CN100402597C - Elastomeric composition - Google Patents

Abstract

The present invention is a composition including an isobutylene-based copolymer and polybutene. The copolymers may be mixed with an exfoliating compound and clay, the entire composition forming a nanocomposite. The clay may or may not have an additional exfoliating treatment present prior to mixing with the interpolymer. The composition of the invention has improved air barrier properties and processing properties, and is suitable as an air barrier. One embodiment of the invention is an elastomeric composition including at least one random copolymer of at least a C4 to C7 isomonoolefin derived unit, at least one filler, and polybutene oil having a number average molecular weight greater than 400. The copolymer may be selected from a halogenated poly(isobutylene-co-p-methylstyrene), a halogenated star-branched butyl rubber, or a halogenated butyl rubber, and mixtures thereof.

Description

Elastic composition

Invention field

The present invention relates to comprise the low-permeability elastic composition of nanoclay, relate more particularly to a kind of isobutylene based copolymer of air retaining wall such as tire flap and composition of filler such as carbon black and clay and polybutene treated oil of forming.

Background of invention

Bromination butyl and chlorinated butyl rubber are for making tubeless tyre have the polymkeric substance that air retention (capacity) is selected.Similarly, when thermotolerance or another kind of key property outbalance, typically use iso-butylene-p-methylstyrene multipolymer (BIMS) as disclosed bromination in US5 162 445 and 5 698 640.Desired performance balance and application and end-use are depended in the selection of commercial elastomerics system component.For example, at tire industry, give birth in the tire plant processing characteristics of (unvulcanized) sizing material with respect to the use properties of vulcanized rubber tire matrix material, and tire be bias tyre with respect to radial and tyres for passenger cars with respect to truck tyre with respect to the character of plane tyre all be must balance important consideration.

Changing product property and improving bubble-tight a kind of method is to add clay to form " nano composite material " in elastomerics.Nano composite material is the polymeric system that comprises the inorganic particulate of at least one yardstick in nanometer range.Its some examples are disclosed among the US 6 060 549,6,103 817,6 034 164,5 973 053,5 936 023,5 883 173,5 807629,5 665 183,5 576 373 and 5 576 372.A class inorganic particulate commonly used in the nano composite material is phyllosilicate (phyllosilicate), and it is the inorganics from so-called " nanoclay " or " clay " class.Ideally, in nano composite material intercalation should take place, in the space or tunnel between the wherein said polymkeric substance insertion surface of clay.Finally, wish to have scaling off almost completely, wherein said polymkeric substance disperses fully with the clay platelet thing of each nanoscale.Owing to the resistance to air loss of various polymer compositions is strengthened, so wish to have the nano composite material of low air penetrability.

Make nano composite material with the iso-butylene of bromination and the multipolymer of p-methylstyrene.Referring to for example Elspass etc., US 5 807 629,5 883 173 and 6 034 164.Use processing aid can further improve the not sulfuration and the curability of these elastic compositions.Usable resins and oil (or " processing aid) improve the processing characteristics of elastomer glue stock as cycloparaffin series, paraffinic and aliphatic resin.Increase to cost but in the presence of oil and resin, improve processing characteristics with loss air penetrability and undesirable color, multiple other performance is also had undesirable influence.

Polybutene and paraffin wax type treated oil are disclosed among US4 279 284 (Spadone), US5 964 969 (Sandstrom etc.) and the EPO 314416 (Mohammed).The paraffin wax type treated oil is disclosed among the US5 631316 (Costemalle etc.).WO94/01295 (Gursky etc.) also discloses the application at the rubber combination that is used for the tire tyre sidewall of paraffin and cycloparaffin series's oil and resin, and Waddell etc. disclose colorable rubber combination at the U.S.S.N.09/691764 (having transferred transferee of the present invention) of application on October 18th, 2000.Other that comprises the elastomerics of treated oil or resin or binder composition openly comprises US 5 005625,5 013 793,5 162 409,5 178 702,5 234 987,5 234987,5 242 727,5 397 832,5 733 621,5 755 899, EP 0 682071A1, EP 0 376 558B1, WO92/16587 and JP11005874, JP05179068A and J03028244.These open all unresolved problems of when keeping or improving air penetrability, improving the processibility of the elastic composition that is used for tire, air retaining wall etc.

Therefore, obtain to be applicable to air retaining wall, particularly mix C ₄-C ₇Isomonoolefin and p-methylstyrene and the nano composite material of the air retaining wall of halogenated methyl styrol copolymer (or " terpolymer ") and/or halogenated side chain isoprene-isobutylene rubber still had problems.Though the barrier properties of elastic composition strengthens, it is cost that the formation nano composite material is tending towards with the loss processing characteristics.

And, in the blend of these multipolymers is arranged, mix natural rubber and also be a problem, because when adding natural rubber, lose some ideal performance.Even the elastic composition and the nanocomposite composition that need to keep desired air retaining wall quality but the processing characteristics of treated oil and the available improvement of resin is also arranged in the presence of the natural rubber blend.

Summary of the invention

Specific embodiments of the present invention comprises a kind of elastic composition, comprises at least a C of comprising ₄-C ₇The random copolymers of isomonoolefin derived units, at least a filler and number-average molecular weight are greater than 400 and at the polybutene oil of 100 ℃ of following viscosity greater than 35cSt.Described multipolymer be selected from iso-butylene-p-methylstyrene multipolymer, halogenated iso-butylene-p-methylstyrene multipolymer, halogenated star-branched isoprene-isobutylene rubber, halogenated butyl rubber, and composition thereof.Described composition can also comprise thermoplastic resin, filler and/or exfoliated clays.The thermoplastic resin that is suitable for comprises polyolefine, nylon and other polymkeric substance.Described filler be selected from lime carbonate, clay, mica, silicon oxide and silicate, talcum, titanium dioxide, starch and other organic filler such as wood powder (wood flower) and carbon black, and composition thereof.Described exfoliated clays be selected from exfoliate natural or synthetic polynite, nontronite, beidellite, volkonskoite, LAPONITE (laponite), hectorite, saponite, sauconite, magadiite (magadite), fibrous morphology crystals (kenyaite), rich magnesium montmorillonite (stevensite), vermiculite, halloysite, aluminate oxide compound, hydrotalcite, and composition thereof.These compositions are applicable to the liner of air retaining wall application as tire.

Detailed Description Of The Invention

Term " phr " is the umber of per hundred parts of rubber, is this area linear module commonly used, wherein based on 100 weight part elastomericss, with respect to the component of main elastomeric component set of measurements compound.

" family " of periodictable used herein adopts the new periodictable meter family scheme in HAWLEY ' S CONDENSEDCHEMICAL DICTIONARY 852 (the 13rd editions, 1997).

Term used herein " elastomerics " means any polymkeric substance or the polymer composition that meets ASTM D1566 definition.Term " elastomerics " can exchange with term " rubber " and use herein.

Elastomerics

The present composition comprises at least a elastomerics.Elastomerics described in the one embodiment of this invention is isobutenyl homopolymer or multipolymer.These polymkeric substance can be described as C ₄-C ₇The random copolymers of isomonoolefin derived units such as iso-butylene derived units and at least a other polymerized unit.Described isobutylene based copolymer can be halogenation or not halogenated.

In the one embodiment of this invention, described isobutylene-based elastomer is the butyl-type rubber of butyl-type rubber or branching, especially these elastomeric halogenated form.The elastomerics that is suitable for is the homopolymer of undersaturated isoprene-isobutylene rubber such as alkene or isoolefine and polyene hydrocarbon and the homopolymer of multipolymer or polyene hydrocarbon.The elastomerics that is applicable to these and other type of the present invention is known, and (Maurice Morton edits, Chapman ﹠amp to be described in RUBBER TECHNOLOGY 209-581; Hall 1995), (Robert F.Ohm edits THE VANDERBILT RUBBER HANDBOOK 105-122, R.T.Vanderbilt Co., Inc.1990) and Edward Kresge and H.C.Wang, 8 KIRK-OTHMER ENCYCLOPEDIA OF CHEMICALTECHNOLOGY 934-955 (John Wiley ﹠amp; Sons, Inc., the 4th edition, 1993) in.The limiting examples that is applicable to the unsaturated elastic body of the inventive method and composition be isobutylene-isoprene copolymer, polyisoprene, polyhutadiene, polyisobutene, styrene-butadiene copolymer, natural rubber, star-branched isoprene-isobutylene rubber, and composition thereof.Be applicable to that elastomerics of the present invention can the invention is not restricted to described elastomerics production method herein by any appropriate methodology preparation known in the art.

Isoprene-isobutylene rubber is by the monomer mixture prepared in reaction, and described mixture has (1) C at least ₄-C ₁₂Isoolefine monomer component such as iso-butylene and (2) multi-olefin monomer component.Isoolefine described in one embodiment in the scope of 70 to 99.5% (weights) of total monomer mixture, in another embodiment in the scope of 85 to 99.5% (weights).The amount of polyene hydrocarbon component described in one embodiment in described monomer mixture is 30 to 0.5% (weights), is 15 to 0.5% (weights) in another embodiment.In another embodiment, 8 to 0.5% of described monomer mixture is a polyene hydrocarbon again.

Described isoolefine is C ₄-C ₁₂Compound, its limiting examples are such as compounds such as iso-butylene, (isobutylene), iso-butylene (isobutene), 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butylene, 2-butylene, methylvinylether, indenes, vinyl trimethylsilane, hexene and 4-methyl-1-pentenes.Described polyene hydrocarbon is C ₄-C ₁₄Polyene hydrocarbon such as isoprene, divinyl, 2,3-dimethyl-1,3-divinyl, myrcene, 6, disclosed other monomer in 6-dimethyl-fulvene, hexadiene, cyclopentadiene and piperylene and EPO279 456 and US5 506 316 and 5 162 425.Other polymerisable monomer such as vinylbenzene and dichlorostyrene also are applicable to the homopolymerization or the copolymerization of isoprene-isobutylene rubber.One of butyl rubber polymer of the present invention embodiment obtains by 0.5 to 5.0% (weight) isoprene reaction in 95 to 99.5% (weight) iso-butylenes and 0.5 to 8% (weight) or another embodiment.Isoprene-isobutylene rubber and production method thereof for example are described in detail among the US2 356 128,3,968 076,4 474 924,4 068 051 and 5 532 312.

One of ideal isoprene-isobutylene rubber commodity example is EXXON ^TMThe isobutylene-isoprene copolymer of BUTYL Grades, its mooney viscosity are 32 ± 2 to 51 ± 5 (ML 1+8 is under 125 ℃).Another example of ideal butyl-type rubber commodity is VISTANEX ^TMPolyisobutylene rubber, its viscosity-average molecular weight are 0.9 ± 0.15 to 2.11 ± 0.23 * 10 ⁶

Another embodiment that is applicable to isoprene-isobutylene rubber of the present invention is the isoprene-isobutylene rubber of branching or " star-branched ".These rubber for example are described among EP 0 678 529B1, the US5 182333 and 5 071 913.In one embodiment, described star-branched isoprene-isobutylene rubber (" SBB ") is the composition of isoprene-isobutylene rubber (halogenation or not halogenated) and polydiene or segmented copolymer (halogenation or not halogenated).The present invention is not limited by described SBB formation method.Described polydiene/segmented copolymer or branching agent (hereinafter " polydiene ") generally are cation activities, are present in the polymerization process of butyl or halogenated butyl rubber, perhaps can form described SBB with the isoprene-isobutylene rubber blend.Described branching agent or polydiene can be any suitable branching agents, the invention is not restricted to prepare the used polydiene type of SBB.

In one embodiment, described SBB is butyl or halogenated butyl rubber and polydiene and be selected from the composition of multipolymer of the partial hydrogenation polydiene of vinylbenzene, polyhutadiene, polyisoprene, poly-piperylene, natural rubber, styrene butadiene rubbers, ethylene-propylene-elastoprene (EPDM), ethylene-propylene rubber (EPM), styrene-butadiene-styrene and styrene isoprene styrene block copolymer (SIS) as mentioned above typically.The amount of these polydiene greater than 0.3% (weight), is 0.3 to 3% (weight) based on monomer % (weight) in another embodiment in one embodiment, is 0.4 to 2.7% (weight) again in another embodiment.

The commercial embodiment of one of SBB of the present invention is SB Butyl 4266 (ExxonMobil Chemical Company, Houston TX), and its mooney viscosity (ML1+8 under 125 ℃, ASTM D 1646) is 34 to 44.In addition, the vulcanization characteristics of SB Butyl 4266 is as follows: MH is 69 ± 6dN*m, and ML is 11.5 ± 4.5dN*m (ASTMD2084).

Be applicable to and also can make the halogenation of described isobutenyl rubber in the desirable embodiment of one of isobutylene based copolymer of the present invention.Halogenated butyl rubber is produced in halogenation by above-mentioned isoprene-isobutylene rubber product.Can carry out halogenation by any way, the present invention is not limited by described herein halogenation method.The halogenation method of polymkeric substance such as butyl polymer is disclosed in US2 631 984,3 099644,4 554 326,4 681 921,4 650 831,4 384 072,4 513 116 and 5 681 901.In one embodiment, in the hexane thinner, use bromine (Br down in 4 to 60 ℃ ₂) or chlorine (Cl ₂) make the isoprene-isobutylene rubber halogenation as halogenating agent.The mooney viscosity of halogenated butyl rubber described in one embodiment is 20 to 70 (ML 1+8 is under 125 ℃), is 25 to 55 in another embodiment.Halogen % (weight) is 0.1 to 10% (weight) based on the weight of halogenated butyl rubber in one embodiment, is 0.5 to 5% (weight) in another embodiment.In another embodiment, the halogen % (weight) of halogenated butyl rubber is 1 to 2.5% (weight) again.

The commercial embodiment of one of halogenated butyl rubber of the present invention is Bromobutyl2222 (ExxonMobil Chemical Company).Its mooney viscosity is 27 to 37 (ML1+8 is under 125 ℃, and ASTM 1646, remodeling), and bromine content is 1.8 to 2.2% (weights) with respect to described Bromobutyl2222.In addition, the vulcanization characteristics of Bromobutyl 2222 is as follows: MH is 28 to 40dN*m, and ML is 7 to 18dN*m (ASTM D2084).The commercial embodiment of another of described halogenated butyl rubber is Bromobutyl 2255 (ExxonMobilChemical Company).Its mooney viscosity is 41 to 51 (ML 1+8 is under 125 ℃, and ASTM 1646), and bromine content is 1.8 to 2.2% (weights).In addition, the vulcanization characteristics of Bromobutyl 2255 is as follows: MH is 34 to 48dN*m, and ML is 11 to 21dN*m (ASTMD2084).

In another embodiment of rubber bromide component of the present invention, use the halogenated butyl rubber of branching or " star-branched ".In one embodiment, described halogenated star-branched isoprene-isobutylene rubber (" HSSB ") is the composition of isoprene-isobutylene rubber (halogenation or not halogenated) and polydiene or segmented copolymer (halogenation or not halogenated).Described halogenation method is described in detail in US4 074035,5 071 913,5 286 804,5 182 333 and 6 228 978.The present invention is not limited by described HSSB formation method.Described polydiene/segmented copolymer or branching agent (hereinafter " polydiene ") generally are cation activities, are present in the polymerization process of butyl or halogenated butyl rubber, perhaps can form described HSSB with butyl or halogenated butyl rubber blend.Described branching agent or polydiene can be any suitable branching agents, the invention is not restricted to prepare the used polydiene type of HSSB.

In one embodiment, described HSSB is butyl or halogenated butyl rubber and polydiene and be selected from the composition of multipolymer of the partial hydrogenation polydiene of vinylbenzene, polyhutadiene, polyisoprene, poly-piperylene, natural rubber, styrene butadiene rubbers, ethylene-propylene-elastoprene, styrene-butadiene-styrene and styrene isoprene styrene block copolymer (SIS) as mentioned above typically.The amount of these polydiene greater than 0.3% (weight), is 0.3 to 3% (weight) based on monomer % (weight) in another embodiment in one embodiment, is 0.4 to 2.7% (weight) again in another embodiment.

The commercial embodiment of one of HSSB of the present invention is Bromobutyl6222 (ExxonMobil Chemical Company), (ML 1+8 is under 125 ℃ for its mooney viscosity, ASTM D1646) be 27 to 37, bromine content is 2.2 to 2.6% (weights) with respect to HSSB.In addition, the vulcanization characteristics of Bromobutyl 6222 is as follows: MH is 24 to 38dN*m, and ML is 6 to 16dN*m (ASTM D2084).

Another embodiment that is applicable to isobutylene-based elastomer of the present invention is the isoolefin copolymers that comprises halogenated methyl vinylbenzene derived units.Elastomerics described in the one embodiment of this invention is to comprise C at least ₄-C ₇The random copolymers of isoolefine derived units such as iso-butylene derived units and halogenated methyl vinylbenzene derived units.Described halogenated methyl styrene units can be adjacent-,-or the styrene units that replaces of right-alkyl.In one embodiment, described halogenated methyl vinylbenzene derived units be comprise at least 80%, more preferably at least 90% (weight) para-isomeride to halogenated methyl vinylbenzene.Described " halogen " can be any halogen, is desirably chlorine or bromine.Described halogenated elastomer can also comprise functionalized interpolymer, and at least some contain described other functional group of benzylic halogen or some back the alkyl substituent that exists in the wherein said styrene monomer unit.These interpolymers are called " isoolefin copolymers that comprises halogenated methyl vinylbenzene derived units " herein or abbreviate " isoolefin copolymers " as.

Described isoolefin copolymers can also comprise other monomer derived units.The isoolefine of described multipolymer can be C ₄-C ₁₂Compound, its limiting examples are such as compounds such as iso-butylene (isobutylene), iso-butylene (isobutene), 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butylene, 2-butylene, methylvinylether, indenes, vinyl trimethylsilane, hexene and 4-methyl-1-pentenes.Described multipolymer can also comprise the polyene hydrocarbon derived units.Described polyene hydrocarbon is C ₄-C ₁₄Polyene hydrocarbon such as isoprene, divinyl, 2,3-dimethyl-1,3-divinyl, myrcene, 6, disclosed other monomer among 6-dimethyl-fulvene, hexadiene, cyclopentadiene and piperylene and EPO 279 456 and the US5 506 316 and 5,162 425.The ideal styrene monomer derived units that described multipolymer can comprise comprises vinylbenzene, vinyl toluene, chloro-styrene, methoxy styrene, indenes and indene derivative and combination thereof.

In another embodiment of the present invention, described interpolymer is ethylene-derived units or C ₃-C ₆The random elastomeric copolymers of alpha-olefin derived unit and halogenated methyl vinylbenzene derived units (preferably contain at least 80%, more preferably at least 90% (weight) para-isomeride to halogenated methyl vinylbenzene), also comprise functionalized interpolymer, at least some contain benzylic halogen or some other functional group the alkyl substituent that exists in the wherein said styrene monomer unit.

Preferred isoolefin copolymers can be described as and contains along the polymer chain interpolymer of isolated following monomeric unit randomly:

Wherein R and R ¹Be hydrogen, low alkyl group (preferred C independently ₁-C ₇Alkyl) and uncle or secondary alkylogen, X is functional group such as halogen.The ideal halogen is chlorine, bromine or its combination.Preferred R and R ¹Be hydrogen.-CRR ₁H and-CRR ₁The X group can be adjacent, or contraposition (preferred contraposition) be substituted on the vinylbenzene ring.Cinnamic maximum 60% (moles) of the para-orientation that exists in the copolymer structure described in one embodiment can be above-mentioned functionalized structure (2), are 0.1 to 5% (mole) in another embodiment.In another embodiment, the amount of functionalized structure (2) is 0.4 to 1% (mole) again.

The described X of functional group can be that halogen maybe can be by the benzylic halogen by other group such as carboxylic acid; Carboxylate salt; Carboxylicesters, acid amides and imide; Hydroxyl; Alkoxide; Phenates; Thiolate; Thioether; Xanthogenate; Prussiate; Cyanate; Some other functional groups that amino and composition thereof nucleophilic substitution is mixed.These functionalized isomonoolefin copolymers, its preparation method, functionizing method and sulfuration are disclosed among the US5 162 445 in more detail.

This type of the most suitable functionalised materials is that iso-butylene and maximum 60% (moles) of containing the methyl substituents that exists on the wherein said benzyl ring of 0.5 to 20% (mole) p-methylstyrene contain bromine or chlorine atom, the preferred p-methylstyrene of bromine atoms (to brooethyl vinylbenzene); And wherein said halogen atom is by the elasticity random copolymer of maleic anhydride or metathetical acid of acrylic or methacrylic acid functional group or ester functional variant.These interpolymers are called " halogenated iso-butylene-p-methylstyrene multipolymer " or " iso-butylene of bromination-p-methylstyrene multipolymer ", can trade(brand)name EXXPRO ^TMElastomers (ExxonMobil Chemical Company, Houston TX) is purchased.Should understand and use term " halogenation " or " bromination " to be not limited to the halogenation method of described multipolymer, only explanation comprises iso-butylene derived units, p-methylstyrene derived units and to the multipolymer of halogenated methyl vinylbenzene derived units.

These functionalized polymerics preferably have basically form uniformly distribute so that at least 95% (weight) of described polymkeric substance have described polymkeric substance average to ring-alkylated styrenes content 10% with interior to ring-alkylated styrenes content.Preferred polymkeric substance also has following feature: be lower than 5, the narrow molecular weight distributions more preferably less than 2.5 (Mw/Mn), 200,000 to 2,000, preferred viscosity-average molecular weight in 000 scope, with the preferred number average molecular weight in 25,000 to 750,000 scopes by gel permeation chromatography.

Described multipolymer can prepare by the following method: make described monomer mixture slurry polymerization with lewis acid catalyst, halogenation in the presence of halogen and radical initiator such as heat and/or light and/or chemical initiator in solution then (preferred bromination), and make bromine alternatively by different sense derived units electrophilic substitution.

Preferred halogenated iso-butylene-p-methylstyrene multipolymer is the brominated polymer that generally contains 0.1 to 5% (weight) brooethyl.In another embodiment, the amount of brooethyl is 0.2 to 2.5% (weight) again.Expression in another way, preferred multipolymer contain 0.05 to 2.5% (mole) bromine (based on the weight of described polymkeric substance), more preferably 0.1 to 1.25% (mole) bromine, and are substantially free of nuclear halogen or the halogen in main polymer chain.In one of the present invention embodiment, described interpolymer is C ₄-C ₇Isomonoolefin derived units, p-methylstyrene derived units and to the multipolymer of halogenated methyl vinylbenzene derived units, the amount to the halogenated methyl styrene units in the wherein said interpolymer is 0.4 to 1% (mole) based on described interpolymer.In another embodiment, described is to brooethyl vinylbenzene to halogenated methyl vinylbenzene.Mooney viscosity (1+8,125 ℃, ASTM D1646, remodeling) is 30 to 60MU.

The elastomeric component that exists in the present composition can contain, two or multiple different elastomerics of different amounts.For example, the specific embodiments of the present composition can contain 5 to 100phr halogenated butyl rubbers, 5 to 95phr star-branched isoprene-isobutylene rubber, 5 to 95phr halogenated star-branched isoprene-isobutylene rubbers or 5 to 95phr halogenated iso-butylene-p-methylstyrene multipolymers.In another embodiment, described composition contains 40 to 100phr halogenated iso-butylene-p-methylstyrene multipolymers and/or 40 to 100phr halogenated star-branched isoprene-isobutylene rubbers (HSSB).Elastic composition of the present invention can contain other elastomerics or what is called " is assisted " elastomeric component.

The elastomer-assisted component

Can there be the elastomer-assisted component in the present composition.These rubber include but not limited to natural rubber, polyisoprene rubber, styrene butadiene rubbers (SBR), polybutadiene rubber, isoprene-butadiene rubber (IBR), styrene isoprene butadiene rubber (SIBR) (SIBR), ethylene-propylene rubber, ethylene-propylene-elastoprene (EPDM), polysulphide, paracril, epoxypropane polymer, star-branched isoprene-isobutylene rubber and halogenated star-branched isoprene-isobutylene rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, star-branched bromination butyl (iso-butylene/isoprene copolymer) rubber; An iso-butylene/methylstyrene copolymer such as iso-butylene/brooethyl vinylbenzene, iso-butylene/brooethyl vinylbenzene, iso-butylene/1-chloro-4-methyl-benzene, halogenated isobutylene/cyclopentadiene and iso-butylene/1-chloro-4-methyl-benzene and composition thereof.

Also can there be the auxiliary rubber component in composition of the present invention and the air retaining wall.One of the auxiliary rubber component that exists embodiment is a natural rubber.Natural rubber is described in detail in Subramaniam, among the RUBBER TECHNOLOGY 179-208 (1995).The desirable embodiment of natural rubber of the present invention is selected from Malaysian rubber such as SMR CV, SMR 5, SMR 10, SMR 20 and SMR 50 and composition thereof, and the mooney viscosity of wherein said natural rubber under 100 ℃ (ML 1+4) is 30 to 120, more preferably 40 to 65.Indication mooney viscosity test is herein undertaken by ASTM D-1646.

Some commercial examples that are applicable to auxiliary synthetic rubber of the present invention are NATSYN ^TM(Goodyear Chemical Company) and BUDENE ^TM1207 or BR1207 (Goodyear Chemical Company).Ideal rubber is high-cis-polyhutadiene (cis-BR)." cis-polyhutadiene " or " high-cis-polyhutadiene " means and uses 1, the 4-cis-polybutadiene, and wherein the amount of cis component is at least 95%.One of used high-cis-polyhutadiene commodity example is BUDENE in the described composition ^TM1207.The ethylene-propylene rubber that is suitable for can VISTALON ^TM(ExxonMobil Chemical Company) is purchased.

In the one embodiment of this invention, exist so-called semi-crystalline co-polymers (SCC) as described auxiliary rubber.Semi-crystalline co-polymers is described among the U.S.S.N.09/569 363 (having transferred transferee of the present invention) of application on May 11st, 2000.Usually, SCC described in one embodiment is ethene or propylene derived unit and alpha-olefin derived unitary multipolymer, described alpha-olefin has 4 to 16 carbon atoms, SCC described in another embodiment is ethylene-derived units and alpha-olefin derived unitary multipolymer, described alpha-olefin has 4 to 10 carbon atoms, and wherein said SCC has certain degree of crystallinity.In another embodiment, described SCC is 1-butylene derived units and another kind of alpha-olefin derived unitary multipolymer, and described another kind of alpha-olefin has 5 to 16 carbon atoms, and wherein said SCC also has certain degree of crystallinity.Described SCC can also be ethene and cinnamic multipolymer.

The amount of the auxiliary rubber component of elastic composition described in one embodiment can be in the scope of maximum 50phr, maximum 40phr in another embodiment, maximum 30phr in another embodiment again.

Thermoplastic resin

The present composition can randomly comprise thermoplastic resin.Be applicable to that implementing thermoplastic resin of the present invention can be used alone or in combination, be contain nitrogen, oxygen, halogen, sulphur or can with the resin of aromatic functional group such as halogen or interactional other group of acidic-group.Described resin is present in the described nano composite material, accounts for 30 to 90% (weights) of described nano composite material in the embodiment, accounts for 40 to 80% (weights) in another embodiment, accounts for 50 to 70% (weights) again in another embodiment.Again in another embodiment, described resin exists with the content greater than 40% (weight) of described nano composite material, in another embodiment greater than 60% (weight).

The thermoplastic resin that is suitable for comprises and is selected from polymeric amide, polyimide, polycarbonate, polyester, polysulfones, polylactone, polyacetal, acrylonitrile-butadiene-styrene resin (ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polystyrene, styrene-acrylonitrile resin (SAN), vinylbenzene-maleic anhydride resin (SMA), aromatics polyketone (PEEK, PED and PEKK) and composition thereof.

The polyamide thermoplastic (nylon) that is suitable for comprises crystallization or arborescens high molecular solid polymer, comprises binary and terpolymer that the repetition amide units is arranged in the polymer chain.Polymeric amide can be by one or more ε-lactan such as hexanolactam, pyrrolidone, lauryl lactam and aminoundecanoic acid lactan or amino acid whose polymerization or the condensation prepared by diprotic acid and diamines.Become fibre and molding graae nylon all to be suitable for.The example of this type of polymeric amide is polycaprolactam (nylon-6), polylauryllactam (PA-12), polyhexamethylene adipamide (nylon-6,6), poly-azelaoyl hexanediamine (nylon-6,9), polyhexamethylene sebacamide (nylon 6,10), poly-6I hexamethylene isoterephalamide (nylon-6, IP) and the condensation product (nylon-11) of the amino undecanoic acid of 11-.Other example (especially softening temperature is lower than those of 275 ℃) of suitable polymeric amide is described in " chemical industry technology encyclopedia 16 " (16ENCYCLOPEDIA OF CHEMICALTECHNOLOGY), 1-105 (John Wiley ﹠amp; Sons 1968), " simple and clear polymer science and technology encyclopedia " (CONCISE ENCYCLOPEDIA OF POLYMERSCIENCE AND TECHNOLOGY), 748-761 (John Wiley ﹠amp; Sons, 1990) and " polymer science and technology encyclopedia 10 " (10 ENCYCLOPEDIAOF POLYMER SCIENCE AND TECHNOLOGY), 392-414 (John Wiley ﹠amp; Sons 1969) in.The polyamide thermoplastic that is purchased can be advantageously used in enforcement the present invention, preferred softening temperature or the line style crystalline polyamide of fusing point between 160 and 260 ℃.

Adoptable suitable thermoplastic polyester comprises the polymeric reaction products of a kind of or mixture of a kind of or mixture of aliphatic series or aromatic multi-carboxy acid's ester or acid anhydride and dibasic alcohol.The example of suitable polyester comprises poly-(C _2-6Alkane dicarboxylic acid's anti-form-1,4-cyclohexylidene ester) as poly-(succsinic acid anti-form-1,4-cyclohexylidene ester) and poly-(hexanodioic acid anti-form-1,4-cyclohexylidene ester); Suitable or the anti-form-1 of polyalkane dicarboxylic acid, 4-cyclohexanedimethyleterephthalate ester is as poly-oxalic acid cis-1,4-cyclohexanedimethyleterephthalate ester and poly-succsinic acid cis-1,4-cyclohexanedimethyleterephthalate ester; Poly terephthalic acid C _2-4Alkylene ester such as polyethylene terephthalate and poly terephthalic acid Aden ester; Poly-m-phthalic acid C _2-4Materials such as alkylene ester such as polyethylene isophthalate and poly-m-phthalic acid Aden ester.Preferred polyester is by aromatic dicarboxylic acid such as naphthalene diacid or phthalic acid and C ₂-C ₄The glycol deutero-is as polyethylene terephthalate and poly terephthalic acid Aden ester.Preferred polyester has the fusing point in 160 to 260 ℃ of scopes.

According to the present invention spendable polyphenylene oxide (PPE) thermoplastic resin be the oxidative coupling polymerization of phenols known, that replace by alkyl produce be purchased material.They generally are the amorphous polymers of line style, and second-order transition temperature is in 190 to 235 ℃ scope.These polymkeric substance, its preparation method reach and the composition of polystyrene is described among the US3 383 435 further.

The similar thing of polycarbonate that spendable other thermoplastic resin comprises above-mentioned polyester such as ether-phthalic acid ester block copolymer; Polycaprolactone; Styrene resin such as vinylbenzene and be lower than the multipolymer and the arborescens Acrylonitrile-Butadiene-Styrene Copolymer (ABS) of 50% (mole) vinyl cyanide (SAN); Sulfone polymer such as polyphenylsulphine; Ethene and C ₂-C ₈The multipolymer of alpha-olefin and homopolymer thermoplastic resins such as (being the homopolymer of propylene derived unit in the embodiment, are the random copolymers or the segmented copolymer of ethylene-derived units and propylene derived unit in another embodiment), as known in the art.

The polybutene treated oil

There is the polybutene treated oil in the present composition.In the one embodiment of this invention, described polybutene treated oil is to have the lower molecular weight of the alkene derived units of 3 to 8 carbon atoms, preferred 4 to 6 carbon atoms (to be lower than 15,000Mn) homopolymer or multipolymer.In another embodiment, described polybutene is C ₄The homopolymer of raffinate or multipolymer.One of this type of low-molecular weight polymer embodiment that is called " polybutene " polymkeric substance for example is described in " synthetic lubricant and performance function fluid " (SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS), 357-392 (Leslie R.Rudnick﹠amp; Ronald L.Shubkin, ed., Marcel Dekker 1999) in (hereinafter " polybutene treated oil " or " polybutene ").

In the one embodiment of this invention, described polybutene treated oil is the multipolymer of iso-butylene derived units, 1-butylene derived units and 2-butylene derived units at least.In one embodiment, described polybutene is these three kinds of unitary homopolymer, copolymer or terpolymers, wherein said iso-butylene derived units accounts for 40 to 100% (weights) of described multipolymer, described 1-butylene derived units accounts for 0 to 40% (weight) of described multipolymer, and described 2-butylene derived units accounts for 0 to 40% (weight) of described multipolymer.In another embodiment, described polybutene is this three kinds of unitary copolymers or terpolymer, wherein said iso-butylene derived units accounts for 40 to 99% (weights) of described multipolymer, described 1-butylene derived units accounts for 2 to 40% (weights) of described multipolymer, and described 2-butylene derived units accounts for 0 to 30% (weight) of described multipolymer.Again in another embodiment, described polybutene is these three kinds of unitary terpolymers, wherein said iso-butylene derived units accounts for 40 to 96% (weights) of described multipolymer, described 1-butylene derived units accounts for 2 to 40% (weights) of described multipolymer, and described 2-butylene derived units accounts for 2 to 20% (weights) of described multipolymer.Again in another embodiment, described polybutene is the homopolymer or the multipolymer of iso-butylene and 1-butylene, wherein said iso-butylene derived units accounts for 65 to 100% (weights) of described homopolymer or multipolymer, and described 1-butylene derived units accounts for 0 to 35% (weight) of described multipolymer.

Being applicable to that polybutene treated oil of the present invention typically has in one embodiment is lower than 10,000, has in another embodiment be lower than 8000 and have and be lower than 6000 number-average molecular weight (Mn) in another embodiment again.In one embodiment, the number-average molecular weight of described polybutene oil greater than 400, in another embodiment greater than 700, again in another embodiment greater than 900.Embodiment preferred can be the combination of any lower limit and any upper limit.For example, in one of polybutene of the present invention embodiment, the number-average molecular weight of described polybutene is 400 to 10,000, is 700 to 8000 in another embodiment.Polybutene treated oil described in a kind of embodiment be suitable for 100 ℃ of following viscosity in the scope of 10 to 6000cSt (centistokes), be 35 to 5000cSt under 100 ℃ in another embodiment, being greater than 35cSt again under 100 ℃ in another embodiment, is greater than 100cSt again under 100 ℃ in another embodiment.

The commercial examples of this treated oil is PARAPOL ^TMSeries treated oil (ExxonMobilChemical Company, Houston TX) is as PARAPOL ^TM450,700,950,1300,2400 and 2500.The PARAPOL that is purchased ^TMSeries polybutene treated oil is the liquid polybutene of synthetic, and each prescription all has certain molecular weight, and all prescriptions all can be used for the present composition.Described PARAPOL ^TMThe molecular weight of oil is 420Mn (PARAPOL ^TM450) to 2700Mn (PARAPOL ^TM2500), pass through gel permeation chromatography.PARAPOL described in one embodiment ^TMThe MWD of oil is 2 to 2.8 in another embodiment in 1.8 to 3 scope.

Following table 1 illustrates the PARAPOL that is applicable to embodiment of the present invention ^TMSome performances of oil, its medium viscosity is measured by ASTM D445-97, and molecular weight is by gel permeation chromatography.

Each PARAPOL of table 1. ^TMThe performance of grade

Grade	Mn	Nian Du @100 ℃, cSt
			450	420	10.6
700	700	78
			950	950	230
1300	1300	630
			2400	2350	3200
2500	2700	4400

PARAPOL ^TMOther performance of treated oil is as follows: PARAPOL ^TMThe density of treated oil (g/ml) is at about 0.85 (PARAPOL ^TM450) to 0.91 (PARAPOL ^TM2500) in the scope.PARAPOL ^TMOil bromine number (CG/G) at 40 (450Mn treated oils) to the scope of 8 (2700Mn treated oils).

The polybutene that elastic composition of the present invention can comprise one or more type as mixture, in adding to elastomerics before blend or with elastomer blended.The amount of described polybutene treated oil mixture and person's character (for example viscosity, Mn etc.) can change in this way.The present composition can use PARAPOL when requiring low viscosity ^TM450, and can use PARAPOL when having relatively high expectations viscosity ^TM2500, or its combination is to obtain other viscosity or molecular weight.The rerum natura of the described composition of may command like this.More particularly, phrase " polybutene treated oil " or " polybutene treated oil " be included as obtain desired (scope dictates as disclosed herein) any viscosity or molecular weight (or other performance) and use singlely plant oil or two or the combination of multiple oil.

The amount of polybutene treated oil described in one embodiment in elastic composition of the present invention is 1 to 60phr, is 2 to 40phr in another embodiment, is 4 to 35phr in another embodiment, is 5 to 30phr again in another embodiment.Preferred described polybutene treated oil does not contain aryl or unsaturated.

Filler and clay

Described elastic composition can have one or more filler component such as lime carbonate, clay, mica, silicon oxide and silicate, talcum, titanium dioxide, starch and other organic filler such as wood powder and carbon black.In one embodiment, described filler is carbon black or modified carbon black.Preferred filler is half reinforcement level carbon black, with described composition 10 to 150phr, more preferably 30 to 120phr content exists.The carbon black grade that is suitable for described in RUBBER TECHNOLOGY 59-85 (1995) is in the scope of N110 to N990.More desirably, be applicable to that for example the sooty embodiment of tire tread is N229, N351, N339, N220, N234 and the N110 that provides among the ASTM (D3037, D1510 and D3765).Be applicable to that for example the carbon black embodiment of tire tyre sidewall is N330, N351, N550, N650, N660 and N762.The carbon black embodiment that is applicable to the liner for example or the inner tube of a tyre be N550, N650, N660, N762, N990 and Regal 85 (Cabot Corporation Alpharetta, GA) etc.

Also can there be exfoliated clays in the described composition.These clays (being also referred to as " nanoclay ") are known, and its person's character, preparation method reach and the blend of polymkeric substance is disclosed in for example JP2000109635,2000109605,11310643; DE 19726278; WO98/53000; Among the US5 091 462,4 431 755,4 472 538 and 5 910 523.Be applicable to that swellable layered clay material of the present invention comprises natural or the synthetic phyllosilicate, particularly smectic clays if you would be taken off soil, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite etc., and vermiculite, halloysite, aluminate oxide compound and hydrotalcite etc.These laminated claies generally comprise and contain the particle that many thickness are the silicate platelets of 4-20 dust (being the 8-12 dust in another embodiment), are bonded together, and contain crosslinkable positively charged ion such as the Na that is present in interlayer surface ⁺, Ca ^{+ 2}, K ⁺Or Mg ^{+ 2}

The organic molecule (swelling agent) of the positively charged ion generation ion exchange reaction that available energy and layered silicate interlayer surface exist is handled and is made the laminated clay intercalation and scale off.The swelling agent that is suitable for comprises that cats product is as ammonium, alkylamine or the alkylammonium of aliphatic series, aromatics or aryl aliphatic amine, phosphine and sulfide (primary, secondary, uncle and Ji), Phosphonium or sulfonium derivative.Ideal aminated compounds (or corresponding ammonium ion) is that those of following structure are arranged: R ₁R ₂R ₃N, wherein R ₁, R ₂, and R ₃Be C ₁-C ₂₀Alkyl or alkene can be identical or different.In one embodiment, the described agent that scales off is so-called long chain tertiary amine, wherein R at least ₁Be C ₁₄-C ₂₀Alkyl or alkene.

Another kind of swelling agent comprise can with those of described interlayer surface covalent bonding.These comprise the polysilane of following structure :-Si (R ' ₂) R ², wherein each R ' that occurs is identical or different, is selected from alkyl, alkoxyl group or oxosilane, R ²Be the organic group compatible with the matrix polymer of described matrix material.

Other swelling agent that is fit to comprises protonated amino acid and the materials such as salt such as 12 amino dodecanoic acid, ε-Ji Neixianan thereof that contain 2-30 carbon atom.The swelling agent that is suitable for and the intercalation method of layered silicate are disclosed among US4 472 538,4 810 734,4 889 885 and the WO92/02582.

In the present invention's one preferred embodiment, described scale off additive and halogenated polymer combination.In one embodiment, described additive comprise all primary, the second month in a season and tertiary amine and phosphine; Alkyl and aromatic yl sulfide and mercaptan; And multifunctional variant.The ideal additive comprises: long chain tertiary amine such as N, N-dimethyl-stearylamine, N, N-two (octadecyl)-methylamine, so-called dihydro tallow alkyl-methylamine etc. and the end capped polytetrahydrofuran of amine; Long-chain mercaptan and thiosulfuric acid salt compound such as hexylidene Sulfothiorine.In another embodiment of the present invention, improve the opacity of interpolymer by having multifunctional solidifying agent such as hexylidene two (Sulfothiorine) and hexylidene two (phenylacrolein).

The incorporation of nano composite material medium clay soil of the present invention or exfoliated clays is enough to improve the mechanical property or the barrier properties of described nano composite material, for example air penetrability of tensile strength or air/oxygen.This amount is 1 to 10% (weight) in another embodiment in the scope of 0.5 to 15% (weight) in one embodiment, is 1 to 5% (weight) in another embodiment again, based on the polymer content of nano composite material.Umber with per hundred parts of rubber represents that the amount of clay or exfoliated clays can be 1 to 30phr described in the embodiment, is 3 to 20phr in another embodiment.In one embodiment, described exfoliated clays is alkylamine-exfoliated clays.

Solidifying agent and promotor

The composition of producing by the present invention typically contains other component and additive commonly used in rubber stock, as pigment, promotor, crosslinked and solidify material, antioxidant, antiozonidate and filler.In one embodiment, can exist 1 to 30phr processing aid (resin) as cycloparaffin series, aromatics or paraffinic extending oil.In another embodiment, described composition does not exist cycloparaffin series, aliphatic series, paraffinic and other aromatic resin and oil basically." not existing basically " to mean exists (if present) to be not more than cycloparaffin series, aliphatic series, paraffinic and other aromatic resin of 2phr in the described composition.

Usually, it is crosslinked to make polymer composition for example be used to produce those polymer compositions of tire.It is directly related to form crosslinked quantity (cross-linking density) and type in the rerum natura of known vulcanized rubber sizing material, performance characteristic and weather resistance and the vulcanization reaction process.(referring to for example Helt etc., " postcure that is used for NR is stable ", RUBBER WORLD 18-23 (1991)).Crosslinked and vulcanizing agent comprises sulphur, zinc oxide and lipid acid.Also can use the peroxide cure system.Usually, can for example sulphur, metal oxide (being zinc oxide), organometallic compound, radical initiator etc. heat then and make polymer composition crosslinked by adding the solidifying agent molecule.Especially, below be to can be used for common solidifying agent of the present invention: ZnO, CaO, MgO, Al ₂O ₃, CrO ₃, FeO, Fe ₂O ₃, and NiO.These metal oxides can with respective metal stearate radical title complex (Zn (stearate radical) for example ₂, Ca (stearate radical) ₂, Mg (stearate radical) ₂, and Al (stearate radical) ₃) or use with stearic acid and sulphur compound or alkyl peroxide.(also referring to " formulating of recipe and the vulcanization characteristics that are used for the NBR mixture of sealing member ", RUBBER WORLD 25-30 (1993).This method can be promoted, and is usually used in the sulfuration of elastic composition.

Promotor comprises amine, guanidine class, Thiourea, thiazoles, thiurams, sulfenamide, sulfenamide class, thiocarbamates, xanthate class etc.Can promote described solidification process by in composition, adding a certain amount of promotor.The complexity that the mechanism of promotion caoutchouc vulcanization relates between solidifying agent, promotor, activator and the polymkeric substance interacts.Ideally, all available solidifying agent all consume in effectively crosslinked formation, and two polymer chains are linked together, and strengthen the total intensity of polymeric matrix.A lot of promotor known in the art, include but not limited to following promotor: stearic acid, vulkacit D (DPG), tetramethyl-thiuram disulfide (TMTD), 4,4 '-dithio morpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2,2 '-benzothiazyl disulfide (MBTS), two hydration hexylidenes-1,6-dithio sulfuric acid disodium salt, 2-(morpholino sulfo-) benzothiazole (MBS or MOR), the composition of 90%MOR and 10%MBTS (MOR90), N tert butyl benzothiazole 2 sulfenamide (TBBS), with N-oxydiethylene thiocarbamyl-N-oxydiethylene sulphonamide (OTOS), 2 ethyl hexanoic acid zinc (ZEH), N, N '-diethyl thiourea.

In the one embodiment of this invention, having 0.2 to 15phr at least a solidifying agent, is 0.5 to 10phr in another embodiment.Solidifying agent comprises promotion noted earlier or influences those compounds of elastomeric solidified, as metal, promotor, sulphur, superoxide and this area other reagent commonly used, as previously described.

Processing

Can be by described polymeric constituent and clay with the intercalation form at any suitable mixing device such as Banbury ^TMMixing tank, Brabender ^TMThe mixing of described component is carried out in combination in mixing tank or the preferred mixing tank/forcing machine.In one embodiment in being up to described composition in the melting range of used elastomerics and/or auxiliary rubber, in another embodiment in 80 to 340 ℃ of scopes, again in another embodiment under the temperature in 120 to 300 ℃ of scopes, be enough to that clay intercalated being evenly dispersed in to scaling off under the shearing condition that forms nano composite material in the polymkeric substance mixed.

In the composition of enumerating, at BR Banbury ^TMMix by technology known in the art in the Banbury mixer.Typically, 70 to 100% elastomerics was mixed 20 to 90 seconds, perhaps reach 40 to 60 ℃ until temperature.Then, the elastomerics (if present) of 3/4 and surplus of described filler is added described mixing tank, continue to mix and reach 90 to 150 ℃ until temperature.Then, add remaining filler and treated oil, continue mixing and reach 140 to 190 ℃ until temperature.Make final mixture compressing tablet in mill then, make it to be cooled to 60 to 100 ℃ when adding solidifying agent.

Carry out with mixing by technology well known by persons skilled in the art of clay, wherein an embodiment medium clay soil and carbon black add in the polymkeric substance simultaneously.Typically in elastomer matrix, fully add the polybutene treated oil in the later stage of described mixing period after the dispersion at carbon black and clay.

Curing composition of the present invention can comprise various elastomericss and filler and polybutene treated oil.The present composition typically comprises isobutylene-based elastomer such as halogenated iso-butylene-p-methylstyrene multipolymer, isoprene-isobutylene rubber or halogenated star-branched isoprene-isobutylene rubber (HSSB), these elastomericss can be used alone or in combination, and the amount of polybutene treated oil described in the embodiment is 5 to 30phr.

In one embodiment, described composition is the halogenated iso-butylene-p-methylstyrene multipolymer (50 to 100phr) that can comprise natural rubber (5 to 50phr) and polybutene treated oil (5 to 30phr), filler such as carbon black (20 to 80phr) and exfoliated clays (2 to 15phr in the embodiment 0.5 to 20phr, in another embodiment).The amount of solidifying agent such as resol, sulphur, stearic acid and zinc oxide can be 0.1 to 5phr.

In another embodiment, described composition is to comprise the HSSB (50 to 100phr) of halogenated iso-butylene-p-methylstyrene multipolymer (20 to 70phr in the embodiment 5 to 95phr, in another embodiment) and polybutene treated oil (3 to 30phr), filler such as carbon black (20 to 80phr) and exfoliated clays (2 to 15phr in the embodiment 0.5 to 20phr, in another embodiment).The amount of solidifying agent such as resol, sulphur, stearic acid and zinc oxide can be 0.1 to 5phr.

Again in another embodiment, described composition is to comprise the halogenated butyl rubber (50 to 100phr) of halogenated iso-butylene-p-methylstyrene multipolymer (20 to 70phr in the embodiment 5 to 95phr, in another embodiment) and polybutene treated oil (3 to 30phr), filler such as carbon black (20 to 80phr) and exfoliated clays (2 to 15phr in the embodiment 0.5 to 20phr, in another embodiment).The amount of solidifying agent such as resol, sulphur, stearic acid and zinc oxide can be 0.1 to 5phr.

Be applicable to isobutylene-based elastomer of the present invention can with various other rubber or especially thermoplastic resin such as nylon or polyolefine such as polypropylene or polypropylene copolymer blend of plastics disclosed herein.These compositions are applicable to air retaining wall such as air bag and liner, wind sock (as in air cushion shock absorber), barrier film and other application that requires high air or oxygen retentivity.In one embodiment, the air penetrability of described curing composition (air under 65 ℃, oxygen or nitrogen) is 1.2 * 10 ^-8To 4 * 10 ^-8Cm ³-cm/cm ²-sec-atm is 1.5 * 10 in another embodiment ^-8To 3.5 * 10 ^-8Cm ³-cm/cm ²-sec-atm.

In one embodiment, can prepare air retaining wall by the following method: make at least a C of comprising ₄-C ₇The random copolymers of isomonoolefin derived units, at least a filler and number-average molecular weight make up greater than 400 polybutene oil and at least a solidifying agent; The component of described combination is solidified.

Testing method

Shown in measure curing performances with ODR 2000 under temperature and the 1 or 3 degree arcs.Make sample shown in temperature (typically 150 to 160 ℃) solidify down and T _cThe suitable molding of 90+ lags behind the corresponding time.Under possible situation, with the rerum natura (seeing Table 2) of the described curing sizing material of standard A STM test determination.At room temperature measure stress/strain performance (tensile strength, extension at break, modulus value, energy-to-break) with Instron 4202.At room temperature measure Xiao A hardness with Zwick Duromatic.The error of measuring in 100% modulus (2 σ) is ± 0.11MPa unit; The error of measuring in the elongation (2 σ) is ± 13% unit.

Used herein " MH " and " ML " value mean " peak torque " and " minimal torque " respectively." MS " value is a mooney scorch value, and " ML (1+4) " value is a Mooney viscosity value.Error (2 σ) during back one is measured is ± 0.65 mooney viscosity unit." Tc " value be set time (minute), " Ts " value for time of scorch (minute).

PARAPOL ^TMThe molecular weight of polybutene treated oil is by gel permeation chromatography, and the value of gained number-average molecular weight (Mn) has ± 20% error.The technical description that is used for determining molecular weight (Mn and Mw) and molecular weight distribution (MWD) is at US4540753 (Cozewith etc. are incorporated herein for reference) and Verstrate etc., among the 21MACROMOLECULES 3360 (1988).In typical the measurement, one group of operation under 30 ℃ of 3 posts.Used eluent can be stable tetrahydrofuran (THF) (THF) or 1,2,4-trichlorobenzene (TCB).The accurately polystyrene standards calibration of known molecular amount of described post.The polystyrene retention volume that obtains by described standard substance and the related molecular weight that obtains described polymkeric substance of the retention volume of test polymer.PARAPOL ^TMPolybutene processing oil viscosity (table 1) is pressed ASTM D445-97 and is measured.

Stretch to measure and on Instron Series IX Automated Materials TestingSystem 6.03.08, under envrionment temperature, carry out.Use the small tension specimen (splayed) of wide 0.08 inch (0.20cm), long 0.2 inch (0.5cm) (length between two fins).Change the thickness of sample, and the Mitutoyo DigimaticIndicator manual measurement by linking to each other with system computer.With the pinblock speed tension specimen of 20 inches/min (51cm/min), record stress/strain data.Mean stress/the strain value of at least three samples of report.Error (2 σ) was ± 0.47MPa unit during stretching was measured.

Peel off adhesion with one inch and test adhesive power, wherein prepare 1 inch * 3 inches adhints that stick at kraft paper.Sample is flatly hung (with separation mode) in air circulation oven, from the free end suspension 100g of described joint counterweight.Make 10 (4.1 ℃) of oven temperature rising in per 15 minutes.Described peeling off-damaged temperature is the mean value of three readings.

Fatigue is ± 20% with the error of the ratio of breakage.

Press R.A.Pasternak etc., 8JOURNAL OF POLYMER SCIENCE:PARTA-2 467 (1970) disclosed oxygen are measured oxygen-permeable by the dynamic measurement principle of film migration with MOCONOxTran Model 2/61.Measure unit is cc-mil/m ²-sky-mmHg.Usually, method is as follows: flat film or rubbery sample are clipped in the diffuser casing, remove residual oxygen with oxygen-free carrier gas.Make carrier gas lead to transmitter until setting up stable null value.Introduce purity oxygen or air in the described diffuser casing outside then.Be sent to transmitter by described film diffusion to indoor oxygen, measure oxygen diffusion speed.

Testing air permeable rate by the following method.To be installed in the diffuser casing by the thin sulfuration sample that sample composition is made, in 65 ℃ oil bath, nurse one's health.Record air infiltration is passed through given sample required time to determine its air penetrability.Sample is the disk of diameter 12.7cm, thick 0.38mm.The measuring error of air penetrability (2 σ) is ± 0.245 (* 10 ⁸) unit.Other testing method is described in table 2.

Embodiment

Composition 1-15 (table 3-5) illustrates the benefit of mixing the polybutene treated oil in the blend of the isobutylene copolymers that comprises halogenated methyl vinylbenzene part.Composition 1,6 and 11 representatives comprise the halogenated iso-butylene-p-methylstyrene multipolymer (seeing Table 3) of the p-methylstyrene (PMS) of the halogenation of different amounts and different amounts.Mix PARAPOL ^TMComposition improved air penetrability is arranged, improve simultaneously or keep such as green strength and processing characteristicies such as ratio (showing 6-8) tired and breakage.

Composition 16-21 (table 9) illustrates the benefit of mixing the polybutene treated oil in the blend of isobutylene-based polymers such as HSSB and another kind of rubber such as natural rubber and exfoliated clays.Composition 16 be only HSSB (SBB-6222,100phr), composition 17 is that natural rubber and PARAPOL are only arranged ^TM(90phr SBB, 10phr natural rubber).Typically, halogenated rubber such as HSSB have required low air penetrability (with as only natural rubber compare).Air penetrability rises when adding natural rubber in known these compositions, as " liner that is used for high-performance tire ", C.W.van Hellens, " Rubber processing fascicle " (PROCEEDINGS OFRUBBER DIVISION), (the Indianapolis of american chemical association, Indiana, in May, 1984) and " brombutyl and chlorobutyl: their chemistry; the comparison of performance and application " (Bromobutyl and Chlorobutyl:A Comparison of TheirChemistry, Properties and Uses), W.Hopkins, R.H.Jones, J.Walker, disclosed among the INTERNATIONAL RUBBER CONFERENCE PROCEEDINGS205 (Kyoto, in October, 1985).But as shown in composition 17, when having polybutene,, air penetrability is maintained or improves even have natural rubber in the described composition.

Add the air penetrability that exfoliated clays can further be improved these halogenated elastomer compositions.Composition 18-21 mixes the exfoliated clays of different amounts.These data presentation natural rubbers improve the processibility (table 10A and 10B) of described HSSB.Add clay and PARAPOL ^TMThe time further improve air penetrability (lower value).Comprise naphthenic oil (CALSOL in the composition 19 ^TM) improve the air penetrability of described blend in fact unfriendly.

Composition 22-23 (table 11) illustrates the benefit of mixing the polybutene treated oil in the elastomer blend of natural rubber, the isobutylene copolymers that comprises halogenated methyl vinylbenzene part and exfoliated clays.These data presentation are adding PARAPOL ^TMImprove when the time is reduced air penetrability or the maintenance processing characteristics.

Composition 24-28 (table 12) further illustrates the benefit of mixing the polybutene treated oil in the elastomer blend of natural rubber, the isobutylene copolymers that comprises halogenated methyl vinylbenzene part and exfoliated clays.PARAPOL ^TMTreated oil (polybutene) improves the resistance to air loss of described blend once more when keeping or improving processing characteristics.For example, add PARAPOL ^TMThe fatigue of the described composition of Shi Gaishan and the ratio of breakage are also improved green strength (table 13A and 13B).Composition 27 and 28 is represented the minimum preferred elastomer blend of air permeability values, wherein EXXPRO ^TM89-4 and SBB-622 and natural rubber and PARAPOL ^TMExist together.

Composition 29-44 illustrates the benefit of mixing the polybutene treated oil in the various blends of isobutylene based copolymer.Composition 29-32 is brominated butyl rubber (Bromobutyl 2222) and the PARAPOL that has and do not have clay ^TMBlend.These data presentation add PARAPOL in the composition of (composition 30) exfoliated clays (composition 31) being arranged and do not have ^TMProcessing characteristics is improved as tired ratio with breakage, improve air permeability values simultaneously.There is the two relative other butyl rubber bromide glue composition of composition of clay and polybutene to be improved.

It is the EXXPRO of 5% (weight) with respect to total copolymer that composition 33-36 illustrates PMS content ^TMElastomeric application.These data presentation only add polybutene treated oil (composition 34) improves the air retaining wall quality of blend, only adds exfoliated clays (composition 35) the air retaining wall quality is improved.Adding polybutene treated oil and clay the two (composition 36) improves the air retaining wall quality.5% (weight) PMS EXXPRO when having polybutene and clay (separately or together) ^TMThe processing characteristics of blend improves, and is card with for example green strength with tired ratio with breakage.

It is the EXXPRO of 7.5% (weight) with respect to total copolymer that composition 37-40 illustrates PMS content ^TMElastomeric application.In a word, add PARAPOL ^TMAnd/or air penetrability improves during exfoliated clays.At last, to illustrate PMS content be the EXXPRO of 12% (weight) with respect to total copolymer to composition 41-44 ^TMElastomeric application.Add polybutene PARAPOL ^TMAnd/or improve air penetrability and processing characteristics during exfoliated clays once more.And fatigue is improved with ratio relative 7.5% (weight) the PMS multipolymer of breakage in 12% (weight) PMS multipolymer.

In the iso-butylene-p-methylstyrene multipolymer of brominated butyl rubber and bromination and nanoclay composition, comprise polybutene and be tending towards improving air penetrability, as shown in composition 29-44 among the table 15B.In one embodiment, the air penetrability of these compositions (under 65 ℃) is 1.20 * 10 ^-8To 1.90 * 10 ^-8Cm ³-cm/cm ²In the scope of-sec-atm, in another embodiment 1.30 * 10 ^-8To 1.8 * 10 ^-8Cm ³-cm/cm ²In the scope of-sec-atm.

In a word, comprise polybutene treated oil (number-average molecular weight is 400 to 6000 in the embodiment, another embodiment medium viscosity is 10 to 10,000cSt@100 ℃) and can improve green strength and improvement or keep processibility, and improve (reduction) air penetrability.For example, comprise the ratio that polybutene improves (raising) fatigue and breakage in the elastic composition.Improve ratio tired and breakage when especially in elastomerics/nanoclay composition, adding polybutene.

In one of the described elastomer nanocomposites composition embodiment, described elastomerics is a brominated butyl rubber, and the ratio of not aged fatigue and breakage is greater than 40,000 unit, in another embodiment greater than 50,000, again in another embodiment greater than 60,000.In another embodiment, described elastomerics is the iso-butylene-p-methylstyrene multipolymer of bromination, and the ratio of described fatigue and breakage is greater than 70,000, in another embodiment greater than 80,000.Fatigue when mixing polybutene in the composition and the ratio of breakage are increased in particularly advantageous when having clay, because be tending towards making these values decline when adding clay in elastomerics.In another embodiment of elastic composition, green strength is greater than 45 units, in another embodiment greater than 50 units.Certainly, can further improve these values by the amount of each component or the viscosity and/or the molecular weight of described polybutene in the change composition.

The specific embodiments of the final nano composite material of the present invention is suitable as air retaining wall, as is used to produce liner or the inner tube of a tyre or the automobile-used flexible pipe of tire for vehicles.Especially, described nano composite material is adapted in truck tyre, bus tyre, passenger tyre, motorcycle tyre, the off-the-highway tire etc. as liner.The resistant to thermal aging property improvement of liner composition of the present invention makes it to be specially adapted to truck tyre to improve the tyre soles process ability of tire.

Though invention has been described and explanation in conjunction with specific embodiments, it is conspicuous for those of ordinary skills that invention helps unaccounted many different changes herein.For this reason, reaction is determined true scope of the present invention according to appended claims.

At all authorities that allow this introducing, all formerly document all be incorporated herein for reference.To comprise that testing method all is incorporated herein for reference for all documents of Yin Ruing herein.

Table 2. testing method

Parameter	Unit	Test
			Mooney viscosity (BIMS polymkeric substance)	ML 1+8，125℃，MU	ASTM D 1646 (remodeling)
Mooney viscosity (composition)	ML 1+4，100℃，MU	ASTM D 1646
			Air penetrability	cm 3-cm/cm 2-sec-atm	See text
Fragility	℃	ASTM D 746
			Green strength (100% modulus)	PSI	ASTM D 412
Mooney viscosity (sizing material)	ML 1+4，100℃，MU	ASTM D 1646
			Mooney scorch time	T s5,125 ℃, minute	ASTM D 1646
Vibration disc type rheometer (ODR), ± 3 ° of arc ML MH T s2 T c90 solidification rates	Divide newton. rice d newton .m minute minute dN.m/ minute	ASTM D 2084
			The dull and stereotyped solidified T of rerum natura c90+2 minute hardness modulus 100% tensile strength extension at break	Shore A MPa MPa %	ASTM D 2240 ASTM D 412 die head C
Hot air aging, 72 Xiao Shi @125 ℃ of changes in hardness stretch and change the variable elongation changes in weight	％ ％ ％ ％	ASTM D 573
			Tear strength die head B and die head C	N/mm	ASTM D 624
The ratio of tired and breakage	Cycle	ASTM 4482, with cam 24 (136% elongation)

Table 3. component and commercial source

Component	Summary	Commercial source
			BENTON TM-34	The montmorillonitic clay of chlorination dimethyl two tallow alkyl ammonium modifications	Elementis Specialties (Belleville，NJ)
Bromobutyl 2222	The isobutylene-isoprene copolymer of bromination, mooney viscosity (1+8,125 ℃) is 27-37MU	ExxonMobil Chemical Company(Houston，TX)
			CALSOL TM810	Naphthenic oil ASTM type 103	R.e.Carroll.Inc (Trenton，NJ)
CAPTAX TM	2-mercaptobenzothiazole	R.T.Vanderbilt
			CLAYTONE TM-40	The montmorillonitic clay of chlorination dimethyl two tallow alkyl ammonium modifications	Southern Clay Products (Gonzalez，TX)
CLOISITE TM-25	The montmorillonitic clay of chlorination dimethyl two tallow alkyl ammonium modifications	Southern Clay Products (Gonzalez，TX)
			ESCOREZ TM	Aromatic modified aliphatic resin, 95 ℃ of softening temperatures	ExxonMobil Chemical Company(Houston，TX)
EXXPRO TM3035	5wt%PMS, 0.5mol%BrPMS, mooney viscosity 40-50	ExxonMobil Chemical Company(Houston，TX)
			EXXPRO TM89-4	5wt%PMS, 0.75mol%BrPMS, mooney viscosity 45 native 5MU (1+8,125 ℃)	ExxonMobil Chemical Company(Houston，TX)
EXXPRO TM01-4	7.5wt%PMS, 0.85mol%BrPMS, mooney viscosity 45 ± 5MU (1+8,125 ℃)	ExxonMobil Chemical Company(Houston，TX)
			EXXPRO TM96-4	12wt%PMS, 0.85mol%BrPMS, mooney viscosity 45 ± 5MU (1+8,125 ℃)	ExxonMobil Chemical Company(Houston，TX)
KADOX TM930	High purity French process(for zine extraction) zinc oxide	Zinc Corp.of America (Monaca，Pa)
			Maglite-K	Vulcanizing agent	C.P.Hall(Chicago，IL)
PARAPOL TM	C 4Raffinate	ExxonMobil Chemical Company(Houston，TX)
			Rosinol MR-1085A	Tackifier	Sovereign Chemical (Akrom，OH)
SP-1068	Brominated phenolic resin	Schenectady International (Schenectady，NY)
			SBB	Star-branched isoprene-isobutylene rubber 6222	ExxonMobil Chemical Company(Houston，TX)
Stearic acid	Solidifying agent	e.g.，C.K.Witco Corp.(Taft，LA)
			Sulphur	Solidifying agent	e.g.，R.E.Carroll (Trenton，NJ)
TMTD	Tetramethyl-thiuram disulfide	e.g.，R.T.Vanderbilt (Norwalk，CT)
			Zinc oxide 911,720-C	Activator	C.P.Hall(Chicago，IL)

The component of table 3. contrast and example composition 1-5

Component (phr)	1	2	3	4	5
						EXXPRO TM 89-4 (5wt％PMS，0.75mol％BrPMS)	100.00	100.00	100.00	100.00	100.00
Carbon black N660	60.00	60.00	60.00	60.00	60.00
						CALSOL TM-810	8.00	-	-	-	-
STRUKTOL TM-40MS	7.00	7.00	7.00	7.00	7.00
						SP-1068	2.00	2.00	2.00	2.00	2.00
ESCOREZ TM-2510	2.00	2.00	2.00	2.00	2.00
						Stearic acid	1.00	1.00	1.00	1.00	1.00
PARAPOL TM-700	-	8.00	-	-	-
						PARAPOL TM-950	-	-	8.00	-	-
PARAPOL TM-1300	-	-	-	8.00	-
						PARAPOL TM-2400	-	-	-	-	8.00
Zinc oxide 911	1.00	1.00	1.00	1.00	1.00
						MBTS	1.25	1.25	1.25	1.25	1.25
Sulphur	0.50	0.50	0.50	0.50	0.50

The component of table 4. contrast and example composition 6-10

Component (phr)	6	7	8	9	10
						EXXPRO TM 01-4 (7.5wt％PMS，0.85mol％BrPMS)	100.00	100.00	100.00	100.00	100.00
Carbon black N660	60.00	60.00	60.00	60.00	60.00
						CALSOL TM-810	8.00	-	-	-	-
STRUKTOL TM-40MS	7.00	7.00	7.00	7.00	7.00
						SP-1068	2.00	2.00	2.00	2.00	2.00
ESCOREZ TM-2510	2.00	2.00	2.00	2.00	2.00
						Stearic acid	1.00	1.00	1.00	1.00	1.00
PARAPOL TM-700	-	8.00	-	-	-
						PARAPOL TM-950	-	-	8.00	-	-
PARAPOL TM-1300	-	-	-	8.00	-
						PARAPOL TM-2400	-	-	-	-	8.00
Zinc oxide 911	1.00	1.00	1.00	1.00	1.00
						MBTS	1.25	1.25	1.25	1.25	1.25
Sulphur	0.50	0.50	0.50	0.50	0.50

The component of table 5. Comparative Examples and example composition 11-15

Component (phr)	11	12	13	14	15
						EXXPRO TM 96-4 (12wt％PMS，0.85mo1％BrPMS)	100.00	100.00	100.00	100.00	100.00
Carbon black N660	60.00	60.00	60.00	60.00	60.00
						CALSOL TM-810	8.00	-	-	-	-
STRUKTOL TM-40MS	7.00	7.00	7.00	7.00	7.00
						SP-1068	2.00	2.00	2.00	2.00	2.00
ESCOREZ TM-2510	2.00	2.00	2.00	2.00	2.00
						Stearic acid	1.00	1.00	1.00	1.00	1.00
PARAPOL TM-700	-	8.00	-	-	-
						PARAPOL TM-950	-	-	8.00	-	-
PARAPOL TM-1300	-	-	-	8.00	-
						PARAPOL TM-2400	-	-	-	-	8.00
Zinc oxide 911	1.00	1.00	1.00	1.00	1.00
						MBTS	1.25	1.25	1.25	1.25	1.25
Sulphur	0.50	0.50	0.50	0.50	0.50

The performance of table 6. composition 1-5

The performance of table 7. composition 6-10

The performance of table 8. composition 11-15

The performance of table 10A. composition 16-21

The performance of table 10B. composition 16-21

Performance	16	17	18	19	20	21
							Green strength, Mo Liang @100%PSI	44.23	59.16	55.68	43.21	66.41	67.43
From the strain terminal point to decaying time of 75%, minute	2.81	9.10	9.38	6.79	14.85	24.57
							Die head B tear strength-N/mm	47.74	48.27	49.93	39.86	50.04	47.61
Die head C tear strength-N/mm	25.01	30.38	28.38	20.87	27.20	27.39
							@65 ℃ of air ，, cm 3-cm/cm 2- sec-atm(×10 8)	3.31	2.49	2.86	3.57	2.66	2.78
N 2@65 ℃ of rate of permeation ，, cm 3-cm/cm 2-sec- atm(×10 8)	2.98	2.31	2.57	2.99	2.36	2.71
							Fragility, ℃	-45	-37	-37	-44	-37	-41

Component and the performance of table 11. example composition 22-23

The performance of table 13A. example composition 24-28

The performance of table 13B. example composition 24-28

Performance	24	25	26	27	28
						Green strength, Mo Liang @100%PSI	44.23	62.93	70.18	94.83	119.19
From the strain terminal point to decaying time of 75%, minute	2.81	11.91	46.92	-	-
						Die head B tear strength-N/mm	47.74	41.46	58.02	60.12	63.12
Die head C tear strength-N/mm	25.01	22.79	30.41	37.58	33.94
						@65 ℃ of air ，, cm 3-cm/cm 2- sec-atm(×10 8)	3.29	2.63	2.70	2.79	2.75
N 2@65 ℃ of rate of permeation ，, cm 3-cm/cm 2-sec- atm(×10 8)	2.97	2.96	2.74	1.86	2.19
						Fragility, ℃	-45	-42	-42	-42	-41

Claims (24)

1. liner that comprises elastic composition, this elastic composition comprise and comprise C ₄-C ₇The elastomerics random copolymers of isomonoolefin derived units and 0.5-20mol% p-methylstyrene derived units, at least a filler, number-average molecular weight are 700 to 6,000 polybutene oil and at least a solidifying agent, the maximum 60mol% methyl substituents that are present in the wherein said p-methylstyrene derived units on the benzyl ring contain bromine or chlorine atom.

2. the liner of claim 1, wherein the air penetrability of solidified liner is 1.2 * 10 under 65 ℃ ^-8To 4 * 10 ^-8Cm ³-cm/cm ²-sec-atm.

3. the liner of claim 1 also comprises thermoplastic resin.

4. the liner of claim 1, the molecular weight of wherein said polybutene oil is greater than 900.

5. the liner of claim 1, the amount of wherein said polybutene oil are 2 to 40phr.

6. the liner of claim 1, wherein said filler be selected from lime carbonate, clay, mica, silicon oxide and silicate, talcum, titanium dioxide, starch, wood powder and carbon black, and composition thereof.

7. the liner of claim 1, wherein said elastic composition also comprise be selected from exfoliate natural or synthetic polynite, nontronite, beidellite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite, fibrous morphology crystals, rich magnesium montmorillonite, vermiculite, halloysite, aluminate oxide compound, hydrotalcite, and composition thereof exfoliated clays.

8. the liner of claim 1, the C of wherein said elastomerics random copolymers ₄-C ₇The isomonoolefin derived units is an iso-butylene.

9. the liner of claim 8, wherein said elastomerics random copolymers is halogenated iso-butylene-p-methylstyrene multipolymer.

10. the liner of claim 9, wherein said halogenated iso-butylene-p-methylstyrene multipolymer have based on described multipolymer weight 0.1 to 5 weight % to the brooethyl styrene content.

11. each liner among the claim 1-10, the viscosity of wherein said polybutene oil under 100 ℃ are 10 to 6000cSt.

12. each liner among the claim 1-10, the amount of wherein said polybutene oil are 2 to 30phr.

13. wherein there is not naphthenic oil basically in each liner among the claim 1-10.

14. each liner among the claim 1-10, the viscosity of wherein said polybutene oil under 100 ℃ are 35 to 5000cSt.

15. each liner among the claim 1-10, the unaged fatigue of wherein said elastic composition and the ratio of breakage are greater than 40,000 units.

16. each liner among the claim 1-10, the unaged fatigue of wherein said elastic composition and the ratio of breakage are greater than 70,000 units.

17. each liner among the claim 1-10, wherein said filler is a carbon black.

18. each liner among the claim 1-10, wherein said air penetrability are 1.5 * 10 under 65 ℃ ^-8To 3.5 * 10 ^-8Cm ³-cm/cm ²-sec-atm.

19. each liner among the claim 1-10, wherein said polybutene oil are the multipolymers of iso-butylene derived units and 1-butylene derived units.

20. each liner among the claim 1-10 also comprises being selected from natural rubber, polyisoprene rubber, styrene butadiene rubbers, polybutadiene rubber, isoprene-butadiene rubber, styrene isoprene butadiene rubber (SIBR), ethylene-propylene rubber, ethylene-propylene-elastoprene, polysulphide, paracril, epoxypropane polymer, star-branched isoprene-isobutylene rubber and halogenated star-branched isoprene-isobutylene rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, star-branched bromination butyl (iso-butylene/isoprene copolymer) rubber, iso-butylene/methylstyrene copolymer, halogenated iso-butylene/cyclopentadiene, the elastomer-assisted of iso-butylene/1-chloro-4-methyl-benzene and composition thereof.

21. the liner of claim 20, wherein said iso-butylene/methylstyrene copolymer are an iso-butylene/brooethyl vinylbenzene, iso-butylene/brooethyl vinylbenzene or iso-butylene/1-chloro-4-methyl-benzene.

22. each liner among the claim 1-10, wherein said elastic composition is a solidified.

23. tire that is used for motor vehicle that comprises each liner among the claim 1-22.

24. flexible pipe that is used for motor vehicle that comprises each liner among the claim 1-22.