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WO2007111584A1 - Composition d'elastomere thermoplastique presentant d'excellentes proprietes a basse temperature - Google Patents

Composition d'elastomere thermoplastique presentant d'excellentes proprietes a basse temperature Download PDF

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Publication number
WO2007111584A1
WO2007111584A1 PCT/US2006/011002 US2006011002W WO2007111584A1 WO 2007111584 A1 WO2007111584 A1 WO 2007111584A1 US 2006011002 W US2006011002 W US 2006011002W WO 2007111584 A1 WO2007111584 A1 WO 2007111584A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
rubber
weight
copolymer
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2006/011002
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English (en)
Inventor
Yoshihiro Soeda
Andy Haishung Tsou
Yuichi Hara
Matthew Brian Measmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yokohama Rubber Co Ltd
ExxonMobil Chemical Patents Inc
Original Assignee
Yokohama Rubber Co Ltd
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority to PCT/US2006/011002 priority Critical patent/WO2007111584A1/fr
Publication of WO2007111584A1 publication Critical patent/WO2007111584A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to an improved thermoplastic elastomer composition and blend having excellent heat resistance, durability and. flexibility, while possessing superior air impermeability for
  • the present invention relates to a soft thermoplastic elastomer composition having excellent flexibility at a low temperature utilizing a finely dispersed softener.
  • the present invention relates to a soft thermoplastic elastomer composition having excellent flexibility at a low temperature utilizing a finely dispersed softener.
  • thermoplastic elastomer composition containing 1 to 20 weight % of a reactive compatibilizable softener having a dispersion size of 1 ⁇ m or less.
  • EP 722850B1 disclosed a low-permeability thermoplastic elastomer composition that is superior as a gas-barrier layer in a pneumatic tire. This
  • thermoplastic elastomer composition comprises a low- permeability thermoplastic matrix such as a polyamide, a blend of a polyamide or a copolymer of a polyamide, in which a low-permeability rubber such as a ⁇ brominated poly(isobutylene-co-paramethylstyrene) (i.e., BIMS), is
  • thermoplastic matrix a viscosity ratio between the thermoplastic matrix and the rubber dispersion was specified both as a function of the volume fraction ratio and independently . to be close to one in order to, achieve phase continuity
  • elastomers for delivering acceptable durability,, especially for their usage as an innerliner in a pneumatic tire.
  • thermoplastic elastomers 5 based on a vulcanized blend of a polyamide and BIMS to be used as an innerliner in a tire, it is preferable to have a low modulus at a low temperature.
  • Kn innerliner is commonly laminated to a soft elastomer compound such as a tie compound (or a squeeze compound) or a carcass
  • BIMS typically have a Tg at -60 0 C, their modulus starts to rise when a temperature is lowered below O 0 C. This unique earlier modulus rise before an ambient temperature approaching Tg is the result of the rather unique broad glass transition in an isobutylene-based
  • elastomer such as brominated copolymers of isobutylene and paramethylstyrene.
  • a thermoplastic elastomeric innerliner that also has a low modulus
  • One method to lower the low temperature modulus of a polyamide/B ⁇ MS thermoplastic elastomer is to increase the BIMS rubber content. Although BIMS is slightly stiffened at -2O 0 C, it is still significantly softer than the
  • thermoplastic elastomer or raising the viscosity of BIMS is required to maintain polyamide as the continuous phase, while raising the BIMS content.
  • overall softening of the resulting thermoplastic elastomer can be accomplished 5 with an increasing BIMS rubber content, enlargement of the dispersion is unavoidable with the increase rubber collision frequency during mixing. The enlargement of rubber dispersion discourages the formation of trans- crystallinity in a polyamide leading to the erosion of 10 their fatigue resistance.
  • references of interest include, for example, WO 2004/081107, WO 2004/081106, WO 2004/081108, WO 2004/081116, and WO 2004/081099.
  • the object of the present invention is to provide a thermoplastic elastomer composition or a blend for a tire innerliner and barrier film having an excellent
  • thermoplastic elastomer composition or a blend comprising a thermoplastic elastomer composed of at least partially vulcanized first
  • thermoplastic elastomer composition comprising a thermoplastic elastomer composed of at least partially vulcanized first rubber component discretely
  • a blend comprising a first rubber component 5 at least partially vulcanized dispersed as particles having a size of 1 micron or less in a polyamide matrix; and a second polymer component different from the first rubber component, where the second polymer component has a Tg spread of less than 20 0 C as measured by DMTA run at
  • the present invention is directed to use one or more reactive softeners in a thermoplastic elastomer composition based on a polyamide and halogenated copolymer of a Cs to C 7 isoolefin and a para-alkylstyrene at a concentration of 20% by weight or less, based upon
  • Polymer may be used to refer to homopolymers, 30 copolymers, interpolymers, terpolymers, etc.
  • a copolymer may refer to a polymer comprising at least two monomers, optionally with other monomers.
  • a polymer When a polymer is referred to as comprising a monomer, the monomer is present in the polymer in the 35 polymerized form of the monomer or in the derivative form the monomer.
  • the phrase 5 When a polymer is referred to as comprising a monomer, the monomer is present in the polymer in the 35 polymerized form of the monomer or in the derivative form the monomer.
  • the phrase 5 For ease of reference the phrase 5
  • catalyst components comprising the (respective) monomer or the like is used as shorthand. likewise, when catalyst components are described as comprising neutral stable forms of the components, it is well understood by one skilled in the 5 art, that the active form of the component is the form that reacts with the monomers to produce polymers.
  • Isoolefin refers to any olefin monomer having two substitutions on the same carbon.
  • Multiolefin refers to any monomer having two double
  • the multiolefin is any monomer comprising two double bonds, preferably two conjugated double bonds such as a conjugated diene like isoprene.
  • Elastomer or elastomers as used herein refers to
  • Alkyl refers to a paraffinic hydrocarbon group which may be derived from an alkane by dropping one or more
  • Aryl refers to a hydrocarbon group that forms a ring structure characteristic of aromatic compounds such as, for example, benzene, naphthalene, phenanthrene,
  • An aryl group is thus a group derived from an aromatic compound by dropping one or more hydrogens from the formula such as, for example, phenyl, or C 6 H 5 .
  • the present invention utilizes a secondary rubber component in the thermoplastic elastomer composition.
  • the secondary rubber is based on functionalized rubbers with a low Tg.
  • the functionality is typically maleic anhydride, maleic acid, acyllactam,
  • the Tg of the secondary rubber is typically -3O 0 C or less, alternately -40 0 C or less, alternately -50 0 C or less.
  • the functionality typically promotes reactive compatibilization between the secondary 5 rubber and the polyamide . leading to fine dispersion of secondary rubber with an average dispersion size of 1 ⁇ m or less, most particularly with a dispersion size of 0.5 ⁇ m or less.
  • the low Tg helps ensure the softness of the secondary rubber at -20 0 C. Considering that most
  • anhydride grafted rubbers useful herein could be maleic anhydride modified or grafted ABS (acrylonitrile- butadiene-styrene) , EPDM (ethylene-propylene-diene), SEBS (styrene-ethylene/butadiene-styrene) and others.
  • Other useful maleated ethylene copolymer rubbers include
  • maleated ethylene-propylene maleated ethylene-butene, maleated ethylene-hexene, maleated ethylene-octene, maleated ethylene-decacene, maleated ethylene-propylene- diene, maleated ethylene-vinyl acetate, maleated ethylene-methyl aerylate, maleated ethylene-ethyl
  • Useful maleated copolyper rubbers also include copolymers of maleic anhydride or its derivatives with one or more comonomers such as ethylene, methacrylate, butyl acrylate, and the like.
  • thermoplastic elastomer composition or the blend according to the present invention which comprises the first rubber component dispersed in the polyamide matrix, is subjected to dynamic vulcanization.
  • the resin and the first rubber component are vulcanized under conditions of high shear.
  • the first vulcanizable rubber component is simultaneously vulcanized and dispersed as fine particles of a "micro 5 gel" within the polyamide resin matrix.
  • the dynamic vulcanization is effected by mixing the ingredients at a temperature which is at or above the curing temperature of the rubber in an equipment such . as a roll mill, Banbury ® mixer, continuous mixer, kneader or
  • the unique characteristic of the dynamically vulcanized composition is that, notwithstanding the fact that the rubber component may be partially or fully vulcanized, the composition can be processed arid reprocessed by a twin screw extruder.
  • the first rubber component usable in the present invention includes, for example, halogenated rubber.
  • halogenated rubber is defined as a rubber having at least about 0.1 mole% halogen, such halogen selected from the group consisting of bromine, chlorine and iodine.
  • Preferred halogenated rubbers useful in the present invention include halogenated isobutylene-based
  • copolymer is a butyl-type rubber or branched butyl-type rubber, especially brominated versions of these elastomers.
  • Useful unsaturated butyl rubbers such as homopolymers and copolymers of olefins or isoolefins and other types of elastomers suitable for the invention are
  • Butyl rubbers are typically prepared by reacting a mixture of monomers, the mixture having at least (1) a Cj to Ci 2 isoolefin monomer component such as isobutylene with (2) a multiolefin, monomer component.
  • the isoolefin is in a range from 70 to 99.5% by weight of the total
  • the multiolefin component is present in the monomer mixture from 30 to 0.5% by weight in one embodiment, and from 15 to 0.5% by weight in another embodiment. In yet another embodiment, from 8
  • the isoolefin is preferably a C4 to C ⁇ 2 compound, non- limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-l-butene, 3-methyl-l- butene, 2-methyl-2-butene, l ⁇ butene, 2-butene, methyl
  • the multiolefin is a C 4 to Ci 4 multiolefin such as isoprene, butadiene, 2,3-dimethyl- 1,3-butadiene, myrcene, 6, 6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene, and other monomers such
  • Halogenated butyl rubber is produced by the 9
  • halogenation of the butyl rubber product described above can be carried out. by any means, and the invention is not herein limited by the halogenation process.
  • Methods of halogenating polymers such as butyl 5 polymers are disclosed in U.S. Patent Nos. 2,631,984, 3,099,644, 4,288,575, 4,554,326, 4,632,963, 4,681,921, 4,650,831, 4,384,072, 4,513,116 and 5,681,901.
  • the butyl rubber is halogenated in hexane diluent at from 4 to 60 0 C using bromine (Br ⁇ ) or chlorine
  • halogenation agent 10 CI 2
  • Post-treated halogenated butyl rubber can also be used, as disclosed in US Patent No- 4,288,575.
  • Useful halogenated butyl rubber typically has a Mooney Viscosity of about 20 to about 70 (Ml ⁇ + s at 125°C) ; for example, and about 25 to about 55 in another
  • the preferred halogen content is typically about 0.1 to 10% by weight based on the weight of the halogenated rubber; for example, about 0.5 to 5% by weight; alternatively, about 0.8 to about 2.5% by weight; for example, about 1 to about 2% by weight.
  • halogenated butyl rubber contains a high content of the following halogenated structure, preferably 60 to 95% as measured by NMR, where X represents the halogen and, in a particularly preferred embodiment, the halogen is bromine; alternatively the
  • a commercial embodiment of a halogenated butyl 30 rubber useful in the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company) . Its Mooney Viscosity is typically about 27 to 37 (MLi +8 at 125°C, ASTM 1646, modified), and its bromine content is about 1.8 to 2.2% by weight relative to the Bromobutyl 2222. Furthermore, 10
  • halogenated butyl rubber is halogenated, branched or "star-branched" butyl rubber. These rubbers are described in, for example, EP
  • the star-branched butyl rubber is a composition comprising butyl rubber and a polydiene or block copolymer.
  • polydienes are typically cationically reactive and are present during the polymerization of the butyl or halogenated butyl rubber, or can be blended with
  • the branching agent or polydiene can be any suitable branching agent, and the invention is not limited to the type of polydiene or branching agent used to make the SBB.
  • the SBB is a composition of butyl
  • Polydienes can be present, based on the total monomer content in % by weight, typically greater than 0.3% by weight; alternatively, about 0.3 to about 3% by weight; or about 0.4 to 2.7% by weight.
  • the halogenated star-branched butyl rubber (“HSBB”) comprises a butyl rubber, either halogenated or not, and a polydiene or block copolymer, either halogenated or not.
  • HSBB halogenated star-branched butyl rubber
  • polydiene/block copolymer or branching agents (hereinafter “polydienes”) , are typically cationically reactive and
  • the branching agent or polydiene can be any suitable branching agent, and the invention is not limited by the
  • the HSBB is typically a composition comprising halogenated butyl rubber as described above and a copolymer of a polydiene and a partially hydrogenated polydiene selected from the group
  • polystyrene polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, ethylene-propylene diene rubber, styrene-butadiene- styrene and styrene-isoprene-styrene block copolymers .
  • Polydienes can be present, based on the total monomer
  • 35 content in % by weight typically greater than about 0.3% by weight, alternatively about 0.3 to 3% by weight, or about 0.4 to 2.7% by weight. 12
  • a commercial embodiment of HSBB useful in the present invention is Bromobutyl 6222 (ExxonMobil Chemical Company) , having a Mooney Viscosity (ML 1+8 at 125°C, ASTM D1646) of about 27 to 37, and a bromine content of about 5 2.2 to 2.6% by weight. Further, cure characteristics of Bromobutyl 6222, as disclosed by the manufacturer, are as follows: MH is from 24 to 38 dN-m, ML 1+8 is from 6 to 16 dN-m (ASTM D2084).
  • halomethylstyrene may be an ortho-, meta-, or para-alkyl-substituted styrene. In one embodiment, the halomethylstyrene is a p-
  • halomethylstyrene containing at least 80%, more preferably at least 90% by weight o£ the para-isomer.
  • the "halo" group can be any halogen, desirably chlorine or bromine.
  • the copolymer may also include functionalized interpolymers wherein at least some of the
  • alkyl substituent groups present on the styrene monomer units contain benzyli ⁇ halogen or another functional group described further below.
  • These interpolymers are herein referred to as "isoolefin copolymers comprising a halomethylstyrene" or simply “isoolefin copolymer.”
  • Preferred isoolefin copolymers can include monomers selected from the group consisting of isobutylene or isobutene, 2-methyl-l-butene, 3-methyl-l-butene, 2- methyl-2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, and 4-methyl-l-
  • isoolefin copolymers may also further comprise multiolefins, preferably a C ⁇ to C ⁇ multiolefin such as isoprene, butadiene, 2,3-dimethyl-l, 3-butadiene, myrcene, 6,6-dime.thyl-fulvene, hexadiene, cyclopentadiene, and piperylene, and other monomers such
  • Desirable styrenic monomers in the isoolefin copolymer include styrene, methylstyrene, 13
  • chlorostyrene methoxystyrene, indene and indene derivatives, and combinations thereof.
  • Preferred isoolefin copolymers may be characterized as interpolymers containing the following monomer units 5 randomly spaced along the polymer chain: 1. 2.
  • R and R 1 are independently hydrogen, lower alkyl, preferably Cj to C 7 alkyl and primary or secondary alkyl
  • X is a functional group such as halogen.
  • Desirable halogens are chlorine, bromine or combinations thereof, preferably bromine.
  • R and R ⁇ are each hydrogen.
  • the -CRRiH and -CRRiX groups can be substituted on the styrene ring in either the ortho, meta, or para
  • the interpolymer structure 15 positions, preferably the para position.
  • Up to 60 mole% of the p-substituted styrene present in the interpolymer structure may be the functionalized structure (2) above in one embodiment, and in another embodiment from 0.1 to 5 ⁇ tole%. In yet another embodiment, the amount of
  • the 20 functionalized structure (2) is from 0.4 to 1 mole%.
  • the functional group X may be halogen or some other functional group which may be incorporated by nu ⁇ leophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy
  • esters, amides and imides 25 esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate? thioether; xanthate; cyanide; cyanate; amino and mixtures thereof.
  • These functionalized isomonoolefin copolymers, tjieir method of preparation, methods of functionalization and cure are more particularly
  • Such copolymers of isobutylene and p-methylstyrene are those containing from 0.5 to 20 mole % p-methylstyrene wherein up to 60 roole% of the methyl substituent groups present on the benzyl 5 ring contain a bromine or chlorine atom, preferably a bromine atom (p-bromomethylstyrene) , as well as acid or ester functionalized versions thereof wherein the halogen atom has been displaced by iualeic anhydride or by acrylic or methacrylic acid functionality.
  • These interpolymers are those containing from 0.5 to 20 mole % p-methylstyrene wherein up to 60 roole% of the methyl substituent groups present on the benzyl 5 ring contain a bromine or chlorine atom, preferably a bromine atom (p-bromomethylstyrene) , as well as acid or ester functionalized versions thereof wherein the halogen
  • halogenated poly(isobutylene- ⁇ o-p- methylstyrene) or “brominated poly (isobutylene-co-p- methylstyrene) ", and are commercially available under the name EXXPROTM Elastomers (ExxonMobil Chemical Company, Houston TX) . It is understood that the use of the terms
  • halogenated or brominated are not limited to the method of halogenation of the copolymer, but merely descriptive of the copolymer which comprises the isobutylene derived units, the p-methylstyrene derived units, and the p-halomethylstyrene derived units.
  • These functional!zed polymers preferably have a substantially homogeneous compositional distribution such that at least 95% by weight of the polymer has a p- alkylstyrene content within 10% of the average p- alkylstyrene content of the polymer as measured by gel
  • More preferred polymers are also characterized by a narrow molecular weight distribution (Mw/Mn) of less than 5, more preferably less than 2.5, a preferred viscosity average molecular weight in the range
  • 35 methylstyrene) polymers are brominated polymers which generally contain from about 0.1 to about 5% by weight of bromomethyl groups.
  • the interpolymer is a copolymer of C ⁇ to C 7 isomonoolefin derived units, p- iuethylstyrene derived units and p-halomethylstyrene
  • the p-halomethylstyrene units are present in the interpolymer from about 0.4 to about 1 mole% based on the interpolymer.
  • the p-halomethylstyrene is p-bromomethylstyrene.
  • the Mooney Viscosity (MLi +8 , 125°C, ASTM D1646) is about 30 to
  • A is the molar ratio of p-alkylstyrene to isoolefin in the copolymer and,
  • F is the p-alkylstyrene-isool ⁇ fin-p- 30 alkylstyrene triad fraction in the copolymer. .
  • m is from 35 less than 38; alternatively, from less than 36; alternatively, from less than 35; and alternatively, from less than 30. In other embodiments, m is from 1-38; 16
  • the isoolefin/para- alkylstyrene copolymer is substantially free of long chain branching.
  • a polymer that is substantially free of long chain branching is defined to be a polymer for which Cf'vis.avg.
  • 10 is determined to be greater than or equal to 0.978, alternatively, greater than or equal to 0.980, alternatively, greater than or equal to 0.985, alternatively, greater than or equal to 0.990, alternatively, greater than or equal to 0.995,
  • F is the isoolefin-multiolefin-multiolefin triad fraction in the copolymer.
  • m is from greater than 1.5; 5 alternatively, from greater than 2.0; alternatively, from greater than. 2.5; alternatively, from greater than 3.0; and alternatively, from greater than 3.5. In other embodiments, m is from 1.10 to 1.25; alternatively, from 1.15 to 1.20; alternatively, from 1.15 to 1.25; and
  • m is about 1.20.
  • Halogenated rubbers that have these characteristics are disclosed in WO 2004- 058825 and WO 2004-058835.
  • the halogenated rubber is substantially free of long chain branching.
  • a polymer that is substantially free of long chain branching is defined to be a polymer for which g'vis.avg. is determined to be greater than or equal to 0.978, alternatively, greater than or equal to 0.980, alternatively/ greater than or
  • triple detection SEC 25 presence or absence of long chain branching in the polymers is determined using triple detection SEC.
  • Triple detection SEC is performed on a Waters (Milford, Massachusetts) 150C chromatograph operated at 4O 0 C equipped a Precision Detectors (Bellingham,
  • Viscotek Houston, Texas
  • Model 150R viscometry detector and a Waters differential refractive index detector (integral with the 150C) .
  • the detectors are connected in series with the light scattering detector being first,
  • Linear polyisobutylene is used to establish the relationship between the intrinsic viscosity [ ⁇ hinea r determined by the 10 viscometry detector) and the molecular weight (M w , determined by the light scattering detector) , The relationship between [ ⁇ u rt ear and M w is expressed, by the Mark-Houwink equation.
  • g' is defined to be less than or equal to one and greater than or equal to zero.
  • g 1 is equal or nearly equal to one, the polymer is considered to be linear.
  • g 1 is significantly less than one, the sample is long chain branched. See e.g. E. F. Casassa
  • a g' is calculated for each data slice of the chromatographic curve.
  • a viscosity average g' or g'vis.avg, i ⁇ calculated 5 across the entire molecular weight distribution.
  • the scaling factor g'vis.avg. is calculated from the average intrinsic viscosity of the sample:
  • g'vis.avg. [ ⁇ ]avg. / (KM/) .
  • halogenated elastomers or rubbers include halogenated isobutylene-p-methylstyrene ⁇ isoprene copolymer as described in WO 01/21672A1.
  • Preferred blends of the present invention typically include
  • a functionalized polymer having one or more functional groups
  • functionalized polymer is meant that the polymer is contacted with a functional group, and, optionally, a catalyst, heat, initiator, and/or free
  • the functlocalized polymer useful in the present invention comprises the contact
  • “functionalized polymer” is also defined to include polymer directly polymerized from monomers comprising olefin monomers and a monomer containing a functional group, (or using initiators having a functional group) to produce a polymer having a
  • maleated polymer i$ meant a polymer 20
  • maleic acid or malei ⁇ anhydride which has been contacted! with maleic acid or malei ⁇ anhydride, and / optionally, a catalyst, heat, initiator, and/or free radical source, to cause all or part of the maleic acid or maleic anhydride to incorporate, graft, 5 bond to, physically attach to, and/or chemically attach to the polymer.
  • “functional group” is meant any compound with a weight average molecular weight of 1000 g/mol or less that contains a heteroatom and or an unsaturation.
  • Preferred functional groups include any compound with a weight average molecular weight of 750 or less, that contain one or more a hetero atoms and or one or more sites of unsaturation.
  • the functional group is a compound containing a heteroatom and an
  • Preferred functional groups include organic acids and salts thereof, organic amides, organic iiaid.es, organic amines, organic esters, organic anhydrides, organic alcohols, organic acid halides (such as acid chlorides,
  • Examples of preferred functional groups useful in this invention include compounds comprising a carbonyl bond such as carboxylic acids, esters of carboxylic
  • Aromatic vinyl compounds, hydrolyzable unsaturated silane compounds, saturated halogenated hydrocarbons, and unsaturated halogenated hydrocarbons may also be used.
  • Examples of particularly preferred functional groups useful in this invention include, but are not limited, to maleic anhydride, citraconic anhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride, 2 , 3-dimethyl ⁇ aleic anhydride, bicyclo[2,2,l]-5-heptene-2,3-dicarboxylic
  • the polymer is grafted with maleic anhydride so the maleie anhydride covalently bonded to the backbone polymer chain of the polymer.
  • the anhydride functionality grafted onto the polymsr may
  • the functionalized polymer may be produced in a solution or a slurry process (i.e., with a solvent), or in a melt
  • the functionalized polymer may also be prepared in a high shear mixer, a fluidized bed reactor, and/or the like.
  • the polymer is combined with a free radical initiator and a grafting monomer at a
  • the functionalized polymer may be obtained by heating the polymer and a radical polymerizable functional group
  • Useful radical initiator catalysts include:, diacyl peroxides, peroxy esters, peroxy .ketals, dialkyl 5 peroxides, and the like. Specific examples include benzoyl peroxide, methyl ethyl ketone peroxide, tert- butyl peroxy benzoate, tert-butylperoxy acetate, 00-tert- butyl-Q- ⁇ 2 ⁇ ethylhexyl)-nonoperoxy carbonate, n-butyl 4,4- di ⁇ (tert-butyl peroxy) valerate, 1,1-bis (tert-
  • the functionalization is conducted at a temperature above the melting point of the polymer but below the decomposition temperature of the initiator.
  • Useful temperature ranges include from 35" C to 350° C, preferably from 40° C to 250° C, preferably from 45° C to
  • the radical initiator catalyst is preferably used in a ratio of from 0.00001 to 100% by weight, more 30 preferably from 0.1 to 10% by weight, based on the weight of the functional group.
  • the heating temperature depends upon whether or not the reaction is carried out in the presence of a solvent, but it is usually from about 50 0 C to 350 ⁇ C. 35 In the solvent based process, the reaction may be carried out using the polymer in the form of a solution 23
  • Preferred solvents include hexane and cyclohexane.
  • the functionalised polymer comprises roaleic anhydride at less than about 50% by weight, preferably less than about 45% by weight, preferably less than about 40% by weight, preferably less than about 35% by weight, preferably less than about 30% by weight,
  • maleic anhydride 25 weight, preferably less than about 6% by weight, preferably less than about 5% by weight, preferably less than about 4% by weight, preferably less than about 3% by weight, preferably less than about 2% by weight maleic anhydride. Also preferably the level of maleic anhydride
  • the functionalized polymer may comprise 0.1 to about 10% by weight of the
  • 35 maleic anhydride more preferably 0.25 to about 5% by weight more preferably 0.5 to 4% by weight, more preferably 0.75 to 3.5% by weight, more preferably 1.5 to 24
  • the functional group content of the grafted polymer may be determined by Fourier Transformed Infrared spectroscopy based on a calibration with standards whose 5 absolute functional group content has been determined.
  • the maleic anhydride content of the grafted polymer may be determined by Fourrier Transformed Infrared spectroscopy based on a calibration with standards whose absolute maleic anhydride content has
  • ethylene polymers and propylene polymers include ethylene polymers and propylene polymers.
  • Particularly preferred polymers include polymers of ethylene copolymerized with one or more of propylene, butene, pentene, hexane, heptene, octane, nonene-dece ⁇ e, undecene, dodecene, methyl acrylate, ethyl acry.late,
  • Such ethylene polymers are modified with maleic acid or maleic anhydride.
  • Another class of particularly preferred polymers include polymers of propylene copolymerized with one or more of ethylene, butene, 5 pentene, hexane, heptene, octane, nonene-decene, undecene, dodecene, methyl acrylate, ethyl acrylate, ' butyl acrylate, pentyl acrylate, hexyl acrylate, o ⁇ tyl acrylate, acrylic acid, methacrylic acid, ethacrylic acid, but acrylic acid, or vinyl acetate.
  • propylene polymers are modified with maleic acid or maleic anhydride.
  • Another class of particularly preferred polymers include polymers of a C 4 to C 7 isoolefin (such as . isobutylene) copolymerized with one or more of isoprene,
  • isobutylene Preferably such isobutylene polymers are modified with maleic acid or maleic anhydride.
  • Particularly preferred functionalized polymer include maleated copolymers of isobutylene and isoprene, maleated copolymers of isobutylene and paramethylstyrne, maleated
  • thermoplastic polyamides comprising crystalline or resinous, high molecular weight solid polymers including copolymers and terpolymers having recurring amide units within the polymer chain.
  • Polyamides may be prepared by polymerization of one or
  • epsilon lactams such as caprolactam, pyrrolidione, lauryllactam and aminoundecanoic lactam, or amino acid, or by condensation of dibasic acids and diamines.
  • epsilon lactams such as caprolactam, pyrrolidione, lauryllactam and aminoundecanoic lactam, or amino acid, or by condensation of dibasic acids and diamines.
  • fiber-forming and molding grade nylons are suitable.
  • polyamides are polycaprolactam
  • polyhexamethylenesebacamide Nylon 610
  • polyhexamethyleneisophthalamide Nylon 6IP
  • Nylon 46 Nylon MXD6, Nylon 6/66
  • the condensation product of 11-aminoundecanoi ⁇ acid Nylon 11
  • Nylon 610 (N610) Nylon 46, Nylon MXD6, Nylon 69 and Nylon 612 (N612) may also be used.
  • the copolymers thereof any blends thereof may also be used- Additional examples of satisfactory polyamides (especially those
  • thermoplastic polyamides may be advantageously
  • linear crystalline polyamides having a softening point or melting point between 160 0 C - 230 0 C being preferred.
  • the amounts of the first rubber component and the polyamide matrix usable in the present invention are the same.
  • thermoplastic elastomer The method for producing the thermoplastic elastomer
  • composition in the present invention typically comprises mixing the first rubber component, the polyamide and the optional dispersion aid by a biaxial kneader/extruder etc. to disperse the rubber in the polyamide forming the continuous phase.
  • a vulcanization agent When vulcanizing the rubber, a vulcanization agent can be added, while mixing, and the rubber component is dynamically vulcanized. Further, the various compounding agents (except vulcanization agent) for the rubber and the polyamide may be added during the above kneading, but
  • the kneader used for mixing the polyamide and the rubber is not particularly limited. Examples thereof are a screw 27
  • thermoplastic polyamide resin e.g., polyethylene glycol dimethacrylate copolymer
  • kneader e.g., polyethylene glycol dimethacrylate copolymer
  • Banbury mixer e.g., polypropylene glycol
  • biaxial kneader/e ⁇ truder for the mixing of the thermoplastic polyamide resin and the rubber and the 5 dynamic vulcanization of the rubber.
  • two or more types of kneaders may be used for successive . kneading.
  • the temperature should be at least the temperature where the polyamide melts. Further, the
  • 10 shear rate at the time of kneading is preferably 1000 to 7500 sec "1 .
  • the time for the overall kneading is from 30 seconds to 10 minutes.
  • the vulcanization time after addition is preferably 30 seconds to 5 minutes.
  • the 15 elastomer composition produced by the above method is then extruded or calendered into a film.
  • the method of forming the film may be a usual method of forming a film from a thermoplastic resin or thermoplastic elastomer..
  • a vulcanization or cross-linking agent may contain, in addition to the above-mentioned essential ingredients, a vulcanization or cross-linking agent, a vulcanization or cross-linking accelerator, various types of oils, an antiaging agent, reinforcing agent, plasticizer, softening agent, or other various
  • additives generally mixed into general rubbers.
  • the compounds are mixed and vulcanized by general methods to make the composition which may then be used for vulcanization or cross-linking.
  • the amounts of these additives added may be made the amounts generally added
  • compatibilizers include ethylenically unsaturated nitrile-conjugated diene-based high saturation copolymer 28
  • HNBR epoxylated natural rubbers
  • EMR epoxylated natural rubbers
  • NBR hydrin rubbers
  • acryl rubbers and mixtures thereof Compatibilizers are thought to function by modifying, in particular reducing, the surface tension between the ' 5 rubber and resin components.
  • Other compatibilizers include copolymers such as tho$e having the structure of both or one of the polyamide and rubber polymer or a structure of a copolymer having an epoxy group, carbonyl group, halogen group, amine group, maleated group,
  • oxazoline group capable of reacting with the polyamide or rubber polymer.
  • useful copolymers typically include, e.g., a styrene/ethylene-butylene/styrene block
  • 20 is not particularly limited, but, when used, typically is about 0.5 to about 10 parts by weight, based upon 100 parts by weight of the polymer component, in other words, the total of the polyamide and rubber polymer.
  • the terms "cured,” “vulcanized,” or “crosslinked” refer to the chemical reaction comprising forming bonds as, for example, during chain extension, or crosslinks between polymer chains comprising the polymer or elastomer to the extent that the elastomer undergoing
  • a tire comprising an innerliner layer composition based on 29
  • the present invention is sufficiently cured when the tire of which it is a component passes the necessary product specification tests during and after manufacturing and performs satisfactorily when used on a vehicle. 5 Furthermore, the composition is satisfactorily, sufficiently or substantially cured, vulcanized or crosslinked when the tire can be put to use even if additional curing time could produce additional crosslinks.
  • polymer compositions e.g., those used to produce tires, are crosslinked in the finished tire product.
  • Crosslinking or vulcanization is accomplished by incorporation of curing agents and/or accelerators; the overall mixture of such agents being typically referred to
  • Curing agents include those components described above that facilitate or influence the cure of elastomers, and generally include metals, metal oxides, accelerators, sulfur, peroxides, and other agents common in
  • Crosslinking or curing agents include at least one of, e.g., sulfur, zinc oxide, and fatty acids and mixtures thereof. Peroxide- containing cure systems may also be used. Generally, polymer compositions may be crosslinked by adding curative
  • agents for example sulfur, metal oxides (i.e., zinc oxide, ZnO), organometallic compounds, radical initiators, etc. and heating the composition or mixture.
  • the polyamide i.e. the polyamide
  • at least one vulcanizable rubber are mixed under conditions of high shear and elevated temperature in the presence of a curing agent or curing system for the rubber (s).
  • the rubber is 5 simultaneously crosslinked and dispersed as particles, preferably in the form of a microgel, within the polyamide which forms a continuous matrix.
  • the resulting composition is known in the art as a ' "dynamically vulcanized alloy" or DVA.
  • dynamically vulcanized alloy or DVA.
  • 10 vulcanization is effected by mixing the ingredients at a .temperature which is at or above the curing temperature of the rubber, and at or above the melting temperature of the polyamide, using equipment such as roll mills, Banbury®- mixers, continuous mixers, kneaders, or mixing
  • the unique characteristic of the dynamically vulcanized or cured composition is that, notwithstanding the fact that the rubber is cured the composition can be processed and reprocessed by conventional thermoplastic processing
  • vulcanizable components in a composition comprising at least one vulcanizable rubber, elastomer or polymer and at least one polymer or resin not vulcanizable using the vulcanizing agent (s) for the at least one vulcanizable component.
  • a composition comprising at least one vulcanizable rubber, elastomer or polymer and at least one polymer or resin not vulcanizable using the vulcanizing agent (s) for the at least one vulcanizable component.
  • accelerators for the vulcanization of elastomer compositions To the curative agent (s) there are often added accelerators for the vulcanization of elastomer compositions.
  • the curing agent (s), with or without the use 5 of at least one accelerator, is often referred to in the art as a curing "system” for the elastomer (s) .
  • a cure system is used because typically more than one curing agent is employed for beneficial effects, particularly where a mixture of high diene rubber and a less reactive ' elastomer
  • the rubber (s) and cure system can be combined by means known to those skilled in the art r e.g., on a two-roll mill, Banbury mixer or mixing extruder. .
  • a sample of the mixture often
  • the accelerated compound 25 can be cured under static conditions, such as in the form of a thin sheet using a mold that is subjected to heat and pressure in a press. Samples of the accelerated compound, cured as thin, pads for progressively longer times and/or at higher . .
  • the degree of cure it is preferable to dynamically vulcanize the first or preceding stage rubber (s) added to the dynamically vulcanizable mixture to the extent that the degree of cure of such rubber ⁇ &) is selected from the 5 group consisting of about 50%, for example, about 60 % to greater than about 95 %; about 65 % to about 95 %; about 70 % to about 95 %; about 75 % to greater than about , 90 %; about 80 % to about 90 %; in a time period less than or substantially equivalent to about the residence
  • a fluid ⁇ air or liquid retention barrier such as a innerliner for a tire.
  • a state of cure can be referred to as “substantially fully cured.”
  • the rubber component 25 less than the maximum state of cure of which the rubber is capable so that the flexibility, as measured, for example, by Young*s modulus, of the rubber component is at a suitable level for the end-use to which the composition is to be put, e.g., a tire innerliner or hose
  • the state of cure of the rubber (s) used in the composition may be less than or equal to about 95% of the maximum degree of cure of which they a ⁇ :e capable, as described above.
  • any conventional curative 33 for purposes of dynamic vulcanization in the presence of an engineering resin to form, for example, a highly impermeable layer or film, any conventional curative 33
  • a system which is capable of vulcanizing saturated or unsaturated halogenated polymers may be used to vulcanize at least the elastomeric halogenated copolymer of a Cj to C 7 isomonoolefin and a para-alkylstyrene, except that 5 peroxide curatives are specifically excluded from the practice of this invention when there is present one or more thermoplastic engineering resins such that peroxide would cause such resins themselves to crosslink. In that circumstance, if the polyamide would itself vulcanize or
  • Suitable curative systems for the elastomeric halogenated copolymer component of the present invention include zinc oxide in combination with zinc stearate or stearic acid and, optionally, one
  • accelerators or vulcanizing agents Permalux (the di-ortho-tolylguanidine salt of dicatechol borate) ; HVA-2 (m-phenylene bis inaleimide) ; Zisnet (2,4, 6-trimercapto-5-triazine) ; ZDBDC (zinc diethyl dithiocarbamate) and also including for the following accelerators or vulcanizing agents: Permalux (the di-ortho-tolylguanidine salt of dicatechol borate) ; HVA-2 (m-phenylene bis inaleimide) ; Zisnet (2,4, 6-trimercapto-5-triazine) ; ZDBDC (zinc diethyl dithiocarbamate) and also including for the following accelerators or vulcanizing agents: Permalux (the di-ortho-tolylguanidine salt of dicatechol borate) ; HVA-2 (m-phenylene bis inaleimide) ; Zisnet (2,4, 6-
  • phenylene diamine 25 phenylene diamine
  • salicylic acid ortho-hydroxy benzoic acid
  • wood rosin abietic acid
  • TMTDS tetramethyl thiuram disulfide
  • Curative accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfanamides,
  • Acceleration of the cure process may be accomplished by adding to the composition an amount of the accelerant.
  • the mechanism for accelerated vulcanization of rubber involves complex interactions between the curative, accelerator,
  • Suitable accelerators include, but are not limited to, the following: stearic acid, diphenyl guanidine (DPG), tetramethylthiuram 5 disulfide (TMTD), 4 , 4 ' -dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2,2 f -benzothiazyl disulfide (MBTS), hexamethylene-1, 6-bisthiosulfate disodium salt dihydrate, 2- (morpho ⁇ inothio) benzothiazole (MBS or MOR), compositions of 90% MOR and 10% MBTS (MOR 90) ,
  • N-tertiarybutyl-2-benzothiazole sulfenamide (TBBS)
  • TBBS N-tertiarybutyl-2-benzothiazole sulfenamide
  • OTOS N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide
  • ZH zinc 2-ethyl hexanoate
  • N, N'-diethyl thiourea N-diethyl thiourea.
  • crosslinkable polymers are well-known in. the art.
  • the cure system can be dispersed in a suitable concentration into the desired portion of the rubber component, the rubber component optionally containing one or more filler, extender and/or plasticizer by, e.g., mixing the rubber and
  • the cure system components in a step prior to addition of the rubber-containing composition to the thermoplastic using any mixing equipment commonly used in the rubber industry for such purpose, e.g., a two-roll rubber mill, a Banbury mixex, a mixing extruder and the like.
  • any mixing equipment commonly used in the rubber industry for such purpose e.g., a two-roll rubber mill, a Banbury mixex, a mixing extruder and the like.
  • the rubber composition 25 is commonly referred to as "accelerating" the rubber composition.
  • the rubber composition can be accelerated in a stage of a mixing extruder prior to carrying out dynamic vulcanization. It is particularly preferred that the cure system be dispersed in the rubber
  • thermoplastic resin (s) in the mixing equipment in which it is intended to carry out dynamic
  • At least one curing agent is typically present at about 0.1 to about 35
  • curatives, cure modifiers and 5 accelerators can be illustrated as follows:
  • a general rubber vulcanization agent e.g., a sulfur vulcanization agent, powdered sulfur, precipitated sulfur, high dispersion sulfur, surface-treated sulfur, insoluble sulfur, dimorpholinedisulfide, alkylphenoldisulfide, and ⁇ O mixtures thereof are useful.
  • Such compounds may be used ⁇ in an amount of about 0.5 phr to about 4 phr.
  • the use of such a material is feasible in view of other polymer and resin components present an organic peroxide vulcanization agent,
  • phenol resin vulcanization agents such as a bromide of an alkylphenol resin or a mixed crosslinking agent system containing stannous chloride, chloroprene, or another halogen donor and an alkylphenol resin and mixtures
  • Such agents can be used at a level of about 1 phr to about 20 phr.
  • other useful curing agents, cure modifiers and useful levels include zinc oxide and/or zinc stearate (about 0.05 phr to about 5 phr), stearic acid (about 0.1 phr to about 5 phr),
  • magnesium oxide about 0.5 phr to about 4 phr
  • lyserge 10 to 20 phr or so
  • p-quinonedioxime about diber.2oylquinonedioxime
  • tetrachloro-p-benzoquinone poly-p-dinitrosobenzene
  • poly-p-dinitrosobenzene about 0.5 phr to about 10 phr
  • methylenedianiline about 0.05 phr to about 10 phr
  • a vulcanization accelerator may be added in combination with the vulcanization agent, including for 36
  • composition described herein may also have one or more filler components such as calcium carbonate, clay, mica, silica and silicates, talc, titanium dioxide, starch and other organic fillers such as wood flour, and
  • Suitable filler materials include carbon black such as channel black, furnace black, thermal black, acetylene black, lamp black, modified carbon black such as silica treated or silica coated carbon black ⁇ described, for example, in U.S. Patent No. 5,916,934,
  • the filler may also include other reinforcing or non-reinforcing materials such as silica, clay, calcium carbonate, talc, titanium dioxide and the like.
  • the filler may be present
  • Exfoliated, intercalated, or dispersed clays may also be present in the composition. These clays, also referred to as “nanoclays”, are well known, and their
  • materials suitable for the purposes of the present invention include natural or synthetic phyllosilicates, particularly smectic clays such as montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite,
  • These layered clays generally comprise particles 37
  • a plurality of silicate platelets haying a thickness typically about 4 to about 2 ⁇ A in one embodiment, and about 8 to about 12A in another embodiment, bound together and containing exchangeable 5 cations such as Na + , Ca +2 , K + or Mg +2 present at the interlayer surfaces.
  • Layered clay may be intercalated and exfoliated by treatment with organic molecules (swelling agents) capable of undergoing ion exchange reactions with the
  • Suitable swelling agents include cationic surfactants such as, ammonium, alkylamines or alkylammonium (primary, secondary, tertiary and quaternary) , phosphonium or sulfonium derivatives of
  • Desirable amine compounds are those with the structure RiR 2 RsN, wherein R 1 , R 2 , and R 3 are C 1 to C 30 alkyls or alkenes which may be the same or different.
  • the exfoliating agent is a so-called long chain tertiary amine, wherein at least Ri is a C 12 to C 2 o alkyl or alkene.
  • Another class of swelling agents include those which can be covalently bonded to the interlayex surfaces.
  • the exfoliating or swelling agent is combined with a 38
  • the agent includes all primary, secondary and tertiary amines and phosphines; alfcyl and aryl sulfides and thiols; and their polyfunctional versions.
  • Desirable additives include: 5 long-chain tertiary amines such as N,N-dimethyl- octadecylamine, N,N-dioctadecyl ⁇ :methylamine, dihydrogenated tallowalkyl-raethylamine and the like, and amine-terminated polytetrahydrofuran; long-chain thiol and thiosulfate compounds such as hexamethylene sodium
  • thiosulfate 10 thiosulfate.
  • improved interpolymer impermeability is achieved by the use of polyfunctional curatives such as hexamethylene bis (sodium thiosulfate ⁇ and hexamethylene bis(cinnamaldehyde) .
  • the amount of exfoliated, intercalated, or dispersed clay incorporated in the composition in accordance with this invention is an amount sufficient to develop an improvement in the mechanical properties or barrier properties of the composition, e.g. tensile strength or
  • Amounts typically can be from about 0.5 to about 15% by weight in one embodiment, or about 1 to about 10% by weight in another embodiment, and about 1 to about 5% by weight in yet another embodiment, based on the polymer content of the composition.
  • the exfoliated, intercalated, or dispersed clay may be present at about 1 to about 30 phr in one embodiment, and about 3 to about 20 phr in another embodiment.
  • the exfoliating clay is an alkylamine-exfoliating clay.
  • process oil means both the petroleum derived process oils and synthetic plasticizers.
  • a process or plasticizer oil may be present in air barrier compositions. Such oils are primarily used to improve the processing of the
  • Suitable plasticizer oils include aliphatic acid esters or hydrocarbon plasticizer 39
  • oils such as paraffinic or naphthenic petroleum oils.
  • the preferred plasti ⁇ iser oil for use in standard, non-DVA, non-engineering resin-containing innerliner compositions is a paraffinic petroleum oil; suitable hydrocarbon plasticizer oils for use in such innerliners include oils having the following general characteristics.
  • the process oil may be selected from paraffinic oils,, aromatic oils, naphthenic oils, and polybutene oils.
  • Polybutene process oil is a low molecular weight (less than 15,000 Mn) homopolymer or copolymer of olefin-derived units having from about 3 to
  • the polybutene oil is a homopolymer or copolymer of a C 4 raffinate.
  • Low molecular weight "polybutene" polymers is described in, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL
  • polybutene processing oil 20 FLUIDS 357-392 (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999) (hereinafter "polybutene processing oil” or “polybutene”) .
  • useful examples of polybutene oils are the PARAPOLTM series of processing oils (previously available form ExxonMobil Chemical
  • polybutene processing oils are typically synthetic liquid polybutenes having a certain molecular weight, preferably from about 420 Mn to about 2700 Mn. 5
  • the molecular weight distribution -Mw/Mn- ( rt MWD") of • preferred polybutene oils is typically about from 1.8 to about 3, preferably about 2 to about 2.8.
  • the preferred density (g/ml) of useful polybutene processing oils varies from about 0,85 to about 0.91.
  • CG/G for preferred polybutene oils ranges from about 40 for the 450 Mn process oil, to about 8 for the 2700 Mn process oil.
  • Rubber process oils also have ASTM designations depending on whether they fall into the class of
  • process oil 15 paraffinic, naphthenic or aromatic hydrocarbonaceous process oils.
  • process oil utilized will be that customarily used in conjunction with a type of elastomer component and a rubber chemist of ordinary skill in the art will recognize which type of oil should
  • the oil is typically present at a level of 0 to about 25% by weight; preferably about 5 to 20% by weight of the total composition.
  • a thermoplastic elastomer composition For a thermoplastic elastomer composition
  • the oil may be present at a level of 0 to about 20% by weight of the total composition; preferably oil is not included in order to maximize impermeability of the composition.
  • plasticizers such as organic esters and
  • a particularly preferred plasticizer for use in a DVA composition is N-butylsulfonamide or other plasticizers suitable for polyamides.
  • rubber. process .oils such as naphthenic, aromatic or paraffinic extender oils
  • naphthenic, aliphatic, paraffinic and other aromatic oils are substantially absent from the 41
  • composition substantially absent, it is meant that naphthenic, aliphatic, paraffinic and other aromatic oils may be present, if at all / to an extent no greater than 2 phr in the composition.
  • the degree of cure of the vulcanized rubber can be described in terms of gel content, cross-link density, the amount of extractable components or it can be based on the state of cure that would be achieved in the rubber were it to be cured in the absence of the resin.
  • the halogenated elastomer achieve about 50 to about 85% of full cure based on the elastomer per se as measured, e.g., by tensile strength or using the oscillating disc cure meter test (ASTM D 2084, Standard Test Method for
  • thermoplastic elastomer composition obtained into a sheet, film, or tube using a T-sheeting die, straight or crosshead structure tubing die,
  • the composition as the air permeation preventive layer, e.g., an innerliner, of a pneumatic tire and as a component or layer of a hose, etc.
  • the thermoplastic e.g., an innerliner, of a pneumatic tire and as a component or layer of a hose, etc.
  • 25 elastomer compositions of the present invention may be taken up into strands once, pelletized, then molded by using a single-screw extruder that is typically used for resin.
  • the low permeability characteristics of the composition are suitable for uses with fluids other than gasses, e.g., liquids such as
  • vulcanized, high elastomer-content composition comprising at least one isobutylene-containing elastomer and at least one thermoplastic suitable for use, for example, in a pneumatic tire or hose, or as a tire innerliner,
  • this invention relates to:
  • a blend preferably dynamically vulcanized, comprising a first rubber component at least partially . vulcanized dispersed as particles having a size of 1
  • a weight average molecular weight greater than 20,000 preferably from 30,000 to 1,000,000, more preferably from 50,000 to 750,000, and comprises at least 0.1 to 25% by weight, preferably from 5 0.1 to 15% by weight, more preferably 0.5 to 10% by ⁇ weight, of a functional group, based upon the total weight of the second polymer component.
  • second polymer component different from the first rubber component is meant that the rubbers and
  • polymers comprise different molecular weights (by more than 20,000 Daltons, preferably by more than 30,000 Daltons) , different functional groups, different monomers . and or comonomers or if they have the same comonomer, then they have comonomer contents that are not within 2%
  • a BlMS copolymer having 3% by weight para-methyl styrene (PMS) and 5% by weight bromine is considered different from a BIMS copolymer having 11% by weight PMS and 5% by weight bromine.
  • first rubber component and the second polymer component differ in permeability, at 60 0 C
  • the first rubber component and the second polymer component differ in Tg spread.
  • the first rubber component has a Tg spread of greater than 20 0 C (preferably greater than 30 0 C, preferably
  • the second polymer component has a Tg spread of less than 20 0 C (preferably less than 15 0 C, as measured by DMTA run at 10 °C per minute at 1 hertz) .
  • Glass transition appears as a peak in the plot of loss 10 tangent as a function of temperature determined by running temperature-scan dynamic mechanical (DMTA) testing of a polymer.
  • the glass transition spread (also called Tg spread) is defined as the temperature spread from the onset of the glass transition to its ending. 15
  • the definitions of the onset and the ending of a glass transition are the intercepts of loss tangent base line to the line tangents of either the uphill glass transition peak slope or the downhill glass transition peak slope, respectively.
  • Nll-1 (Nylon 11) : Rilsan BMN O (Atochem) .
  • Nll-2 Rilsan BESN 0 TL (Atoch ⁇ O .
  • 30 N6/66-1 (Nylon 6/66 copolymer) : ⁇ be 5033B (Ube) .
  • N6/66-2 Nylon 6/66 copolymer: CM 6001FS (Toray) .
  • R3 Reactive softener 3, Exxelor 1840, maleated EO copolymer, Tg - -5O 0 C (ExxonMobil Chemical) .
  • Pl Plasticizer 1, BM4, N-butylsulfonamide
  • Sl Stabilizer package, includes Irganox (Ciba) ,
  • ExxproTM 89-4 brominated isobutylene p-methyl styrene copolymer, 0.75% Br, 5% PMS, (ExxonMobil Chemical)
  • G 1 storage shear modulus
  • Dispersion size (also called particle size) was determined based on the number average equivalent dispersion diameter in microns calculated from image processing the tapping phase AFM morphological images of
  • M50 at RT means 50% modulus measured at room temperature (RT) according to ASTM D412-92;
  • M50 at -20 0 C means 50% modulus measured at -20 0 C according to ASTM D412-92.
  • the blends of Examples 6 to 8 were prepared using a Brabender internal mixer at 220*C and 60 RPM.
  • the nylon was added first with BIMS added 1 minute after.
  • the additive was added 2 minutes after the nylon and the total mix time was 5 minutes.
  • plasticizer of either Pl or . P3 was added in all blends to lower the Nylon viscosity for incorporation of more rubbers.
  • Pl or . P3 plasticizer of either Pl or . P3 was added in all blends to lower the Nylon viscosity for incorporation of more rubbers.
  • Total rubber weight percent includes both the BIMS rubber and the reactive-compatilizable rubber softerner.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition d'élastomère thermoplastique comprenant un élastomère thermoplastique composé d'un premier composant de caoutchouc au moins en partie vulcanisé discrètement dispersé dans une matrice de polyamide et d'un second composant de caoutchouc, différent du premier composant de caoutchouc, présentant une température de transition vitreuse Tg inférieure ou égale à -30 °C.
PCT/US2006/011002 2006-03-24 2006-03-24 Composition d'elastomere thermoplastique presentant d'excellentes proprietes a basse temperature Ceased WO2007111584A1 (fr)

Priority Applications (1)

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PCT/US2006/011002 WO2007111584A1 (fr) 2006-03-24 2006-03-24 Composition d'elastomere thermoplastique presentant d'excellentes proprietes a basse temperature

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PCT/US2006/011002 WO2007111584A1 (fr) 2006-03-24 2006-03-24 Composition d'elastomere thermoplastique presentant d'excellentes proprietes a basse temperature

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WO2007111584A1 true WO2007111584A1 (fr) 2007-10-04

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Cited By (18)

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WO2009048472A1 (fr) * 2007-10-11 2009-04-16 Exxonmobil Chemical Patents Inc. Procédé de mélange efficace pour produire un élastomère thermoplastique
EP2123479A1 (fr) * 2008-05-21 2009-11-25 The Goodyear Tire & Rubber Company Pneu avec couche pare-air
CN101831094A (zh) * 2009-03-13 2010-09-15 横滨橡胶株式会社 热塑性弹性体组合物
US20120041108A1 (en) * 2008-12-17 2012-02-16 The Yokohama Rubber Co., Ltd. Stabilized dynamically vulcanized thermoplastic elastomer compositions useful in fluid barrier applications
US8299165B2 (en) 2011-02-24 2012-10-30 The Goodyear Tire & Rubber Company Pneumatic tire
JP2013502506A (ja) * 2009-08-27 2013-01-24 エクソンモービル・ケミカル・パテンツ・インク エラストマー組成物及びそれらの製品における使用
EP2574635A1 (fr) * 2011-09-28 2013-04-03 Lanxess Inc. Processus de production continue de compositions d'élastomère thermoplastique sans halogène
CN104169369A (zh) * 2012-03-13 2014-11-26 横滨橡胶株式会社 热塑性弹性体组合物
JP2015504931A (ja) * 2011-12-19 2015-02-16 エクソンモービル ケミカル パテンツ インコーポレイテッド エラストマー組成物及び物品におけるその使用
CN104513434A (zh) * 2014-11-27 2015-04-15 北京化工大学 一种丁基橡胶/长碳链聚酰胺热塑性硫化胶及其制备方法
EP3081394A1 (fr) 2015-04-16 2016-10-19 The Goodyear Tire & Rubber Company Pneu avec film intérieur multicouche épissé
EP3006531A4 (fr) * 2013-05-27 2017-01-04 Kolon Industries, Inc. Film de polymère
EP3196011A1 (fr) 2016-01-11 2017-07-26 The Goodyear Tire & Rubber Company Pneumatique avec film de calandrage intérieur multicouches sans collure
US9889703B2 (en) 2014-12-16 2018-02-13 The Goodyear Tire & Rubber Company Tire with spliced film innerliner
CN109666225A (zh) * 2018-12-25 2019-04-23 宁国市日格美橡塑制品有限公司 一种耐高温耐磨定制密封圈及其制备方法
CN109836709A (zh) * 2019-01-25 2019-06-04 上海交通大学 一种高气密性的溴化丁基橡胶尼龙热塑性弹性体及其制备
US10752806B2 (en) 2014-06-18 2020-08-25 Ppg Industries Ohio, Inc. Elastic gas barrier coating compositions
EP4174135A1 (fr) * 2021-10-27 2023-05-03 SHPP Global Technologies B.V. Polyamide renforcé par des fibres présentant une meilleure résistance pour des applications à basse température

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WO2004081116A1 (fr) * 2003-03-06 2004-09-23 Exxonmobil Chemical Patents, Inc. Film elastomere thermoplastique oriente et son procede de production
WO2004081107A1 (fr) * 2003-03-06 2004-09-23 Exxonmobil Chemical Patents, Inc. Procede de gestion de la taille de la dispersion d'un elastomere dans une composition elastomere thermoplastique
WO2004081099A1 (fr) * 2003-03-06 2004-09-23 Exxonmobil Chemical Patents, Inc. Composition elastomere thermoplastique comprenant des dispersions d'elastomere vulcanise a viscosite accrue

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WO1993006174A1 (fr) * 1991-09-19 1993-04-01 Exxon Chemical Patents Inc. Compositions thermoplastiques et leur procede de preparation
EP0857761A1 (fr) * 1996-05-29 1998-08-12 The Yokohama Rubber Co., Ltd. Pneumatique constitue d'une composition elastomere thermoplastique faiblement permeable comprise dans une couche barriere impermeable aux gaz, et composition elastomere thermoplastique utilisee dans un tel pneumatique
US20040031550A1 (en) * 2001-09-05 2004-02-19 Daisuke Kanenari Pneumatic tire having run flat capability
WO2004081116A1 (fr) * 2003-03-06 2004-09-23 Exxonmobil Chemical Patents, Inc. Film elastomere thermoplastique oriente et son procede de production
WO2004081107A1 (fr) * 2003-03-06 2004-09-23 Exxonmobil Chemical Patents, Inc. Procede de gestion de la taille de la dispersion d'un elastomere dans une composition elastomere thermoplastique
WO2004081099A1 (fr) * 2003-03-06 2004-09-23 Exxonmobil Chemical Patents, Inc. Composition elastomere thermoplastique comprenant des dispersions d'elastomere vulcanise a viscosite accrue

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009048472A1 (fr) * 2007-10-11 2009-04-16 Exxonmobil Chemical Patents Inc. Procédé de mélange efficace pour produire un élastomère thermoplastique
CN101821335B (zh) * 2007-10-11 2013-03-27 埃克森美孚化学专利公司 生产热塑性弹性体组合物的有效混合工艺
US8450396B2 (en) 2007-10-11 2013-05-28 Exxonmobil Chemical Patents Inc. Efficient mixing process for producing thermoplastic elastomer composition
EP2123479A1 (fr) * 2008-05-21 2009-11-25 The Goodyear Tire & Rubber Company Pneu avec couche pare-air
US20120041108A1 (en) * 2008-12-17 2012-02-16 The Yokohama Rubber Co., Ltd. Stabilized dynamically vulcanized thermoplastic elastomer compositions useful in fluid barrier applications
US9540510B2 (en) * 2008-12-17 2017-01-10 The Yokohama Rubber Co., Ltd Stabilized dynamically vulcanized thermoplastic elastomer compositions useful in fluid barrier applications
CN101831094A (zh) * 2009-03-13 2010-09-15 横滨橡胶株式会社 热塑性弹性体组合物
JP2013502506A (ja) * 2009-08-27 2013-01-24 エクソンモービル・ケミカル・パテンツ・インク エラストマー組成物及びそれらの製品における使用
US8299165B2 (en) 2011-02-24 2012-10-30 The Goodyear Tire & Rubber Company Pneumatic tire
US9371443B2 (en) 2011-09-28 2016-06-21 Arlanxeo Singapore Pte. Ltd. Process for continuous production of halogen-free thermoplastic elastomer compositions
EP2574635A1 (fr) * 2011-09-28 2013-04-03 Lanxess Inc. Processus de production continue de compositions d'élastomère thermoplastique sans halogène
EP2760919A4 (fr) * 2011-09-28 2015-10-07 Lanxess Butyl Pte Ltd Procédé pour la production en continu de compositions d'élastomère thermoplastique exemptes d'halogène
US9670348B2 (en) 2011-12-19 2017-06-06 Exxonmobil Chemical Patents Inc. Elastomeric compositions and their use in articles
JP2017048403A (ja) * 2011-12-19 2017-03-09 エクソンモービル ケミカル パテンツ インコーポレイテッド 動的加硫アロイ
JP2015504931A (ja) * 2011-12-19 2015-02-16 エクソンモービル ケミカル パテンツ インコーポレイテッド エラストマー組成物及び物品におけるその使用
CN104169369A (zh) * 2012-03-13 2014-11-26 横滨橡胶株式会社 热塑性弹性体组合物
US20150057414A1 (en) * 2012-03-13 2015-02-26 The Yokohama Rubber Co., Ltd. Thermoplastic elastomer composition
US10005891B2 (en) 2013-05-27 2018-06-26 Kolon Industries, Inc. Polymer films
EP3006531A4 (fr) * 2013-05-27 2017-01-04 Kolon Industries, Inc. Film de polymère
US10752806B2 (en) 2014-06-18 2020-08-25 Ppg Industries Ohio, Inc. Elastic gas barrier coating compositions
CN104513434A (zh) * 2014-11-27 2015-04-15 北京化工大学 一种丁基橡胶/长碳链聚酰胺热塑性硫化胶及其制备方法
US9889703B2 (en) 2014-12-16 2018-02-13 The Goodyear Tire & Rubber Company Tire with spliced film innerliner
EP3081394A1 (fr) 2015-04-16 2016-10-19 The Goodyear Tire & Rubber Company Pneu avec film intérieur multicouche épissé
EP3196011A1 (fr) 2016-01-11 2017-07-26 The Goodyear Tire & Rubber Company Pneumatique avec film de calandrage intérieur multicouches sans collure
US10160263B2 (en) 2016-01-11 2018-12-25 The Goodyear Tire & Rubber Company Tire with non-spliced multilayered film innerliner
CN109666225A (zh) * 2018-12-25 2019-04-23 宁国市日格美橡塑制品有限公司 一种耐高温耐磨定制密封圈及其制备方法
CN109836709A (zh) * 2019-01-25 2019-06-04 上海交通大学 一种高气密性的溴化丁基橡胶尼龙热塑性弹性体及其制备
EP4174135A1 (fr) * 2021-10-27 2023-05-03 SHPP Global Technologies B.V. Polyamide renforcé par des fibres présentant une meilleure résistance pour des applications à basse température
WO2023073579A1 (fr) * 2021-10-27 2023-05-04 Shpp Global Technologies B.V. Polyamide renforcé par des fibres présentant une ténacité améliorée pour des applications à basse température

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