WO2020117495A1 - Compositions de polyoléfine cationomérique et leurs procédés de production et d'utilisation - Google Patents

Compositions de polyoléfine cationomérique et leurs procédés de production et d'utilisation Download PDF

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WO2020117495A1
WO2020117495A1 PCT/US2019/062810 US2019062810W WO2020117495A1 WO 2020117495 A1 WO2020117495 A1 WO 2020117495A1 US 2019062810 W US2019062810 W US 2019062810W WO 2020117495 A1 WO2020117495 A1 WO 2020117495A1
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monomer
polyolefin
random
cationomeric
polyolefin composition
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Jason A. MANN
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Exxonmobil Chemical Patents 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
    • 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
    • C08F212/08—Styrene
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes

Definitions

  • the present disclosure relates to polyolefins having cationomeric side chain modification.
  • Polyolefin elastomers are commodity polymeric materials that are increasingly being employed in applications where natural and synthetic rubber materials and other synthetic elastomers have been more traditionally used.
  • polyolefin elastomers may be crosslinked (vulcanized) or non-crosslinked. When crosslinked, various crosslinking strategies may be employed.
  • polyolefin elastomers often lack sufficient green strength or low shear viscosity values needed for functionality in certain applications. For example, poor rheological properties may limit the ability of some polyolefin elastomers to form a stable foam. In addition, the rheological properties of many polyolefin elastomers may be insufficient to promote a desired extent of viscosity modification when the polyolefin elastomer is dissolved in a solvent. Fatigue and abrasion resistance in dynamic applications may also be problematic with conventional polyolefin elastomers.
  • the rheological properties of unmodified polyolefin elastomers may influenced by mechanical relaxation along the polyolefin polymer backbone.
  • a second relaxation mode may be introduced to polyolefin elastomers to improve their performance.
  • long chain alkyl branching i.e., side chains
  • the long chain alkyl branching e.g ., C6+ alkyl groups
  • the polyolefin elastomers are more properly considered to constitute a copolymer comprising both unbranched and branched olefinic monomers.
  • Long chain alkyl branching is typically introduced to polyolefin elastomers by copolymerizing two different olefmic monomers, one of which contains a substituted olefin having the long chain alkyl group. Since the two olefmic monomers may react at different rates during a polymerization reaction, it can sometimes be difficult to control the amount of long chain alkyl branching that is present along the polyolefin polymer backbone.
  • the present disclosure provides foamed polyolefin compositions comprising: a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, and a gas component disposed in a plurality of voids within the random cationomeric polyolefin copolymer.
  • the first monomer is a neutral monomer and the second monomer has a side chain bearing a cationic moiety.
  • liquid polyolefin compositions comprising: a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, and a solvent in which the random cationomeric polyolefin copolymer is dissolved.
  • the first monomer is a neutral monomer and the second monomer has a side chain bearing a cationic moiety.
  • FIGS. 1-6 show graphs of illustrative rheological behavior of Polymers 1-6, each of which is a random cationomeric polyolefin copolymer.
  • the present disclosure generally relates to polyolefin elastomers and, more specifically, to polyolefin elastomers having a cationic moiety and methods for production and use thereof.
  • polyolefin elastomers may sometimes be used as a substitute for natural rubber and synthetic elastomeric polymers.
  • polyolefin elastomers exhibit rheological properties or behavior that may preclude their use in certain instances.
  • polyolefin elastomers lacking long alkyl groups as a side chain may lack green strength and exhibit poor low shear viscosity values, which may prevent such polyolefin elastomers from being foamed and/or providing viscosity modification when disposed in a liquid phase.
  • incorporating long chain alkyl groups m a polyolefin elastomer may at least partially address these issues, it may be difficult to incorporate the alkyl groups other than during the initial polymerization reaction. As a result, it may be difficult or impossible to control the extent of branching that does occur. These difficulties may result in product quality issues, such as gel formation in certain polyolefin elastomer compositions. Thus, it may be a laborious and time-consuming process to identify a suitable polyolefin elastomer for use in a particular application.
  • Polyolefin elastomers having lonomeric substitution in the polymer side chains may afford similar benefits to those having long chain alkyl groups.
  • the terms “ionomeric” and“ionomer” refer to the feature of having an lonicaliy charged group in a polymer, particularly within a side chain. lonomers may he positively charged (cationomeric) or negatively charged (anionomeric). Non-protonated cationomers may maintain their charge over all pH conditions. Although ionomeric groups may be present during a polymerization reaction, this approach leads to issues similar to those of introducing long chain alkyl groups.
  • incorporation of the ionomeric groups is similarly non-convergent, and identification of a particular ionomeric polyolefin for a given application may be a laborious and time- consuming process.
  • ionomeric polyolefins may exhibit elevated low shear viscosit ⁇ values that can facilitate their use in various applications, the elevated low shear viscosity values can lead to problematic processing during and/or following a polymerization reaction.
  • the present disclosure provides a much more convergent approach for synthesizing ionomeric polyolefin copolymers.
  • the present disclosure describes a post-polymerization functionalization approach, in which a nucleophile (nucleophilic component) reacts with a highly reactive leaving group in a side chain of the polyolefin to introduce a positively charged group (cationic moiety) therein.
  • the leaving group may be located upon the polymer backbone, and the positively charged group may be present within a newly introduced side chain.
  • the ionomeric polyolefin copolymers disclosed herein are cationomeric.
  • the highly reactive leaving groups in the polyolefin are henzyfic or ally lie halides, particularly benzyhc or ally lie chlorides or bromides, which may undergo ready displacement when exposed to a suitable nucleophile.
  • the incoming nucleophile may be chosen such that a positively charged nitrogen atom or a positively charged phosphorus atom is located at the site of nucleophilic displacement.
  • a positively charged nitrogen atom or a positively charged phosphorus atom may be tethered to the site of nucleophilic displacement, in which case a non-protonated atom is present at the site of nucleophilic displacement.
  • Other reaction strategies for introducing a cationic moiety to a previously synthesized polyolefin may also be feasible and are discussed further herein below.
  • the cationomeric polyolefin copolymers of the present disclosure and processes for formation thereof may afford a number of advantages. From a processing standpoint alone, post-polymerization incorporation of a cationomeric group may be particularly advantageous. Namely, introducing a cationomeric group to the polyolefin post-polymerization represents a much more convergent synthetic approach than pre-polymerization eationomer group introduction. In addition, introducing a cationomeric group at a post-polymerization stage can simplify processing compared to pre-polymerization eationomer introduction. Although both approaches may lead to elevated low shear viscosity values, the elevated low shear viscosity values may be more effectively managed at a stage following the polymerization reaction.
  • elevated low shear viscosity values may be addressed by the cationomeric polyolefin copolymers of the present disclosure in several ways.
  • elevated low shear viscosity values may occur when the copolymer is undergoing finishing, which may result m the copolymer forming under high shear conditions and resting after introduction of the cationic moieties.
  • the use of a polymer solution during formation of the cationomeric polyolefin copolymers may also alleviate elevated low shear viscosity values.
  • the cationomeric polyolefin copolymers may be plasticized with a wide range of plasticizers during processing.
  • introducing a cationomeric group to a side chain of a polyolefin elastomer may afford significant application advantages as well.
  • the aforementioned enhanced low shear viscosity values may facilitate use of the cationomeric polyolefin copolymers in such applications. Namely, sufficiently enhanced low' shear viscosity values may allow' the cationomeric polyolefin copolymers to form stable foams.
  • Foams may comprise the neat (solvent-free) cationomeric polyolefin copolymer or a foamed solution containing the cationomeric polyolefin copolymer.
  • sufficiently enhanced low shear viscosity values may allow' the cationomeric polyolefin copolymers to exhibit rheological properties sufficient to promote viscosity modification of a liquid.
  • the foregoing features can facilitate use of the cationomeric polyolefin copolymers in applications where other polyolefin elastomers might not otherwise be feasible. Additional advantages of the cationomeric polyolefin copolymers disclosed herein include, for example, fatigue and abrasion resistance, and potential self-healing properties.
  • the new numbering scheme for groups of the Periodic Table is used.
  • the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides).
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight. Suitable measurement techniques for each type of molecular weight measurement will be familiar to one having ordinary skill in the art.
  • Molecular weight distribution also referred to as the polydispersity index (PDI)
  • PDI polydispersity index
  • hydrocarbon refers to a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms.
  • C n refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer.
  • Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic.
  • saturated or“saturated hydrocarbon” refer to a hydrocarbon or hydrocarbyl group in which all carbon atoms are bonded to four other atoms or are bonded to three other atoms with one unfilled valence position thereon.
  • saturated or“saturated hydrocarbon” refer to a hydrocarbon or hydrocarbyl group in which one or more carbon atoms are bonded to less than four other atoms, optionally with one unfilled valence position on the one or more carbon atoms.
  • hydrocarbyl and“hydrocarbyl group” are used interchangeably herein.
  • the term“hydrocarbyl group” refers to any Ci-Cioo hydrocarbon group bearing at least one unfilled valence position when removed from a parent compound.
  • “Hydrocarbyl groups” may be optionally substituted, in which the term“optionally substituted” refers to replacement of at least one hydrogen atom or at least one carbon atom with a heteroatom or heteroatom functional group. Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te.
  • R is a hydrocarbyl group or H.
  • Suitable hydrocarbyl groups may include alkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, cycloalkyl, heterocyclyl, and the like, any of which may be optionally substituted.
  • alkyl refers to a hydrocarbyl group having no unsaturated carbon-carbon bonds, and which may be optionally substituted.
  • alkylene refers to an alkyl group having at least two open valence positions.
  • alkenyl refers to a hydrocarbyl group having a carbon-carbon double bond, and which may be optionally substituted.
  • alkene and“olefin” are used synonymously herein.
  • alkenic and“olefmic” are used synonymously herein. Unless otherwise noted, all possible geometric isomers are encompassed by these terms.
  • diiene refers to an alkenyl group having two carbon-carbon double bonds.
  • aromatic and“aromatic hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a cyclic arrangement of conjugated pi-electrons that satisfy the Hiickel rule.
  • aryl is equivalent to the term“aromatic” as defined herein.
  • aryl refers to both aromatic compounds and heteroaromatic compounds, either of which may be optionally substituted. Both mononuclear and polynuclear aromatic and heteroaromatic compounds are encompassed by these terms.
  • arylene refers to an aryl group having at least two open valence positions.
  • saturated hydrocarbyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues.
  • unsaturated hydrocarbyl groups include, but are not limited to, ethenyl, propenyl, allyl, butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and the like, including their substituted analogues.
  • aromatic hydrocarbyl groups include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, and the like, including all possible isomeric forms thereof.
  • Heteroaryl and polynuclear heteroaryl groups may include, but are not limited to, pyridine, quinoline, isoquinoline, pyrimidine, quinazoline, acridine, pyrazine, quinoxaline, imidazole, benzimidazole, pyrazole, benzopyrazole, oxazole, benzoxazole, isoxazole, benzisoxazole, imidazoline, thiophene, benzothiophene, furan and benzofuran.
  • Polynuclear aryl hydrocarbyl groups may include, but are not limited to, naphthalene, anthracene, indane, indene, and tetralin.
  • linear refers to a hydrocarbon or hydrocarbyl group having a continuous carbon chain without side chain branching, in which the continuous carbon chain may be optionally substituted with heteroatoms or heteroatom groups.
  • alpha olefin refers to an alkenic hydrocarbon bearing a carbon-carbon double bond at a terminal (end) carbon atom of the main carbon chain.
  • the terms“branch” and“branched” refer to a hydrocarbon or hydrocarbyl group having a linear main carbon chain or cyclic carbon ring in which a hydrocarbyl side chain extends from the linear main carbon chain or cyclic carbon ring.
  • Optional heteroatom substitution may be present in the linear main carbon chain, the cyclic carbon ring, or in the hydrocarbyl side chain.
  • the term“liomopoiymer” refers to a polymer in which all monomers are the same.
  • the term“copolymer” refers to a polymer in which two or more different monomers are present.
  • the term“terpolymer” refers to a polymer in which three different monomers are present.
  • the term“different” indicates that the monomers differ from one another by the presence or absence of at least one atom and/or isomerically.
  • benzylic refers to a sp 3 carbon atom directly bonded to an aromatic or heteroaromatic ring.
  • allylic refers to a sp 3 carbon atom directly bonded to an olefmie carbon atom.
  • Polyolefin elastomers of the present disclosure may comprise a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, in which the first monomer is a neutral monomer and the second monomer has a side chain bearing a cationic moiety.
  • the first monomer may comprise two or more neutral monomers that differ from one another and that are disposed randomly throughout the polymer backbone.
  • at least one of the two or more neutral monomers comprising the first monomer may comprise a neutral variant of the second monomer, in which the neutral variant has not undergone a reaction with a nucleophilic component to form a cationic moiety.
  • the neutral variant may comprise a leaving group (e.g., a benzylic or aliylic chloride or bromide) that remains unreacted with the nucleophilic component.
  • a leaving group e.g., a benzylic or aliylic chloride or bromide
  • Particular compositions comprising the random cationomeric polyolefin copolymers of the present disclosure are discussed in more detail herein below.
  • the cationomeric polyolefins of the present disclosure are random copolymers.
  • any particular monomer ordering shown in the structural formulas of the present disclosure is intended to he illustrative and non-limiting.
  • the structural formulas herein have depicted a head-to-tail bonding between adjacent monomers, but it is to be appreciated that head-to-head bonding also falls within the scope of the present disclosure
  • random cationomeric polyolefin copolymers of the present disclosure may have a structure exemplified by Formula 1,
  • M is a first olefimc monomer or mixture of olefimc monomers
  • M2 is a second olefinic monomer or mixture of olefimc monomers
  • A is a hydrocarbyl spacer group containing a benzylic carbon atom or an aliylic carbon atom
  • X is a leaving group (particularly a chloride or a bromide) or a cationic moiety bonded to the benzylic or aliylic carbon atom.
  • the first olefinic monomer Mi is one or more neutral olefinic monomers. Side chains are encompassed within the structure(s) associated with Mi.
  • At least one of the second olefimc monomers M2 in the random cationomeric polyolefin copolymer has a side chain hearing a cationic moiety, but all second olefinic monomers M2 need not necessarily be functionalized with a cationic moiety.
  • At least a portion of the first olefimc monomers defined by Mi may comprise any second olefinic monomers defined by M2-A which have not been functionalized with a cationic moiety.
  • the side chain in second olefinic monomer(s) Mi is defined by A-X.
  • Variable a is an integer ranging from 0 to about 1,000
  • variable b is an integer ranging from 0 to about 100
  • variable c is an integer ranging from about 1,000 to about 1,000,000.
  • hydrocarbyl spacer A may be a benzyhdene group or substituted henzyiidene group.
  • the benzylidene group may be a 1,2-benzylidene group, a 1,3- benzylidene group, or a 1,4-benzylidene group, according to various embodiments in certain embodiments described in more detail herein, hydrocarbyl spacer A may be a 1,4-benzylidene.
  • random cationomeric polyolefin copolymers of the present disclosure may optionally be cross linked (vulcanized). Suitable crosslinking strategies are discussed in more detail below.
  • the random cationomeric polyolefin copolymers of the present disclosure may have Mw values ranging from about 100,000 to about 10,000,000, or about 200,000 to about 5,000,000, or about 250,000 to about 1,000,000.
  • PDi values may range from 1 to about 3, or about 1.5 to about 2.5.
  • the total olefinic monomers in the random cationomeric polyolefin copolymers of the present disclosure may feature a cationic moiety within a side chain.
  • about 0.1% to about 10% of the total olefinic monomers may include a side chain cationic moiety, or about 0.5% to about 5%, or about 0.1 to about 3%, or about 1% to about 2.5%.
  • Some of the random cationomeric polyolefin copolymers disclosed herein may be formed by nucleophilic displacement of a leaving group. Up to about 2% of the total olefinic monomers in the random cationomeric polyolefin copolymers of the present disclosure may retain a leaving group following their exposure to a nucleophilic component to introduce one or more cationic moieties.
  • up to about 0.5% of the total olefinic monomers may comprise a residual leaving group, or up to about 0.1 % of the total olefinic monomers may comprise a residual leaving group in some embodiments, a non-zero amount of the total olefinic monomers may feature residual leaving groups, up to about 2% of the total olefinic monomers.
  • the olefinic monomers in the random cationomeric polyolefin copolymer may be substantially free of residual leaving groups.
  • olefinic monomers that originally bore a leaving group before undergoing a reaction to introduce the cationic moieties up to about 75% of the olefinic monomers that originally bore a leaving group may retain their leaving group, with some or all of the remaining olefinic monomers originally bearing a leaving group undergoing functionalization to introduce the cationomeric moieties.
  • counterions for the cationic moieties are not shown in the Formulas depicted herein. It is to be recognized, however, that a counterion may be associated with the cationic moieties to maintain charge balance.
  • the counterion to the cationic moieties may be chloride or bromide, depending upon which leaving group was displaced in the course of introducing the cationic group to the polymer side chain it is to be further appreciated that alternative counterions for the cationic moiety may be introduced through suitable ion-exchange techniques, if desired. Exchange of the counterion may be performed, for example, to promote compatibility with a particular application.
  • synthesis of the random cationomeric polyolefin copolymers of the present disclosure may be realized through displacement of a leaving group with an incoming nucleophile (nucleophilic component), which results in introduction of a positive charged nitrogen atom or a positively charged phosphorus atom upon at least a portion of the polymer side chains.
  • the leaving group is present upon a benzylic carbon atom or an al!yhc carbon atom.
  • Displacement of the leaving groups from the pol olefin starting material may be complete (i.e., no leaving groups remain) or partial (l.e., a mixture of Mb monomers is present, some with a leaving group and some with a cationic moiety).
  • the general synthetic scheme for production of the random cationomeric polyolefin copolymers of the present disclosure through leaving group displacement is shown in Scheme 1,
  • the nucleophilic component may be a tertiary amine, a pyridine moiety , an N-substituted imidazole moiety, or a tertiary' phosphine, thereby forming upon leaving group displacement, respectively, the corresponding quaternary ' ammonium moiety, pyridmium moiety, imidazobum moiety, or quaternary' phosphonium moiety.
  • suitable nucleophilic components and cationic moieties resulting therefrom are discussed m further detail below.
  • random cationomeric polyolefin copolymers of the present disclosure may be defined by Formula 2 below',
  • A is defined as above, and may comprise a benzylie carbon atom or an allylic carbon atom in particular embodiments in more particular embodiments, A is 4-benzylidene.
  • LG is a leaving group, particularly chloride or bromide, bonded to a benzylie carbon atom or an allylic carbon atom in A
  • Cat is a cationic moiety directly bonded to or tethered to a benzylie carbon or an allylic carbon atom in A. in some or other more particular embodiments, Cat may feature a nitrogen atom or a phosphorus atom bearing a positive charge.
  • cationic moieties featuring a positively charged nitrogen atom or a positively charged phosphorus atom may include quaternary ammonium moieties, quaternary ’ phosphomum moieties, imidazolium moieties, pyridinium moieties, and any combination thereof.
  • leaving group displacement from the polyolefin side chains may be complete or substantially complete, such that variable b2 has a value of 0 or substantially 0.
  • oiefinic monomer M21 is not present in the polymer backbone and the random caiionomeric polyolefin copolymers of the present disclosure have a structure defined by Formula 3 below.
  • the random caiionomeric polyolefin copolymers of the present disclosure may comprise at least isobutylene as a first monomer.
  • Particularly suitable random caiionomeric polyolefin copolymers of the present disclosure may comprise isobutylene and an aryl olefin, such as styrene or p-methylstyrene, as a mixture of first monomers, or isobutylene and a diene as a mixture of first monomers, and a second monomer comprising an aryl olefin having a cationic moiety bonded to a benzylie carbon atom.
  • random caiionomeric polyolefin copolymers of the present disclosure may comprise isobutylene and isoprene as a mixture of first monomers and a second monomer comprising isoprene having a cationic moiety bonded to an allylic carbon atom thereof
  • Still other suitable random caiionomeric polyolefin copolymers may comprise one or more of isobutylene, butadiene, or isoprene as a first monomer and a second monomer having a cationic moiety bonded to an aflylic carbon atom thereof.
  • Suitable random caiionomeric polyolefin copolymers may comprise one or more of butadiene or isoprene as a first monomer and a second monomer having a cationic moiety added across a double bond thereof, wherein the cationic moiety may be tethered to a carbon atom previously forming the double bond or directly bonded to a carbon atom previously forming the double bond
  • random caiionomeric polyolefin copolymers of the present disclosure may have structures defined by Formulas 4- 7, in which a benzylic halide or allylic halide is completely reacted with a nucleophilic component (Formulas 4 and 5) and or is incompletely reacted with a nucleophilic component (Formulas 6 arid 7),
  • Qk represents optional aromatic ring functionality selected from any combination of hydrocarbyl, halogen, perha!oaikyi, carboxylic acid, carboxylic ester, carboxamide, aldehyde, ketone, phenol, aikoxy, aiyloxy, perhaioalkoxy, perhaloaryloxy, amine, nitro, nitrile, sulfonamide, and the like, wherein variable k has a maximum value of the number of open valence positions upon the aromatic ring.
  • Variables m and q are integers ranging from 0 to about 1,000.
  • Variables n, o, p, r, s and t are integers ranging from 0 to about 100.
  • Variable u is an integer ranging from about 1,000 to about 1,000,000.
  • Formulas 8-11 (1,2-polymerization of isoprene shown) provide alternative regioisomer configurations corresponding to Formulas 5 and 7 (1,4- polymerization of isoprene shown) that also reside within the scope of the present disclosure.
  • any mixture of isoprene regioisomers may be present in the cationomeric polyolefins disclosed herein.
  • the depicted structures in Formulas 5, 7 and 8-11 should be considered exemplary of tire scope of the polymer structures disclosed herein it is to be further noted that the cationic moiety and the leaving group, if still present, do not necessarily all reside at the same regioisomeric position in a given polymer chain.
  • the double bond geometry may be cis or trans and is not limited to the depicted geometric isomer.
  • Residual leaving groups within the random cationomeric polyolefin copolymers disclosed herein may be used to promote vulcanization (crosslinking) in some further embodiments of the present disclosure, as discussed additional detail below.
  • the foregoing random cationomeric polyolefin copolymers feature a cationic moiety that is directly bonded to a henzyiic carbon atom or an aliyiic carbon atom that was previously functionalized with a leaving group.
  • Other random cationomeric polyolefin copolymers of the present disclosure may feature a cationic moiety that is tethered (i.e., indirectly bonded) to a henzyiic carbon atom or an aliyiic carbon atom by a spacer group.
  • an alkyl spacer group or an aryl spacer group may feature an amine nucleophile (e.g , a primary amine) at a first location and a cationic moiety (e.g. , a quaternary ammonium moiety, a quaternary phosphonium moiety, a pyridinium moiety, or an imidazoiium moiety) at a second location, wherein the amine nucleophile may promote leaving group displacement to tether the cationic moiety to the polyolefin side chain.
  • an amine nucleophile e.g , a primary amine
  • a cationic moiety e.g. a quaternary ammonium moiety, a quaternary phosphonium moiety, a pyridinium moiety, or an imidazoiium moiety
  • nucleophiles such as an aikoxide group or a thiolate group, for example, may be used similarly to promote tethered attachment of the cationic moiety to a benzylic carbon atom or an aliyiic carbon atom through nucleophilic displacement.
  • Suitable tethers may include an optionally substituted C2-C10 alkyl group or an optionally substituted aryl group, for example.
  • cationic moieties may be introduced to random polyolefin copolymers having a benzylic carbon atom or an aliyiic carbon atom without a leaving group being present in such embodiments, a sulfur radical may be utilized to introduce a tethered cationic moiety' to the benzylic carbon atom or the aliyiic carbon atom. More specifically, under suitable conditions, a thiol compound or a disulfide compound may form a sulfur radical, which may then react with the benzylic carbon atom or the aliyiic carbon atom to affect bonding of the cationic moiety to the polyolefin by a sulfur-containing tether.
  • Suitable conditions may include, for example elevated temperatures (e.g., about 40°C to about 120°C) in the presence of a peroxide or similar radical initiator.
  • the sulfur atom is directly bonded to the benzylic carbon atom or the aliyiic carbon atom following the reaction.
  • the sulfur-containing tether may comprise an optionally substituted C2-C10 alkylene group.
  • Functionalization of the random polyolefin copolymer with the sulfur- containing tether may be conducted under conditions similar to those used for promoting sulfur-based vulcanization of such polyolefins, except for choosing a sulfur-containing compound to tether a cationic moiety rather than bond to a second polymer backbone.
  • Particular examples of random cationomeric polyolefin copolymers that may be produced using sulfur radical chemistry are shown in Formulas 12 and 13 below,
  • Z is a hydrocarbyl tether (e.g., an optionally substituted alkylene group or an optionally substituted arylene group)
  • Qk is optional aromatic ring functionality defined as above
  • variables m, n, o, q, r, s and u are defined as above in particular illustrative embodiments
  • Z may be an optionally substituted C2-C10 alkylene group.
  • EPDM polyolefins may be functionalized with a cationic moiety in accordance with certain aspects of the disclosure herein. More particularly, EPDM polyolefins may be functionalized with a tethered cationic moiety using sulfur radical chemistry according to the disclosure herein. Like the sulfur-based radical tethering discussed above, no leaving group is present in EPDM polyolefins.
  • the random cationomeric polyolefin copolymer may comprise a random terpolymer of ethylene, propylene, and a diene monomer, in which particularly suitable diene monomers may include, for example, dicydopentadiene,
  • the cationic moiety' may be indirectly bonded (tethered) to an ally 1 ic carbon atom of the diene monomer by a tether comprising a thiol moiety'.
  • the thiol moiety' is directly bonded to the a!lylie carbon atom.
  • Formula 14 shows a particular ⁇ example of an ethyiidene-2-norbomene diene monomer functionalized with a tethered cationic moiety in accordance with the disclosure above. Either geometric isomer of the double bond may be present.
  • the wavy bonds extending from the norbomene ring are attached to other monomer units such as ethylene, propylene, unfunctionalized diene monomers, or other sulfur-functionalized diene monomers. Accordingly, it is to be appreciated that all of the diene monomers in an EPDM polymer of the present disclosure need not be functionalized with a tethered cationic moiety. As referenced above, other functionalization modalities that are also compatible with the present disclosure may include, for example, a thiol addition across a double bond of a diene monomer (e.g, by hydroihiolation) or disulfide addition across a double bond of a diene monomer.
  • Cat may be a cationic moiety selected from among Formulas 15-18, and LG may be a halide selected from chloride and bromide, more particularly bromide.
  • R’ is a C1-C20 hydrocarbyl group selected from alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, and the like, any of winch may be optionally further substituted with heteroatom functionality.
  • Each R’ may be selected independently, such that they are the same or different. Two or more of R’ may be optionally joined together to form a ring (e.g, an alkyfene ring) in Formulas 15 and 16.
  • Qk represents optional heteroaromatic ring functionality selected from any combination of hydrocarbyl, halogen, perhaloa!kyl, carboxylic acid, carboxylic ester, carboxamide, aldehyde, ketone, phenol, alkoxy, aryloxy, perhaloalkoxy, perhaloaryloxy, amine, mtro, nitrile, sulfonamide, and the like, wherein variable k has a maximum value of the number of open valence positions upon the aromatic or heteroaromatic ring. Namely, variable k may range from 0 to 5 in the pyridinium moiety of Formula 17 and from 0 to 3 m the imidazolium moiety of Formula 18.
  • nucleophilic components that may be reacted to form the cationic moieties within the random cationomeric polyolefin copolymers of the present disclosure include, but are not limited to, trimethylamine, triethylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, benzyldimethylamine, dimethylphenylamine, triphenylamine, meihyl(bis ⁇ 3-(dimeihyiphenylsilyl))amine, dimethyl(3- di methylphenylsilyl)amine, tributylphospbine.
  • triphenylphospbine pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-t-butylpyridine, 3-t-butylpyridine, 4- t-butylpyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, nicotinic acid, nicotinamide, N-methylimidazole, N-butylirnidazole, N-benzylimidazole, 2-bromo-N- methyli midazole, and the like.
  • the random cationomeric polyolefin copolymers disclosed herein may comprise a reaction product obtained from a reaction between 1) a random terpolymer of styrene, 4-vmyIbenzyl bromide or 4-vinylbenzyl chloride, and isobutylene, and 2) a nucleophilic component selected from the group consisting of a tertian amine, a tertian phosphine, an N-substituted imidazole (e.g., an N-alkylimidazole), and a pyridine.
  • a nucleophilic component selected from the group consisting of a tertian amine, a tertian phosphine, an N-substituted imidazole (e.g., an N-alkylimidazole), and a pyridine.
  • the random cationomeric polyolefin copolymers disclosed herein may comprise a reaction product obtained from a reaction between 1) a random copolymer of isoprene and isobutylene that is brominated or chlorinated in at least one allylic position, and 2) a nucleophilic component selected from the group consisting of a tertiary amine, a tertiary phosphine, an N-substituted imidazole (e.g., an N-alkylimidazole), and a pyridine.
  • a nucleophilic component selected from the group consisting of a tertiary amine, a tertiary phosphine, an N-substituted imidazole (e.g., an N-alkylimidazole), and a pyridine.
  • the random cationomeric polyolefin copolymers disclosed herein may be prepared from a random terpolymer of isobutylene, p-methylstyrene, and p-bromobenzylstyrene.
  • Such terpolymers may have weight average molecular weights ranging from about 50,000 to about 500,000, or about 100,000 to about 1,000,000, or from about 125,000 to about 400,000, or from about 150,000 to about 300,000.
  • PDl values may range from about 1 to about 3, or from about 1.5 to about 2.5, or from about 1.75 to about 2.25.
  • Such terpolymers may also feature a molar ratio of isobutylene:styrene:p- bromobenzylstyrene, which the molar ratio of isobutylene ranges from about 80-95, the molar ratio of styrene ranges from about 0.5-18, and the molar ratio of p-bromobenzylstyrene ranges from about 0.4-1.4.
  • the isobutylene and styrene ratios may be maintained in the corresponding random cationomeric polyolefin copolymer, and the molar ratio of p-bromobenzylstyrene may range from about 0-1, depending on the extent of nucleophilic displacement that has occurred.
  • the random cationomeric poly olefin copolymers disclosed herein may exhibit very high viscosity values at low shear rates, which results in significant green strength as well as shape persistent behavior at low to moderate temperatures.
  • the viscosity of the resulting polymer compositions decreases significantly at elevated shear rates (i.e., the compositions are shear thinning), which is consistent with the introduction of an additional relaxation mode beyond the main chain relaxation present m the precursor polymers lacking the cationomeric moieties. This behavior and its associated dependence on the cationomeric moieties provides a means to overcome the otherwise difficult processing of non-plasticized ionomers.
  • the random cationomeric polyolefin copolymers disclosed herein may be thermoplastic elastomers m some embodiments.
  • thermoplastic elastomers of the present disclosure there is no covalent crosslinking between adjacent polymer chains. Instead, the cationic groups associate ionical!y to provide a sufficiently stable network structure to promote elastomeric behavior.
  • the random cationomeric polyolefin copolymers of the present disclosure may be thermoset elastomers.
  • Such thermoset elastomers may be crosslinked with a suitable crosslinking agent, as discussed further herein below.
  • Polyolefins having an unsubstituted ally lie carbon atom may be crosslinked using crosslinking agents such as, for example, sulfur plus an organic accelerator (e.g., thiurams or thiocarhonat.es), phenolic resms (e.g. , phenol- formaldehyde resins), bisazidoformates, quinones (e.g., quinone dioxime), and the like.
  • crosslinking agents such as, for example, sulfur plus an organic accelerator (e.g., thiurams or thiocarhonat.es), phenolic resms (e.g. , phenol- formaldehyde resins), bisazidoformates, quinones (e.g., quinone dioxime), and the like.
  • Polyolefins having an ally e carbon that is halogen-substituted may be crosslinked using crosslinking agents such as, for example, zinc oxide, bismaleimides, diamines, peroxides, thioureas, dithiols and disulfides, optionally employing accelerators such as thiazoles, thiocarbamates, alkoxythiocarbonyl compounds, dialky!thiophosphoryl compounds, and diamino-2, 4, 6-triazines.
  • crosslinking agents such as, for example, zinc oxide, bismaleimides, diamines, peroxides, thioureas, dithiols and disulfides, optionally employing accelerators such as thiazoles, thiocarbamates, alkoxythiocarbonyl compounds, dialky!thiophosphoryl compounds, and diamino-2, 4, 6-triazines.
  • crosslinking halobutyl rubber and related polymers such as epoxidized soybean oil, butylated hydroxy toluene, zinc stearate, zinc octanote, and/or calcium stearate.
  • Polyolefins having a benzylic halide, particularly a benzylic bromide may be crosslinked using crosslinking agents such as, for example, zinc stearate, zinc bromide, diamines, phenolic resins, thiosulfates, and Friedel-Crafts alkylation catalysts.
  • Suitable crosslinking conditions and the crosslinked polyolefin structures that are produced using a particular crosslinking agent will be familiar to one having ordinary skill in the art.
  • the various random cationomeric polyolefin copolymers formed according to the present disclosure may also be blended with further additives to form compositions that can then be used in articles of manufacture or for an intended application.
  • Suitable additives may include, for example, antioxidants, nucleating agents, acid scavengers, plasticizers, stabilizers, anticorrosion agents, blowing agents, gases, solvents, foaming agents, ultraviolet light absorbers, quenchers, antistatic agents, slip agents, phosphites, phenolics, pigments, dyes, fillers, fibers, cure agents, and any combination thereof.
  • the present disclosure further provides various compositions comprising the random cationomeric polyolefin copolymers. Additional disclosure directed to the compositions and uses thereof is provided hereinafter. Any of the random cationomeric polyolefin copolymers described hereinabove may be incorporated in the various compositions of the present disclosure.
  • the present disclosure provides foamed polyolefin compositions.
  • the foamed polyolefin compositions comprise a gas component, and a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, in which the first monomer is a neutral monomer and the second monomer has a side chain bearing a cationic moiety.
  • the gas component is disposed in a plurality of voids within the random cationomeric polyolefin copolymer. Any of the random cationomeric polyolefin copolymers described hereinabove may be incorporated as the polyolefin component in the foamed polyolefin compositions disclosed herein.
  • Suitable uses for the foamed polyolefin compositions may include, but are not limited to, seals and sealing applications, gaskets, shock-absorbing structures, and soundproofing foams
  • Gas components suitable for use in the foamed polyolefin compositions may include any gas capable of introducing voids in a matrix of the random cationomeric polyolefin copolymer.
  • Suitable gas components may include, for example, air, oxygen, nitrogen, carbon dioxide, noble gases, or the like.
  • the voids introduced into the random cationomeric polyolefin copolymer may be closed ceil or open cell, depending on the void density and the method employed for introducing the voids.
  • the random cationomeric polyolefin copolymer may be foamed by placing the random cationomeric polyolefin copolymer and the gas component under pressure and then rapidly depressurizing.
  • the rapid depressurization may introduce voids comprising the gas component within the random cationomeric polyolefin copolymer.
  • the porosity (void space) within a matrix defined by the random cationomeric polyolefin copolymer may range from about 50% to about 95%, or about 60% to about 90%, or about 70% to about 85%.
  • Higher density foamed polyolefin compositions also reside within the scope of the present disclosure, such as foamed polyolefin compositions having a porosity below about 50%, or below about 25%, or below' about 10%.
  • the porosity may range from about 1% to about 10%, or about 10% to about 30%, or about 30% to about 50%.
  • Higher density polyolefin foams may be particularly useful in applications requiring shock absorption, for example. Shock absorption applications may include, but are not limited to, shoe soles, mattress components, components of automotive shock absorbers, and shock absorption coatings for tool and w ork piece handles to promote user comfort
  • the foamed polyolefin compositions disclosed herein may further comprise a surfactant, which may aid in the foaming process.
  • Suitable surfactants may include various surface active agents, which may be cationic, anionic, amphoteric, or neutral. Surfactants that may be suitable for use in the disclosure herein will be familiar to one having ordinary skill in the art.
  • the foamed pol olefin compositions of the present disclosure may further comprise a foaming agent.
  • Suitable foaming agents may include, but are not limited to, azobisformamide, azobisisobutyronitrile (AIBN), diazoaminobenzene, N,N- dimethyl-N,N-dinitrosoterephthalamide, N,N-dinitrosopentamethylenetetramine, benzenesulfonyl hydrazide, benzene- 1, 3 -disulfonyl hydrazide, 4,4'-oxybisbenzene sulfonyl hydrazide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, butylamine nitrile, nitroureas, trihydrazino triazine, peroxides, wax-encapsulated hydrocarbon blowing agents, and inorganic blowing agents such as am
  • the foamed polyolefin compositions may be foamed neat without a solvent being present. In other embodiments, the foamed polyolefin compositions may be foamed when dissolved in a solution, such as in a hydrocarbon solvent, particularly a linear alpha olefin solvent.
  • Foamed polyolefin compositions lacking a solvent may further comprise various additives, such as one or more plasticizers. Suitable plasticizers will be familial to one having ordinary skill in the art.
  • the present disclosure provides liquid polyolefin compositions.
  • the liquid polyolefin compositions comprise a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, in which the first monomer is a neutral monomer and the second monomer has a side chain bearing a cationic moiety, and a solvent m which the random cationomeric polyolefin copolymer is dissolved.
  • Any of the random cationomeric polyolefin copolymers described hereinabove may be incorporated as the polyolefin component m the liquid polyolefin compositions disclosed herein.
  • the solvent in which the random cationomeric polyolefin copolymer is dissolved is a hydrocarbon solvent.
  • the hydrocarbon solvent may be aliphatic or aromatic in particular examples of the present disclosure in still more specific embodiments, the hydrocarbon solvent may be an alpha olefin solvent, such as 1 -hexene, 1-octene 1-decene, or 1-dodecene, for example.
  • a concentration of the random cationomeric polyolefin copolymer in the solvent of the liquid polyolefin compositions may range from about 0.5% to about 10% by weight of the composition or about 1% to about 10% by weight of the composition, according to various embodiments.
  • the concentration of the random cationomeric polyolefin copolymer may be selected to provide viscosity modification of the solvent, which may entail a viscosity' increase or a viscosity decrease depending on concentration and temperature, among other factors.
  • the liquid polyolefin compositions may he foamed or unfoamed, according to various embodiments if foamed, the liquid polyolefin compositions may further comprise a gas component, a surfactant, and/or a foaming agent. Suitable gas components, surfactants, and foaming agents are provided hereinabove.
  • This invention further relates to
  • a foamed polyolefin composition comprising:
  • a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, the first monomer being a neutral monomer and the second monomer having a side chain bearing a cationic moiety;
  • the cationic moiety comprises at least one cationic moiety selected from the group consisting of a quaternary ammonium moiety, an imidazolium moiety, a pyridinium moiety, and a quaternary phosphonium moiety.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a liquid polyolefin composition comprising:
  • a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, the first monomer being a neutral monomer and the second monomer having a side chain bearing a cationic moiety;
  • the cationic moiety comprises at least one cationic moiety selected from the group consisting of a quaternary ammonium moiety, an imidazolium moiety, a pyridinium moiety, and a quaternary phosphonium moiety.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • liquid polyolefin composition of paragraph 26, wherein the cationic moiety is bonded to the diene monomer by hydrothiolating a double bond in the diene monomer or by adding a disulfide across a double bond in the diene monomer.
  • liquid polyolefin composition of paragraph 15 wherein the liquid polyolefin composition is foamed and further comprises a gas component disposed in a plurality of voids.
  • liquid polyolefin composition of paragraph 15 further comprising a foaming agent.
  • This invention also relates to:
  • a foamed polyolefin composition comprising:
  • a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, the first monomer being a neutral monomer and the second monomer having a side chain bearing a cationic moiety;
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a liquid polyolefin composition comprising:
  • a random cationomeric polyolefin copolymer comprising at least a first monomer and a second monomer, the first monomer being a neutral monomer and the second monomer having a side chain bearing a cationic moiety;
  • a random terpolymer of styrene, 4-vinylbenzyl bromide or 4-vinylbenzyl chloride, and isobutylene and 2) a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a nucleophilic component selected from the group consisting of a tertiary amine, an N-substituted imidazole, a pyridine, and a tertiary phosphine.
  • a series of random cationomeric polyolefin copolymers were prepared by reacting a random terpolymer of isobutylene, styrene, and p-bromobenzyl styrene with the nucleophiles listed in Table 1 below. Reactions were conducted in a glove box.
  • the random terpolymer was BIMSM (brominated copolymer of isobutylene and paramethylstyrene having a bromine content of about 1.2 mol% and a Mooney Viscosity (1+8, 125°C) of about 45 MU (available from ExxonMobil Chemical Company, Baytown Texas as EXXPROTM 3745 Specialty Elastomer).
  • FIGS. 1-6 show graphs of illustrative rheological behavior of Polymers 1-6. Tests were completed on an ARES-G2 rheometer using an 8 mm parallel plate geometry at 170°C and 5% strain and an angular frequency from 0.01 to 100 rad/s. Temperature sweeps were performed on the same instrument at 0.1% strain over a temperature range of -80°C to 170°C. The random cationomeric polyolefin copolymers showed very high viscosity at lo shear rates.
  • compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein.
  • composition, element, or elements are considered synonymous with the term“including.”
  • transitional phrase“comprising” it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

Bien que les élastomères de polyoléfine soient des polymères de produits largement utilisés, il existe des inconvénients pour ce type de polymères pour certaines applications. Par exemple, les propriétés rhéologiques de certains élastomères de polyoléfine peuvent être insuffisantes pour fournir la résistance initiale ou la faible viscosité de cisaillement nécessaire pour former des mousses stables, ou pour fournir des effets de modification de viscosité suffisants lorsqu'ils sont présents dans un solvant. La modification cationomérique d'élastomères de polyoléfine peut atténuer ces difficultés. Lesdits élastomères de polyoléfine peuvent comprendre un copolymère de polyoléfine cationomérique aléatoire comprenant au moins un premier monomère et un second monomère, le premier monomère étant un monomère neutre et le second monomère ayant un segment latéral portant une fraction cationique. Les élastomères de polyoléfine peuvent être présents dans des compositions de polyoléfine expansée comprenant un composant gazeux et/ou dans des compositions liquides comprenant un solvant dans lequel l'élastomère de polyoléfine est dissous.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007055793A2 (fr) * 2005-11-07 2007-05-18 Exxonmobil Chemical Patents Inc. Compositions nanocomposites et leurs procedes de fabrication
WO2013147989A1 (fr) * 2012-03-29 2013-10-03 3M Innovative Properties Company Adhésifs comprenant des copolymères de poly(isobutylène) portant un substituant ammonium quaternaire latéral polymérisable par voie radicalaire

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007055793A2 (fr) * 2005-11-07 2007-05-18 Exxonmobil Chemical Patents Inc. Compositions nanocomposites et leurs procedes de fabrication
WO2013147989A1 (fr) * 2012-03-29 2013-10-03 3M Innovative Properties Company Adhésifs comprenant des copolymères de poly(isobutylène) portant un substituant ammonium quaternaire latéral polymérisable par voie radicalaire

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DAVID L TOMASKO ET AL: "A Review of CO2 Applications in the Processing of Polymers", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 42, no. 25, 6 September 2003 (2003-09-06), pages 6431 - 6456, XP055003779, ISSN: 0888-5885, DOI: 10.1021/ie030199z *
J.SCOTT PARENT ET AL: "SYNTHESIS AND CHARACTERIZATION OF ISOBUTYLENE-BASED AMMONIUM AND PHOSPHONIUM BROMIDE IONOMERS", MACROMOLECULES, vol. 37, no. 20, 3 September 2004 (2004-09-03), pages 7477 - 7483, XP003009417, ISSN: 0024-9297, DOI: 10.1021/ma049158k *
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