022051126 W CA2022051126 W CA 2022051126W WO 2023000098 A1 WO2023000098 A1 WO 2023000098A1
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Prior art keywords
polyfarnesene
polymer
branched
compound
pib
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Jeremy L. BOURQUE
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Arlanxeo Canada Inc
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Arlanxeo Canada Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical

Definitions

  • This application relates to polymers and processes for producing polymers, in particular to branched isoolefin polymers, processes for producing the same and rubber compounds produced therefrom.
  • polyisoolefins as well as their halogenated analogues, are mostly linear polymers, and for the case of butyl rubber (HR), the level of branching or linearity is dictated primarily by the amount of isoprene that is added to the reactor.
  • HR butyl rubber
  • the level of linearity for HR can range from what is observed in polyisobutylene (PIB) to commercial polymers with higher isoprene loadings (e.g., with 2.25 mol% isoprene). Without adding a branching agent, increasing the isoprene beyond 3-4 mol% will poison the polymerization reaction too much, lowering molecular weight substantially.
  • Branched polyisoolefins are generally obtained by adding a reagent that is active in cationic polymerization and leads to termination of a propagating polymer chain onto the branching agent.
  • the branching agent is required to have unsaturation that allows the growing polymer chains to react with the additive.
  • Polyisoolefin polymers have been commercially available in several forms for decades.
  • Polyisoolefin polymers have been produced using divinylbenzene (DVB) as a crosslinking/branching agent.
  • the product was cross-linked (20-80%) and was mostly used in adhesives. Production of DVB crosslinked polyisoolefin polymers is undesirable due to environmental concerns around the use of DVB.
  • DVB divinylbenzene
  • a starbranched bromobutyl rubber (EMC 6222, Exxon Mobil Corporation) has been produced commercially, which is mainly used in tire innerliner compounds.
  • the commercial starbranched bromobutyl rubber uses a styrene-butadiene-styrene (SBS) resin as the branching agent, giving a starbranched fraction and a linear fraction.
  • SBS styrene-butadiene-styrene
  • the proposed reactivity of the SBS resin is much different to the reactivity of DVB.
  • DVB the propagating butyl polymer chain grows through the vinyl groups, giving a long chain HR with an additional pendant vinyl group.
  • This second vinyl group can participate in the propagation of a second growing chain, leading to a crosslinked polymer with a higher molecular weight than the parent material without DVB.
  • the SBS resin added to the polymerization, the growing polymer chains terminate onto the unsaturated butadiene portion of the SBS resin, leading to multiple HR chains being attached to a single chain of SBS, giving rise to the star branched structure.
  • multiple shorter chains terminate onto the resin, which gives a fraction with a higher molecular weight, but one that is not crosslinked.
  • a polyfarnesene having 5 or more farnesene units can be used as a branching agent for producing a branched isoolefin polymer.
  • the branched isoolefin polymer, and halogenated branched isoolefin polymer produced therefrom, have reduced cold flow and improved green strength.
  • Described herein is a process for producing a branched isoolefin polymer comprising polymerizing at least one isoolefin monomer in a reaction mixture in presence of a branching agent, the branching agent comprising a polyfarnesene having 5 or more farnesene units.
  • Also described herein is a branched isoolefin polymer comprising isoolefin units and farnesene units.
  • Also described herein is a rubber compound comprising the branched isoolefin polymer and a filler.
  • the present process requires less branching agent on a weight basis to produce branched unsaturated isoolefin copolymers having desirably reduced cold flow and improved green strength, which leads to less impurities in the resulting polymer, which is highly desirable in pharmaceutical applications.
  • the branched isoolefin polymer, and halogenated branched isoolefin polymer produced therefrom have higher levels of chain branching in comparison to star branched polymers produced with the SBS resin and similar branching agents, and halogenated polymers produced therefrom.
  • a polyfarnesene as a branching agent. Higher green strength at equivalent Mooney viscosity is realized, therefore improving milling and calendaring operations. Less creep at equivalent Mooney viscosity and unsaturation is realized, therefore leading to less cold flow for raw polymer and mixed compounds.
  • the polyfarnesene branching agent is biosourced, therefore leading to a sustainable process, which is useful for all applications.
  • the polyfarnesene is a more effective branching agent, therefore providing less loading in the produced polymer leading to less potential for extractables and higher level of incorporation in the produced polymer.
  • the polyfarnesene introduces an alternative monomer into the produced polymer, therefore leading to new properties. Different rheological behavior of uncurable polymers is realized, therefore providing a different mouthfeel/behavior, which is particularly useful for chewing gum applications and applications as thickeners.
  • Fig. 1 depicts a van Gurp-Palmen plot of a lab-prepared butyl rubber control (Control) prepared without branching agent, a starbranched bromobutyl rubber and lab- prepared branched butyl rubbers prepared using varying amounts of a polyfarnesene (KrasolTM F 3000).
  • Fig. 2 depicts a van Gurp-Palmen plot of a starbranched bromobutyl rubber and lab-prepared branched butyl rubbers (PF-IIR Solution 1 and PF-IIR Solution 2) prepared using a polyfarnesene (KrasolTM F 3000) in two recipes determined using design of experiment (DoE) based on the results shown in Fig. 1.
  • Fig. 3 depicts a graph of creep compliance (Pa-1) versus time (s) of lab-prepared branched butyl rubbers (PF-IIR Solution 1 and PF-IIR Solution 2) prepared using a polyfarnesene (KrasolTM F 3000) and commercial butyl rubbers (ARL RB100 and RB402).
  • Fig. 4 depicts a stress-strain plot of lab-prepared branched butyl rubbers (PF-IIR Solution 1 and PF-IIR Solution 2) prepared using a polyfarnesene (KrasolTM F 3000) and commercial butyl rubbers (ARL RB100 and RB402).
  • Fig. 5 depicts a van Gurp-Palmen plot of a commercial polyisobutylene control (Control) prepared without branching agent, lab-prepared branched polyisobutylene polymers prepared using varying amounts of a polyfarnesene (KrasolTM F 3000) and branched butyl rubbers also prepared using a polyfarnesene (KrasolTM F 3000).
  • Fig. 6 depicts a van Gurp-Palmen plot of lab-prepared branched poly(isobutylene- co-paramethylstyrene) (IB-co-pMS) using a polyfarnesene (KrasolTM F 3000) branching agent, a brominated poly(isobutylene-co-paramethylstyrene) (BIB-co-pMS), a starbranched bromobutyl rubber, a lab-prepared butyl rubber and a lab-prepared branched butyl rubber using a polyfarnesene (KrasolTM F 3000) branching agent.
  • KrasolTM F 3000 polyfarnesene
  • Fig. 7 depicts a van Gurp-Palmen plot of comparative runs where lab-prepared branched butyl rubbers were produced with different polyfarnesene polymers with varying molecular weight and enchainment.
  • Fig. 8 depicts a van Gurp-Palmen plot of butyl rubber controls (Control) prepared without a branching agent, butyl rubber products produced from a polyfarnesene (KrasolTM F 3000) and from other cyclic polyterpenes (poly-a-pinene and poly-d- limonene) as branching agents for butyl rubber polymerization.
  • Control prepared without a branching agent, butyl rubber products produced from a polyfarnesene (KrasolTM F 3000) and from other cyclic polyterpenes (poly-a-pinene and poly-d- limonene) as branching agents for butyl rubber polymerization.
  • Fig. 9 depicts a van-Gurp-Palmen plot of isobutylene-type polymers produced using a solution polymerization process, including branched polymers produced using a polyfarnesene (KrasolTM F 3000) branching agent and controls which did not contain a branching agent.
  • KrasolTM F 3000 polyfarnesene
  • Fig. 10 depicts a van Gurp-Palmen plot of polyfarnesene branched polyisobutylene screening experiments.
  • Fig. 11 depicts a van Gurp-Palmen plot of control polyisobutylene and branched PIBs generated using polyfarnesenes of various molecular weight and composition.
  • Fig. 12 depicts a van Gurp-Palmen plot of control polyisobutylene and PIBs generated using polyfarnesenes of various molecular weight and composition.
  • Fig. 13 depicts a van Gurp-Palmen plot of a control and a polyfarnesene-branched polyisobutylene polymer produced by solution polymerization in hexane.
  • Fig. 14 depicts a 1 H NMR spectrum of polyfarnesene (bottom), lab-produced polyisobutylene (middle) and lab-produced PF-PIB (top).
  • Fig. 15 depicts a pyrolysis-GCMS chromatogram of PF-PIB (top, black), polyfarnesene (middle, light grey) and N50 (bottom, dark grey).
  • Fig. 16 depicts a GPC chromatogram of N100 and PF-PIB.
  • Fig. 17 depicts creep compliance versus time of commercial PIB grades and glovebox prepared PF-PIB recipes.
  • Fig. 18 depicts creep compliance data showing decrease in creep compliance (improved stability) as samples were aged for PF-PIB while production PIB samples generally increased (worse stability).
  • Fig. 19 depicts a viscosity vs shear rate amplitude plot generated using an RPA at 200°C of commercial and lab produced polyisobutylene samples.
  • Fig. 20 depicts a mixer torque curve of uncured PIB in window seal compounds.
  • Fig. 21 depicts a tan delta (frequency sweep at 100 °C) plot of uncured window seal compounds with PIB, showing improved processability with higher tan delta.
  • Fig. 22 depicts a Payne effect (strain sweep at 60 °C) plot of uncured window seal compounds with PIB, showing improving filler dispersion with lower G’ at 0.06 % dynamic amplitude.
  • Fig. 23 depicts a stress-extension plot of combined uncured window seal compounds with PIB using the T2000 tensile instrument.
  • Fig. 24 depicts a mixer torque curve of uncured PIB in black sheeting compounds.
  • Fig. 25 depicts a tan delta (frequency sweep at 100 °C) plot of uncured black sheeting compounds with PIB, showing improved processability with higher tan delta.
  • Fig. 26 depicts a Payne effect (strain sweep at 60 °C) plot of uncured black sheeting compounds with PIB, showing improving filler dispersion with lower G’ at 0.06 % dynamic amplitude.
  • Fig. 27 depicts a stress-extension plot of combined uncured black sheeting compounds with PIB using the T2000 tensile instrument.
  • Fig. 28 depicts unaged vs aged (dotted lines) black sheeting compounds tested on the T2000 tensile instrument, demonstrating that linear PIBs harden overtime.
  • Fig. 29 depicts unaged vs aged (dotted lines) black sheeting compounds tested on the T2000 tensile instrument, demonstrating that the majority of PF-PIB soften over time.
  • Production of the isoolefin polymer involves polymerizing at least one isoolefin monomer in an organic diluent in the presence of an initiator system (a Bransted acid or a Lewis acid catalyst and a proton source) capable of initiating the polymerization process.
  • an initiator system a Bransted acid or a Lewis acid catalyst and a proton source
  • Polymerization occurs in a polymerization reactor.
  • Suitable polymerization reactors include, for example, flow-through polymerization reactors, plug flow reactor, moving belt or drum reactors, and the like.
  • the process may be a continuous or batch process. In a preferred embodiment, the process is a continuous polymerization process.
  • the process may comprise slurry or solution polymerization of the monomers.
  • Isoolefin polymers (i.e., polyisoolefins) comprise repeating units derived from an isoolefin monomer.
  • the isoolefin polymers comprise repeating units derived from one isoolefin monomer and repeating units derived from at least one copolymerizable monomer.
  • Suitable isoolefin monomers include hydrocarbon monomers having 4 to 16 carbon atoms. In one embodiment, the isoolefin monomer has from 4 to 7 carbon atoms. Examples of suitable isoolefins include isobutene (isobutylene), 2-methyl-1-butene, 3- methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and 4-methyl-1-pentene. A preferred isoolefin monomer is isobutene (isobutylene).
  • Suitable copolymerizable monomers comprise one or more of a different isoolefin monomer from the one isoolefin monomer and a copolymerizable unsaturated monomer that is not an isoolefin.
  • Copolymerizable unsaturated monomers that are not isoolefins include, for example, multiolefin monomers, styrenic monomers, b-pinene, cyclopentadiene, methylcyclopentadiene, indene and the like.
  • Multiolefin monomers include, for example, hydrocarbon monomers having 4 to 14 carbon atoms.
  • the multiolefin monomers are conjugated dienes.
  • suitable conjugated diene monomers include butadiene, 2-methyl-1,3- butadiene (isoprene), 2,4-dimethylbutadiene, piperylene, 3-methyl-1,3-pentadiene, 2,4- hexadiene, 2-neopentylbutadiene, 2-methyl-1 ,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,3- dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1, 3-butadiene, 2-methyl-1,6- heptadiene,
  • Styrenic monomers include, for example, alkyl-substituted vinyl aromatic co monomers, including but not limited to a Ci-C 4 alkyl substituted styrene.
  • Some examples of styrenic monomers are styrene, a-methylstyrene, p-methylstyrene and chlorostyrene.
  • a preferred styrenic monomer is p-methylstyrene.
  • the isoolefin polymer is a terpolymer of isoolefin with two other different copolymerizable monomers.
  • the isoolefin polymer is an unsaturated isoolefin copolymer.
  • the unsaturated isoolefin copolymer is formed by copolymerization of a monomer mixture.
  • the monomer mixture comprises about 80-99.9 mol% of at least one isoolefin monomer and about 0.1-20 mol% of at least one multiolefin monomer, based on the monomers in the monomer mixture. More preferably, the monomer mixture comprises about 90-99.9 mol% of at least one isoolefin monomer and about 0.1-10 mol% of at least one multiolefin monomer.
  • the monomer mixture comprises about 92.5-97.5 mol% of at least one isoolefin monomer and about 2.5-7.5 mol% of at least one multiolefin monomer. In another embodiment, the monomer mixture comprises about 97.4-95 mol% of at least one isoolefin monomer and about 2.6-5 mol% of at least one multiolefin monomer.
  • the monomer mixture may also comprise from 0.01% to 1% by weight of at least one multiolefin cross-linking agent, and when the multiolefin cross-linking agent is present, the amount of multiolefin monomer is reduced correspondingly.
  • the at least one multiolefin monomer is preferably a conjugated diene. If the monomer mixture comprises an additional copolymerizable monomer that is not a multiolefin, the additional copolymerizable monomer preferably replaces a portion of the multiolefin monomer.
  • PIB polyisobutylene
  • HR poly(isobutylene-co-isoprene)
  • IMS poly(isobutylene-co-paramethylstyrene)
  • Suitable organic diluents may include, for example, alkanes, chloroalkanes, cycloalkanes, aromatics, hydrofluorocarbons (HFC) or any mixture thereof.
  • Chloroalkanes may include, for example methyl chloride, dichloromethane or any mixture thereof. Methyl chloride is particularly preferred.
  • Alkanes and cycloalkanes may include, for example, isopentane, cyclopentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylpentane, 3- methylpentane, n-hexane, methylcyclopentane, 2,2-dimethylpentane or any mixture thereof.
  • Alkanes and cycloalkanes are preferably C6 solvents, which include n-hexane or hexane isomers, such as 2-methyl pentane or 3-methyl pentane, or mixtures of n-hexane and such isomers as well as cyclohexane.
  • the monomers are generally polymerized cationically in the diluent at temperatures in a range of from -120°C to +20°C, preferably -100°C to -50°C, more preferably -95°C to -65°C. The temperature is preferably about -70°C or colder or -80°C or colder.
  • the initiator system comprises a Bransted acid or a Lewis acid catalyst and a proton source.
  • the Lewis acid catalyst preferably comprises aluminum trichloride (AICI 3 ).
  • Alkyl aluminum halide catalysts are also useful for catalyzing the polymerization reaction.
  • alkyl aluminum halide catalysts include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride and any mixture thereof.
  • alkyl aluminum halide catalysts are diethyl aluminum chloride (Et 2 AICI or DEAC), ethyl aluminum sesquichloride (EtisAICh s or EASC), ethyl aluminum dichloride (EtAICh or EADC), diethyl aluminum bromide (Et 2 AIBr or DEAB), ethyl aluminum sesquibromide (EtisAIBr s or EASB) and ethyl aluminum dibromide (EtAIBr 2 or EADB) and any mixture thereof.
  • a particularly preferred alkyl aluminum halide catalyst comprises ethyl aluminum sesquichloride, preferably generated by mixing equimolar amounts of diethyl aluminum chloride and ethyl aluminum dichloride, preferably in a diluent.
  • the diluent is preferably the same one used to perform the copolymerization reaction.
  • the proton source when a Lewis acid is the catalyst includes any compound that will produce a proton when added to the catalyst or a composition containing the catalyst.
  • Protons are generated from the reaction of the catalyst with proton sources to produce the proton and a corresponding by-product.
  • Proton sources include, for example, water (H2O), alcohols, phenols, thiols, carboxylic acids, and the like or any mixture thereof.
  • the most preferred proton source is water.
  • a preferred ratio of catalyst to proton source is from 5:1 to 100:1 by weight, or from 5:1 to 50:1 by weight.
  • the initiator system is preferably present in the reaction mixture in an amount providing 0.0007-0.02 wt% of the catalyst, more preferably 0.001-0.008 wt% of the catalyst, based on total weight of the reaction mixture.
  • the initiator system is dissolved in an organic solvent to produce an initiator solution, which is then contacted with the reaction mixture to initiate polymerization of the monomers.
  • the organic solvent may comprise any of the organic diluents described above.
  • the organic solvent comprises a polar organic solvent.
  • Methyl chloride is particularly preferred.
  • the catalyst is preferably present in the initiator solution at a concentration of 0.01 wt% to 0.6 wt%, based on total weight of the initiator solution, more preferably 0.05 wt% to 0.6 wt%, 0.075 wt% to 0.5 wt% or 0.1 wt% to 0.4 wt%.
  • the initiator system is preferably soluble in the reaction mixture.
  • the branching agent comprises a polyfarnesene.
  • Polyfarnesenes can be prepared by anionic polymerization of farnesene monomers. Polyfarnesenes have been used in the past as processing additives after polymerization is complete. Farnesene monomers are terpenes and exist in a number of different isomeric forms. The chemical structures of the isomers of farnesene are shown in Scheme 1. Commercial farnesene generally exists as an approximately 1:1 mixture of (E,E)-a- and trans-p-farnesene with other isomers present as minor impurities.
  • a polyfarnesene having 5 or more farnesene units i.e., a degree of polymerization (DP) of 5 or more
  • DP degree of polymerization
  • the branching effectiveness of such polyfarnesenes is much higher than that of the styrene- butadiene-styrene (SBS) resin and similar branching agents mentioned above.
  • the weight amount of polyfarnesene used as branching agent can be 10 or more times less than the amount of SBS resin.
  • the polyfarnesene comprises from 5 to 640 farnesene units, more preferably 5 to 425 farnesene units, yet more preferably 15 to 105 farnesene units.
  • the polyfarnesene may be a homopolymer or a copolymer.
  • Polyfarnesene homopolymers preferably have an average number average molecular weight (M n ) in a range of 1,000-130,000 g/mol, more preferably 1,000-85,000 g/mol, yet more preferably 3,000-21,000 g/mol.
  • the polyfarnesene may be a copolymer comprising at least one comonomer.
  • the at least one comonomer preferably comprises a conjugated diene or a styrenic. Conjugated dienes and styrenics may be selected from the list of conjugated dienes and styrenics provided above in connection with the at least one copolymerizable monomer.
  • the at least one comonomer comprises isoprene, 1,3-butadiene, piperylene, styrene, a-methylstyrene, p-methylstyrene, ocimene or myrcene.
  • the at least one comonomer is preferably present in the polyfarnesene copolymer in an amount in a range of 1-75 mol%, for example 1-49 mol%.
  • the polyfarnesene may be a 1,4-co-1 ,2-addition polymer or solely a 1 ,4-polymer.
  • the polyfarnesene may be linear or branched (e.g., star branched).
  • the polyfarnesene may be terminated with a functional group or not terminated with a functional group.
  • the terminal functional group may be hydroxy, carboxy or the like, especially hydroxy- terminated. Table 1 provides some known grades of polyfarnesene.
  • the polyfarnesene is preferably derived from farnesene comprising at least 95 mol% of trans-p-farnesene.
  • Scheme 2 illustrates the structures of trans-p-farnesene and a polyfarnesene derived from farnesene comprising at least 95 mol% of trans-p- farnesene.
  • the resulting polyfarnesene is generally a mixture of addition isomers, a 1,4- isomer and a 1 ,2-isomer, which gives rise to the bottle-brush structure illustrated in Scheme 2.
  • the polyfarnesene is introduced into the reaction mixture before polymerization is complete.
  • the polyfarnesene is introduced into the reaction mixture before initiation, at initiation or shortly after initiation of the polymerization.
  • the branching agent can be introduced neat to the reaction mixture, but is preferably introduced into the reaction mixture as a solution in a solvent, preferably an organic solvent, for example methyl chloride, dichloromethane, hexane, cyclohexane or mixtures thereof. Control of the level of branching can be achieved by adjusting the amount of the polyfarnesene in the reaction mixture.
  • the branching agent is preferably present in the reaction mixture in a minimum amount of 0.01 wt%, based on weight of the isoolefin monomer in the reaction mixture. In some embodiments, the minimum amount may be 0.03 wt% or 0.05 wt%.
  • the branching agent may be present in the reaction mixture in a maximum amount of 2 wt%, based on weight of the isoolefin monomer in the reaction mixture. In some embodiments, the maximum amount may be 1.5 wt% or 1.25 wt% or 1 wt% or 0.8 wt%. In some embodiments, the amount of branching agent may be 0.01-2 wt% or 0.01-1.5 wt% or 0.01-1 wt% or 0.01-0.8 wt%.
  • the branched isoolefin polymer that is produced preferably comprises up to 2 wt% of farnesene units, based on weight of the isoolefin units in the polymer.
  • the minimum content of farnesene units is 0.01 wt%.
  • the minimum amount may be 0.03 wt% or 0.05 wt%.
  • the maximum amount may be 1.5 wt% or 1.25 wt% or 1 wt% or 0.8 wt%.
  • the content of farnesene units may be 0.01-2 wt% or 0.01-1.5 wt% or 0.01- 1 wt% or 0.01-0.8 wt%.
  • a chain transfer agent can be added to the reaction mixture.
  • the chain transfer agent further controls the rheology of the resulting isoolefin polymer by controlling the level of branching and the number of short chains in the isoolefin polymer.
  • the chain transfer agent improves processibility of the isoolefin polymer produced in the process by reducing the average molecular weight of the isoolefin polymer.
  • the chain transfer agent preferably comprises diisobutylene, piperylene, 1-methylcycloheptene, 1-methylcyclopentene, 2-ethyl-1 -hexene, 2,4,4- trimethyl-1-pentene, indene or any mixture thereof.
  • the chain transfer agent comprises diisobutylene (DIB).
  • DIB diisobutylene
  • the chain transfer agent is preferably added to the reaction mixture in an amount of from 0.001 wt% to 1 wt%, based on weight of the isoolefin monomer in the reaction mixture. More preferably, the amount of chain transfer agent is in a range of from 0.005 wt% to 0.7 wt%.
  • the isoolefin polymer can be subjected to a halogenation process in order to produce a halogenated branched isoolefin polymer. Halogenation preferably comprises bromination or chlorination.
  • Halogenation agents useful for halogenating an isoolefin polymer may comprise elemental chlorine (Ch) or bromine (Br2) and/or organo-halide precursors thereto, for example dibromo-dimethyl hydantoin, tri-chloro isocyanuric acid (TCIA), n-bromosuccinimide, or the like.
  • the halogenation agent comprises or is bromine.
  • the amount of halogenation during this procedure may be controlled so that the final polymer has a preferred amount of halogen.
  • the specific mode of attaching the halogen to the polymer is not particularly restricted and those of skill in the art will recognize that modes other than those described above may be used while achieving the benefits of the invention.
  • the branched isoolefin polymer may be formulated into a compound.
  • the compound comprises the branched isoolefin polymer and a filler.
  • One or more fillers may be in the compound.
  • the compound may be uncured or cured.
  • the filler may comprise a non-mineral filler, a mineral filler or mixtures thereof.
  • the filler may be functionalized or unfunctionalized.
  • Non-mineral fillers include, for example, carbon blacks, rubber gels and mixtures thereof.
  • Suitable carbon blacks are preferably prepared by lamp black, furnace black or gas black processes. Carbon blacks preferably have BET specific surface areas of 20 to 200 m.sup.2/g. Some specific examples of carbon blacks are SAF, ISAF, HAF, FEF and GPF carbon blacks. Rubber gels are preferably those based on polybutadiene, butadiene/styrene copolymers, butadiene/acrylonitrile copolymers or polychloroprene.
  • Mineral fillers include, for example, silica, silicates, clay, bentonite, vermiculite, nontronite, beidelite, volkonskoite, hectorite, saponite, laponite, sauconite, magadiite, kenyaite, ledikite, gypsum, alumina, talc, glass, metal oxides (e.g., titanium dioxide, zinc oxide, magnesium oxide, aluminum oxide), metal carbonates (e.g., magnesium carbonate, calcium carbonate, zinc carbonate), metal hydroxides (e.g., aluminum hydroxide, magnesium hydroxide) or mixtures thereof.
  • metal oxides e.g., titanium dioxide, zinc oxide, magnesium oxide, aluminum oxide
  • metal carbonates e.g., magnesium carbonate, calcium carbonate, zinc carbonate
  • metal hydroxides e.g., aluminum hydroxide, magnesium hydroxide
  • Dried amorphous silica particles suitable for use as mineral fillers may have a mean agglomerate particle size in the range of from 1 to 100 microns, or 10 to 50 microns, or 10 to 25 microns. In one embodiment, less than 10 percent by volume of the agglomerate particles may be below 5 microns. In one embodiment, less than 10 percent by volume of the agglomerate particles may be over 50 microns in size.
  • Suitable amorphous dried silica may have, for example, a BET surface area, measured in accordance with DIN (Deutsche Industrie Norm) 66131, of between 50 and 450 square meters per gram. DBP absorption, as measured in accordance with DIN 53601, may be between 150 and 400 grams per 100 grams of silica.
  • a drying loss, as measured according to DIN ISO 787/11 may be from 0 to 10 percent by weight.
  • High aspect ratio fillers useful in the present invention may include clays, talcs, micas, etc. with an aspect ratio of at least 1:3.
  • the fillers may include acircular or nonisometric materials with a platy or needle-like structure.
  • the aspect ratio is defined as the ratio of mean diameter of a circle of the same area as the face of the plate to the mean thickness of the plate.
  • the aspect ratio for needle and fiber shaped fillers is the ratio of length to diameter.
  • the high aspect ratio fillers may have an aspect ratio of at least 1:5, or at least 1:7, or in a range of 1:7 to 1:200.
  • High aspect ratio fillers may have, for example, a mean particle size in the range of from 0.001 to 100 microns, or 0.005 to 50 microns, or 0.01 to 10 microns. Suitable high aspect ratio fillers may have a BET surface area, measured in accordance with DIN (Deutsche Industrie Norm) 66131, of between 5 and 200 square meters per gram.
  • the high aspect ratio filler may comprise a nanoclay, such as, for example, an organically modified nanoclay. Examples of nanoclays include natural powdered smectite clays (e.g., sodium or calcium montmorillonite) or synthetic clays (e.g., hydrotalcite or laponite).
  • the high aspect filler may include organically modified montmorillonite nanoclays.
  • the clays may be modified by substitution of the transition metal for an onium ion, as is known in the art, to provide surfactant functionality to the clay that aids in the dispersion of the clay within the generally hydrophobic polymer environment.
  • onium ions are phosphorus based (e.g., phosphonium ions) or nitrogen based (e.g., ammonium ions) and contain functional groups having from 2 to 20 carbon atoms.
  • the clays may be provided, for example, in nanometer scale particle sizes, such as, less than 25 microns by volume.
  • the particle size may be in a range of from 1 to 50 microns or 1 to 30 microns or 2 to 20 microns.
  • the nanoclays may also contain some fraction of alumina.
  • the nanoclays may contain from 0.1 to 10 wt% alumina, or 0.5 to 5 wt% alumina, or 1 to 3 wt% alumina, based on weight of the branched isoolefin polymer.
  • the branched isoolefin polymer may be present in the compound in an amount of about 1-100 phr, or 1 to 90 phr or about 5-75 phr, or less than 50 phr, or about 1-50 phr, or about 1 phr to less than 50 phr, or about 10-50 phr, or about 5-30 phr, or about 15-30 phr.
  • Fillers may be present in the compound in an amount of about 1-100 phr, or about 3- 80 phr, or about 5-60 phr, or about 5-30 phr, or about 5-15 phr.
  • the compound may contain further auxiliary products, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry.
  • the aids are used in conventional amounts, which depend inter alia on the intended use.
  • the compound furthermore may contain in the range of 0.1 to 20 phr of an organic fatty acid, such as an unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10 wt% or more of a conjugated diene acid having at least one conjugated carbon-carbon double bond in its molecule.
  • organic fatty acid such as an unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10 wt% or more of a conjugated diene acid having at least one conjugated carbon-carbon double bond in its molecule.
  • those fatty acids have in the range of from 8-22 carbon atoms, or for example, 12-18. Examples include stearic acid, palmitic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium- and ammonium salts.
  • the compound may further contain other natural or synthetic rubbers such as ABR (butadiene/acrylic acid-Ci-C -alkylester-copolymers), CR (polychloroprene), IR (polyisoprene), SBR (styrene/butadiene-copolymers) with styrene contents in the range of 1 to 60 wt%, NBR (butadiene/acrylonitrile-copolymers with acrylonitrile contents of 5 to 60 wt%, HNBR (partially or totally hydrogenated NBR-rubber), FKM (fluoropolymers or fluororubbers), PIB (polyisobutylene), HR (butyl rubber), IMS (poly(isobutylene-co- paramethylstyrene)) and mixtures thereof.
  • ABR butadiene/acrylic acid-Ci-C -alkylester-copolymers
  • CR polychloroprene
  • the compound may be prepared by blending the branched isoolefin polymer and the filler, and optionally then curing the blend.
  • the ingredients of the final compound can be mixed together in any known manner. Normally the mixing time does not exceed one hour and a time in the range from 2 to 30 minutes is usually adequate.
  • Ingredients may be compounded together using conventional compounding techniques. Suitable compounding techniques include, for example, mixing the ingredients together using, for example, an internal mixer (e.g., a Banbury mixer), a miniature internal mixer (e.g., a Haake or Brabender mixer) or a two-roll mill mixer. An extruder also provides good mixing, and permits shorter mixing times.
  • an internal mixer e.g., a Banbury mixer
  • a miniature internal mixer e.g., a Haake or Brabender mixer
  • An extruder also provides good mixing, and permits shorter mixing times.
  • the choice of curing system suitable for use is not particularly restricted and is within the purview of a person skilled in the art.
  • the curing system may be sulphur-based, peroxide-based, resin-based or ultraviolet (UV) light- based.
  • a sulfur-based curing system may comprise: (i) a metal oxide, (ii) elemental sulfur and (iii) at least one sulfur-based accelerator.
  • metal oxides as a component in the sulphur curing system is well known in the art.
  • a suitable metal oxide is zinc oxide, which may be used in the amount of from about 1 to about 10 phr. In another embodiment, the zinc oxide may be used in an amount of from about 2 to about 5 phr.
  • Elemental sulfur is typically used in amounts of from about 0.2 to about 2 phr.
  • Suitable sulfur-based accelerators may be used in amounts of from about 0.5 to about 3 phr.
  • useful sulfur-based accelerators include thiuram sulfides (e.g., tetramethyl thiuram disulfide (TMTD)), thiocarbamates (e.g., zinc dimethyl dithiocarbamate (ZDC)) and thiazyl or benzothiazyl compounds (e.g., mercaptobenzothiazyl disulfide (MBTS)).
  • TMTD tetramethyl thiuram disulfide
  • ZDC zinc dimethyl dithiocarbamate
  • MBTS mercaptobenzothiazyl disulfide
  • Peroxide based curing systems may also be suitable.
  • a peroxide-based curing system may comprises a peroxide curing agent, for example, dicumyl peroxide, di-tert- butyl peroxide, benzoyl peroxide, 2,2'-bis(tert.-butylperoxy diisopropylbenzene, benzoyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3, 2,5-dimethyl-2,5- di(benzoylperoxy)hexane, (2, 5-bis(tert-butylperoxy)-2, 5-dimethyl hexane and the like.
  • a peroxide curing agent for example, dicumyl peroxide, di-tert- butyl peroxide, benzoyl peroxide, 2,2'-bis(tert.-butylperoxy diisopropylbenzene, benzoyl peroxid
  • a preferred peroxide curing agent comprises dicumyl peroxide.
  • Peroxide curing agents may be used in an amount of about 0.2-15 phr, or about 1-6 phr, or about 4 phr.
  • Peroxide curing co-agents may also be used. Suitable peroxide curing co-agents include, for example, triallyl isocyanurate (TAIC), N,N'-m-phenylene dimaleimide, triallyl cyanurate (TAC) or liquid polybutadiene.
  • TAIC triallyl isocyanurate
  • TAC triallyl cyanurate
  • Peroxide curing co-agents may be used in amounts equivalent to those of the peroxide curing agent, or less.
  • the compound may be cured by resin cure system and, if required, an accelerator to activate the resin cure.
  • Suitable resins include but are not limited to phenolic resins, alkylphenolic resins, alkylated phenols, halogenated alkyl phenolic resins and mixtures thereof.
  • curing may be achieved by heating the compound at a suitable curing temperature in the presence of the curing system.
  • the curing temperature may be about 80°C to about 250°C., or 100°C to about 200°C., or about 120°C to about 180°C.
  • branched isoolefin polymers halogenated branched isoolefin polymers and compounds thereof are useful in the production of articles of manufacture.
  • Branched polymers produced by the process described herein have reduced cold flow and improved green strength, which are particularly beneficial for the production of tire parts (e.g., tire innerliners, tire inner tubes, tire sidewalls and tire treads), curing bladders, curing envelopes, seals, gaskets, adhesives, sealants, building and construction applications, chewing gum, food contact applications (e.g., conveyor belts, closures, etc.), pharmaceutical closures, medical devices (e.g., plungers, vacuum tube stoppers, etc.), tank linings, personal protective equipment (e.g., gloves, masks, clothing, etc.), hoses, thermoplastic vulcanizates (TPV), shoe soles, diaphragms in water contact applications, septa, vibration dampers, viscosity modifiers, and roofing materials.
  • tire parts e.g., tire inner
  • Branched isoolefin polymers are also useful as tackifiers for greases and as a motor oil additive to provide suitable viscosity characteristics.
  • Branched HR and IMS copolymers in particular also find use in vibration dampers.
  • Branched PIB is in particular also added as a component with other polymers in other articles, generating a blended material.
  • the process and the branched isoolefin polymers, halogenated branched isoolefin polymers and rubber compounds thereof have one or more of the following advantages: ability to produce a branched polymer in one step that performs equally to a post-modified cross-linked isoolefin polymer; faster dissolution of the polyfarnesene in comparison to other branching agents; improved slurry stability during polymerization; higher mixer torque with similar creep; reduced mixing time when compounding; less processing oil required when compounding to produce uncured articles of the same processability but improved permeability; better filler dispersion with similar creep; higher green modulus with similar creep; similar raw polymer Mooney viscosity but lower compound Mooney viscosity; higher tan delta values across a frequency sweep; lower G’ values across a range of dynamic amplitudes; higher viscosity polymer produced with a small amount of branching agent within a given production process; maintaining molecular weight at higher polymerization temperatures; higher PDI but lower oli
  • Mooney viscosity was measured according to ASTM 1646.
  • Green strength was measured according to ASTM 6746.
  • Isobutylene (IB) (99.5%) was purchased from Air Liquide.
  • Methyl chloride (MeCI) (99.5%) was purchased from Praxair.
  • Hexanes a mixture of isomers, 98+%, anhydrous
  • isoprene IP, 3-methyl-1, 3-butadiene
  • paramethylstyrene pMS
  • aluminum chloride AlCh
  • diethylaluminum chloride DEC, 1.0 M in hexanes and 100%
  • hydrogen chloride gas 99%
  • isopropyl alcohol and DIB (3 parts 2,4,4-trimethyl-1-pentene + 1 part 2,4,4-trimethyl-2-pentene) were purchased from Sigma-Aldrich.
  • Isoprene was distilled over calcium hydride before use; paramethylstyrene was passed over an inhibitor removal column; hexanes, methyl chloride, aluminum chloride, DEAC, EADC and DIB were used as received.
  • Polyfarnesene (Krasol F 3000) was obtained from Total Cray-Valley and used as received. Other polyfarnesenes were obtained from Kuraray (US) and Polymer Source (CA).
  • IrganoxTM 1076 was purchased from Cieba and used as received. Additional hexanes, ethanol and sodium hydroxide were purchased from VWR and used as received.
  • a stock initiator solution of aluminum trichloride (AICI 3 ) is prepared by dissolving 0.3 g in 100 mL of methyl chloride at -30°C and stirring for 30 mins, which is then set aside for subsequent use.
  • a stock solution of polyfarnesene is prepared by dissolving 0.2 g in 100 mL of methyl chloride at -30°C, which is then set aside for subsequent use.
  • a cooling bath is cooled to -95°C.
  • Isobutylene (10 mL if no other comonomer is present, otherwise 20 mL) and methyl chloride (180 mL) and a desired amount of branching agent are added to a stainless steel 600 mL reactor being cooled by the cooling bath.
  • isoprene (0.7 mL unless otherwise noted) was also added with the isobutylene.
  • p-methylstyrene (2 mL) was also added with the isobutylene.
  • a desired amount of chain transfer agent is also added, if desired.
  • a catalyst solution was prepared by mixing approximately 1 part 1.0 M DEAC in hexanes, 1 part 1.0 M EADC in hexanes with 8 parts hexanes, generating a solution of ethylaluminum sesquichloride (EASC). The solution was stirred for approximately 5 minutes, after which point a small amount of deionized water is added dropwise ( ⁇ 40 pL per 1 mL of DEAC/EADC). The solution was allowed to stir for approximately 15 minutes, after which point it was filtered through a 0.45 pm filter disc and collected into a new Erlenmeyer flask.
  • EASC ethylaluminum sesquichloride
  • Polymerizations were allowed to continue for 30 minutes or until the temperature rise exceeded 15°C, at which point 1-2 mL of a 1 wt% NaOH solution in ethanol was added to quench the reaction.
  • the reactors were removed from the glovebox and hexanes (about 200 mL) and a 1 wt% IrganoxTM 1076 solution in hexanes (1 mL) were added. After allowing to stand overnight, the polymers were coagulated by adding ethanol (about 500 mL) to the reactors. The polymers were dried at 60°C under vacuum. Polymers used in compounding studies were dried on the mill at 100°C prior to compounding.
  • Typical brominations were performed in a 300 mL ChemRxnHubTM jacketed lab reactor. Polymer cement was prepared overnight with stirring at 100 rpm by adding hexane (210 mL), 25 g of polymer, and 0.125 g of calcium stearate to the reactor. 30 minutes before brominations were to commence, stirring was increased to 350 rpm, water (87.5 mL) was added to the reactor, and the temperature control unit was set to 20°C. Bromination was commenced by adding 0.29 mL of liquid bromine to the reactor via a glass syringe. The reaction was allowed to proceed for 5 minutes at which point 10 mL of a 2.5 M sodium hydroxide solution was added to quench the reaction and HBr byproduct.
  • SBS Styrene-butadiene-styrene copolymer
  • KR01 Chevron Phillips Chemicals now produced by INEOS
  • An SBS resin solution was prepared by dissolving about 4.4 g of resin in 100 mL MeCI in a 250 mL Erlenmeyer flask at -30°C with minor agitation for 30-60 minutes, unless otherwise stated.
  • starbranched copolymer was then isolated as described above for slurry polymerizations and brominated as described above for bromination reactions.
  • a similar procedure to the slurry polymerization procedure described above A stock solution of EADC was prepared, 20 wt% EADC in hexane.
  • a stock solution of diluted HCI was prepared by mixing 1 mL of liquid HCI (by cooling the HCI cylinder in the cold pentane bath) with 14 mL methyl chloride to make 1/15 diluted HCI solution.
  • Catalyst feed was prepared by mixing 8.8 mL of EADC stock solution and 7.02 mL of HCI stock solution in to 800 mL methyl chloride.
  • Monomer feed mixture 2200 mL, was prepared by mixing MeCI, IB, and pMS in the ratio of 85:13.5:1.5 by wt%, of which 400 mL was placed in a stainless steel reactor prior to the start of the polymerization.
  • the monomer feed, a 10 wt% pMS and 90 wt% IB feed in methyl chloride was stored at -95°C to -98°C in the cold bath during use.
  • Catalyst solution (mixture of EADC and HCI) was prepared in methyl chloride and stored was stored at -95°C to -98°C in the cold bath for use.
  • Polymerizations were performed semi-continuously by continual addition of monomer feed to the reactor. The reactions were quenched with about 10 ml of isopropyl alcohol.
  • the polymer obtained was separated after evaporating the MeCI in a ventilated hood, and the precipitated polymer was removed from the reactor and collection pot. The polymer was dried in a vacuum oven at 40°C.
  • Bromination was carried out in a two-liter stirred glass reactor with nitrogen purge.
  • the dried polymer prepared from the polymerization step was used for bromination reactions.
  • 110 g of polymer was dissolved in 1200 mL dried hexane in the bromination reactor.
  • the required amount of bromine needed ( ⁇ 3.5 g) to achieve the target was weighed in a beaker.
  • the bromine was added slowly to the polymer solution with vigorous stirring.
  • a light was placed over the reactor to shine on the reaction mixture.
  • the bromination reaction was quenched by adding 1.5 M aqueous sodium hydroxide solution.
  • the reaction mixture was washed four times with 500 mL portions of distilled water, stirring each washing vigorously for 15 minutes, settling, and removing the aqueous layer. Washing was repeated until the pH of the aqueous phase was about 7.
  • the brominated polymer was isolated from the hexane by precipitation by pouring the mixture in to a beaker containing excess acetone. The polymer was separated and dried in a vacuum oven at 40°C.
  • branched HR branched butyl rubbers
  • KrasolTM F 3000 polyfarnesene
  • the rheology of the branched butyl rubbers produced was studied and compared to the rheology of a butyl rubber Control prepared in the same way without branching agent and compared to the rheology of a starbranched bromobutyl rubber (SB-BIIR) prepared using about 1.4 wt% of a styrene-butadiene-styrene (SBS) resin (KR-01 Resin, INEOS) as a branching agent in the polymerization reaction.
  • SB-BIIR starbranched bromobutyl rubber
  • the number of short chains is higher in the SB- BIIR than in the branched butyl rubbers produced using polyfarnesene, except for the butyl rubber sample that was prepared using both the polyfarnesene branching agent and DIB chain transfer agent.
  • Rheological analysis using the van Gurp-Palmen plot allowed for the use of design of experiments (DoE) to determine recipes of polyfarnesene (KrasolTM F 3000) and chain transfer agent (DIB) that are required to generate a branched butyl rubber with a similar level of chain branching, a similar number of short chains and a similar modulus to SB-BIIR.
  • PF- HR Solution 1 and PF-IIR Solution 2 The recipes of the branched butyl rubbers produced using polyfarnesene (PF- HR Solution 1 and PF-IIR Solution 2) as well as the butyl rubber Control and SB-BIIR are shown in Table 2.
  • PF-IIR Solution 1 contains 20 mg of polyfarnesene added to the polymerization along with 70 pl_ of diisobutylene (DIB) as a chain transfer agent, while PF-IIR Solution 2 contains 11 mg of polyfarnesene and 40 mI_ of DIB.
  • DIB diisobutylene
  • PF-IIR Solution 1 and PF-IIR Solution 2 and the SB- BIIR material are shown in Fig. 2. It is evident from Fig. 2 and Table 2 that far less polyfarnesene than SBS resin is needed to produce branched butyl rubber having similar rheological characteristics.
  • branched butyl rubber products produced from use of a polyfarnesene branching agent (PF-IIR Solution 1 and PF-IIR Solution 2) were both analyzed as raw polymers.
  • the branched butyl rubber products produced from use of a polyfarnesene branching agent (PF-IIR Solution 1 and PF-IIR Solution 2) were halogenated on a small scale to produce halogenated versions of each product.
  • the branched bromobutyl products (PF-BIIR Solution 1 and PF-BIIR Solution 2) are alternatives to starbranched bromobutyl rubbers.
  • the raw polymer properties of the brominated butyl rubbers in comparison to a commercial ARLANXEO regular bromobutyl polymer (BB2030) and a starbranched bromobutyl rubber are shown in Table 4.
  • the general polymerization procedure above was used to produce branched polyisobutylene polymers using polyfarnesene (KrasolTM F 3000) together with diisobutylene (DIB) chain transfer agent.
  • the rheology of the branched polyisobutylene polymers produced was studied and compared to the rheology of a commercial PIB Control prepared without branching agent and compared to the rheology of branched poly(isobutylene-co-isoprene) (butyl rubbers: PF-IIR Solution 1 and PF-IIR Solution 2) also produced using KrasolTM F 3000 as a branching agent.
  • the polymerization recipes used are shown in Table 5.
  • P5 IB-co-pMS + Polyfarmesene + DIB (branched IMS)
  • P6 IB-co-pMS + DIB (IMS control with DIB)
  • P7 BIB-co-pMS (brominated IMS control)
  • polyfarnesene is also an effective branching agent for isobutylene-co-paramethylstyrene polymerizations, giving a branched version of IMS, which is the precursor to brominated IMS (BIB-co-pMS).
  • BIB-co-pMS has about 5 mol% paramethylstyrene, about 0.85 mol% brominated paramethylstyrene units and a Mooney viscosity of 35 (MU 1+8, 125°C).
  • BIB-co-pMS is a very linear polymer in comparison to HR, as there are no mechanisms by which branching can be introduced during polymerization.
  • Branched butyl rubber samples were produced in accordance with the general polymerization reaction described above using 20 mg of various polyfarnesenes having various molecular weights and enchainment. The samples were produced using the polyfarnesenes listed in Table 1.
  • cyclic polyterpenes were screened for their ability to branch butyl rubber during polymerization.
  • Poly-a-pinene, poly-b-pinene, poly-d-limonene, mixed polypinene, styrenated poly-a-pinene and terpene phenolic resins were all screened for branching ability for butyl rubber and it was shown that with the examples that were used, there was no difference in rheology between control experiments and experiments with 100 mg of cyclic polyterpene added.
  • Polyfarnesene can be used to generate branched polyisobutylene polymers.
  • polyfarnesene is added to polyisobutylene polymerizations in the amounts outlined in Table 10, all of the polymers produced are branched, with fewer short chains than the N50 PIB production sample, as per rheological testing using a modular compact rheometer (MCR) shown in a van Gurp-Palmen plot in Fig. 10. It was found that the addition of greater than 50 mg of Krasol F 3000 (25 mL of a 2 mg/ml_ solution) per 10 mL of isobutylene resulted in some poisoning of the polymerization.
  • MCR modular compact rheometer
  • Pyrolysis-GCMS also demonstrated that polyfarnesene was chemically bound to the PIB polymer chains and was not simply behaving as an additive causing alternative rheological behaviour.
  • a sample of PF-PIB was purified by dissolving in hexane and coagulating with acetone three times to ensure that any residual, unbound polyfarnesene was removed from the polymer matrix.
  • the pyrolysis-GCMS was performed on a CDS Analytical Pyroprobe 5250T coupled to a Agilent 7890B GC with a 5977B MSD. 100 ug of sample was used and pyrolyzed at 500°C for 15 s. The sample was then run through an HP-5MS Ul column (30 m x 0.25 mm x 1 urn) using helium as the carrier gas, at a flow of 0.8 mL/min, with an inlet temperature of 250°C, and an initial column temperature of 50°C (held for 2 mins), followed by a ramp rate of 20°C per minute to 280°C, held for 10 min.
  • GPC was also used to analyzed the PF-PIB polymers prepared.
  • a sample solution with 0.5 mg/ml_ in THF was prepared and analyzed using a Waters Alliance e2695 Separations module equipped with a Water 2414 Differential Refractometer.
  • THF was used as the eluent at a flow rate of 0.8 mL/min at 35°C and passed through three Agilent Technologies PLgel 10 urn MIXED-B LS 300x7.5 mm columns.
  • Example 16 demonstrates a chromatogram of a N100 PIB production sample and a PF-PIB sample with similar creep behaviour.
  • the MP of the PF-PIB sample has shifted to longer retention times (lower molecular weight) as shown by the chromatogram in Fig. 16, due to the increased number of shorter polymer chains.
  • a significant high molecular weight shoulder is shown in the chromatogram, corresponding to the branched fraction of the polymer.
  • Example 12- Scale up using design of experiments for recipe determination
  • the normal PIB recipe was used as a foundation for the DoE, where half of the isobutylene and half the initiator loading of the PF-IIR recipe was used (10 mL and 2.5 mL, respectively). A wider range of polyfarnesene loading was used due to the highly linear nature of the PIB polymer and the high activity of the polymerization. 2.5 to 23 mL of a 0.2 g / mL solution of Krasol F 3000 was used in the DoE, as well as a range of 7.6 to 92.5 uL of DIB. GPC data and creep data at 100°C were collected and analyzed by Design Expert 11 software.
  • Three different recipes were determined by alternating the priority level of the following responses: maximizing yield, minimizing Mn, Mw and Mz, while maximizing zero shear viscosity (inverse of the slope of the creep curve) and minimizing creep compliance (the end point after 7000 s).
  • the three recipes obtained were 38 mg polyfarnesene, 23 uL DIB; 22 mg polyfarnesene, 50 uL DIB; and 30 mg polyfarnesene, 43 uL DIB.
  • the recipes were scaled up and analyzed for their creep behaviour. They were compared to commercial production samples of N50, N80, N100 and N150.
  • PF-PIB 1 with 38 mg PF and 23 uL DIB, has a better zero shear viscosity with a roughly equivalent creep compliance to N150. The lower slope (inverse of zero shear viscosity) indicates that over longer time, this material will creep less.
  • the reason for the slightly increased creep compliance at 7000 s is likely due to the higher number of short chains which cause an initially high slope in the first portion of the test. This also suggests that the material will be more processable than N150 but have comparable creep performance over time.
  • the molecular weight data of PF-PIB 1 demonstrates a much lower Mn and Mw, which are roughly 1 million g/mol less and approximately half the values for N150, respectively.
  • PF-PIB 2 with 22 mg PF and 50 uL DIB, is a more comparable material to N50, with comparable Mn and slightly higher Mp, but with much improved zero shear viscosity and creep compliance, both by an order of magnitude.
  • PF-PIB 2 has a better zero shear viscosity and similar creep compliance to N80 at 7000 s, again with the benefit of a lower overall molecular weight than N80.
  • PF-PIB 3 with 30 mg PF and 43 uL DIB, behaves similarly to N100 in terms of zero shear viscosity and creep compliance, but having a much lower overall molecular weight, especially in Mn, giving rise to the expected improvements in processability.
  • a second set of PF-PIB samples were scale up for further analyses.
  • the properties of these samples are shown in Table 16.
  • a portion of these samples were aged in a hot air oven at 60°C for 161 days, simulating 5 years.
  • the samples were analyzed by GPC and creep compliance was measured using MCR at various times.
  • Overall, the aged behaviour of the PF-PIB was improved in comparison to production samples of PIB.
  • the PF-PIB samples experienced either no change, or a slight improvement in creep compliance, whereas linear production PIB samples demonstrated worse creep behaviour after two years, as shown in Fig. 18.
  • the results suggest that there is another process at play in the PF-PIB samples, preventing the loss of performance and improving the creep compliance overtime.
  • B200 is a grade of PIB previously produced using a different polymerization process that has a higher molecular weight and higher viscosity than the current N150 grade, which is the upper limit of the current production process in terms of molecular weight.
  • Fig. 19 which is a plot of viscosity vs shear rate amplitude measured at 200°C, at a shear rate of 0.05 s _1 , B200 and N150 have a different viscosity, with B200 being higher.
  • PF-PIB materials were compounded into a white-filled window seals application, the formulation for which is shown in Table 18 and filled properties were measured, shown in Table 19.
  • PF-PIB polymers with similar creep to commercial polymers demonstrated higher mixer torque, better filler dispersion, better processing and higher green modulus, as shown in Fig. 20 to Fig. 23.
  • Table 21 Fig. 28 and Fig. 29 show aged tensile data for a black sheeting compound with production PIB samples and PF-PIB. Overall, the results demonstrate that aged production PIB samples harden after hot air aging at 60°C, whereas PF-PIB samples with lower PF loadings soften after aging (with the exception of the PF-PIB with creep similar to N150). This would be advantageous for roofing applications, as a material that softens over time will maintain flexibility and avoid cracking. It could also improve performance at edges and areas of high curvature.

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Abstract

Des polymères de poly(isooléfine) ramifiés, en particulier des polymères de polyisobutylène, sont préparés par utilisation de polyfamésenènes ayant 5 unités de famesène ou plus en tant qu'agents de ramification. Un composé de caoutchouc comprenant ledit polymère de poly(isooléfine) ramifié et une charge sont préparés. Le composé de caoutchouc est utilisé dans la fabrication d'articles tels que : des dispositifs d'étanchéité, des agents d'étanchéité, des joints d'étanchéité, des adhésifs, des gommes à mâcher, des matériaux de couverture ou des modificateurs de viscosité.
PCT/CA2022/051126 2021-07-21 2022-07-20 Composés de polyisobutylène ramifiés Ceased WO2023000098A1 (fr)

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EP21188259 2021-07-28
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EP2810964A1 (fr) * 2012-02-01 2014-12-10 Sumitomo Rubber Industries, Ltd. Copolymère de diène conjugué ramifié, composition de caoutchouc et pneumatique
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EP2810964A1 (fr) * 2012-02-01 2014-12-10 Sumitomo Rubber Industries, Ltd. Copolymère de diène conjugué ramifié, composition de caoutchouc et pneumatique
KR20190094535A (ko) * 2018-02-05 2019-08-14 한국타이어앤테크놀로지 주식회사 타이어 트레드용 고무 조성물 및 이를 이용하여 제조한 윈터 타이어

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