Termoplastic elastomeric composition and preparation method thereof

FIELD: chemistry.

SUBSTANCE: invention relates to a thermoplastic elastomeric composition and preparation method thereof and can be used as a fluid impermeable layer in pneumatic tyres and tubes. The composition contains a halogenated isobutylene-containing elastomer and a nylon resin, having melting point between 170°C and 230°C. Said elastomer in form of vulcanised or partially vulcanised particles through dynamic vulcanisation is contained in form of a dispersed phase in a continuous phase of nylon in amount greater than 60 vol. % of overall content of elastomer and resin. Said period of time for dynamic vulcanisation is equal to or less than the defined holding time of the mixer. The method involves steps for mixing the elastomer with a vulcanising system thereof with fractional addition thereof into the nylon resin. The step for dynamic vulcanisation of the fractionally added amount of elastomer in the presence of a vulcanised composition from the previous step is repeated several times necessary to obtain total amount of halogenated elastomer in the said composition.

EFFECT: invention enables to achieve excellent longevity and elasticity properties with excellent air-tightness.

20 cl, 1 dwg, 5 tbl

 

The technical field to which the invention relates

The present invention relates to thermoplastic elastomer compositions, in particular, used for tires and other industrial applications of rubber, and to methods of producing such compositions.

Background of invention

Thermoplastic elastomeric compositions, in particular, used for tires and other industrial applications. For example, EP V considering the low permeability thermoplastic elastomer composition, which is the best as gatbering layer in the pneumatic tire. The specified thermoplastic elastomer composition contains a low-permeability thermoplastic matrix, such as a polyamide or a mixture of polyamides, in which the dispersed low-permeability rubber, such as the commercially available brominated copolymer of isobutylene and para-methylstyrene. In EP I and EP A the ratio of the viscosity of thermoplastic matrix and the dispersed rubber phase is determined as a function of the ratio of the volume fraction and independently is close to its value in order to obtain a high concentration of particles of vulcanized rubber small size, dispersed in thermoplastic phase. EP A, in addition, considers that the rubber particles of small size, dispersed in termoplastichny matrix, are important to achieve acceptable durability of the obtained composition, especially when such compositions are intended for use as interlayers in the pneumatic tire.

Compositions having the characteristic of low permeability (i.e. functioning as a gas barrier consisting of thermoplastic resin/blends containing thermoplastic resin such as high density polyethylene and nylon 6 or nylon 66 (HDPE/PA6,66, polyethylene terephthalate and an aromatic nylon (PET/MXD6), poly (ethylene terephthalate and a copolymer of ethylene-vinyl alcohol (PET/EVOH), where one thermoplastic resin is superimposed on top of another layer with the formation of multiple layers in forming them, and methods of making are considered, for example, in the work of I. Hata, Kobunshi (Polymers), 40 (4), 244 (1991). In addition, the application considering the use of such compositions as prozaicznego layer bus, is discussed in Japanese patent application No. 7-55929. However, since these materials are thermoplastic resin/the mixture of thermoplastic resins, although they are best gazobalonnoj characteristics, they lose their elasticity, and therefore, such films are destroyed when the bus is in use.

In addition, there are also examples of the application of a thermoplastic elastomer comprising a rubber and a thermoplastic resin, for use as a strip or bus (see Japanese patent application No. 8-183683), but usually elastic material of the type discussed here, and having the best durability, has a low heat resistance. In the case of thermoplastic elastomer using a thermoplastic resin having a melting temperature lower than the temperature of vulcanization of the tire, as a matrix, when the diaphragm vulcanization of the tire is released at the end of the cycle vulcanization of the tire, the inner surface of the tire is exposed to the appearance of defects due to adhesion of thermoplastic resin or abrasion of the diaphragm.

Regulation of the differences in viscosity between the rubber and the resin during mixing in order to reduce the particle size of the dispersed rubber described in S. Wu, Polym. Eng. Sci., 27 (5), 1987. It States that the size of dispersed particles of the rubber is reduced when the ratio of melt viscosities of the rubber/resin is brought close to 1, i.e. there is no difference in viscosities. However, in EP A stated that when attempting to obtain a thermoplastic elastomer composition having sufficient elasticity, strength and elongation, as well as better durability when the magnification ratio of the rubber and the curing ratio of the melt viscosities of the rubber/resin 1, the rubber becomes a matrix and the composition no longer has thermo is elasticnet.

In Japanese patent applications No. 8-193545, 9-175150 and 10-235386 it is assumed that in a layered structure in which you want the resistance to dynamic fatigue, such as the bus or the sleeve, when used to prevent the permeability thermoplastic elastomer composition consisting of rubber and resin, dispersed in it, you know getting the balance between elasticity and characterization prevent gas permeability obtained when using a mixture of elastic N11-nylon or 12-nylon and having the best characteristics prevent gas permeability N6-of nylon or N66-nylon. In addition, it is proposed to determine the volume fraction and viscosity of the melt using the following equation:

d/ϕm) × (ηmd) < 1,0,

in which φdand ϕmrepresent the volume fraction of the component of the continuous phase and the dispersed phase in thermoplastic elastomer composition, and ηmand ηdrepresent the viscosity of the melt components, and, in addition, to bring the ratio of viscosities ηmdto close to 1, to reduce the interval size of dispersed particles of rubber to improve durability. However, in EP A indicated that the durability at low temperatures is insufficient even when reducing the size of the cha is TIC rubber.

By overcoming the shortcomings of earlier attempts to obtain improved characteristics desired compositions containing rubber particles in the range of small size, dispersed in a thermoplastic matrix, the composition showing improved barrier properties to the fluid (gas or liquid) and the desired levels of strength and durability, suitable for use in tires and bag applications, was obtained using the method of the present invention.

Other links related to the present invention, include WO 2004/081107, WO 2004/081106, WO 2004/081108, WO 2004/081116, WO 2004/081099, US 4480074, US 4873288, US 5073597, US 5157081, US 6079465, US 6346571 and US 6538066.

Brief description of the invention

This invention relates to a thermoplastic elastomer composition containing (A) at least one halogenated isobutyramide elastomer; and (B) at least one nylon resin having a melting point of about 170-230°C, in which: (1) at least one halogenated isobutyramide elastomer is present as a dispersed phase of small vulcanized particles in a continuous phase of a specified nylon, where the particles are formed by dynamic vulcanization and particles comprise more than about 60 vol.% the specified volume of the elastomer and the resin.

In a particularly preferred variant of this is completed with the invention also relates to a method for producing a thermoplastic elastomer composition, carried out in a suitable mixer, and the specified mixer has a certain retention time, and the specified composition contains more than about 60 vol.% dispersed particles of the total amount, of at least one halogenated isobutylester elastomer, the said particles dispersed in a continuous thermoplastic matrix nylon resin, and the method includes steps: (1) mixture containing halogenated elastomer composition (A), and the specified composition (A) contains a first fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified first elastomeric fraction and a thermoplastic nylon resin (B) in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (C); (2) mixing of the composition (C) containing halogenated elastomer composition (D), and the specified composition (D) contains the second fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified second elastomeric fraction in suitable conditions of dynamic vulcanization time, temperature and shear to education to the notizie (E); (3) if the sum of the first and second fractions, halogenated elastomer is less than the total amount of halogenated elastomer in the specified thermoplastic elastomer composition, the mixing of the composition (S) containing halogenated elastomer composition (F), and the specified composition (F) contains a third fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified third elastomeric fraction in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (G), in which stage dynamic vulcanization fractional input amount of halogenated elastomer in the presence of dynamically vulcanized the composition of the previous step is repeated as many times as necessary in order to obtain the total amount of halogenated elastomer in the specified thermoplastic elastomer composition, and in which every specified conditions of dynamic vulcanization are sufficient to obtain a vulcanized condition in said elastomeric particles, at least about 50% of the maximum vulcanized condition specified elastomer and a curing system, and in which period of time the decree which authorized the dynamic vulcanization is approximately equal to or less than a certain retention time specified mixer.

Brief description of drawings

The drawing shows a microstructure according to a variant of example 13, i.e micrograph of 20 μm × 20 μm, obtained by using the atomic force microscope in which the light phase is nylon and the dark phase is a commercially available brominated copolymer of para-methylsterol-isobutylene (BIMS).

Detailed description of the invention

The preferred application of this invention relates to thermoplastic elastomer compositions for filling tires and barrier films, in particular to thermoplastic elastomer compositions showing excellent durability and impermeability to fluid media such as air, and liquids. Preferred features of the composition is aimed at maximizing content dispersed halogenated isobutilene elastomers in the form of vulcanized particles dispersed in the polyamide thermoplastic matrix. In addition, especially preferred aspects of the present invention relate to methods for producing a thermoplastic elastomer composition capable of providing a domain of rubber containing particles of small size, although these domains are also vysokochastotnymi and elastic. In addition, the present invention includes methods of obtaining Pneumatics is their tires and hoses, using the above composition. The preferred elastomer has low permeability and is preferably a polymer, such as halogenated isobutylester elastomers, and particularly preferred are brominated elastomers, especially brominated copolymers of para-methylsterol-isobutylene (BIMS); preferred are bromobutyl elastomers having a high content structure shown below; and also preferred are industrial bromobutyl elastomers or mixtures thereof with one or more of the above brominated elastomers with one another or with other polymers.

As used here, the new numbering scheme of the groups of the periodic system of elements is used, as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985). All molecular weights are srednevekovye, unless otherwise noted.

Throughout the application, including the claims, the expression "contain" and variations such as "contains" and "contain"and "have," "having," "includes" and "including" and its variants mean that the mentioned stages, elements or materials to which they relate, are essential, but other stages, elements or materials may be included and to include in the scope of the claims or description. If it is specified in the description and claims izaberete the Oia means, the invention and the claims of the invention allow a broad interpretation. These terms, especially in the case of the use in the claims, are inclusive or open-loop, and do not exclude additional unspecified elements or stages of the method.

In the present context, the expression "consisting essentially of" means excluding any element or combination of elements, as well as any number of any element or combination of elements that would change the basic and novel characteristics of the invention. Thus, only by way of example, thermoplastic composition, which is obtained by a method other than the method including dynamic vulcanization, or by using the method of dynamic vulcanization, in which the rubber component is introduced in a single amount or in which wysokometanowy rubber or other polymer or combination of polymers is used with the exception of halogenated isobutylester rubber in such compositions should be excluded. Alternatively, and again only by way of example, thermoplastic composition in which the curing system for the rubber gives the time of vulcanization with achieving the required level of vulcanization in the rubber, which is significantly greater than the retention time of the mixer, the use of which has been created for dynamic vulcanization, should be excluded.

For the purposes of the present invention, unless defined otherwise in relation to an individual property, characteristic, or parameter, the term "essentially"as applied to any criteria, such as a property, characteristic or parameter means according to the criterion established to such an extent that the specialist in the art will understand that the advantage is achievable or corresponds to the desired condition or property.

The term "polymer" may be used to refer to homopolymers, copolymers, interpolymers, terpolymers etc. Similarly, the term "copolymer" may refer to a polymer containing at least two monomer, optionally with other monomers.

When the polymer is indicated as containing monomer, the monomer present in the polymer in the polymerized form of the monomer or derivative form of the monomer. However, for ease of reference, the expression "containing the (appropriate) a monomer or the like is used in an abbreviated form. Similarly, when the catalytic components are described as containing neutral stable forms of the components, specialist in the art will understand that the active form component is a form that interacts with the monomers to obtain a polymer.

The term "otoolefan" refers to the any of the olefinic monomer, having two substitutions on the same carbon atom.

The term "multilevel" refers to any monomer having two double bonds. In a preferred embodiment, multilevel is any monomer containing two double bonds, preferably two conjugated double bonds such as conjugated diene, such as isoprene.

The term "elastomer" or "elastomeric"as used here, refers to any polymer or composition of polymers corresponding to the definition of ASTM D1566. The terms may be used interchangeably with the term "rubber" ("rubbers").

The term "alkyl" refers to a group of paraffin hydrocarbons, which can be derived from the alkane with the exception of one or more hydrogen atoms of the formula, such as, for example, methyl group (CH3or ethyl group (CH3CH2and so on

The term "aryl" refers to a hydrocarbon group which forms a cyclic structure, characteristic of aromatic compounds, such as, for example, benzene, naphthalene, phenanthrene, anthracene, etc. and usually has alternating double bonds (unsaturation) in its structure. The aryl group thus represents a group derived from aromatic compounds with the exception of one or more hydrogen atoms of the formula, such as, for example, phenyl, or C6 H5.

The term "substituted" refers to at least one of hydrogen group, substituted by at least one Deputy, selected from, for example, halogen (chlorine, bromine, fluorine or iodine), amino-, nitro-, sulfoxy- (sulfonate or alkylsulfonate), thiol-, alkylthio - and hydroxy-groups; alkyl straight or branched chain having 1-20 carbon atoms which includes methyl-, ethyl-, propyl-, tert-butyl-, isopropyl-, isobutyl group, etc.; the alkoxy, the alkoxy group with a straight or branched chain having 1-20 carbon atoms, which includes, for example, methoxy, ethoxy-, propoxy-, isopropoxy, butoxy, isobutoxy-, second -, butoxy-, tert-butoxy-, pentyloxy, isopentane, hexyloxy, heptyloxy-, octyloxy-, nonyloxy and decyloxy group; halogenoalkane, which means alkyl straight or branched chain having 1-20 carbon atoms, which contains at least one halogen, and includes for example, chloromethyl, methyl bromide, vermeil, iodomethyl, 2-chloroethyl, 2-bromacil, 2-foretel, 3-chloropropyl, 3-bromopropyl, 3-forprofit, 4-chlorobutyl, 4-terbutyl, dichloromethyl, dibromomethyl, deformity, diiodomethyl, 2,2-dichloroethyl, 2,2-dibromo-ethyl, 2,2-dottorati, 3,3-dichloropropyl, 3,3-direcror, 4,4-dichloroethyl, 4,4-deformaty, trichloromethyl, 4,4-deformaty, trichloromethyl, trifluoromethyl, 2,2,2-triptorelin, 2,3,3-cryptochromes, 1,1,22-tetraborate and 2,2,3,3-tetrafluoropropyl. Thus, the "substituted styrene link includes a pair of methylsterol, para-atistical etc.

The present invention contains at least one halogenated isobutyramide rubber. Usually it is present in the composition with a thermoplastic structural resin (preferably nylon), as described herein, in a volume ratio of the rubber:resin from about 50:45 to 80:20, preferably from about 60:40 to about 75:25, more preferably from about 65:35 to about 75:25. Halogenated rubber is defined as a rubber having at least about 0.1 mol.% halogen, such halogen as selected from the group consisting of bromine, chlorine and iodine. Preferred halogenated rubbers used in this invention include halogenated isobutylester elastomers (also referred to as halogenated isobutylester the homopolymers and copolymers). These elastomers can be described as a statistical copolymer link that is derived from C4-C7-samanaleya, such as a link that is derived from isobutene and at least one other polymerizable link. In one embodiment of the invention, halogenated isobutyramide copolymer is a butyl rubber or branched butyl rubber, especially brominated options indicated the data elastomers. (Used unsaturated butylketone, such as homopolymers and copolymers of olefins or isoolefine, and other types of elastomers suitable for the invention are well known and are described in RUBBER TECHNOLOGY 209-581 (Maurice Morton ed., Chapman & Hall 1995), THE VANDERBILT RUBBER HANDBOOK 105-122 (Robert F. Ohm ed., R.T. Vanderbilt Co., Inc. 1990), andEdward Kresge and H.C. Wangin 8 KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY 934-955 (John Wiley & Sons, Inc. 4th ed. 1993)).

Butylketone is usually obtained from the interaction of a mixture of monomers, the mixture has at least (1) component With4-C12-souleimanova monomer such as isobutylene, with (2) component multilingo monomer. The number of isoolefine is in the range from 70 to 99.5 wt.% the total Monomeric mixture in one embodiment, and from 85 to 99.5 wt.% in another embodiment. Multiliteracy component is present in an amount of from 30 to 0.5 wt.% in one embodiment, and from 15 to 0.5 wt.% in another embodiment. In yet another embodiment, multilevel is from 8 to 0.5 wt.% Monomeric mixture. Otoolefan represents preferably4-C12connection, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, simple metilidinovy ether, inden, vinyltrimethylsilane, hexene and 4-methyl-1-penten. Multilevel represents a C4-C14-multilife is, such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, MIRCEN, 6,6-dimethylfuran, hexadiene, cyclopentadiene and piperylene and other monomers, such as described in EP 0279456 and in U.S. patent No. 5506316 and 5162425. Other polymerizable monomers such as styrene and dichlorotris are also appropriate for copolymerization or copolymerization in butylcatechol. One version of the butyl rubber polymer used in the invention is obtained by the interaction of from 95 to 99.5 wt.% of isobutylene with from 0.5 to 8 wt.% isoprene, or from 0.5 wt.% to 5.0 wt.% isoprene in another version. Butylketone and methods for their preparation are described in detail, for example, in U.S. patent No. 2356128, 3968076, 4474924, 4068051 and 5532312.

Halogenated butyl rubber is produced by halogenoalkanes butyl product described above. Halogenoalkane may be performed by any method, and the invention is not limited here by way of halogenation. Methods of halogenation of polymers, such as butyl polymers are discussed in U.S. patents№№ 2631984, 3099644, 4288575, 4554326, 4632963, 4681921, 4650831, 4384072, 4513116 and 5681901. In one embodiment, the butyl rubber halogenous in hexane diluent at a temperature of from 4 to 60°C using bromine (Br2) or chlorine (Cl2as the halogenation agent. Can also be used post-processed the halogenated butilka the Chuck, as discussed in US 4288575. Used halogenated butyl rubber typically has, for example, the Mooney viscosity from about 20 to about 70 (ML 1+8 at 125°C) and from about 25 to about 55 in another embodiment. The preferred halogen is usually from about 0.1 wt.% up to 10 wt.% in relation to the weight of halogenated rubber, for example from about 0.5 wt.% up to 5 wt.%, alternatively, from about 0.8 wt.% up to about 2.5 wt.%, for example, from about 1 wt.% to about 2 wt.%. Particularly preferred form of the halogenated butyl rubber has a high content of the following halogenated patterns (preferably 60-95%, as measured by NMR), where X is a halogen, and in a particularly preferred embodiment, the halogen is bromine, alternatively, the halogen is chlorine:

Industrial option halogenated butyl rubber used in the present invention is Bromobutyl 2222 (company ExxonMobil Chemical Company). Its Mooney viscosity is usually about 27-37 (ML 1+8 at 125°C, ASTM 1646, modified), and the bromine content is about 1.8-2.2 wt.% in relation to the Bromobutyl 2222. Furthermore, the characteristics of vulcanization Bromobutyl 2222, as provided by the manufacturer, are as follows: MN of about 28-40 DN·m, ML approximately 7-18 DN·m (ASTM D2084). Other industrial variant of Galaga the new butyl rubber, used in the present invention is Bromobutyl 2255 (company ExxonMobil Chemical Company). Its Mooney viscosity is about 41-51 (ML 1+8 at 125°C, ASTM D1646), and its bromine content is about 1.8-2.2 wt.%. In addition, it features vulcanization as described by the manufacturer, are as follows: MN ranges from 34 to 48 DN·m, ML is from 11 to 21 DN·m (ASTM D2084). Industrial polymers of isobutylene described in detail in the article R.N. Webb, T.D. Shaffer and A.H. Tsou, “Commercial Isobutylene Polymers”, Encyclopedia of Polymer Science and Technology, 2002, John Wiley & Sons, shown here as a reference.

Others used a variant of the halogenated butyl rubber is halogenated branched or zvezdoobrazovanie" butyl rubber. These rubbers are described, for example, in EP V, US 5182333 and US 5071913, each of which is given here as a reference. In one embodiment, zvezdoobrazovanie butyl rubber (SBB) is a composition containing butyl rubber and politian or a block copolymer. For the purposes of the present invention a method of forming SBB is not a limitation. Polydiene, block-copolymer, or branching agents (hereinafter "polydiene"), are usually nationalaction-able and are present during polymerization of butyl rubber or halogenated butyl rubber, or may be blended with the butyl rubber with the formation of the SBB. Agent-fu is tvline, or polydienes may be any suitable branching agent, and the present invention is not limited to the type of polydiene, or branching agent used to obtain the SBB.

In one embodiment, the SBB is a composition of butyl rubber or halogenated butyl rubber as described above and a copolymer of polydiene and partially hydrogenated of polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypopylene, natural rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), block copolymers of styrene-butadiene-styrene and styrene-isoprene-styrene. Polydiene may be present in amounts relative to the total monomer content in wt.% usually more than 0.3 wt.%, alternatively, from about 0.3 wt.% to about 3 wt.% or from about 0.4 wt.% up to about 2.7 wt.%.

Preferably branched or zvezdoobrazovanie" butyl rubber, used here, is halogenated. In one embodiment, the halogenated, zvezdoobrazovanie butyl rubber (HSBB) contains butyl rubber or halogenated or dehalogenating, and politian or block copolymer, or a halogenated or dehalogenating. The method of halogenation is described in detail in US 4074035, US 5071913, US 5286804, US 5182333 and US 6228978. This izobreteny is not limited to the method of formation of HSBB. Polidan/block-copolymer, or branching agents (hereinafter "polydiene"), are usually nationalaction-able and are present during polymerization of butyl rubber or halogenated butyl rubber, or can be mixed with butyl rubber or halogenated butyl rubber with the formation of the HSBB. The branching agent, or polydienes may be any suitable branching agent, and the present invention is not limited to the type of polydiene used to obtain the HSBB.

In one embodiment, the HSBB is typically a composition comprising a halogenated butyl rubber as described above and a copolymer of polydiene and partially hydrogenated of polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypopylene, natural rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber, block copolymers of styrene-butadiene-styrene and styrene-isoprene-styrene. Polydiene may be present in amounts relative to the total monomer content in wt.% usually more than 0.3 wt.%, alternatively, about 0.3-3 wt.% or about 0.4 to 2.7 wt.%.

Industrial option HSBB used in the present invention is Bromobutyl 6222 (company ExxonMobil Chemical Company), having a Mooney viscosity (ML 1+8 at 125°C, ASTM D1646) about 27-37 and bromine content of about 2.2 to 2.6 wt.%. In addition, features and advantages of the CI vulcanization Bromobutyl 6222, as described by the manufacturer, are as follows: MN is from 24 to 38 DN·m, ML is from 6 to 16 DN·m (ASTM D2084).

The preferred copolymers of otoolefan/para-alkylthiol used here include random copolymers containing4-C7-souletin, such as isobutylene, and halogenmethyl. Halogenmethyl can be ortho-, meta -, or para-alkyl substituted styrene. In one embodiment, halogenmethyl is para-halogenmethyl containing at least 80 wt.%, more preferably at least 90 wt.% para-isomer. "Halogen"group can be any halogen, preferably chlorine or bromine. The copolymer may also include functionalityand interpolymer, in which at least part of the alkyl substituted groups present on the parts of styrene monomer, contain benzyl halogen or other functional group that is described next. These interpolymer here referred to as "isorevenue copolymers containing halogenmethyl" or simply "isorevenue copolymer".

Preferred isorevenue copolymers may include monomers selected from the group consisting of isobutylene or isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, simple metilfenidato ether, indene, vinyltrimethylsilane, hexene 4-methyl-1-pentene. Preferred isorevenue copolymers may also optionally contain multiline, preferably4-C14-multi-olefin, such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, MIRCEN, 6,6-dimethylfuran, hexadiene, cyclopentadiene and piperylene and other monomers, such as described in EP 279456 and US 5506316 and US 5162425. Desirable styrene monomers in isoretinoin copolymer include styrene, methylsterol, chloresterol, mitoxantron, inden and derivatives of indene, and combinations thereof.

Preferred isorevenue copolymers may be characterized as interpolymer containing the following monomer units, statistically placed along the polymer chain:

in which R and R1represent independently hydrogen, lower alkyl, preferably1-C7-alkyl, and primary or secondary alkylhalogenide, and X represents a functional group, such as halogen. Desirable Halogens are chlorine, bromine or combinations thereof, preferably bromine. Preferably each R and R1represents hydrogen. Group-CRR1H-CRR1X can be substituted for the styrene ring in either the ortho-, meta-, or para-positions, preferably in the para-position. Up to 60 mol.% para-substituted styrene is present in the interpolymer structure of the ur, can be functionalized structure (2)above, in one embodiment, be from 0.1 to 5 mol.% in another embodiment. In yet another embodiment, the amount of functionalized structure (2) is from 0.4 to 1 mol.%. The functional group X may be halogen or some other functional group that can be introduced by nucleophilic substitution of benzyl halogen other groups, such as carboxylic acids, salts of carboxylic acids, esters of carboxylic acids, amides and imides, hydroxy, alcoholate, phenolate, tiolet, simple tiefer, xantac, cyanide, cyanate, amino and mixtures thereof. These functionalityand somnolence copolymers, method for their preparation and methods of functionalliteracy and vulcanization more specifically addressed in the US 5162445.

Especially used of such copolymers of isobutylene and para-methylstyrene are copolymers containing from 0.5 to 20 mol.% para-methylstyrene, in which up to 60 mol.% methylseleninic groups present on the benzyl ring contain a bromine atom or chlorine, preferably bromine atom (para-methyl bromide-styrene)and its variants with acid or ester functional groups, where the halogen atom substituted functional groups of maleic anhydride or acrylic or methacrylic acid. These interpolymer referred to as the halogenated copolymers of isobutylene and para-methylstyrene or brominated copolymers of isobutylene and para-methylstyrene, and are commercially available under the trademark EXXPRO Elastomers (ExxonMobil Chemical Company, Houston, Texas). It is clear that the use of the terms "halogenated" or "octabromodiphenyl" does not limit the method of halogenation of the copolymer, but only describes a copolymer which contains units derived from isobutylene, links - derived para-methyl styrene and links - derived para-halogenmethyl.

These functionalityand polymers preferably have essentially homogeneous structural distribution, so that at least 95 wt.% the polymer has a water vapor content of alkylthiol 10% of the average water vapor content of alkylthiol in the polymer as determined by gel chromatography (as shown in US 5162445). More preferred polymers are also characterized by a narrow molecular weight distribution (Mw/Mn) of less than 5, more preferably less than 2.5, preferably srednevekovoi molecular weight in the range of from about 20,000 to about 2000000 and preferred srednekamennogo molecular weight in the range of from about 25,000 to about 750,000 people, as determined by gel chromatography.

Preferred halogenated copolymers of isobutylene and para-methylstyrene are brominated polymers which generally contain from about 0.1 to about 5 wt.% brometalia groups. In another embodiment, the number brometalia groups ranges from approximately 0.2 is about 2.5 wt.%. Being expressed in another way, the preferred copolymers contain from about 0.05 to about 2.5 mol.% bromine relative to the weight of the polymer, more preferably from approximately 0.1 to approximately 1.25 mol.% bromine and essentially do not contain ring halogen or halogen in the main chain of the polymer. In one embodiment of the present invention interpolymer is a copolymer of units derived From4-C7-samanaleya, links - derivatives of para-methylstyrene and links - derived para-halogenmethyl, which links a pair of halogenmethyl present in interpolymer in the amount of from about 0.4 to about 1 mol.% in relation to interpolymer. In another embodiment, the pair-halogenmethyl is para-brometalia. The Mooney viscosity (1+8, 125°C, ASTM D1646) is from about 30 to about 60 Mooney units.

In another embodiment, the ratio between the fraction of triads isoolefine and para-alkylthiol and mol.% para-alkylthiol introduced in the copolymer is described by the equation of distribution of sequences of the copolymer below, and is characterized by the parameter of the distribution of sequences of copolymer m.

F = 1 - {m A / (1 + mA)},

where m is a parameter of the distribution of sequences copolymer,

And represents the molar ratio of para-alkylthiol to and is olefine in the copolymer, and

F represents the fraction of triads para-alkylthiol-otoolefan-para-alkylthiol in the copolymer.

The best fit of this equation gives the value of m for the copolymerization of isoolefine and para-alkylthiol in particular diluent. In some embodiments, m is less than 38 alternative minimum 36, alternative less than 35 and alternative less than 30. In other embodiments, m is 1-38, alternative 1-36, alternative 1-35 and alternative 1-30. Copolymers having such characteristics, are discussed in WO 2004/058825 and WO 2004/058835.

In another embodiment, the copolymer is otoolefan/para-alkylthiol essentially does not contain long chain branching. For the purposes of this invention, the polymer which essentially does not contain long chain branching is defined as a polymer, for which g'srves.is more than or equal to 0,978 alternative is greater or equal to 0,980 alternative is greater or equal to 0,985, alternative more than or equal to 0,990 alternative is greater or equal to 0,995 alternative more than or equal to is 0.998, alternative more than or equal to 0,999, as defined pressure by size chromatography (SEC) with triple detection, as described below. Such polymers are also discussed in WO 2004/058825 and WO 2004/058835.

In another embodiment, the ratio between the fraction of triads isoolefine and multilatina and mol.% multilatina, vvedeno what about in halogenated rubber copolymer, is described by the equation of distribution of sequences of the copolymer below, and is characterized by the parameter of the distribution of sequences of copolymer m.

F = m A / (1 + mA)2,

where m is a parameter of the distribution of sequences copolymer,

Rather it represents a molar ratio of multilatina to isolario in the copolymer, and

F represents the fraction of the triad otoolefan-multilevel-multilevel in the copolymer.

Determination of the fraction of the triad of isoolefine and multilatina and mol.% multilatina introduced into the copolymer described below. The best fit of this equation gives the value of m for the copolymerization of isoolefine and multilatina each diluent. In some embodiments, m is 1.5, alternative more than 2.0, the alternative of more than 2.5, alternatively greater than 3.0, an alternative more than 3.5. In other embodiments, m is 1,10-1,25 alternative 1,15-1,20, alternative 1,15-1,25; and alternative m is about 1,20. Halogenated rubbers having these characteristics are discussed in WO 2004/058825 and WO 2004/058835.

In another embodiment, the halogenated rubber essentially does not contain long chain branching. For the purposes of this invention, the polymer which essentially does not contain long chain branching is defined as a polymer, for which g'vis.avg.with whom is more than or equal to 0,978, the alternative is greater or equal to 0,980 alternative is greater or equal to 0,985, alternative more than or equal to 0,990 alternative is greater or equal to 0,995 alternative more than or equal to is 0.998, alternative more than or equal to 0,999, as defined pressure by size chromatography (SEC) with triple detection, as described below. The presence or absence of long chain branching in polymers is determined using pressure size exclusion chromatography (SEC) with triple detection. SEC with triple detection is carried out on a Waters chromatograph 150C (Milford, mA)operating at 40°C, equipped with detectors of light scattering Precision Detectors PD2040 (Bellingham, Massachusetts), viscometry detector Viscotek model 150R (Houston, Texas) and a differential detector refractive index of Waters (integral with 150C). The detectors are connected in series with the detector light scattering, which is the first detector viscosity - and second differential detector refractive index of the third. Tetrahydrofuran is used as the eluent (0.5 ml/min) with a system of three 10 μm mixed-B/LS GPC columns firm Polymer Laboratories, Ltd. (Shropshire, UK). The instrument is calibrated using a 16 narrow polystyrene standards (firm Polymer Laboratories, Ltd.). Data are obtained using TriSEC software (Viscotek) is injected into the program WaveMetric's Igor Pro for analysis. Linear polyisobutylene is used to establish the relationship between the characteristic viscosity [η]lineardetermined by viscometry detector, and a molecular mass Mwdefined by the detector light scattering. The relationship between [η]linearand Mwis expressed by the equation Mark-Hovinga

[η]linear= Mwα

The parameters K and α are obtained from the double logarithmic graph of the characteristic viscosity of Mwα represents the tangent of an angle, It is a straight-line segment. Significant deviations from the dependency set for linear patterns which indicate the presence of long chain branching. Generally, samples that show a larger deviation from the linear dependence, contain more significant long chain branching. The scale factor g' indicates the deviation from a certain linear dependence

[η]sample =g' [η]linear

It is established that the value of g' must be less than or equal to 1 and greater or equal to 0. When g' is equal or close to 1, it is considered that the polymer is linear. When g' is significantly less than 1, the sample has long chain branching. See, for example, E.F. Casassa and G.C. Berry, “Comprehensive Polymer Science”, Vol. 2, (71-120), G. Allen and J.C. Bevington, Ed., Prgamon Press, New York, 1988. In the case of triple SEC-detecting g' is calculated for each data slice of the chromatographic curve. The average viscosity g'or g'srves.calculated for the full molecular mass distribution. The scale factor g'srves.calculated on the average of the characteristic viscosity of the sample:

g'srves.= [η]cf./(Mwα)

Other preferred halogenated elastomers, or rubbers include halogenated copolymer of isobutylene-para-methylsterol-isoprene as described in WO 01/21672A1.

Isobutylester elastomers used in thermoplastic elastomer compositions used as a layer for preventing the penetration of body fluid, as described herein, may be different or the same as halogenated elastomers present in other layers of the product received. For example, if permeable to the fluid layer is a layer of the tire, then the other layers of the tire, in particular layers in contact with the intermediate layer may also contain the same isobutylester elastomers. Similarly, halogenated isobutyramide elastomer used in the layer, preventing the passage of air, and the elastomers used in the connection layer, the adhesive layer and/or the frame may be Odin is new or different elastomer. In a preferred embodiment, halogenated isobutyramide elastomer used in the layer, preventing the passage of air, and the elastomer used in the connection layer, the adhesive layer and/or the frame are the same elastomer. In another embodiment, they are different. The same is understood that the elastomer content of the co monomer and halogen in the range of 2 wt.% from each other, respectively. Under various is understood that the elastomers contain different Halogens or comonomers or that the elastomers have the content of the co monomer or halogen, which is not in the range of 2 wt.% from each other. For example, BIMS-copolymer with 3 wt.% para-methylstyrene (PMS) and 5 wt.% bromine, is different with respect to BIMS-copolymer with 11 wt.% PMS and 5 wt.% bromine. In a preferred embodiment, the elastomer is present in the layer, preventing the passage of air, is a commercially available brominated copolymer of isobutylene and para-methylstyrene, and halogenated isobutyramide elastomer present in the coupling layer, the adhesive layer and/or the frame is the same or different brominated copolymer of isobutylene and para-methylstyrene. In another embodiment, the elastomer is present in the layer, preventing the passage of air, is a commercially available brominated copolymer is of isobutylene and para-methylstyrene, and halogenated isobutyramide elastomer present in the coupling layer, the adhesive layer and/or the frame is the brominated butyl rubber.

Used DVA compositions described herein also contain thermoplastic or structural resin (such as nylon) in addition to the elastomer.

For the purposes of the present invention structural resin (also called "structural thermoplastic resin", "thermoplastic resin or thermoplastic structural resin") is defined as any thermoplastic polymer, copolymer or their mixture, which have a young's modulus of more than 500 MPa and preferably the coefficient of permeability of less than 60×10-12cm3/cm2·cm Hg (at 30°C) and preferably a melting point of from about 170 to about 230°C, including (but not limited to) one or more of the following:

(a) the polyamide resin include nylon 6 (N6), nylon 66 (N66), nylon 46 (#46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), a copolymer of nylon 6/66 (N6/66), nylon 6/66/610 (N6/66/610), nylon MXD6 (MXD6), nylon 6T (N6T), a copolymer of nylon 6/6T copolymer of nylon 66/PP copolymer, nylon 66/PPS;

b) koinopolitia resins include polybutylene terephthalate (RHT), polyethylene terephthalate (PET), polietilentireftalat (PEI), a copolymer of PET/PEI, polyacrylate (PAR), polybutylenterephthalate (PBN), zhidkokristal the definition of complex polyester, the copolymer of polyoxyalkylenetriol/polybutylenterephthalate and other aromatic polyesters;

C) polyarylene resin: polyacrylonitrile (PAN), polymethacrylamide, copolymers of Acrylonitrile-styrene (AS), copolymers of Methacrylonitrile-styrene copolymers Methacrylonitrile-styrene-butadiene;

d) polymethacrylate resin: poly (methyl methacrylate), politicalit;

e) polyvinylene resin (for illustration, but without limitation): vinyl acetate (EVA), polyvinyl alcohol (PVA), copolymers of vinyl alcohol/ethylene (EVOA), grades (PVDC), polyvinyl chloride (PVC), copolymers of polyvinyl/polyvinylidene copolymer grades/methacrylate;

f) cellulose resin: cellulose acetate, acetylbutyrate cellulose;

g) fluorine-containing resin include polyvinylidene fluoride (PVDF), polivinilhlorid (PVF), PalaLottomatica (PCTFE), a copolymer of a tetrafluoroethylene/ethylene (ETFE);

h) a polyimide resin: aromatic polyimides;

i) polysulfones;

j) Polyacetals;

k) polylactones;

l) Polyphenylene oxyde and polyster;

m) a styrene-maleic anhydride;

(n) aromatic polyketone; and

a) a mixture of any and all of (a)-n), inclusive, and mixtures of any of the illustrated or described structural resins in each of a)to (n) inclusive.

For the purposes of the present invention the definition of structural resin includes alimera olefins, such as polyethylene and polypropylene.

Preferred structural resins include polyamide resins and mixtures thereof; particularly preferred resins include nylon 6, copolymer nylon 6/66, nylon 11, nylon 12, nylon 610, nylon 612, and mixtures thereof. In accordance with an alternative preferred variant of the present invention thermoplastic elastomer composition can be retseptoriani using component a thermoplastic resin, where the component is nylon resin contains nylon 11 or nylon 12 and copolymers of nylon 6/66 when the ratio of the composition (ratio by weight) from about 10:90 to about 90:10, preferably from about 30:70 to about 85:15. Such a thermoplastic elastomer composition based mixed resin can provide a thermoplastic elastomer composition having better durability and appearance, for example, vulcanized surface layer of the tire, as well as the best vozdukhosoderzhaniya properties and a good balance of these properties.

Optionally, other rubbers, or elastomers, can be used in combination with halogenated isobutylester elastomer. Such optional rubber component includes vysokovoltnoye rubbers and their hydrates. Rubbers, or elastomers, with a high content of diene are also referred to as vysokovolnom the second rubber. Usually a rubber containing typically at least 50 mol.% With4-C12-diene monomer, typically, at least about 60 mol.% to about 100 mol.%, more preferably, at least about 70 mol.% to about 100 mol.%, more preferably, at least about 80 mol.% to about 100 mol.%. Used vysokodekorativnye rubbers include homopolymers and copolymers of olefins or isoolefine and multilatinas or homopolymers of multilatinas. They are well known and are described in RUBBER TECHNOLOGY, 179-374 (Maurice Morton ed., Chapman & Hall, 1995) and in THE VANDERBILT RUBBER HANDBOOK 22-80 (Robert F. Ohm ed., R.T.Vanderbilt Co., Inc., 1990). Usually other optional rubber used in the present invention include, for example, natural rubber (NR), isoprene rubber (IR), apostilirovannye natural rubber, the best choice rubber (SBR), polybutadiene rubber (BR) (including high CIS-BR and low CIS BR), on BNR the rubber (NBR), hydrogenated NBR, olefin rubbers (for example, ethylene propylene diene monomer rubber (EPDM and EPM), modified maleic acid ethylene-propylene rubber (M-EPM), butyl rubber (IIR), copolymers of isobutylene and aromatic vinyl or diene monomer, acrylic rubber (ACM), and ionomers, other halogen-containing rubbers (for example, chloroprene rubbers (CR), hydrino the s rubber (CHR), chlorosulphurized polyethylene (CSM), chlorinated polyethylene (CM), modified maleic acid chlorinated polyethylene (M-CM), silicone rubbers (for example, methylphenylamine silicone rubber, dimethyl silicone rubber, methylphenylimino silicone rubbers), sulfur-containing rubbers (for example, polysulfide rubber), florkowski (for example, vinylidenefluoride rubbers, fluorine-containing (simple vinyl ether)containing rubbers, tetrafluoroethylene-propylene rubbers, fluorine-containing silicone rubbers, fluorine-containing postagedue rubbers), thermoplastic elastomers (for example, steroidogenesis elastomers, olefin elastomers, ester elastomers, urethane elastomers and polyamide elastomers) and mixtures thereof.

Preferred examples of high(diene monomer)containing rubbers include polyisoprene, polybutadiene rubber, the best choice rubber, natural rubber, chloroprene rubber, butadiene-Acrylonitrile rubber and the like, which can be used individually or in combinations and mixtures.

Since thermoplastic engineering resin and halogenated isobutyramide rubber significantly differ in solubility, in order to improve the compatibility of these polymers can be used an additional ingredient, str is cause compatibility. Such components that improves the compatibility, include guideline Acrylonitrile rubber (HNBR), epoxysilane natural rubber (ENR), NBR, hydranova rubbers, acrylic rubbers, and mixtures thereof. It is believed that the components that improves the compatibility, operating, modifying, in particular, reducing the surface tension between the components of the rubber and resin. Other components that improves the compatibility, include copolymers such as copolymers having the structure of one or both of thermoplastic resin and rubber polymer, or a structure of a copolymer having an epoxy group, carbonyl group, halogen group, amino group, maleic group, oxazoline group, hydroxyl group, etc. that can interact with a thermoplastic resin or a rubber polymer. They can be selected based on the type of mixed polymer of thermoplastic resin and rubber polymer, but used the copolymers typically include, for example, the block copolymer is a styrene/ethylene-butylene/styrene (SEBS) and its shape, modified maleic acid, EPDM, EPDM/styrene or grafted copolymer EPDM/Acrylonitrile, modified maleic acid; thermoplastic reaction paroxysmal; and mixtures thereof. The number miscible component that improves the compatibility, is not specifically limited, but when the line is to be generated, typically ranges from about 0.5 parts by weight to about 10 parts by weight per 100 parts by weight of the polymer component, in other words, in relation to the total number of polymer thermoplastic engineering resin and rubber polymer.

With regard to polymers and/or elastomers specified here, the terms "cured", "vulcanized" or "crosslinked" refers to a chemical reaction, containing education relations, as, for example, in the process chain-extending or crosslinking between the polymer chains that make up the polymer or elastomer, to such an extent that the elastomer subjected to such a process provides the desired functional properties of the resulting vulcanization reaction, when the bus comes into operation. For the purposes of the present invention to elastomers.grade composition was considered "utverzhdenii", "vulcanized or cross-linked, the absolute completeness of such the curing reaction is not required. For example, for the purposes of the present invention, the tire containing a composition layer on the basis of the present invention is sufficiently vulcanized, when the bus with the specified component withstands the tests required by the technical conditions during and after manufacture, and operates satisfactorily when used in the vehicle. In addition, the composition is udovletvoritel is but enough or essentially utverzhdenii, vulcanized or crosslinked, when the tire can be put into operation, even if the additional curing time can provide additional crosslinking.

Typically, polymeric compositions, such as polymer compositions used to get the tires are sewn into the finished tire products. Cross-linking or vulcanization is carried out with the introduction of cross-linking agents and/or accelerators; the total mixture of such agents is usually called vulcanizing "system". It is known that the physical properties, characteristics and durability of vulcanized rubber compounds directly related to the number (density knitting) and type of crosslinks formed during the vulcanization reaction. (See, for example, Helt et al.,The Post Vulcanization Stabilization for NR, RUBBER WORLD 18-23 (1991)). The vulcanization agents include components described above that facilitate or influence the vulcanization of elastomers and typically include metals, metal oxides, accelerators, sulfur, peroxides, and other agents known in the art and described above. Cross-linking or vulcanizing agents include at least one of, for example, sulfur, zinc oxide and fatty acids and mixtures thereof. You can also use peroxide-based vulcanizing system. Typically, the polymer composition can be crosslinked with the introduction of cross-linking agents, which for example sulfur, metal oxides (e.g. zinc oxide ZnO), ORGANOMETALLIC compounds, radical initiators, etc. and heating the composition or mixture.

When using a method known as "dynamic vulcanization", a method of vulcanizing dispersion system is modified, as described below. Usually the term "dynamic vulcanization" is used to denote the vulcanization method in which a thermoplastic, or structural, resin and at least one vulcanizes rubber are mixed under conditions of high shear and elevated temperature in the presence of a vulcanization agent or vulcanizing system rubber (caoutchouc). As a result, the rubber is simultaneously closed and dispersed as particles are preferably in the form of a microgel, in the resin, which forms a continuous matrix. The resulting composition known in the art as "dynamically vulcanized blend", or DVA. Usually dynamic vulcanization is effected by mixing the ingredients at a temperature equal to or higher than the temperature of vulcanization of rubber or of equal to or higher than the melting point of thermoplastic resin, when the use of equipment such as roll mills, Banbury mixers (Banbury®), continuous mixers, elasticator or mixing extruders such as twin screw extras is dairy). The unique feature of dynamically vulcanized, or utverzhdenii, composition is that, despite the fact that the rubber is utverzhdennym, the composition can be processed and re-processed the traditional technology of processing of thermoplastics, such as extrusion, injection molding, direct pressing, etc. Waste and/or Burr can also be disposed of and recycled. In a typical method of dynamic vulcanization curing additive effect so that essentially simultaneously mixes and vulcanized, knits or at least one of vulcanizate components in the composition containing at least one vulcanizes rubber, elastomer or polymer, and at least one polymer or resin, not vulcanized when using a vulcanizing agent (agents) for at least one vulcanizers component. (See, for example, US 6079465 and references here). However, in the present invention, the method of dynamic vulcanization optionally modified as described below, in order to receive special benefits derived from such modification.

The following is a vulcanizing agents that can function in the present invention: ZnO, CaO, MgO, Al2O3, CrO3, FeO, Fe2O3and NiO. Indicated on the LEDs metals can be used in combination with a set of suitable metal stearate (e.g., stearate salts of Zn, Ca, Mg and Al) or stearic acid and sulfur compound or alkylperoxide connection. (See alsoFormulation Design and Curing Characteristics of NBR Mixes for Seals, RUBBER WORLD 25-30 (1993)). To vulcanizing agent (agents) are often added accelerators of vulcanization of the elastomeric composition. Vulcanizing agent (agents) with or without the use of at least one accelerator is often referred to in the technique of curing "system" elastomer (elastomer). Vulcanizing system is used, since usually more than one vulcanizing agent is used for beneficial effects, in particular, when the mixture is used wysokometanowego rubber and less reactive elastomer. In addition, since the present invention uses a specially defined DVA-way, it is necessary that the curing properties of the system approached the blending method, so as to meet the conditions of the invention. In particular, the present DVA-method uses a phased introduction vulcanizers rubber component (components), which dynamically volcanically rubber (rubber) is introduced, at least two portions. In addition, it is necessary that all the rubber, put on the stage, was vulcanized before joining rubber (rubber) at the next stage, so that the time period will be characterized or defined ASU is it holding in the mixer. Usually first or if you have more than two stages of the introduction of rubber, then at the previous stage, caoutchouc (rubber) vulcanized to about 50% of the maximum vulcanization, which is a specific rubber (caoutchouc) and vulcanizing the system is able to achieve at the temperature of vulcanization when determining independently of the process of dynamic vulcanization in the period of time which is less than half retention time of the mixer. For example, in order to determine the characteristics of the specific vulcanization of rubber (rubber)that is present in the composition, the rubber (rubber and vulcanizing system can be combined in a manner known to experts in the art, for example, on a twin roll mill, a Bunbury mixer, or a mixing extruder. The sample mixture, often called "catalyzed" the mixture may be vulcanized in static conditions, such as in the form of a thin sheet, which is subjected to heat and pressure in the press. The samples catalyzed mixture vulcanized in the form of thin plates for gradually increasing periods of time and/or at higher temperatures, and then tested on the characteristics of the stress-strain and/or density of crosslinking by determination of the state of vulcanization (described in detail in ASTM standard D412 American the society for testing and materials).

Alternatively, the catalyzed mixture can be tested on the state of vulcanization using a viscometer with a vibrating disk to determine vulcanization (described in detail in ASTM D2084 American society for testing and materials). Having established the maximum degree of vulcanization, preferably dynamically vulcanized on the first or preceding stage caoutchouc (rubber), introduced in dynamically vulcanized mixture to such an extent that the degree of vulcanization of such rubber (caoutchouc) is selected from a group of approximately 50%, for example from about 60% to more than about 95%; from about 65% to about 95%, from about 70% to about 95%; about 75% to more than about 90%; from about 80% to about 98%; from about 85% to about 95%; and from about 85% to about 99%, over a period of time less than or essentially equal to the approximate retention time of the mixer used for dynamic vulcanization. Essentially additive rubber (rubber) to dynamically vulcanizate mixture similarly vulcanized before other additions rubber (caoutchouc), if they are available. Therefore, at the completion of the method of dynamic vulcanization vulcanizate rubbers, entered into the composition are sufficiently vulcanized with desired properties Ter is plastycznej composition, which they are a part, for example a barrier that holds the fluid (air or liquid), such as a layer of the tire. For the purposes of the present invention such a state of vulcanization can be called as "essentially fully vulcanized".

Note that vulcanizate rubbers are vulcanized at least 50% of the maximum state of vulcanization at which they are able based vulcanizing system, time and temperature, and usually the state of vulcanization of rubbers such exceeds 50% of the maximum vulcanization. If the state of vulcanization of rubber (caoutchouc), entered on one stage, is unvulcanized up to at least about 50% of their maximum, dispersed rubber particles may stick to particles of larger size, in particular, in the operations of mixing, which is undesirable. On the other hand, it may be desirable to vulcanizate rubber particles to less than the maximum state of vulcanization, which is able rubber, so that the elasticity, as defined, for example, the young's modulus, the rubber component is at a level appropriate for the end use for which it is intended composition, for example a layer of tires or component sleeves. Therefore, it may be desirable to adjust the degree of vulcanization of rubber (ka is Chukov), used in the song, so she was less than or equal to about 95% of the maximum possible degree of vulcanization as described above.

For the purposes of dynamic vulcanization in the presence of structural resin with the formation of, for example, vysokopronitsaemogo layer or film any conventional curing system which is capable of vulcanizate saturated or unsaturated, halogenated polymers, can be used for vulcanization, at least, the elastomeric halogenated copolymer With4-C7-samanaleya and para-alkylthiol, except that the peroxide vulcanizing substances, in particular, are excluded from the practice of the present invention, when there are one or more thermoplastic engineering resins, because peroxide will cause the stitching themselves of such resins. In this case, if the structural resin itself will vulcanizates, or to sew, this will result in excessive vulcanized neuroplastic composition. Suitable vulcanizing system for elastomeric halogenated copolymer component of the present invention include zinc oxide in combination with zinc stearate or stearic acid and, optionally, one or more of the following accelerators or vulcanizing agents: Permalux (di-ortho-tolylguanidine with the ü of dietechinacea), HVA-2 (meta-phenylene-bis-maleimide), Zisnet (2,4,6-tri-mercapto-5-triazine), ZDEDC (linktitlenomenu), and including for the purposes of the present invention other dithiocarbamate, Tetrone a (departmentdirectory), Vultac 5 (alkilirovanny phenoldisulfonic), SP1045 (phenol resin), SP1056 (bronirovannaja alkylphenolethoxylate resin), DPPD (diphenylethylenediamine), salicylic acid, ortho-hydroxybenzoic acid, wood resin, abietic acid and TMTDS (tetramethylthiuramdisulphide), used in combination with sulfur. However, in the present invention, since each additive vulcanizers rubber (rubber must be vulcanized to at least 50% of its (or their) maximum state of vulcanization temperature conditions until the next injection rubber (caoutchouc), as determined by the retention time of the mixing device, to obtain such a suitable result, it is also necessary to adjust the composition of the vulcanizing system. The ways in which this can be achieved, are generally known to experts in the art and also described in detail above, for example, using the method presented in ASTM D2084.

The vulcanization accelerators include amines, guanidine, thiourea, thiazole, tirami, sulfenamide, sulfonamide, THIOCARBAMATE, can the ATA, etc. The acceleration of the vulcanization process can be achieved by the introduction into the composition a quantity of the accelerator. The mechanism of accelerated vulcanization of rubber involves a complex interaction between the vulcanizing agent, accelerator, activator and polymers. Theoretically all available curing substance is consumed during the formation of effective crosslinks that connect the individual polymer chains with each other and improve the overall strength of the polymer matrix. Numerous accelerators known in the art and include, but are not limited to) the following: stearic acid, diphenylguanidine (DPG), tetramethylthiuramdisulphide (TMTD), 4,4'-dithiodimorpholine (DTDM), terabyteunlimited (TBTD), 2,2'-benzothiadiazole (MBTS), dihydrate disodium salt hexamethylen-1.6-bestialite, 2-(morpholinothio)benzothiazole (MBS or MOR), the composition of 90% MOR and 10% MBTS (MOR 90), N-tert-butyl-2-benzothiazolesulfenamide (TBBS) and N-oxydiethylene-N-oxydiethylene (OTOS), zinc-2-ethylhexanoate (ZEH) and N,N'-diethyltoluamide. Vulcanizing agents, accelerators and vulcanizing system of which they are part, part of which is used with one or more vulcanizate polymers, are well known in the art. Vulcanizing system can be dispersed in a suitable concentration to the desired parts of the rubber component is, moreover, the rubber component, optionally, contains one or more filler, extender chain and/or the plasticizer, for example, by mixing components rubber and vulcanizing system at the stage before the introduction kouchakzadeh composition in a thermoplastic resin using any mixing equipment commonly used in the rubber industry for this purpose, for example, twin roll mill, a Bunbury mixer, a mixing extruder, etc. This mixture is commonly called "catalysis" of the rubber composition. Alternatively, the rubber composition can be catalyzed at the stage of mixing extruder before dynamic vulcanization. Particularly preferably, vulcanizing system disbelieves in the rubber phase or in the rubber composition also optionally includes one or more fillers, extender chain and other conventional ingredients, intended for the final application, before the introduction of rubber in thermoplastic resin (resin) in the mixing equipment, which is intended for dynamic vulcanization.

In one embodiment of the present invention, at least one curing agent is typically present in amount from about 0.1 parts by weight to about 20 parts by weight per 100 parts by weight of rubber, viola is native, from about 0.5 parts by weight to about 10 parts by weight per 100 parts by weight of rubber.

Used combination of curing agents, modifiers and vulcanization accelerators can be illustrated as follows. As a regular agent, vulcanization of rubber, for example a sulfur vulcanization agent, use powdered sulfur, precipitated sulfur, high dispersion sulfur, sulfur with a surface treatment, insoluble sulfur, demoralizingly, alkylphenolate and mixtures thereof. Such compounds can be used in an amount of from about 0.5 parts by weight to about 4 parts by weight per 100 parts by weight rubber (mass parts per 100 mass parts of the elastomer component). Alternatively, when the use of such material is possible in relation to other components of the polymer and resin, a vulcanization agent, organic peroxide, benzoyl peroxide, tert-butylhydroperoxide, 2,4-dichlorobenzophenone, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane, 2,5-dimethylhexane-2,5-di(peroxybenzoate) and mixtures thereof. When using such curing agents can be present at a level from about 1 parts by weight to about 20 parts by weight per 100 parts by weight of rubber. Other used vulcanizing substances include agents, vulcanization phenolic resin, such as bromide alkylphenolic resin or mixed vulcanizing system, the content is based on the chloride of tin, the chloroprene or other halogen donor and alkylphenol resin, and mixtures thereof. Such agents can be used at a level from about 1 parts by weight to about 20 parts by weight per 100 parts by weight of rubber. Alternatively, other used vulcanizing agents, vulcanization modifiers and levels used include zinc oxide and/or zinc stearate (from approximately 0.05 parts by weight to about 5 parts by weight per 100 parts by weight of rubber), stearic acid (from about 0.1 parts by weight to about 5 parts by weight per 100 parts by weight of rubber), magnesium oxide (from about 0.5 parts by weight to about 4 parts by weight per 100 parts by weight of rubber), lyserg (10-20 parts by weight per 100 parts by weight or so), para-financiacion, para-dibenzoylresorcinol, tetrachloro-para-benzoquinone, poly-para-dinitrosobenzene (from about 0.5 parts by weight to about 10 parts by weight per 100 parts by weight of rubber), methylenedianiline (from approximately 0.05 parts by weight to about 10 parts by weight per 100 parts by weight of rubber) and their mixtures. In addition, if desirable or necessary, one or more vulcanization accelerators can be introduced in combination with the vulcanizing agent, including, for example, aldehyde-ammonia, guanidine, thiazole, sulfenamid thiuram, ditionality salt, thiourea and mixtures thereof, for example, in amounts from about 0.1 parts by weight to about 5 parts by weight per 100 parts by weight of rubber or more.

The way the dynamic vulcanization of the present invention is very different from the methods of dynamic vulcanization, Oba is but known in the art, as a consequence of using the phased introduction of at least one vulcanizers rubber or elastomeric component. Accordingly, the method uses multiple introductions of at least one rubber component, preferably at least two such introduction, although can be used for three, four or more. However, in each case, the division into stages is subjected to criteria of vulcanization, including retention time of the mixer, as described above. As described herein, the preferred polymer components contain halogenated isobutyleneisoprene copolymers as vulcanizers component (components), for example, halogenated butyl, such as chlorinated butyl or commercially available brominated butyl-, and commercially available brominated isobutylene-para-methylstyrene copolymer (BIMS-copolymer), and a thermoplastic polymer, such as nylon or a mix of nylon polymers. Particularly preferably, the dynamically vulcanized composition of the present invention contains a rubber component (s) in the form of dispersed, essentially is completely vulcanized, phase particles of small size in a continuous matrix of thermoplastic resin.

Without wanting to be bound by theory, it is assumed that the fine dispersion of rubber thus obtained in the comp is the dispositions of the present invention, are partly the result of a chemical reaction between, for example, benzyl bromide present in BIMS, or allylic halogen in the halogenated butile and terminal amines in the polyamides on the interface between the dispersed rubber particles and thermoplastic resin, formed in the process of mixing. The presence of such interfacial interactions in the process of mixing and at the same time the interaction of two immiscible polymers prevents coalescence of the dispersed rubber phase particles of small size, resulting in especially fine dispersion of the rubber phase. The presence of such interfacial interactions is usually called "reactionary giving mutual Miscibility and is described, for example, in U.S. patent No. 5571864 and 6469087, shown here as a reference. At the same time due to interfacial stability in these immiscible systems with reaction giving mutual Miscibility inversion phase component polymer mixture of high concentration, low viscosity, the rubber phase is inhibited as a consequence of the stabilizing effect of interfacial give Miscibility.

Usually in polymer mixtures on the basis of two polymers of different viscosity physical properties of the polymer will determine that the phase of the low viscosity of this mixture is a continuous the phase. (See, for example, D. R. Paul and J. W. Barlow, J. Macromol. Sci., Rev. Macromol. Chem., C18(1980), 109; V. I. Metelkin and V. S. Blekht, Kolloid. Zh., 46(1984), 476, and L. A. Ultracki, J. Rheol., 35(1991), 1615). The primary invention, which ultimately leads to the introduction of industrial dynamically vulcanized blends, or DVA, is U.S. patent No. 3037954 (A.M. Gessler). Then were successfully developed and produced by the industry compositions based on EPDM and polypropylene (such as Santoprene®, the company Advanced Elastomer Systems) as a consequence of the fact that high concentration, low viscosity EPDM-component is forced to be the dispersed phase when the vulcanization of EPDM in the process of mixing of polypropylene and EPDM in the mixer. Even in the absence of the reaction giving Miscibility vulcanization leads to the most significant viscosity increase; in other words, the viscosity of vulcanized component is effectively unlimited, and thermoplastic phase may be the continuous phase. When the application of these results to the inversion of the phase of the maximum content of the EPDM rubber in such systems can be increased to more than 70 vol.% rubbers.

In addition, although again without wanting to be bound by theory, it is assumed that according to theory of dense packing of the maximum volume fraction of monodisperse spheres, which can be placed in a fixed volume, based on a hexagonal close-Packed, costal is no 0,74, or 74% of the available volume. The maximum volume fraction achieved on the basis of statistical dense packing and cubic packing of monodisperse spheres, are considered components of 0.64 and 0.52, respectively. These calculations are described in R.K. McGeary, J. Am. Ceram. Soc., 44 (1061), 513. In polymer mixtures, dispersions are polydisperse, which is an advantage in maximizing Packed volume fraction. Taking into account these factors, it is expected that the maximum amount of packing of polydisperse polymer in a binary polymer mixture will be from about 70 vol.% to about 80 vol.%. However, since the interfacial stabilization prevents the phase inversion, the maximum content of the rubber is dynamically vulcanized systems polyamide/BIMS discussed in EP I and EP A, limited to less than 60 vol.%.

Higher rubber content can be achieved in a dynamically vulcanized compositions of the present invention as a consequence for additional packing rubber particles in the multiphase mixture, provided that pre-absorbed rubbers are essentially completely stable and can not stick together in large domains. This can be achieved by forcing the entire rubber (rubber), introduced at this stage of mixing, should be sufficiently vulcanized, etc is in other words, reaching at least about 50% of the maximum vulcanization (preferably, at least about 60%, preferably at least about 70%, preferably at least 80%) before the introduction of the following amounts of rubber, also referred to as the next stage of the introduction of rubber. The preferred content of halogenated isobutilene elastomer, typically present in the composition in the form of particles is more than about 60 vol.%, most preferably more than about 70 vol.%. For example, the elastomeric particles are present in amounts selected from the group consisting of from more than about 60 vol.% to about 80 vol.% (in relation to the volume of the elastomer (elastomers and structural resins (resins)); from about 62% vol. to about 78 vol.%; from about 65% to about 75 vol.%; from about 68% vol. to about 75 vol.%; from about 70 vol.% to about 78 vol.%; from approximately 71% to about 80 vol.%; from about 72 vol.% to about 79 vol.%; and from about 71% to about 80 vol.%; for example, when the above-mentioned elastomeric particles comprise from about 62% vol. to about 76%. In the present invention, a thermoplastic elastomer composition having a high content of rubber is obtained by using multi-stage injection rubber (caoutchouc), in which the speed of vulcanization of rubbers such regulated t is to, to be less than the retention time of the mixer, with the achievement of a result of relatively high degree of vulcanization. Dynamic vulcanization can be carried out in various types of industrial equipment commonly available in rubber and plastic industries, including internal Banbury mixers, roll mixers and mixing extruders. The preferred mixing equipment is a twin screw extruder with screws that are in engagement. As described above, the mixing is usually carried out in such time and temperature conditions that the dispersed particles of rubber are vulcanized to the extent necessary to maintain their stability, i.e. preventing the adhesion of such particles before or during the introduction of the next stage of the introduction of rubber or complete mixing of the composition. A suitable temperature range dynamic vulcanization is usually from about the melting temperature of the resin (resin) to about 300°C; for example, the temperature may be in the range of from about the melting temperature of the matrix resin (resin) to about 275°C. Preferably, the dynamic vulcanization is carried out in the temperature range from about 10°C to about 50°C above the melting temperature of the matrix resin. More preferably, the temperature of the mixture is about is about 20°C to about 40°C above the melting temperature of polyamide or of a mixed polyamide thermoplastic matrix.

In one embodiment of the present invention the required amount of crosslinking agent (agents) or vulcanizing system is dispersed in the elastomeric component by mixing a crosslinking agent, able to sew the elastomer in the elastomer component at low to medium temperatures, insufficient to significantly activated curing system, before contacting thus compounded elastomeric component with a component (components) of the resin for the implementation of dynamic vulcanization of the mixture. In addition, when the elastomer is introduced into the resin in stages or parts to obtain all of the desired composition, each part of the rubber composition may be the same, or, if desirable, the amount of vulcanizing system, present in part of rubber, may be modified to achieve the desired effect, for example greater or lesser degree of crosslinking of the elastomer parts. At the specified method crosslinking agent does not interact significantly with rubber or is able to partially interact with thermoplastic resin, causing either a reduction in molecular weight or crosslinking resin. In addition, easier to achieve speed control linkage and the degree of crosslinking of the elastomer component. Accordingly, compositions of the present invention show improved their is TBA.

One way to obtain thermoplastic elastomer composition can be carried out by the following method. First mixing device such as a Bunbury mixer, a double-roll mill for rubber and so on, are used for pre-mixing the elastomeric component and a certain amount of a crosslinking agent to obtain essentially homogeneous dispersion. At this point, the elastomeric component can be introduced into it the appropriate number of optional fillers, such as carbon black or modified carbon black, clay or modified clay, oil and/or plasticizer. During the specified phase mixing temperature must be regulated at a low enough level for the selected specific elastomer (elastomer) and taking into account the activity vulcanizing system in order to avoid premature crosslinking of elastomers. The temperature used during this stage of mixing, may be below about 120°C.

The desired number thus obtained elastomer component containing a crosslinking agent, and a certain amount of nylon resins (resin) is preferably loaded into a twin-screw mixing extruder or other mixing device capable of efficient dynamic vulcanization in reguliruemykh. The rubber component is dynamically stitched in the implementation of the mixing in the melt resins (resins), which causes the elastomeric component to dispergirujutsja as the dispersed phase (domain) in a nylon resin, which forms a continuous phase or matrix.

In addition, during the above mixing in the nylon resin or the elastomer component can be introduced various compendiosa agents other than curing substances, but it is preferable to mix them at the stage of dynamic vulcanization. The mixing device used to implement the dynamic vulcanization of a nylon resin and elastomer component is not specifically limited, including, for example, a screw extruder, PLASTICOLOR, a Bunbury mixer, twin-screw mixing extruder, etc. Among them for the dynamic vulcanization is preferably used twin-screw mixing extruder. Alternatively, two or more types of mixers can be used in sequential mixing. As conditions stage dynamic vulcanization, comprising mixing in the melt resins (resins), the temperature should be at least the temperature at which melt some nylon resin, but preferably above the melting temperature, as described above. In addition, the shear rate at the time the I mixing is generally above about 500 sec -1preferably from about 500 sec-1to about 7500 sec-1, alternatively from about 1000 sec-1to about 7500 sec-1for example , from about 2000 sec-1to about 7500 sec-1. The total time of mixing in each stage of the process of dynamic vulcanization is preferably from about 30 seconds to about 10 minutes

Since the method of the present invention includes a multi-stage introduction of the rubber component in the resin (resin) or a resin (resin) plus pre dynamically vulcanized and dispersed elastomer, the above stage dynamic vulcanization is repeated with at least one or more additional parts of the rubber composition to obtain the total number of the desired rubber in the final thermoplastic composition. Therefore, this method comprises at least two stages, but may be done for more than two stages, for example three, four, five or more, as desired. In addition, the number of rubber introduced at each stage can vary, provided that upon completion of all operations of mixing is achieved, the total number of the desired rubber in the entire composition, and at each stage introduces a suitable amount of rubber in order to obtain the desired small particle size and high volumetric percentage sod is neigh rubber in the final composition.

Thus obtained thermoplastic elastomer composition is structured elastomeric component, forming a discontinuous phase, dispergirovannoyj as the dispersed phase (domain) in the matrix nylon resin which forms a continuous phase. As a consequence of the dynamic vulcanization of the composition remains thermoplastic, film, layered or listopadova structure of the composition can be molded using conventional injection molding, extrusion or calendering. This result is shown in the drawing, which shows a view of the microstructure shown in the micrograph, performed by atomic force microscope (area 20×20 μm), a thermoplastic elastomer composition obtained according to a variant of example 13 described below. The drawing shows a high concentration areas with small particles or globules of vulcanized brominated isobutylene-para-methylstyrene elastomer, dispersed in a continuous nylon matrix and the continuous matrix has the appearance of a lighter area surrounding discrete elastomeric particles.

The 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 on IESNA flour and carbon black. Suitable filler materials include carbon black, such as a gas channel black, furnace black, thermal black, acetylene black, lamp black, modified carbon black, such as carbon black treated with silica, or carbon black, coated with silica (described, for example, in U.S. patent No. 5916934, shown here as a reference) and the like, Carbon black reinforcing grade is preferred. The filler may also include other reinforcing or newsrevue materials, such as silica, clay, calcium carbonate, talc, titanium dioxide and the like, the Filler can be present at a level of from 0 to about 30 wt.% by weight of rubber present in the composition.

The composition can also be layered intercalated or dispersed clay. These clays, also referred to as "nanoglide", are well known, and their identity, methods of obtaining and mixing with polymers are considered, for example, in JP 2000/109635, JP 2000/109605, JP 11/310643, DE 19726278, WO 98/53000 and in U.S. patent No. 5091462, 4431755, 4472538 and 5910523. Swellable layered clay materials suitable for the purposes of the present invention include natural or synthetic phyllosilicates, particularly smectic clays such as montmorillonite, nontronite, beidellite, volkonskoit, laponite, actarit, saponite, sauquoit, MEGADETH, kenyata, stevensite and the like, as well as vermiculite, halloysite, aluminated, hydrotalcite etc. These layered clays generally contain particles that contain lots of silicate platelets having a thickness of usually from about 4 Å to about 20 Å in one embodiment, and from about 8 Å to about 12 Å in another embodiment, connected together and containing interchangeable cations, such as Na+Ca+2, K+or Mg+2present at the interlayer surfaces.

The layered clay can be interkalirovannyi and stratified by treatment with organic molecules (agents causing swelling), can be subjected to ion-exchange reactions with the cations present at the interlayer surfaces of the layered silicate. Suitable agents that cause swelling include cationogenic surfactants, such as ammonium, alkylamine or alkylammonium- (primary, secondary, tertiary and Quaternary), phosphonium or sulfone-derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides. Desirable amine compounds (or the corresponding ammonium ion) are compounds with the structure of R1R2R3N, in which R1, R2and R3represent1-C30-alkali or-alkenes, which may be dinasovymi or different. In one embodiment, the laminating agent is a so-called long-chain tertiary amine in which at least R1represents a C12-C20-alkyl or alkene.

Another class of agents that cause swelling include agents that cause swelling, which can be covalently linked to the interlayer surfaces. They include polysilane structure-Si(R')2R2in which R' is the same or different in each case and is selected from alkyl, alkoxy or oxirane and R2is an organic radical that is compatible with the matrix polymer of the composite. Other suitable agents that cause swelling include protonated amino acids and their salts containing 2-30 carbon atoms, such as 12-aminododecanoic acid, Epsilon-caprolactam and other such materials. Suitable agents that cause swelling, and methods of intercalation of layered silicates are discussed in US 4472538, US 4810734, US 4889885 and WO 92/02582.

In a preferred embodiment of the present invention dissecting the agent or the agent that causes swelling, combined with the halogenated polymer. In one embodiment, the agent includes all primary, secondary and tertiary amines and phosphines, alkyl and arylsulfonyl and thiols and their multifunctional options. Desirable additives include: glinni the renal tertiary amines, such as N,N-dimethylethanolamine, N,N-dioctadecyl, digidrirovanny haloalkaliphilic etc., and polytetrahydrofuran with amine end; long-chain tirinya and thiosulfate compounds such as hexamethylenediisocyanate. In another embodiment of the invention improved interpolymer tightness can be achieved using a multifunctional curing agent such as hexamethylene-bis(nutritionalist) and hexamethylene-bis(cinnamaldehyde).

The number of layered intercalated or dispersed clay, entered into a composition in accordance with this invention, is a quantity sufficient to develop improve the mechanical properties or barrier properties of the composition, bursting strength or air/kislotonepronitsaemost. The number can typically be from about 0.5 wt.% to about 15 wt.% in one embodiment, or from about 1 wt.% up to about 10 wt.% in another embodiment, and from about 1 wt.% to about 5 wt.% in another embodiment, with respect to the content of polymer in the composition. The content of the layered intercalated or dispersed clay, expressed in parts by weight per 100 parts by weight of rubber, may be from about 1 parts by weight to about 30 parts by weight per 100 parts by weight of rubber in one embodiment, and from about 3 parts by weight to about 20 parts by weight per 100 parts by weight of the rubber is in a different version. In one embodiment, the exfoliating clay is a clay, stratifying by alkylamino.

As used here, the term "process oil" means as obtained from petroleum process oil, and synthetic plasticizers. Technological oil or oil-plasticizer may be present in vodokanalnyh compositions. These oils are mainly used to improve the processability of the composition in the process of receiving layer, for example mixing, calendering, etc. Suitable oil plasticizers include esters of aliphatic acids or hydrocarbon oil plasticizer, such as paraffinic or naphthenic petroleum oil. The preferred oil-plasticizer for use in standard non-DVA, prosloennyh compositions that do not contain structural resin is a paraffinic petroleum oil; hydrocarbon oils plasticizers suitable for use in such strips include oil, having the following General features:

PropertyPreferredMinimumMax
API density at 60°F or 15.5°C)15-30 1035
Flash point (method open Cup), °F (°C)330-450
(165-232°C)
300
(148°C)
700
(371°C)
Temperature fluidity, °F (°C)30 to +30
(from -34 to -1°C)
-35
(-37°C)
60
(15°C)

Usually the process oil may be selected from paraffinic oils, aromatic oils, naphthenic oils and polybutene oils. Polybutene technological oil is a low molecular weight (Mn) less than 15,000) a homopolymer or copolymer with an olefin units having from about 3 to about 8 carbon atoms, more preferably from about 4 to about 6 carbon atoms. In another embodiment, polybutene technological oil is a homopolymer or copolymer With4the raffinate. Low molecular weight "polybutene" polymers are described, for example, in SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS, 357-392 (Leslie R. Rudnick &Ronald L. Shubkin, ed., Marcel Dekker, 1999) (hereinafter "polybutene technological oil or polybutene"). Examples used polybutene oils are a series PARAPOLTMprocess oils (previously available from the firm of ExxonMobil Chemical Company, Houston, Texas, now is available from the company Infineum International Limited, Milton hill, England under the trade mark INFINEUM c, d, f or g), including cultivars, previously identified as PARAPOLTM450, 700, 950, 1300, 2400 and 2500. Other preferred polybutene oils are polybutene oil SUNTEXTMavailable from Sun Chemicals. Preferred polybutene process oils are usually synthetic liquid polybutene having a specific molecular weight, preferably Mn from about 420 to about 2700. Molecular weight distribution (MWD) Mw/Mn preferred polybutene oils typically ranges from about 1.8 to about 3, preferably from about 2 to about 2.8. The preferred density (g/ml) used polybutene technological oils is in the range from about 0.85 to about 0,91. Bromine number (mg/g) preferred polybutene oils is in the range from about 40 to process oil from the Mn 450 to about 8 for process oils with Mn 2700.

Rubber process oils are also ASTM designations depending on whether they are in a class of paraffinic, naphthenic or aromatic hydrocarbon process oils. The type of the process oil is a type commonly used in combination with the type of elastomer component, and chemical resinic specialist in this field, those who nicks - will know what type of oil should be used with a specific rubber in a particular application. For the composition layer of oil is typically present at a level from 0 to about 25 wt.%, preferably about 5-20 wt.%, from the whole composition. For thermoplastic elastomer composition of the oil can be present at a level of from 0 to about 20 wt.% the whole composition, preferably the oil is not included in order to maximize the tightness of the composition.

In addition, can be used plasticizers such as organic esters, and other synthetic plasticizers. Especially preferred plasticizer for use in the DVA compositions is N-butylsulfonyl or other plasticizers suitable for polyamides. In another embodiment, rubber process oils, such as naphthenic, aromatic or paraffinic oil softeners, may be present in an amount of from about 1 parts by weight to about 5 parts by weight per 100 parts by weight of rubber. In yet another embodiment, naphthenic, aliphatic, paraffinic and aromatic oils are essentially absent in the composition. By "essentially absent" means that naphthenic, aliphatic, paraffinic and aromatic oils may be present (if not absent at all) in the composition to the extent not bolee parts by weight of on 100 parts by weight of rubber.

The degree of vulcanization of the vulcanized rubber can be described in terms of gel content, the density of crosslinking, the amount of extractable components, or it can be based on the state of vulcanization, which can be achieved in the rubber when he vulcanized in the absence of resin. For example, in the present invention preferably halogenated elastomer reaches approximately 50-85% of complete cure against the elastomer per se, as defined, for example, bursting strength, or when using a standard testing device with vibrating disk (ASTM, standard Test Method for Rubber Property-Vucanization Using an Oscillating Disc Cure Meter).

When molding the obtained thermoplastic elastomer composition into a sheet, film or tube using the T-shaped listovalnogo head, tubular, straight or cross-head, a cylindrical head for blow molding, etc. at the end of the single screw extruder or celandroni you can use the composition as a layer for preventing air permeability, for example a layer of pneumatic tires and as a component or layer sleeves, etc. of thermoplastic elastomer composition of the present invention can be processed into strands once, granulated, and then molded using the single-screw extrud the RA, which is usually used for resin.

Thus obtained sheet or tubular molded product can be effectively used for filling pneumatic tires, bag or tube, or sleeve of the upper layer sleeves with low gas permeability. In addition, the characteristics of the low permeability of the composition are suitable for use with fluids other than gases, such as liquids, such as water, hydraulic fluid, brake fluid, liquid coolant, etc. provided that the layer is in direct contact with the fluid medium has a suitable resistance to it.

Any interval numbers listed in the description above or paragraphs and claims, the invention further relating to various aspects of the present invention, such as a series of numbers representing a particular set of properties, units of measure, conditions, physical States or percentages, is intended to literally explicit introduction here by reference or otherwise any number that is included in this interval, including any subset of numbers or ranges that potamiaena in any specified interval. In addition, the term "about" when used as a modifier for, or in conjunction with, characteristic or condition is intended to inform you that the number, spacing, reducing the specifications specifications and conditions discussed herein are flexible and that the implementation of the present invention by specialists in the art using temperatures, times, concentrations, amounts, contents, carbon numbers of atoms, properties such as particle size, surface area, bulk density, etc. that are outside of the range or different from a single value, will give the desired result, namely dynamically vulcanized composition with a high content of elastomer containing at least one isobutyramide elastomer and at least one thermoplastic, suitable for use, for example, in the pneumatic tire or sleeve or as a layer of tires.

Examples

For components used in the examples are the following commercially available products:

Components rubberDescription
BIIRBromobutyl™ 2222 (commercially available brominated copolymer of isobutylene-isoprene, 2% Br, ExxonMobil Chemical Company, Houston Texas)
BIMS-2Exxpro™ 96-1 (commercially available brominated copolymer of isobutylene-para-methylstyrene, 0,5% Br, 5% of PMS, ExxonMobil Chemical Company Houston Texas)
BIMS-1 Exxpro™ 89-4 (commercially available brominated copolymer of isobutylene-para-methylstyrene, 0,75% Br, 5% of PMS, ExxonMobil Chemical)
NRNatural rubber SMR-20 (Standard Malaysian Rubber)
SBRCopo™-1502 (best choice rubber, with 23.5% bound styrene, DSM Copolymer, Netherlands)
Components vulcanizing system
ZnOZinc oxide
St-acidStearic acid
ZnStThe zinc stearate
SSulfur
MBTSThe accelerator of sulfur-containing vulcanizing system 2,2'-benzothiazoline
C1The vulcanization modifier 1, 6PPD - N-(1,3-dimethylbutyl)-N'-phenyl-para-phenylenediamine
C2The vulcanization modifier 2, Armeen DMHR,dimethylaminophenyl rapeseed (C20-C27) tertiary amine, Akzo Nobel
Components of the additive
Struktol 40MS A substance that improves compatibility (dark mixture of aromatic hydrocarbon resins, Struktol Company)
Calsol 810Naphthenic process oil (Calumet Lubricants)
FlectolAntioxidant Flectol TMQ (polymerized 1,2-dihydro-2,2,4-trimethylquinoline, Flexsys America)
N660Carbon black (polucilasi grade)
N39S2Carbon black coated silica
T1SP1068 (agent for improving adhesiveness 1 - alkylphenolethoxylate resin, Schenectady International)
T2G100 (substance to improve the adhesiveness of 2 - synthetic policarpova resin (Quintone brand, Nippon Zeon Chemicals)
T3Sylvalite RE100L (substance to improve the adhesiveness of the 3 - ester of pentaerythritol rosin, Arizona Chemical)
Component structural resin
N11nylon 11, supplied as Rilsan BMN O firm Arkema
N6/66-1a copolymer of nylon 6/66, set aemy as Ube 5033B firm Ube
N6/66-2a copolymer of nylon 6/66 supplied as 5034B firm Ube
N6/66-3a copolymer of nylon 6/66 supplied as CM6001FS firm Toray
Component-additive
PPlasticizer, BM4, N-butylsulfonyl
CA substance that improves the compatibility, AR201, maleate copolymer EVA, DuPont-Mitsui
S1The stabilizer 1, the kit includes Irganox (Irganox), Tinuvin and copper iodide (CuI)
S2The stabilizer 2, the kit includes Irgafos (Irgafos) 168; (Tris(2,4-di-(tert)-butylphenyl)FOSFA) (Ciba Specialty Chemicals)

In accordance with the formulations shown in table 1, where the compositions are expressed in parts by weight per 100 parts by weight rubber (unless specified otherwise), receive the materials of examples 1-4 using the method of dynamic vulcanization carried out in a twin-screw extruder at 230°C. In particular, DVA receive in accordance with the method described in EP 0969039, with particular reference to the section entitled "obtaining thermoplastic elastomer composition. The elastomeric component and the volcanic mountain rage the existing system is loaded into elasticator, mix for about 3.5 minutes and discharged at about 90°C to obtain an elastomeric component with a vulcanizing system. The mixture was then granularit granulator rubber. Then the elastomeric component and the components of the resin loaded into a twin-screw mixing extruder and dynamically vulcanized with obtaining thermoplastic elastomer composition. BIMS-content gradually increases until, until there is a phase inversion, i.e. up until BIMS-phase becomes continuous. BIMS-contents in table 1 increases from example 1 to example 4 with increasing feed elastomeric component in the extruder in accordance with the formulations shown in table 1. As shown in table 1, poor dispersion is obtained when the rubber content of 62.5%, and phase inversion when the phase BIMS-rubber becomes continuous, occurs when the rubber content of 70%. Good quality extrudate, usually characterized by a smooth surface and a constant diameter strands are only given for the compositions of examples 1 and 2, as shown in table 1.

Table 1
Example1234
BIMS-2100100100100
ZnO0,150,150,150,15
Stearic acid0,600,600,600,60
ZnSt0,300,300,300,30
N1144,640,236,228,4
N6/66-130,727,724,919,5
P10,59,58,66,7
S0,870,790,710,56
BIMS, vol.%of 57.5 6062,570
Qualitygoodgoodpoorreversed phase
M50 (MPa)6,45,95,8NM
Elongation (%)370340320NM
Fatigue (cycles)1.5 M2.5 M2.3 MNM
M50 is a 50% modulus at room temperature, measured according to ASTM D412-92.
Elongation is the elongation at break at room temperature, measured according to ASTM D412-92.
Fatigue: the samples are tested for tensile strength at 40% amplitude voltage to 6.67 Hz and at room temperature; fatigue strength is expressed in cycles to failure.
M - million
NM cannot be measured

In accordance with the criterion of the phase continuity of the increase in viscosity BIMS-rubber may further extended the ü the content of the rubber. In examples 5-9 for increasing the viscosity of the rubber composition in the rubber composition is administered to 20 parts by weight of the filler, carbon black, coated with silica, per 100 parts by weight of rubber. Elastomeric components, BIMS rubber and its viscosity modifier - black carbon-coated silica are mixed in Bunbury mixer for 3-5 minutes and discharged at a temperature of 120°. Then a mixture of the rubber-carbon black catalyze vulcanizing agents in plasticators and unloaded at a temperature of about 90°C. These elastomeric mixture then granularit in the granulator rubber and used as food elastomeric component for rotating twin screw extruder, mixing with nylon. All nylon and elastomeric components are dosed in a twin-screw mixing extruder, operating at 230°C and at 100 rpm As shown in table 2, the phase inversion still occurs when 70% vol. rubber, although the mixture of good quality can be obtained when the content of rubber to 62.5%. However, the fatigue strength of dynamically vulcanized blends of polyamide/BIMS containing the filler is carbon black, is at risk in these compositions.

td align="center"> 0,7 M
Table 2
Example5 6789
BIMS-2100100100100100
N39S22020202020
ZnO0,150,150,150,150,15
Stearic acid0,600,600,600,600,60
ZnSt0,300,300,300,300,30
N1149,144,339,935,828,7
N6/66-1to 33.830,5 27,424,619,7
Pthe 11.610,59,48,56,8
S10,960,870,780,690,56
BIMS, vol.%of 57.56062,56570
QualitygoodgoodgoodpoorReversed phase
M50 (MPa)7,87,06,35,6NM
Elongation (%)300340360370NM
Fatigue1,0 M0,6 M0,7 MNM
M50 is a 50% modulus at room temperature, measured according to ASTM D412-92.
Elongation is the elongation at break at room temperature, measured according to ASTM D412-92.
Fatigue: the samples are tested for tensile strength at 40% amplitude voltage to 6.67 Hz and at room temperature; fatigue strength is expressed in cycles to failure.
M - million
NM cannot be measured

The materials of examples 10-14 obtained using co-rotating twin screw extruder ZSK-30 with screws which engages, with a ratio of length to diameter of screw (L/D) 29 and a retention time of approximately 1 min, operating at 100 rpm As indicated in table 3, example 10 with long vulcanization time more than 60 minutes has a phase inversion during the first mixing. C1 and C2 represent two vulcanization modifier in combination with a stabilizer S2 and adjusted to provide various times vulcanization. Curing substance is pre-dispersed in BIMS-rubber using internal Bunbury mixer operating at 60 rpm, with the temperature of discharge 100°C. the composition of the BIMS-rubber containing vulcanizing substances, then granularit using the granulate is RA before serving in the mixing extruder. The time of vulcanization of example 11 is slightly larger than the retention time of the extruder and, in turn, leads to a phase inversion in the second mixing. When the vulcanization time is less than 1 min, as in the case of examples 12-14, at the two-stage mixing can be obtained suitable as extrusion with a high content of rubber.

As shown in tables 1 and 2, the maximum content of rubber, can be achieved with single-stage mixing even with higher viscosity rubber, is 62.5%. Table 3 applies the two-stage mixing.

Table 3
Example1011121314
BIMS-1100100100100100
ZnO01,00,50,50,5
Stearic acid01,50,50,5
C110111
C20,50,50,500
N6/66-21200000
N6/66-3078787849
S20,60,40,40,40,25
The vulcanization time> 601,090,790,700,70
The first mixing**55/4555/4555/45 55/4555/45
The particle size of the rubberNM0,180,290,200,20
The second mixing**NM80/2080/2080/2070/30
The final rubber content,% vol.---62626273
The particle size of the rubberNMNM0,170,220,24
Observe qualityReversed phaseReversed phasegoodgoodgood
M50 (MPa)NMNM16218,5
The vulcanization time is a vulcanization time in minutes measured on the basis of the time required to reach 50% of vulcanization at 230°C, with the use of device MDR (ASTM D2084-92A).
The particle size of rubber: srednesemennyh diameter dispersion of rubber in microns, as measured by atomic force microscope and image processing.
NM cannot be measured as there is phase inversion.
M50 is a 50% modulus at room temperature, measured according to ASTM D412-92.
First mix**55/45 means the introduction of a 55 wt.% nylon and 45 wt.% (approximately 50%) rubber bracelet.
The second mixing**80/20 means the introduction of 80 parts by weight of the composition of the first mixing plus 20 parts by weight of rubber.
The second mixing**70/30 means the introduction of 70 parts by weight of the composition of the first mixing plus 30 parts by weight of rubber.

Also define the characteristics of the melt viscosity of the components and mixtures (melt viscosity is determined at 230°C and a shear rate of 1216 sec-1using the device for determining processing AIDS Monsanto) obtaining the following results:

Table 4
Component or mixtureViscosity (PA·s)
Exxpro 89-4 250
N6/66-1600
N6/66-2600
N6/66-3150
N11200
The first mixture200

Thus, the ratio of the viscosity of the resin to the rubber during the first mixture is 0.6, and the ratio of the viscosity of the first mixture to the rubber during the second mixture is 0.8. In addition, since the viscosity of the mixture of rubber plus vulcanizing system in the absence of stitching will be essentially the same as the viscosity of the rubber is obtained a similar value.

All documents described herein are presented as links, including priority documents and/or testing procedures, if they are not in contradiction with the given text. The principles, preferred options and ways of implementation of the present invention described in the above description.

Although the invention is described herein with reference to particular situations, it should be clear that these options are only an illustration of the principles and applications of the present invention. Therefore, it should be clear that can be done numerous modifications of the illustrative is the option and that can be developed in other structures without departure from the essence and scope of the present invention, as defined by the attached claims. Similarly, the term "comprising" is synonymous with the term "including" from the point of view of the Australian legislation.

Various aspects and variations of the present invention are presented in the following numbered paragraphs. This invention is as follows:

1. A thermoplastic elastomer composition containing

(A) at least one halogenated isobutyramide elastomer; and

(C) at least one nylon resin having a melting point of from about 170°C to about 230°C;

in which:

(1) the specified at least one elastomer is present as a dispersed phase of small vulcanized particles in a continuous phase of a specified nylon;

(2) the particles of the elastomer formed by dynamic vulcanization; and

(3) the elastomer particles comprise more than about 60 vol.% the specified volume of the elastomer and the resin.

2. The composition according to claim 1, in which the mentioned elastomeric particles are present in amounts selected from more than 60 vol.% up to 80 vol.%; from approximately 62% to about 78 vol.%; from about 65% to about 75 vol.%; from about 68% vol. to about 75 vol.%; from about 70 vol.% to about 78 vol.%; from approximately 71% to about 80 vol.%; and from about 72 vol.% to about 79%.

3. Composers who ia according to claim 1, in which these elastomer particles comprise more than about 65%.

4. The composition according to claim 1, in which the said elastomer particles comprise more than about 62%vol.

5. The composition according to claim 1, in which the said particles of the elastomer is from about 62% vol. to about 78%.

6. The composition according to claim 1, in which the said particles of the elastomer is from about 62% vol. to about 76%vol.

7. The composition according to claim 1, in which the degree of vulcanization of these elastomer particles is at least about 50% of the maximum degree of vulcanization, which specified the elastomer is able to achieve on the basis of the composition and the conditions in which vulcanized specified elastomer.

8. The composition according to claim 7, in which the rate of vulcanization is selected from the group consisting of from about 60% to more than about 95%; from about 65% to about 95%, from about 70% to about 95%; about 75% to more than about 90%; from about 80% to about 98%; from about 85% to about 95%; and from about 85% to about 99%.

9. The composition according to claim 7, in which the rate of vulcanization is at least about 80%.

10. The composition according to claim 1, additionally containing at least one component selected from the group consisting of fillers and plasticizers.

11. The composition according to claim 1, in which the nylon resin with whom holds a mixture of (i) nylon 11 or nylon 12 and (ii) a copolymer of nylon 6/66 and compositional ratio (i):(ii) ranges from about 10:90 to about 90:10.

12. The composition according to claim 11, in which the specified compositional ratio (i):(ii) ranges from about 30:70 to about 85:15.

13. The composition according to claim 1, in which indicated at least one halogenated isobutyramide elastomer selected from the group consisting of halogenated butyl rubber, halogenated copolymer of otoolefan/para-alkylthiol, halogenated copolymer of isobutylene-para-methylsterol-isoprene, halogenated branched butyl rubber and halogenated zvezdarabuilding butyl rubber.

14. The composition according to item 13, in which the specified halogenated butyl rubber has a high content of the following halogenated patterns, where X is a halogen:

15. The composition according to item 13 or 14, in which the halogen is selected from the group consisting of bromine and chlorine.

16. The composition according to item 13, in which the specified halogenated copolymer of otoolefan/para-alkylthiol contains4-C7-souletin.

17. The composition according to item 16, in which the specified halogenated copolymer of otoolefan/para-alkylthiol contains a halogenated copolymer of isobutylene and para-methylstyrene.

18. The composition according to 17, in which the specified halogen is bromine.

19. Pneumatic tire containing layer that prevents permeability, containing the third thermoplastic elastomer composition according to claim 1.

20. The sleeve containing thermoplastic elastomer composition according to claim 1 as at least one layer of tubular bag material.

21. The method of obtaining thermoplastic elastomer composition is carried out in a suitable mixer, and the specified mixer has a certain retention time, the composition contains more than about 60 vol.% the dispersed particles of the total amount, of at least one halogenated isobutylester elastomer, the said particles dispersed in a continuous matrix of a thermoplastic polyamide resin, and the method includes the following stages:

(1) a mixture containing halogenated elastomer composition (A), and the specified composition (A) contains a first fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified first elastomeric fraction; and a thermoplastic nylon resin (B) in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (C);

(2) mixing the composition (C) containing halogenated elastomer composition (D), and the specified composition (D) contains the second fraction of the total amount of halogenated elastomer in the specified thermopla is partially elastomeric compositions and, also contains a curing system for the specified second elastomeric fraction in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (E);

(3) if the sum of the first and second fractions, halogenated elastomer is less than the total amount of halogenated elastomer in the specified thermoplastic elastomer composition, mixing the composition (S) containing halogenated elastomer composition (F), and the specified composition (F) contains a third fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified third elastomeric fraction in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (G);

in which stage of dynamic vulcanization fractional input amount of halogenated elastomer in the presence of dynamically vulcanized compositions of the previous step is repeated so many times as needed to get the total amount of halogenated elastomer in the specified thermoplastic elastomer composition; and

in which every specified conditions of dynamic vulcanization on each stage are sufficient for up to the achievements of the state of vulcanization in these elastomer particles, at least about 50% of the state maximum specified vulcanization of the elastomer and curing system, and

wherein said period of time dynamic vulcanization equal to or less than about a specific retention time specified mixer.

22. The method according to item 21, containing two fractional introduction of the specified halogenated elastomer.

23. The method according to item 21, containing at least three fractional introduction of the specified halogenated elastomer.

24. The method according to item 21, in which these elastomer particles are present in amounts selected from the group consisting of from more than about 60 vol.% to about 80 vol.%; from approximately 62% to about 78 vol.%; from about 65% to about 75 vol.%; from about 68% vol. to about 75 vol.%; from about 70 vol.% to about 78 vol.%; from approximately 71% to about 80 vol.%; from about 72 vol.% to approximately 79% and from about 71% to about 80 vol.%.

25. The method according to item 21, in which the said elastomer particles comprise more than about 65%.

26. The method according to item 21, in which the said elastomer particles comprise more than about 62%vol.

27. The method according to item 21, in which the said particles of the elastomer is from about 62% vol. to about 78%.

28. The method according to item 21, in which the said particles of the elastomer is from about 62% vol. to about 76%vol.

29. The way p is item 21, in which the rate of vulcanization is selected from the group consisting of from about 60% to more than about 95%; from about 65% to about 95%, from about 70% to about 95%; about 75% to more than about 90%; from about 80% to about 98%; from about 85% to about 95%; and from about 85% to about 99%.

30. The method according to claim 1, in which the rate of vulcanization is at least about 80%.

31. The method according to item 21, in which the specified elastomers.grade composition additionally contains at least one component selected from the group consisting of fillers and plasticizers.

32. The method according to item 21, in which the specified nylon resin comprises a mixture of (i) nylon 11 or nylon 12 and (ii) a copolymer of nylon 6/66 and compositional ratio (i):(ii) ranges from about 10:90 to about 90:10.

33. The method according to p in which the specified compositional ratio (i):(ii) ranges from about 30:70 to about 85:15.

34. The method according to item 21, wherein said at least one halogenated isobutyramide elastomer selected from the group consisting of halogenated butyl rubber, halogenated copolymer of otoolefan/para-alkylthiol, halogenated copolymer of isobutylene-para-methylsterol-isoprene, halogenated branched butyl rubber and halogenated zvezdarabuilding booth is laucala.

35. The method according to clause 34, wherein said halogenated butyl rubber has a high content of the following halogenated patterns, where X is a halogen:

36. The method according to clause 34, in which the halogen is selected from the group consisting of bromine and chlorine.

37. The method according to clause 34, wherein said halogenated copolymer is otoolefan/para-alkylthiol contains4-C7-souletin.

38. The method according to clause 37, wherein said halogenated copolymer is otoolefan/para-alkylthiol contains a halogenated copolymer of isobutylene and para-methylstyrene.

39. The method according to § 38, in which the specified halogen is bromine.

1. thermoplastic elastomer composition used as impermeable to fluid media layer in the pneumatic tire and hose products containing
(A) at least one halogenated isobutyramide elastomer; and
(B) at least one nylon resin having a melting point of from about 170 to about 230°C;
in which:
(1) the specified at least one halogenated isobutyramide elastomer is present as a dispersed phase of small vulcanized or partially vulcanized particles in a continuous phase of a specified nylon;
(2) these particles halogenated isobutylester e is Stomer are formed by dynamic vulcanization; and
(3) these particles halogenated isobutylester elastomer comprise more than about 60 vol.% the specified volume of the elastomer and the resin
moreover, the above thermoplastic elastomer composition produced by the method comprising the stage of:
a) a mixture containing halogenated elastomer composition (A)containing a first fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and,
besides containing vulcanizing system for the specified first elastomeric fraction; and a thermoplastic nylon resin (B) in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (C);
(b) mixing the composition (C) containing halogenated elastomer composition (D), and the specified composition (D) contains the second fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified second elastomeric fraction, in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (E);
(3) if the sum of the first and second fractions, halogenated elastomer is less than the total amount of halogenated elastomer in the specified compositions the AI thermoplastic elastomer, then spend the mixture of compositions (E) and containing halogenated elastomer composition (F), and the specified composition (F) contains a third fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified third elastomeric fraction, in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (G);
and stage dynamic vulcanization fractional input amount of halogenated elastomer in the presence of dynamically vulcanized compositions of the previous step is repeated as many times as needed to get the total amount of halogenated elastomer in the specified thermoplastic elastomer composition; and
and every specified conditions of dynamic vulcanization on each stage are sufficient to achieve the state of vulcanization in these elastomer particles, at least about 50% of the state maximum specified vulcanization of the elastomer and curing system, and
where specified period of time dynamic vulcanization equal to or less than about a specific retention time specified mixer.

2. The composition according to claim 1, in which the mentioned elastomeric particles prisutstvie who are from more than 60 to 80 vol.%.

3. The composition according to any one of claims 1 and 2, in which the degree of vulcanization of these elastomer particles is at least about 50% of the maximum degree of vulcanization, which specified the elastomer is able to achieve on the basis of the composition and the conditions in which vulcanized specified elastomer.

4. The composition according to any one of claims 1 and 2, in which the nylon resin comprises a mixture of (i) nylon 11 or nylon 12 and (ii) a copolymer of nylon 6/66, and the compositional ratio (i):(ii) ranges from about 10:90 to about 90:10.

5. The composition according to any one of claims 1 and 2, in which indicated at least one halogenated isobutyramide elastomer selected from the group consisting of halogenated butyl rubber, halogenated copolymer of otoolefan/para-alkylthiol, halogenated copolymer of isobutylene-para-methylsterol-isoprene, halogenated branched butyl rubber and halogenated star-branched butyl rubber.

6. The composition according to any one of claims 1 and 2, in which the specified halogenated butyl rubber has a high content of the following halogenated patterns, where X is a halogen:

7. The composition according to claim 6, in which the halogen is selected from the group consisting of bromine and chlorine.

8. The composition according to claim 5, in which the specified halogenic the bath copolymer of otoolefan/para-alkylthiol contains 4-C7-souletin.

9. The composition according to claim 1, where the composition is introduced into the product, and the product is a pneumatic tyre or sleeve.

10. The method of obtaining thermoplastic elastomer composition used as impermeable to fluid media layer in the pneumatic tire and hose products, carried out in the mixer, and the specified mixer has a certain retention time, the composition contains more than about 60 vol.% the dispersed particles of the total amount, of at least one halogenated isobutylester elastomer, the said particles dispersed in a continuous matrix of a thermoplastic nylon resin, and the method includes the following stages:
(1) a mixture containing halogenated elastomer composition (A), and the specified composition (A) contains a first fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified first elastomeric fraction; and a thermoplastic nylon resin (B) in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (C);
(2) mixing the composition (C) containing halogenated elastomer composition (D), and the specified composition(D) contains the second fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition, and also contains a curing system for the specified second elastomeric fraction, in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (E);
(3) if the sum of the first and second fractions, halogenated elastomer is less than the total amount of halogenated elastomer in the specified thermoplastic elastomer composition, conducting the mixture of compositions (E) and containing halogenated elastomer composition (F), and the specified composition (F) contains a third fraction of the total amount of halogenated elastomer in the specified thermoplastic elastomer composition and, in addition, contains a curing system for the specified third elastomeric fraction, in suitable conditions of dynamic vulcanization time, temperature and shear with the formation of the composition (G);
in which stage of dynamic vulcanization fractional input amount of halogenated elastomer in the presence of dynamically vulcanized compositions of the previous step is repeated as many times as needed to get the total amount of halogenated elastomer in the specified thermoplastic elastomer composition; and
in which every specified conditions of dynamic vulcanization on each stage are sufficient for the stijene state of vulcanization in these elastomer particles, at least about 50% of the state maximum specified vulcanization of the elastomer and curing system, and
wherein said period of time dynamic vulcanization equal to or less than about a specific retention time specified mixer.

11. The method according to claim 10, containing two fractional introduction of the specified halogenated elastomer.

12. The method according to claim 10, containing at least three fractional introduction of the specified halogenated elastomer.

13. The method according to any of p-12 which includes the elastomeric particles are present in an amount of more than about 60 to about 80 vol.%.

14. The method according to any of PP-12, in which the rate of vulcanization is from about 60 to about 99%.

15. The method according to any of PP-12, in which the specified nylon resin comprises a mixture of (i) nylon 11 or nylon 12 and (ii) a copolymer of nylon 6/66, and the compositional ratio (i):(ii) ranges from about 10:90 to about 90:10.

16. The method according to any of PP-12, wherein said at least one halogenated isobutyramide elastomer selected from the group consisting of halogenated butyl rubber, halogenated copolymer of otoolefan/para-alkylthiol, halogenated copolymer of isobutylene-para-methylsterol-isoprene, halogenated branched Buti is rubber and halogenated star-branched butyl rubber.

17. The method according to item 16, wherein said halogenated butyl rubber has a high content of the following halogenated patterns, where X is a halogen:

18. The method according to 17, in which the halogen is selected from the group consisting of bromine and chlorine.

19. The method according to item 16, wherein said halogenated copolymer is otoolefan/para-alkylthiol contains4-C7-souletin.

20. thermoplastic elastomer composition used as impermeable to fluid media layer in the pneumatic tire and hose products, consisting essentially of dynamically vulcanized mixture:
(A) the brominated isobutylene-para-methylstyrene elastomer; and
(B) a resin of a copolymer of nylon 6/66,
in which the specified elastomer is present as a dispersed phase of small, dynamically vulcanized particles in a continuous phase of a specified nylon, and these elastomer particles comprise about 73% vol. the specified volume of the elastomer and the resin; and where the
(1) the dynamic vulcanization is carried out in two stages in a twin-screw extruder having a retention time of approximately 1 min;
(2) use the elastomer, in which pre-dispersed vulcanizing system, with the specified curing system has a time of volcanic mountain rage is then to, at least 50% of the maximum vulcanization of the elastomer is less than a specified retention time of extruder:
(3) in the first stage dynamically vulcanized a mixture of 55 wt.% nylon and 45 wt.% elastomer, and in the second stage 70 wt.% the mixture obtained in the first stage, advanced, dynamically vulcanized with 30 wt.% elastomer.



 

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2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention refers to elastic composition for many practices, including manufacturing tyre tracks and tyre casing side plates, tyre pillows, tank liners, hoses, rollers, conveyor belts, rubber tubes, gas masks, etc. Elastic composition contains, at least, one halogenated butyl elastomer and, at least, one mineral additive with a surface modified by, at least, one organic compound, containing, at least, one hydroxyl group and one base group including nitrogen atom and chosen of protein and amino alcohol group. Tyre casing tracks made of this composition are characterised with improved mechanical properties, e.g., tensile strength, abrasion resistance, i.e. wear resistance, as well as low rolling resistance and good force transfer especially while wet.

EFFECT: production of composition for tyre tracks improving mechanical properties of the material, ensuring low rolling resistance and good force transfer especially while wet.

6 cl, 6 tbl, 6 ex, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to elastomeric composition, which includes, at least, one halogenated butyl elastomer, at least, one filler and, at least, one organic compound, as organic compound it contains compound, containing, at least, one hydroxyl group and one containing nitrogen atom base group, representing aminoalcohol with nitrogen layer from 0.1 to 5 fractions per a hundred elastomer fractions, and in addition to containing, at least, one hydrated metal halogenide, with definite ratio of separate ingredients (in weight faction). Invention also relates to method of obtaining elastomeric product by mixing components of said elastomeric composition with further vulcanisation of formed mixture, as well as to protector or insert of automobile tyre, produced from elastomeric product, manufactured by claimed method. Claimed elastomeric composition can be applied in many fields of practical application, including using it for manufacturing protectors and side walls of tyres, tyre inserts, reservoir coating, hoses, rollers, conveyor belts, rubber tubes, gas masks, etc. Tyre protectors made from such composition possess enhanced resistance to abrasive attriction, that is, are wear-resistant, and thermal stability, as well as low resistance to rolling, and pass force well, especially in wet state.

EFFECT: ensuring resistance to abrasive attriction, thermal stability and low resistance to protector rolling.

12 cl, 2 tbl, 2 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to thermoplastic compositions, which have better mechanical properties and permanent strength and to a pneumatic tyre, containing such a composition. The elastomer composition is a dynamic vulcanised mixture (A) of halogenated isobutylene elastomer component, (B) polyamide component, (C) amine component and common additives. Elastomer (A) is dispersed in form of a domain in a continuous phase of polyamide (B). Amine component (C) is chosen from a group consisting of secondary diamines and a mixture of the given secondary diamines and tertiary amines. The amine component is taken in a quantity such that, viscosity of the isobutylene elastomer in conjunction with the amine component is the same as the viscosity of the polyamide component during dynamic vulcanisation.

EFFECT: improved impermeability of the thermoplastic elastomer composition, its mechanical properties at low temperature and permanent strength.

3 cl, 7 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to compositions of ternary copolymers on an isobutylene base and can be used in tyres, in particular in motor car components, such as protectors, inner lining of tyres, air bladders and tubes. The vulcanised elastomer composition contains halogenated ternary copolymer links from C4 to C8 derived from iso-olefin, links from C4 to C14 derived from multi-olefin and links derived from p-alkylstyrol. The composition is vulcanised in the presence of a sulphur vulcanising group. The value of adhesion to butadiene-styrene rubber of the vulcanising composition at 100°C is more than 70 N/mm. The composition also optionally contains filler and/or extra rubber. The suitable fillers are modified carbon black, carbon black, silicon dioxide, aluminium oxide, calcium carbonate, clay, mica, talc, titanium dioxide, starch, wood powder and their combination.

EFFECT: improved adhesion to the frame, elasticity with retention of impermeability to air.

52 cl, 1 dwg, 8 tbl

FIELD: transportation; chemistry.

SUBSTANCE: invention relates to to elastomer composition containing at least one halogenated butyl elastomer, at least one mineral filler and at least one compound containing silicon. Note that the composition contains a mix of at least one silazane compound as the silicon-containing compound and at least one agent containing at least one amino alcohols. The invention also relates to the method of making an elastomer product by mixing the components of the given elastomer composition with the subsequent vulcanisation of the mix formed, and to the tread or the car tyre insert from the elastomer product thus produced. This elastomer composition may be used in many industrial branches, including the production of treads and its side walls, tyre inserts, covering of various vessels, hoses, conveyor belts, rubber tubes etc.

EFFECT: improved mechanical properties of tyres, higher anti-abrasion properties and lower rolling friction.

13 cl, 10 tbl, 5 ex, 11 dwg

FIELD: polymer materials.

SUBSTANCE: invention, in particular, relates to isobutylene-based halogenated polymers showing elevated pre-treatment strength and elevated impermeability as well as to and a method for preparation thereof. Non-cured thin barrier layer for rubber products comprises 3-95% isobutylene-based polymer and 95-3% semicrystalline polymer having melting temperature from about 25 to about 105°C and melting heat from about 9 to about 50 J/g as measured by differential scanning calorimetry. This barrier layer is used for inside tire envelope and as inner tube. Rubber compound contains semi-crystalline propylene polymer with about 75 wt % propylene units and is prepared on common rubber manufacture equipment.

EFFECT: improved pre-treatment strength, pre-treatment elongation, and pre-treatment relaxation properties at elevated temperature and improved aging resistance and barrier properties.

35 cl, 8 tbl

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