RU2456311C2 - Method for efficient mixing when producing thermoplastic elastomer composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: thermoplastic elastomer composition is obtained through dynamic vulcanisation in a high-shearing mixer at high temperature. The composition contains dispersed particles of a first halogenated elastomer containing isobutylene, and dispersed particles of a second elastomer having a functional group capable of reacting with a polyamide and being grafted onto the polyamide. Particles of the first and second elastomers are dispersed in a continuous thermoplastic polyamide matrix. The method involves dispersion of a curing agent in the halogenated elastomer and obtaining a pre-formed, preferably granulated composition. Polyamide resin and optional light stabilisers are then fed into the mixer. Shearing action is applied and heating is carried out to melt the polyamide and obtain a mixture. A polyamide plasticiser is then added to reduce viscosity of the polyamide mixture. Granules of the pre-formed elastomer composition are then fed into the mixer and heating and shearing action is then applied. The second elastomer is fed and heating and shearing action is continued in order to disperse the second elastomer. After dynamic vulcanisation, the thermoplastic elastomer composition is discharged from the mixer.

EFFECT: invention enables to obtain improved impermeability characteristics for gases and fluid media, strength and longevity.

20 cl, 9 tbl

Description

FIELD OF TECHNOLOGY

The present invention relates to thermoplastic elastomeric compositions, in particular suitable for use in the fields of application of tires and other rubber products, and, in particular, to methods for producing such compositions.

BACKGROUND OF THE INVENTION

EP 722850 B1 describes a low permeable thermoplastic elastomeric composition that has excellent properties as a gas-tight layer in pneumatic tires. This thermoplastic elastomeric composition includes a low permeable thermoplastic matrix, such as a polyamide or a mixture of polyamides, in which a low permeable rubber, such as the isobutylene-para-methyl styrene brominated copolymer, commonly referred to as BIMS, is dispersed. In documents EP 857761 A1 and EP 969039 A1, it was stated that the ratio of the viscosities of the thermoplastic matrix and the dispersed phase of rubber depends both on the ratio of volume fractions and, independently, should be close to the unit value to obtain a high concentration of vulcanized particles dispersed in the thermoplastic phase rubber characterized by a small particle size. In addition, EP 969039 A1 describes the suitability of a small particle size dispersed rubber dispersed in a matrix of thermoplastic resin to achieve acceptable durability resulting from the composition, in particular if you intend to use such compositions as internal sealing layers of pneumatic tires. Further improvements to the technology for producing thermoplastic elastomeric compositions suitable for use in industrial applications are described by these inventors in this document and others in published US applications 2006/0223941 and 2007/0060684 by reference incorporated herein.

Compositions exhibiting low gas permeability characteristics (i.e., functioning as a gas-tight layer) formed from mixtures based on a thermoplastic resin / thermoplastic resin system, such as in the case of high density polyethylene resin and nylon 6 or nylon 66 (HDPE / PA6 / PA66), polyethylene terephthalate and aromatic nylon (PET / MXD6), polyethylene terephthalate and copolymer vinyl alcohol-ethylene (PET / EVOH), where as a result of molding one thermoplastic resin is layered on top of another layer, getting several layers, and methods for their preparation are described, for example, in the publication I. Hata, Kobunshi (Polymers), 40 (4), 244 (1991). In addition, the scope associated with the use of such a composition as the inner sealing layer of a tire is described in Japanese Patent Application No. 7-55929 (i.e., JP-A-7-55929). However, since these materials are thermoplastic resin / thermoplastic resin mixtures, they exhibit a lack of flexibility in the presence of excellent gas impermeability characteristics, and therefore such films are susceptible to destruction if used in a vehicle tire that is subjected to significant stress and bending.

In addition, there are also examples of the use of a thermoplastic elastomer formed from rubber and a thermoplastic resin as an internal sealing layer or in a tire; see Japanese Patent Application No. 8-183683 (i.e., JP-A-8-183683), but in general, a flexible material of the type described herein and having excellent durability exhibits low heat resistance. In the case of a thermoplastic elastomer using a thermoplastic resin as a matrix having a melting point lower than the vulcanization temperature of the tire, when the pressure is removed from the diaphragm of the vulcanization of the tire at the end of the vulcanization cycle of the tire, the inner surface of the tire is prone to appearance defects due to adhesion of the thermoplastic resin to the vulcanization diaphragm or rubbing thermoplastic resin about it.

The regulation of viscosity differences between rubber and resin during mixing in order to reduce the particle size of the dispersed rubber was reported in S. Wu, Polym. Eng. Sci., 27 (5), 1987. The author of Wu reported that the particle size of the dispersed rubber decreased as the ratio of the melt viscosities of rubber / resin approached 1, that is, if their viscosities were equal to each other. However, as reported in document EP 969039 A1, when trying to obtain a thermoplastic elastomeric composition characterized by sufficient flexibility, strength and elongation, as well as excellent durability, as a result of increasing the rubber content and maintaining the ratio of the melt viscosity of rubber / resin equal to 1, the rubber becomes continuous matrix, and such compositions containing vulcanized rubber, no longer demonstrate the presence of thermoplasticity.

As proposed in Japanese patent applications No. 8-193545, 9-175150 and 10-235386 (i.e., JP-A-8-193545, JP-A-9-175150 and JP-A-10-235386, respectively), in the case of laminate a design that is required to demonstrate dynamic fatigue resistance, such as in the case of a tire or hose, when using a gas penetration prevention thermoplastic elastomeric composition formed of rubber / resin dispersed therein, a balance is known between flexibility and gas permeability due to use of the mixture Flexible N11 or N12 Nylon and N6 or N66 Nylon with its superior gas penetration prevention ability. In addition, it was proposed to determine the volume fraction and viscosity of the melt using the following equation, denoted as alpha:

(ϕ _d / ϕ _m ) x (η _m / η _d ) <1.0,

where the volume fractions of the component in the form of a continuous or matrix phase and the component in the form of a dispersed phase in a thermoplastic elastomeric composition are ϕ _m and ϕ _d, respectively, and the melt viscosity of the components in the form of a matrix and dispersed phase are η _m and η _d, respectively, and, in addition, bring the viscosity ratio η _m / η _d to 1 to reduce the particle size domain of the dispersed rubber particles in order to improve durability. However, as reported in document EP 969039 A1, simply with a decrease in the particle size of the rubber, durability at low temperatures was insufficient.

Thus, the limitations of previous approaches to obtain improved performance characteristics of the desired compositions, including a rubber domain characterized by a small particle size dispersed in a thermoplastic matrix, where the composition would exhibit improved gas or fluid impermeability characteristics and desirable levels of durability suitable for applications in tires and hoses, suggest a constant need for improvement aniyah attained by the use of methods of the present invention.

SUMMARY OF THE INVENTION

A durable, flexible, impermeable thermoplastic elastomeric composition is obtained using a dynamic vulcanization method implemented in a suitable mixer capable of shearing polymer components at elevated temperatures to produce a thermoplastic elastomeric composition, said composition comprising dispersed particles of at least one first an elastomer comprising a halogenated elastomer containing isobutylene and dispersed particles of at least at least one second elastomer having at least one functional group capable of reacting and grafting onto the polyamide, said particles of said at least one first and at least one second elastomer being dispersed in a continuous matrix of thermoplastic nylon resin containing at least one polyamide selected from the group consisting of nylon homopolymers and nylon copolymers, said method comprising the steps of: (1) dispersing said with a halogenated elastomer of at least one representative selected from a hardener or curing system suitable for crosslinking said halogenated elastomer in order to obtain a preformed halogenated elastomer composition using shear conditions, mixing time and temperature sufficient to substantially uniformly disperse said hardener or curing system, but not sufficient to stimulate substantially crosslinking mentioned utogo elastomer, which would prevent its subsequent flow and dispersion when added to the nylon at elevated temperature and shear; (2) introducing said at least one nylon and optionally at least one heat stabilizer or oxidative stabilizer or light stabilizers of nylon or a combination thereof into said mixer and shear and heat enough to stimulate the melting of nylon and disperse said optional a stabilizer in said nylon and obtaining a nylon mixture; (3) the introduction of at least one nylon plasticizer in an amount sufficient to stimulate a substantially correspondence between the viscosity of said nylon mixture and the viscosity of said previously prepared halogenated elastomer composition at temperature and under shear conditions present in said mixer; (4) introducing said preformed halogenated elastomer composition into said mixer and conducting heating and shear, sufficient to initiate dynamic vulcanization of said halogenated elastomer; and (5) introducing said second elastomer and continuing to heat and shear substantially to disperse said second elastomer and essentially to complete said dynamic vulcanization of said halogenated elastomer; and releasing said dynamically vulcanized thermoplastic elastomeric composition from said mixer.

In one preferred embodiment, and in connection with the pre-composition, for the convenience of conducting a controlled supply of the pre-prepared mixture, the pre-halogenated elastomer composition is granulated and the granules are cooled.

The dynamic vulcanization method is preferably implemented in a twin-screw mixing extruder under controlled heating and shear conditions when each of the elastomers (elastomer) and other components of the composition are introduced into the extruder at positions along the length of the extruder screw, providing optimal reaction and dispersion for the components in the nylon matrix. The first elastomer or rubber is preferably introduced after plasticizing the nylon component (s) and before introducing the second elastomer or rubber. The method effectively provides a dynamically vulcanized composition having a preferred morphology comprising stable small particles of a vulcanized elastomer.

DETAILED DESCRIPTION OF THE INVENTION

Preferred applications of the present invention relate to thermoplastic elastomeric compositions for the inner seal layer of a tire and impermeable films, more specifically, to thermoplastic elastomeric compositions exhibiting excellent durability and impermeability to fluids such as air and liquids. Preferred features of the composition relate to an improved or maximized content of dispersed halogenated, preferably brominated, isobutylene elastomers in the form of vulcanized particles dispersed in a continuous polyamide thermoplastic matrix. In addition, particularly preferred aspects of the invention relate to efficient mixing methods suitable for use in the preparation of a thermoplastic elastomeric composition, capable of providing a rubber domain comprising small particles, while such domains are also highly extensible and elastic. In addition, the invention includes methods for producing pneumatic tires and hoses using the above compositions. A preferred elastomer is characterized by low permeability and is preferably a polymer, such as halogenated elastomers containing isobutylene, and brominated elastomers, in particular brominated para-methylstyrene-isobutylene copolymers, are particularly preferred; particularly preferred are bromobutyl elastomers having a high level of structure, as illustrated hereinafter; and also preferred are commercial bromobutyl elastomers or mixtures thereof containing one or more of the aforementioned brominated elastomers in conjunction with one another or with other polymers.

As used herein, the new numbering scheme for the groups of the Periodic Table is what has been described in Chemical and Engineering News, 63 (5), 27 (1985). All molecular weights are mass-average unless otherwise indicated.

Throughout the description of the invention in its entirety, including the claims, the following terms should have the indicated meanings:

Contain or containing: the word “contain” and variations of the word, such as “comprising” and “contains”, as well as “have”, “having”, “includes”, “include” and “including” and their variations, mean that the named process steps, components, elements or materials to which they relate are essential, but other steps, components, elements or materials may be added, and a structure corresponding to the scope of the claims or description of the invention will still be obtained. When they are mentioned in the description of the invention and in the claims, they mean that the invention and what is claimed is considered to be what follows and possibly more. These terms, especially when used in the claims, are inclusive or non-limiting and do not exclude additional, unmentioned components, elements or materials or process steps. For the purposes of Australian patent law, the term “comprising” should be construed as synonymous with the term “including”.

Essentially consisting of: in the present context, "essentially consisting of" means the exclusion of any element or combination of elements, as well as any number of any element or combination of elements that would change the basic and new features of the invention. Thus, by way of example and not by way of limitation, a thermoplastic elastomeric composition obtained using a method that did not include dynamic vulcanization will be excluded.

Essentially: for the purposes of the present invention, unless otherwise defined with respect to a particular property, characteristic or variable, the term “essentially” used for any criteria, such as a property, characteristic or variable, means that the criteria are met to such an extent that a specialist in the relevant field of technology recognizes the achievement of compliance with the resulting benefit or the desired value of the state or property.

The term "polymer" can be used to refer to homopolymers, copolymers, interpolymers, terpolymers and the like. Similarly, the term “copolymer” can mean a polymer containing at least two monomers, optionally in conjunction with other monomers.

If the polymer is called containing monomer, then in the polymer the monomer will be present in the polymerized form of the monomer or in a derivative form of the monomer. However, for convenience of reference, the phrase “containing (corresponding) monomer” and the like are used as abbreviations. Similarly, when describing catalyst components as containing neutral stable forms of components, one skilled in the art should understand well that the active form of the component will be that which reacts with monomers to form polymers.

The term "isoolefin" means any olefin monomer having two substituents on the same carbon atom.

The term "multiolefin" means any monomer having two or more double bonds. In a preferred embodiment, the multiolefin is any monomer having two conjugated double bonds, such as a conjugated diene, like isoprene.

As used herein, the term “elastomer” or “elastomers” means any polymer or polymer composition consistent with the definition from ASTM D1566. These terms can be used interchangeably with the term "rubber (s)".

The term “alkyl” means a paraffinic hydrocarbon group that can be produced from an alkane by eliminating one or more hydrogen atoms from the formula, such as, for example, a methyl group (CH ₃ ) or an ethyl group (CH ₃ CH ₂ ) and the like.

The term “aryl” refers to a hydrocarbon group that forms a ring structure characteristic of aromatic compounds such as, for example, benzene, naphthalene, phenanthrene, anthracene and the like, and usually has an alternating double bond (“unsaturation”) in its structure. Thus, an aryl group is a group derived from an aromatic compound as a result of exclusion from the formula of one or more hydrogen atoms, such as, for example, phenyl or C ₆ H ₅ .

The term “substituted” refers to at least one hydrogen group substituted by at least one substituent selected, for example, from halogen (chlorine, bromine, fluorine or iodine), amino group, nitro group, sulfoxy group (sulfonate or alkyl sulfonate), thiol, alkylthiol and hydroxy group; alkyl, straight or branched chain, containing from 1 to 20 carbon atoms, which includes methyl, ethyl, propyl, tert-butyl, isopropyl, isobutyl and the like; alkoxy group, a straight or branched chain alkoxy group containing from 1 to 20 carbon atoms and including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy , isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; halogenated, which means straight or branched chain alkyl containing from 1 to 20 carbon atoms, which is substituted by at least one halogen and includes, for example, chloromethyl, bromomethyl, fluoromethyl, iodomethyl, 2-chloroethyl, 2-bromoethyl, 2- fluoroethyl, 3-chloropropyl, 3-bromopropyl, 3-fluoropropyl, 4-chlorobutyl, 4-fluorobutyl, dichloromethyl, dibromomethyl, difluoromethyl, diiodomethyl, 2,2-dichloroethyl, 2,2-dibromomethyl, 2,2-difluoroethyl, 3, 3-dichloropropyl, 3,3-difluoropropyl, 4,4-dichlorobutyl, 4,4-difluorobutyl, trichloromethyl, 4,4-difluorobutyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoro Teal, 2,3,3-trifluoropropyl, 1,1,2,2-tetrafluoroethyl, and 2,2,3,3-tetrafluoropropyl. Thus, for example, a “substituted styrene unit” includes para-methyl styrene, para-ethyl styrene and the like.

The present invention includes at least one halogenated rubber containing isobutylene. Typically, it is present in the composition together with the thermoplastic resin described later in this document, with a mass ratio between rubber and resin in the range of about 55/45 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 rubber containing at least about 0.1 mol%. halogen, while such a halogen is selected from the group consisting of bromine, chlorine and iodine. Preferred halogenated rubbers suitable for use in this invention include isobutylene-based halogenated homopolymers or copolymers. These polymers can be described as random copolymers formed from a unit derived from a C ₄ -C ₇ isomonoolefin, such as a unit made from isobutylene, and at least one other polymerizable unit. In one embodiment, the isobutylene-based halogenated copolymer is butyl rubber or branched butyl rubber, in particular brominated versions of these elastomers. (Suitable unsaturated butyl rubbers, such as homopolymers and copolymers of olefins or isoolefins, and other types of elastomers suitable for use in the invention, are well known and are described in Rubber Technology Publications 209-581 (Maurice Morton ed., Chapman & Hall 1995), The Vanderbilt Rubber Handbook 105-122 (Robert F. Ohm ed., RT Vanderbilt Co., Inc. 1990) and Edward Kresge and HC Wang in 8 Kirk-Othmer Encyclopedia of Chemical Technology 934-955 (John Wiley & Sons, Inc. 4th ed . 1993).)

Butyl rubbers are usually obtained by reaction for a mixture of monomers, wherein the mixture contains at least (1) a component in the form of a C ₄ -C ₁₂ isoolefin monomer, such as isobutylene, and (2) a component in the form of a multiolefin monomer. The level of isoolefin is in the range from 70 to 99.5% of the mass. when calculating the mass of the total mixture of monomers in one embodiment, and from 85 to 99.5% of the mass. in another embodiment. The component in the form of a multiolefin in the mixture of monomers is present at a level in the range from 30 to 0.5% of the mass. in one embodiment, and from 15 to 0.5% of the mass. in another embodiment. In yet another embodiment, the multiolefin is from 8 to 0.5% of the mass. from a mixture of monomers. The isoolefin is preferably a C ₄ -C ₁₂ compound, 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, methyl vinyl ether, indene, vinyltrimethylsilane, hexene and 4-methyl-1-pentene. The multiolefin is a C ₄ -C ₁₄ multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene and other monomers such as those described in EP documents 0279456 and US patent No. 5506316 and 5162425. Other polymerizable monomers such as styrene and dichlorostyrene are also suitable for use in homopolymerization or copolymerization to obtain butyl rubbers. One embodiment of a polymer butyl rubber suitable for use in the invention is obtained by reacting isobutylene in an amount in the range of from 95 to 99.5% by weight. and isoprene in an amount in the range from 0.5 to 8% of the mass. or isoprene in an amount in the range from 0.5% of the mass. up to 5.0% of the mass. in yet another embodiment. Butyl rubbers and methods for their preparation are described in detail, for example, in US patent No. 2356128, 3968076, 4474924, 4068051 and 5532312.

Halogenated butyl rubber is obtained by halogenating the product in the form of butyl rubber as previously described. Halogenation can be carried out by any methods, and the invention in this document is not limited to the halogenation method. Methods of halogenating polymers, such as polymeric butyl rubbers, are described in US Pat. ° C when using bromine (Br ₂ ) or chlorine (Cl ₂ ) as a halogenating agent. The post-processing halogenated butyl rubber described in US Pat. No. 4,288,575 can also be used. Halogenated butyl rubber is typically characterized by a Mooney viscosity in the range of from about 20 to about 70 (ML 1 + 8 at 125 ° C); for example, from about 25 to about 55 in another embodiment. The halogen content is usually in the range from about 0.1 to 10% of the mass. when calculating the mass of halogenated butyl rubber; for example, from about 0.5 to 5% of the mass .; in an alternative embodiment, from about 0.8 to about 2.5% of the mass .; for example, from about 1 to about 2% of the mass. One particularly preferred form of halogenated butyl rubber is characterized by a high level of the following halogenated structure, where X is halogen, and in one particularly preferred embodiment, the halogen is bromine; in an alternative embodiment, the halogen is chlorine:

A commercial embodiment of a halogenated butyl rubber suitable for use in the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney viscosity is usually in the range of about 27 to 37 (ML 1 + 8 at 125 ° C., ASTM 1646, modified), and its bromine content is in the range of about 1.8 to 2.2% by weight. when calculating the amount of Bromobutyl 2222. In addition, the curing characteristics of Bromobutyl 2222 according to the manufacturer are as follows: MH in the range of about 28 to 40 dn · m, ML is in the range of about 7 to 18 dn · m (ASTM D2084) . Another commercial embodiment of a halogenated butyl rubber suitable for use in the present invention is Bromobutyl 2255 (ExxonMobil Chemical Company). Its Mooney viscosity is in the range of about 41 to 51 (ML 1 + 8 at 125 ° C., ASTM D1646), and its bromine level is in the range of about 1.8 to 2.2% by weight. In addition, its curing characteristics as described by the manufacturer are as follows: MH is in the range of 34 to 48 days · m, ML is in the range of 11 to 21 days · m (ASTM D2084). Commercial isobutylene polymers are described in detail in R. N. Webb, T. D. Shaffer and A. H. Tsou, Commercial Isobutylene Polymers, Encyclopedia of Polymer Science and Technology, 2002, John Wiley & Sons, by reference incorporated herein.

Another suitable embodiment of halogenated butyl rubber is halogenated, branched or “star-branched” butyl rubber. These rubbers are described, for example, in documents EP 0678529 B1, US 5182333 and 5071913, each of which is incorporated by reference in this document. In one embodiment, the star-branched butyl rubber (“ZRB”) is a composition comprising butyl rubber and a polydiene or block copolymer. For the purposes of the present invention, a method for producing an SAM is not a limitation. Polydienes, a block copolymer, or branching agents (hereinafter referred to as "polydienes") are usually cationic reactive and are present during polymerization to produce butyl rubber or halogenated butyl rubber, or they may be mixed with butyl rubber to produce an RMS. The branching agent or polydiene may be any suitable branching agent, and the invention is not limited to the type of polydiene or branching agent used to make the ZRB.

In one embodiment, the ZRB is a composition of butyl rubber or halogenated butyl rubber described previously and a copolymer of polydiene and partially hydrogenated polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, butadiene-styrene-rubber, rubber diene rubber (EPDM), ethylene-propylene rubber (EPM), styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. Polydienes may be present, when calculated on the total level of monomer content, when expressed in% by mass, in an amount usually greater than 0.3% by mass .; alternatively, in the range from about 0.3 to about 3% of the mass .; or from about 0.4 to 2.7% of the mass.

Preferably, the branched or “star branched” butyl rubber used in the present invention is halogenated. In one embodiment, the halogenated star-branched butyl rubber (“GZRB”) includes butyl rubber, either halogenated or not, and the polydiene or block copolymer, either halogenated or not. The halogenation method is described in detail in documents US 4074035, 5071913, 5286804, 5182333 and 6228978. The present invention is not limited to the method of obtaining GBRS. The polydiene / block copolymer or branching agents (hereinafter “polydienes”) are typically cationic reactive and are present during polymerization to produce butyl rubber or halogenated butyl rubber, or they can be mixed with butyl rubber or halogenated butyl rubber. The branching agent or polydiene may be any suitable branching agent, and the invention is not limited to the type of polydiene used to make GBRS.

In one embodiment, the HZBF is typically a composition comprising the halogenated butyl rubber described previously and a copolymer of polydiene and partially hydrogenated polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, these -diene rubber, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. Polydienes may be present, based on the total level of monomers, when expressed in% by weight, in an amount usually greater than about 0.3% by weight, alternatively in the range of about 0.3 to 3% by weight. or from about 0.4 to 2.7% of the mass.

A commercial embodiment of the GBSB suitable for use in the present invention is Bromobutyl 6222 (ExxonMobil Chemical Company), characterized by a Mooney viscosity (ML 1 + 8 at 125 ° C, ASTM D1646) in the range of about 27 to 37 and bromine content in a range of from about 2.2 to 2.6% of the mass. In addition, the curing characteristics of Bromobutyl 6222 as described by the manufacturer are as follows: MH is in the range of 24 to 38 dn · m, ML is in the range of 6 to 16 dn · m (ASTM D2084).

Preferred isoolefin / para-alkyl styrene copolymers include random copolymers containing a C ₄ -C ₇ isoolefin such as isobutylene and halogenmethyl styrene. Halogenmethyl styrene may be ortho-, meta- or para-alkyl-substituted styrene. In one embodiment, the implementation of halogenated methylstyrene is para-halogenated methylstyrene containing at least 80%, more preferably at least 90%, mass. para isomer. The halogen group may be any halogen, preferably chlorine or bromine, most preferably bromine. The copolymer may also include functionalized interpolymers, where at least some of the groups of alkyl substituents present in the styrene monomer units contain benzyl halogen or another functional group, further described below. These interpolymers are referred to herein as “isoolefin copolymers containing halogenmethyl styrene” or simply “isoolefin copolymer”.

Preferred isoolefin copolymers may contain 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, methyl vinyl ether, indene, vinyltrimethylsilane, hexene and 4-methyl-1-pentene. Preferred isoolefin copolymers may also further comprise multiolefins, preferably a C ₄ -C ₁₄ multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene, and other monomers, such as those described in EP 279456 and US 5506316 and 5162425. Desirable styrene monomers in the isoolefin copolymer include styrene, methyl styrene, chlorostyrene, methoxystyrene, indene and indene derivatives and combinations thereof.

Preferred isoolefin copolymers can be characterized as interpolymers containing the following monomer units randomly distributed along the length of the polymer chain:

where R and R ¹ independently represent hydrogen, lower alkyl, preferably C ₁ -C ₇ alkyl and primary or secondary alkyl halides, and X represents a functional group such as halogen. Desirable halogens are chlorine, bromine, or combinations thereof. Preferably, each of R and R ¹ represents hydrogen. The groups —CRR ₁ H and —CRR ₁ X can act as substituents on the styrene ring in either the ortho, or meta, or para positions, preferably in the para position. The above functionalized structure (2) in one embodiment can comprise up to 60% (mol.) Of para-substituted styrene present in the structure of the interpolymer, and in another embodiment, a value in the range from 0.1 to 5% (mol.) . In yet another embodiment, the amount of functionalized structure (2) is in the range of 0.4 to 1% (mol.). Functional group X may be halogen or some other functional group that may be introduced as a result of nucleophilic substitution of benzyl halogen by other groups, such as carboxylic acid groups; salts of carboxylic acids; esters, amides and imides of carboxylic acids; hydroxy; alkoxide; phenoxide; thiolate; simple thioether; xanthate; cyanide; cyanate; amino and mixtures thereof. These functionalized isomonoolefin copolymers, the method for their preparation, methods of functionalization and curing are more specifically described in US Pat. No. 5,162,445.

The most suitable for use with such copolymers of isobutylene and para-methylstyrene are those containing from 0.5 to 20% (mol.) Para-methylstyrene, where up to 60% (mol.) Groups of methyl substituents present in the benzyl ring contain a bromine or chlorine atom, preferably a bromine atom (para-bromomethylstyrene), as well as variants functionalized with an acid or ester, where the halogen atom has been superseded by the functionality of maleic anhydride or acrylic or methacrylic acid. These interpolymers are called the “halogenated isobutylene-para-methylstyrene copolymer” or the “brominated isobutylene-para-methylstyrene copolymer” and are commercially available under the name EXXPRO ™ Elastomers (ExxonMobil Chemical Company, Houston, Texas). It should be understood that the use of the terms “halogenated” or “brominated” is not limited to the method of halogenating the copolymer, but merely describes a copolymer that contains units made from isobutylene, units made from para-methyl styrene, and links made from para-halogenmethyl styrene.

These functionalized polymers are preferably characterized by a substantially uniform distribution of the ingredients of the composition, such that at least 95% of the mass. polymers are characterized by a level of para-alkylstyrene in the range of 10% of the average level of para-alkylstyrene in the polymer. More preferred polymers also have a narrow molecular weight distribution (Mw / Mn) of less than 5, more preferably less than 2.5, a preferred medium viscosity molecular weight in the range of from about 200,000 to about 2,000,000, and a preferred number average molecular weight in the range of from about 25,000 to about 750,000 as determined by gel permeation chromatography.

Preferred polymeric halogenated isobutylene-para-methylstyrene copolymers are brominated polymers, which generally contain from about 0.1 to about 5% by weight. bromomethyl groups. In yet another embodiment, the amount of bromomethyl groups is in the range from about 0.2 to about 2.5% of the mass. In other words, preferred copolymers contain from about 0.05 to about 2.5% (mol.) Bromine, based on the weight of the polymer, more preferably from about 0.1 to about 1.25% (mol.) Of bromine and essentially do not contain halogen in the ring or halogen in the polymer backbone. In one embodiment, the interpolymer is a copolymer consisting of units made from C ₄ -C ₇ isomonoolefin, units made from para-methyl styrene, and units made from para-halogenmethyl styrene, where the units of para-halogenmethyl styrene in the interpolymer are present in an amount of a range of from about 0.4 to about 1% (mol.) based on the amount of interpolymer. In another embodiment, the para-halogenmethyl styrene is para-bromomethyl styrene. Mooney viscosity (1 + 8, 125 ° C, ASTM D1646, modified) ranges from about 30 to about 60 Mooney viscosity units.

In another embodiment, the ratio between the proportion of triads of isoolefin and para-alkyl styrene and the% (mol.) Of para-alkyl styrene introduced into the copolymer is described by the sequence distribution equation in the copolymer below, and is characterized by the sequence distribution parameter m in the copolymer.

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

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

A represents the molar ratio between para-alkylstyrene and isoolefin in the copolymer and

F represents the fraction of para-alkylstyrene-isoolefin-para-alkylstyrene triads in the copolymer.

The best approximation for this equation allows us to obtain the value of m for the copolymerization of isoolefin and para-alkylstyrene in a specific diluent. In certain embodiments, m is 38 or less; alternatively 36 or less; alternatively 35 or less; and alternatively 30 or less. In other embodiments, m is in the range of 1-38; in an alternative embodiment 1-36; alternatively 1-35 and alternatively 1-30. Copolymers having such characteristics are described in documents WO 2004058825 and WO 2004058835.

In another embodiment, the isoolefin / para-alkyl styrene copolymer is substantially free of long chain branches. For the purposes of this invention, a polymer that essentially has no long chain branches is defined as a polymer for which g ' _{cp. viscous} determined to be greater than or equal to 0.978, alternatively greater than or equal to 0.980, alternatively greater than or equal to 0.985, alternatively greater than or equal to 0.990, alternatively greater than or equal to 0.995, alternatively greater than or equal to 0.998, alternatively greater or equal to 0.999, as determined by the triple-detection size exclusion chromatography (SEC) method described below. Such polymers are also described in WO2004058825 and WO2004058835.

In another embodiment, the ratio between the proportion of triads of isoolefin and multiolefin and the% (mol.) Of multiolefin introduced into the halogenated copolymer rubber is described by the sequence distribution equation in the copolymer described below and is characterized by the sequence distribution parameter m in the copolymer

F = mA / (1 + mA) ² ,

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

A represents the molar ratio between the multiolefin and the isoolefin in the copolymer and

F represents the proportion of triads of isoolefin-multiolefin-multiolefin in the copolymer.

The measurement of the proportion of triads of isoolefin and multiolefin and the% (mol.) Of multiolefin introduced into the copolymer are described below. The best approximation for this equation allows us to obtain the value of m for the copolymerization of isoolefin and multiolefin in each diluent. In certain embodiments, m is 1.5 or more; in an alternative embodiment, 2.0 or more; in an alternative embodiment, 2.5 or more; alternatively 3.0 or more; and alternatively 3.5 or more. In other embodiments, m is in the range of 1.10 to 1.25; alternatively, from 1.15 to 1.20; in an alternative embodiment, from 1.15 to 1.25 and in an alternative embodiment, m is approximately 1.20. Halogenated rubbers that have these characteristics are described in documents WO 2004058825 and WO 2004058835.

In another embodiment, the halogenated rubber is substantially free of long chain branches. For the purposes of this invention, a polymer that essentially has no long chain branches is defined as a polymer for which g ' _{cp. viscous} determined to be greater than or equal to 0.978, alternatively greater than or equal to 0.980, alternatively greater than or equal to 0.985, alternatively greater than or equal to 0.990, alternatively greater than or equal to 0.995, alternatively greater than or equal to 0.998, alternatively greater or equal to 0.999, as determined by the method of ECR with triple detection as follows. The presence or absence of long chain branches in polymers is determined using triple detection ECR. Triple detection ECR is carried out using a Waters chromatograph (Milford, Massachusetts) 150С, operating at 40 ° С and equipped with a Precision Detectors (Bellingham, Massachusetts) PD2040 light scattering detector, a Viscotek viscometer detector (Houston, Texas) Model 150R with a differential (integrated with 150C). The detectors are connected in series, while the light scattering detector is the first, the viscometric detector is the second, and the differential refractive index detector is the third. Tetrahydrofuran (0.5 ml / min) was used as eluent along with a set of three columns of Polymer Laboratories, Ltd. (Shropshire, United Kingdom) 10 micron mixed-B / LS GPC. The instrument is calibrated to 16 narrow molecular weight distribution polystyrene standards (Polymer Laboratories, Ltd.). Data is obtained using TriSEC software (Viscotek) and imported into WaveMetric's Igor Pro (Lake Oswego, Oregon) for analysis. To establish the relationship between the intrinsic viscosity ([η] _linear determined using a viscometric detector) and the molecular weight (M _w determined using a light scattering detector), linear polyisobutylene is used. The relationship between [η] is _linear and M _{w is} expressed using the Mark-Houwink equation

[η] _linear = KM _w ^α

The parameters K and α are obtained from a graph with a logarithmic scale along both axes, constructed for the dependence of the characteristic viscosity on M _w , α represents the slope, K represents the segment cut off on the axis. Significant deviations from the ratio established for linear standards indicate the presence of long chain branches. In the general case, the samples, which are characterized by a more significant deviation from the linear relationship for the linear sample, have more significant long-chain branches. The scaling factor g 'also indicates deviations from a certain ratio for a linear sample:

[η] _sample = g '[η] _linear

The value of g 'is determined to be less than or equal to unity and greater than or equal to zero. If g 'is equal to or almost equal to unity, then the polymer is considered linear. If g 'is significantly less than unity, then the sample will have long chain branches. See, for example, EF Casassa and GC Berry in “Comprehensive Polymer Science,” Vol.2, (71-120) G. Allen and JC Bevington, Ed., Pergamon Press, New York, 1988. For triple-detection ECR, the value g 'is calculated for each section of the chromatographic curve at the experimental point. Viscosities g 'or g' _{cp. viscous} calculated over the entire molecular weight distribution. Scaling factor g ' _{cp. viscous} calculated from the average intrinsic viscosity of the sample:

g ' _{cp. viscous} = [η] _cf. / (KM _w ^α )

Other preferred halogenated elastomers or rubbers include the halogenated isobutylene-para-methylstyrene-isoprene copolymer described in WO 01/21672 A1. Halogenated rubbers suitable for use in a fluid barrier layer may be identical or different.

For the purposes of the present invention, a suitable thermoplastic or structural resin is defined as any thermoplastic polymer, copolymer or mixture thereof, characterized by a Young's modulus greater than 500 MPa and preferably an air permeability coefficient less than 60 × 10 ^-12 cc. cm · cm / cm ² sec cm mercury (at 30 ° C) and preferably a melting point in the range from about 170 ° to about 270 ° C, including one or more of the following, but not limited to:

a) polyamide resins: nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6 copolymer / 66 (N6 / 66), nylon 6/66/610 (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T (N6T), copolymer nylon 6 / 6T, copolymer nylon 66 / PP, copolymer nylon 66 / SFC;

b) polyester resins: polybutylene terephthalate (PBTF), polyethylene terephthalate (PETF), polyethylene isophthalate (PEIF), copolymer PET / PEIF, polyacrylate (PAR), polybutylene naphthalate (PBN), liquid crystalline polyester / other aromatic polymers polyesters;

c) polynitrile resins: polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile-styrene (AC) copolymers, methacrylonitrile-styrene copolymers, methacrylonitrile-styrene-butadiene copolymers;

d) polymethacrylate resins: polymethyl methacrylate, polyethyl acrylate;

f) polyvinyl resins (for illustration, but not limitation: vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl / polyvinylidene copolymer, polyvinylidene chloride / methacrylate;

f) cellulose resins: cellulose acetate, cellulose acetate butyrate;

g) fluoride resins: polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE);

h) polyimide resins: aromatic polyimides;

i) polysulfones;

j) polyacetals;

k) polylactones;

l) polyphenylene oxide and polyphenylene sulfide;

m) styrene-maleic anhydride copolymer;

n) aromatic polyketones and

n) mixtures of all, without exception, representatives a) to n) inclusive, as well as mixtures of any of the resins given as illustrations or examples within each of variants a) to n) inclusive.

For the purposes of the present description, this definition of structural resin excludes olefin polymers 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 one alternative preferred embodiment of the present invention, the formulation of the thermoplastic elastomeric composition can be formulated using a component in the form of a thermoplastic resin, where the component in the form of a nylon resin contains nylon 11 or nylon 12 and a copolymer of nylon 6/66 in the ratio of the ingredients of the composition (mass ratio ) in the range of from about 10/90 to about 90/10; preferably from about 30/70 to about 85/15. Such a thermoplastic elastomeric composition based on mixed resins can provide a thermoplastic elastomeric composition that demonstrates excellent durability and appearance, for example, in the case of a cured surface of the inner sealing layer of the tire, as well as excellent air retention characteristics, as well as a good balance of these properties.

Optionally, other rubbers or elastomers may be used in combination with a halogenated isobutylene containing elastomer. Such an optional rubber component includes high diene rubbers and their hydrates. Rubbers or elastomers characterized by a high level of diene are also called rubbers, characterized by a high level of diene monomer. Usually it is rubber, usually containing at least 50% (mol.) C ₄ -C ₁₂ diene monomer, usually at least from about 60% (mol.) To about 100% (mol.); more preferably at least from about 70% (mol.) to about 100% (mol.); more preferably at least about 80% (mol.) to about 100% (mol.). Suitable rubbers characterized by a high content of diene monomer include homopolymers and copolymers of olefins or isoolefins and multiolefins or homopolymers of multiolefins. They are well known and described in Rubber Technology, 179-374 (Maurice Morton ed., Chapman & Hall, 1995) and The Vanderbilt Rubber Handbook 22-80 (Robert F. Ohm ed., RT Vanderbilt Co., Inc., 1990 ) In general, other optional rubbers suitable for use in the present invention include, for example, natural rubber (NK), isoprene rubber (IR), epoxidized natural rubber, styrene butadiene rubber (BSK), polybutadiene rubber (BK) (including including BK, characterized by a high level of cis units, and BK, characterized by a low level of cis units), nitrile butadiene rubber (BNK), hydrogenated BNK, hydrogenated BSC, olefin rubbers (for example, ethylene-propylene rubbers (including including EPDM and EPM), maleic acid modified ethylene-propylene rubbers (M-EPM)), butyl rubber (IIR), copolymers of isobutylene and aromatic vinyl or diene monomer, acrylic rubbers (AFM), ionomers, other halogen-containing rubbers (e.g. chloroprene rubbers (CR), hydrin rubbers (CHR), chlorosulfonated polyethylenes (CSM), chlorinated polyethylenes modified with maleic acid, (M-CM)), silicone rubbers (e.g. methyl vinyl silicone rubbers, dimethyl silicone rubbers, methylphenyl vinyl silicone rubbers), sulfur-containing rubbers (e.g. polysulfide rubbers), fluoro-rubbers (e.g. vinylidene fluoride rubbers, vinyl ether-based rubbers, tetrafluoroethylene-propylene rubbers, fluorinated rubber, silicone fluorinated rubbers) styrene-containing elastomers, olefin elastomers, ester elastomers, urethane elastomers or polyamide elastomers) and mixtures thereof.

Preferred examples of rubbers characterized by high levels of diene monomer include polyisoprene, polybutadiene rubbers, styrene butadiene rubber, natural rubber, chloroprene rubber, butadiene-acrylonitrile rubber and the like, which can be used individually or in combination and mixtures.

Since the thermoplastic resin and the halogenated rubber containing isobutylene vary significantly in solubility, an additional optional combining ingredient may be suitable for use in order to improve the compatibility of these polymers. In addition, without wanting to be bound by theory, it can be said that the fine dispersions of rubbers obtained in the compositions of the present invention can result, in part, from a chemical reaction (s) between, for example, benzyl bromine present in SIMS or allyl halogen in halogenated butyl rubber and terminal amines in polyamides at the phase boundary between the dispersed rubber particles and the thermoplastic formed during mixing and possibly as a result of modification, in h astnosti, reducing surface tension between the components in the form of rubber and resin. The passage of interfacial reactions during mixing and the simultaneous reaction between two immiscible polymers can help prevent the coalescence of the dispersed rubber phase, which is characterized by a small particle size, which thus leads to the formation of especially fine dispersions of the rubber phase. The passage of such interfacial reactions was called "reaction alignment" and is described, for example, in US patent No. 5571864 and 6469087, by reference included in this document. At the same time, due to interfacial stability in these reaction-combined immiscible systems, the phase inversion of the rubber phase, which is characterized by an increased concentration of the polymer mixture component having a reduced viscosity, is inhibited due to the stabilizing effect of interfacial alignment.

In addition, it may be advantageous from the point of view of improving the low temperature characteristics of the overall composition to use a component in the form of secondary rubber (i.e., a second rubber other than a component in the form of a first (halogenated) rubber, for example, BIMS), which is more effective in lowering the low temperature module elasticity in comparison with BIMS. Preferably, the secondary rubber base is functionalized rubbers exhibiting low glass transition temperatures Tg, preferably lower than −30 ° C. A low Tg value contributes to a reduced modulus of elasticity or softness of the secondary rubber at operating or use temperatures for products containing such rubbers, for example, inner sealing layers of tires of about −20 ° C. or less. Suitable functionality includes maleic anhydride, acyllactam or the like, which can readily react with the amine functionality present in polyamides. The presence of chemically reactive functionality in such rubbers further promotes the reaction alignment between the secondary rubber and the polyamide, resulting in a rubber dispersion having a small particle size in the polyamide matrix, with particles having an average particle size of about 1 micron or less; preferably less than about 0.5 microns. The use of such secondary rubber is described in document PCT / US 2006/011002, filed March 24, 2006 and by reference incorporated herein. Secondary rubber dispersed in the polyamide matrix in the form of the aforementioned small particles may optionally be cured, crosslinked or vulcanized, partially, substantially or completely, as described with respect to the halogenated or SIMS elastomer. Such crosslinking can be carried out during dispersion of the secondary rubber in the polyamide matrix as a result of using the same dynamic vulcanization method as used for the halogenated elastomeric component. In the case of using dynamic vulcanization in the secondary rubber, it will also be necessary to disperse the hardener or curing system suitable for the implementation of vulcanization during mixing and dispersion of the rubber. Alternatively, if the secondary rubber is exposed to thermal crosslinking, it can be vulcanized by supplying sufficient heat energy either during mixing and dispersion using a method corresponding to dynamic vulcanization, or after dispersing it in the form of small particles as a result of supplying heat energy sufficient to conduct such crosslinking after dispersion. In any case, it is preferred that the secondary rubber in the polyamide matrix be dispersed in the form of small particles having an average particle size in the range of about 0.1 microns to about 1 micron; for example, from about 0.1 microns to about 0.75 microns, or from about 0.1 microns to about 0.5 microns.

Secondary polymers that act as compatibilizers may include ethylenically unsaturated, highly saturated copolymer rubbers based on nitrile conjugated diene (HNBR), epoxylated natural rubbers (ENC), BNC, hydrin rubbers, acrylic rubbers and mixtures thereof. Other combiners include copolymers, such as those having the structure of both or one component selected from a thermoplastic resin and polymer rubber, or the structure of a copolymer having an epoxy group, a carbonyl group, a halogen group, an amino group, a maleated group, an oxazoline group, a hydroxy group, and the like. that is capable of reacting with a thermoplastic resin or polymer rubber. Secondary rubber may be selected based on the type of blended polymer thermoplastic resin and polymer rubber. Suitable secondary rubbers are selected from the group consisting of rubbers grafted with maleic anhydride, such as copolymers grafted with maleic anhydride, ABS (acrylonitrile-butadiene-styrene), EPDM (ethylene-propylene-diene rubber), SEBS / styrene-ethylene ethylene similar and maleated ethylene copolymer rubbers such as maleated copolymers of ethylene-propylene (EPM), ethylene-butene, ethylene-hexene, ethylene-octene, ethylene-decene, ethylene-propylene-diene (EPDM), ethylene-vinyl acetate, ethylene-methyl acrylate , uh tylene-ethyl acrylate, ethylene-acrylic acid and the like, and mixtures thereof. In addition, potentially suitable rubbers include the grafted copolymer EPDM / styrene, EPDM / acrylonitrile and their forms modified with maleic acid; styrene / maleic acid copolymer; reactive thermoplastic phenoxy resin; and mixtures thereof.

Examples of suitable preferred functional groups present in the secondary rubber include compounds having a carbonyl bond, such as carboxylic acids, carboxylic acid esters, acid anhydrides, diesters, salts, amides and imides. Aromatic vinyl compounds, hydrolyzable unsaturated silane compounds, saturated halogenated hydrocarbons and unsaturated halogenated hydrocarbons may also be used. Examples of particularly preferred functional groups include, but are not limited to: maleic anhydride, citraconic anhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride, 2,3-dimethyl maleic anhydride, bicyclo [2,2,1] -5-heptene -2,3-dicarboxylic anhydride and 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo anhydride ( 2.2.2) oct-5-en-2,3-dica acid, anhydride of 1,2,3,4,5,8,9,9-octahydronaphthalene-2,3-dicarboxylic acid, 2-oxa-1,3-diketospiro (4.4) non-7-ene, bicyclo anhydride ( 2.2.1) hept-5-ene-2,3-dicarboxylic acid, maleopimaric acid, tetrahydrophthalic anhydride, norborn-5-en-2,3-dicarboxylic anhydride, nadicanhydride, methyl nadic acid hydride, hemicanhydride, methyl hemicanhydride and x-methylbicyclo anhydride ( 2.2.1) hept-5-en-2,3-dicarboxylic acid (XMNA).

In one preferred embodiment, maleic anhydride is grafted onto the functionalizable polymer so that maleic anhydride is covalently linked to the polymer backbone. The anhydride functionality grafted onto the polymer may remain in the form of the anhydride, may be oxidized to acid functional groups and / or may be further reacted by methods known in the art to introduce other functional groups, such as amides, amines alcohols and the like.

Polymers suitable for preparing functionalized polymers suitable for use in the present invention include ethylene polymers and propylene polymers. Particularly preferred polymers include polymers of ethylene copolymerized with one or more compounds selected from propylene, butene, pentene, hexane, heptene, octane, nonene decene, undecene, dodecene, methyl acrylate, ethyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, acrylic acid, methacrylic acid, ethacrylic acid, butacrylic acid or vinyl acetate. Preferably, such ethylene polymers are modified with maleic acid or maleic anhydride. Another class of particularly preferred polymers includes polymers of propylene copolymerized with one or more compounds selected from ethylene, butene, pentene, hexane, heptene, octane, nonene-decene, undecene, dodecene, methyl acrylate, ethyl acrylate, butyl acrylate, pentyl acrylate, pentyl acrylate, octyl acrylate, acrylic acid, methacrylic acid, ethacrylic acid, butacrylic acid or vinyl acetate. Preferably, such propylene polymers are modified with maleic acid or maleic anhydride.

Another class of particularly preferred polymers includes polymers of a C ₄ -C ₇ isoolefin (such as isobutylene) copolymerized with one or more compounds selected from isoprene, isobutylene. Preferably, such isobutylene polymers are modified with maleic acid or maleic anhydride. Particularly preferred functionalized polymers include maleated copolymers of isobutylene and isoprene, maleated copolymers of isobutylene and para-methyl styrene, maleated copolymers of the halogen-butyl type, maleated copolymers of the type ZRB, and maleated copolymers of the type IMS. Various methods are known in the art that can be used to functionalize polymers. They include, but are not limited to, the following: selective oxidation, free radical grafting, ozonolysis, epoxidation, and the like.

Preferably, the functionalized polymer contains maleic anhydride present in a concentration selected from the group consisting of less than about 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30% by weight, 25% by weight. , 20% mass., 15% mass., 10% mass., 9% mass., 8% mass., 7% mass., 6% mass., 5% mass., 4% mass., 3% mass. and 2% of the mass. maleic anhydride. In addition, preferably the content of maleic anhydride (MA) in the polymer-MA grafted copolymer may be greater than about 0.1 wt.%, Preferably greater than about 0.5 wt.%, Alternatively greater than about 1 % wt., maleic anhydride. In one preferred embodiment, the functionalized polymer may contain from about 0.1 to about 10% of the mass. maleic anhydride; preferably from about 0.25 to about 5% of the mass .; more preferably from about 0.5 to about 4% of the mass .; even more preferably from about 0.75 to about 3.5% of the mass .; since from about 1.5 to about 2.5% of the mass., maleic anhydride. Various techniques can be used to characterize functionalized polymers, some of which are described in Structure Characterization, The Science and Technology of Elastomers, F. Eirich, editor, Academic Press 1978, Chapter 3 by G. Ver Strate, which is by reference included in this document. The level of functional group content in the grafted polymer can be determined by the method of infrared spectroscopy with Fourier transform (IKSFP) based on calibration using standards, the absolute level of content of functional groups in which was determined.

Due to the presence of another rubber, the total level of rubber, taking into account both the SIMS rubber and at least one secondary rubber, in the thermoplastic elastomeric composition can be increased while maintaining the desired morphology, including a small particle size dispersion of the rubber components in the polyamide matrix. An increase in the maximum rubber content can be realized, in particular, taking into account the limited coalescence of the SIMS particles in the presence of immiscible secondary rubber. In addition, by controlledly maintaining the concentration of the secondary rubber at a previously described low or non-basic level, the need for curing or vulcanizing the secondary rubber can be substantially eliminated in order to eliminate or prevent its coalescence. This is especially true since secondary rubber demonstrates reactivity in the presence of polyamide and with respect to polyamide and becomes substantially immobilized. In this case, in the absence of the need to add hardeners to the secondary rubber, it is not necessary to pre-mix hardeners to it or to include hardeners in its pre-prepared composition (although optionally, hardeners can be added and the secondary rubber subjected to dynamic vulcanization using the same technologies as for SIMS), and the direct addition of secondary rubber to the extruder mixer during extrusion mixing is possible; the secondary rubber is preferably supplied in granular form. In addition, since most functionalized rubbers, such as maleated ethylene copolymer rubbers and rubbers grafted with maleic anhydride, are quite permeable, it is desirable to maintain the concentration of the secondary rubber low, usually less than about 20% by weight .; preferably in the range from about 1% of the mass. up to about 20% of the mass .; more preferably from about 1% of the mass. up to about 10% of the mass. and less, when calculating the total weight of the total composition. The amount of mixed secondary functionalized combining rubber is usually less than about 20% of the mass .; preferably less than about 10% of the mass .; in the General case, in the range from approximately 0.5% of the mass. up to about 20% of the mass .; for example, from about 5% of the mass. up to about 15% of the mass .; since from about 7.5% of the mass. up to about 12.5% of the mass.

When referring to the polymers and / or elastomers referred to herein, the terms “cured”, “vulcanized” or “crosslinked” refer to a chemical reaction involving the formation of bonds, such as during chain extension, or crosslinking between polymer chains, constituting a polymer or elastomer, to such an extent that the elastomer exposed to this method, when using a tire, can provide the necessary functional properties resulting from the curing reaction. For the purposes of the present invention, to consider the elastomeric-containing composition as “cured”, “vulcanized” or “crosslinked”, the absolute completion of such curing reactions is not required. For example, for the purposes of the present invention, the tire containing the composition of the inner sealing layer based on the present invention will be in a sufficiently cured state when the tire, of which it is a component, successfully passes the necessary tests to determine the technical characteristics of the product during and after manufacture and Demonstrate satisfactory performance when used in a vehicle. In addition, the composition is satisfactorily, sufficiently or substantially cured, cured or crosslinked when the tire can be used, even if the additional curing time can lead to the formation of additional crosslinking.

In general, polymer compositions, for example, those used to make tires, are crosslinked in the final tire product. Crosslinking or vulcanization is carried out as a result of the introduction of hardeners and / or accelerators; however, the cumulative mixture of such agents is usually called the "system" of curing. It is known that the physical properties, performance, and durability of vulcanized rubber compositions are directly related to the amount (density of crosslinks) and the 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).) Hardeners include those components previously described that facilitate or affect the curing of elastomers, and generally include metals, metal oxides, accelerators, sulfur, peroxides and other agents commonly used in the art and described previously. Crosslinkers or hardeners include at least one representative selected, for example, from sulfur, zinc oxide and fatty acids and mixtures thereof. Peroxide-based curing systems may also be used. In general, polymer compositions can be crosslinked by the addition of hardeners, for example, sulfur, metal oxides (i.e. zinc oxide ZnO), organometallic compounds, radical initiators and the like, and heating the composition or mixture.

In the case of using the method known under the name "dynamic vulcanization", the dispersion method of the curing system is modified as described in detail hereinafter. In general, the term “dynamic vulcanization” is used to refer to a vulcanization method in which a thermoplastic or structural resin and at least one vulcanizable rubber are mixed under high shear and elevated temperatures in the presence of a hardener or curing system for rubber (rubbers). As a result, the rubber is simultaneously crosslinked and dispersed in the form of particles, preferably in the form of a microgel, in a resin that forms a continuous matrix. The resulting composition is known in the art as the “dynamically vulcanizable alloy” or ICE. Dynamic vulcanization is usually carried out by mixing the ingredients at a temperature that is equal to or higher than the curing temperature of rubber and equal to or higher than the melting temperature of the resin using equipment such as rollers, Banbury® mixers, continuous mixers, kneading machines or mixing extruders ( such as twin screw extruders). A unique characteristic of a dynamically vulcanized or cured composition is that despite the curing of the rubber, the composition can be processed and recycled using conventional thermoplastics processing techniques such as extrusion, injection molding, direct compression and the like. Waste and / or spray can also be disposed of and recycled. In a typical dynamic vulcanization process, the addition of a curing agent is varied so as to substantially simultaneously mix and cure or crosslink at least one of the curable components in a composition comprising at least one curable rubber, elastomer or polymer and at least , one polymer or resin, not vulcanizable using a vulcanizer (s) for at least one curable component. (See, for example, US Pat. No. 6,079,465 and the references cited therein.) However, in the present invention, the dynamic vulcanization process is further modified as described below in order to achieve the specific advantages resulting from such a modification.

The following are conventional hardeners that can fulfill their function in the present invention: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ and NiO. These metal oxides can be used in combination with an appropriate complex of metal stearate (for example, salts derived from stearic acid and Zn, Ca, Mg and Al) or with stearic acid and either with a sulfur compound or an alkyl peroxide compound. (See also Formulation Design and Curing Characteristics of NBR Mixes for Seals , Rubber World 25-30 (1993).) Vulcanization accelerators for elastomer compositions are often added to the curing agent (s). Hardener (s), with or without the use of at least one accelerator, are often referred to as the “curing system” for elastomer (s) with current technology. The curing system is used because more than one hardener is usually used to achieve beneficial effects, in particular when a mixture of rubber with a high level of diene and a less reactive elastomer is used. In addition, to satisfy the conditions of the invention, the properties of the curing system can be adapted to the mixing method. For example, in order to determine the cure response for a particular rubber (s) present in the composition, the rubber (s) and the cure system can be combined using devices known to those skilled in the art, such as twin roll mills, a Banbury blender or a blender extruder. A mixture sample, often referred to as an “accelerated” composition, can be cured under static conditions, such as in the case of a thin sheet product using a mold that is subjected to heat and pressure in the press. Subsequently, samples of the accelerated composition, which are cured in the form of thin panels for successively longer times and / or at elevated temperatures, are subjected to mechanical and / or crosslinking tests to determine the state of cure (as described in detail in American Society for Testing and Materials, Standard ASTM D412). Alternatively, the accelerated composition can be tested for cure by a cure test using an oscillating disc viscometer (described in detail in American Society for Testing and Materials, Standard ASTM D2084). After that, the total time and temperature of the dynamic vulcanization method can be adjusted so that the vulcanizable rubbers present in the composition are sufficiently cured to achieve the desired properties of the thermoplastic composition, of which they are, for example, an impermeable layer that holds air or fluid, such as in the case of the inner sealing layer of the tire. For the purposes of the present invention, such a curing state may be referred to as “substantially complete cure”.

It must be understood that vulcanizable rubber, usually the first rubber, for example, a halogenated isobutylene elastomer, such as BIMS (or a mixture of such rubbers), will cure to at least 50% of the maximum cure state that it will be able to, based on of the system, the time and temperature of curing, and usually the curing state of such rubber will exceed 50% of the maximum degree of cure. Since the second rubber may also include vulcanizable rubber, where such a second rubber is vulcanized, for example, in accordance with the dynamic vulcanization technology described herein, it will usually also cure by at least 50% of the maximum curing state to which it will be able based on its hardener or curing system and the time and temperature at which it is processed. Alternatively, as discussed herein, such a second rubber can also be grafted onto a polyamide resin, crosslinked and / or associated with or without hardeners, so that its degree of cure is not a limitation provided that it sufficiently dispersed to a particle size small enough to obtain the properties desired for the use case in which the composition will be applied. Conversely, it may be desirable to cure the rubber particles to a degree less than the maximum cure state that the rubber will be capable of, so that the flexibility, as measured, for example, by the Young modulus, of the rubber component (s) is at a level suitable for the final use case for which the composition is intended, for example, in the case of a component of the inner sealing layer of the tire or hose. Therefore, it may be desirable to control the cured state of the rubbers (rubber) used in the composition at a level less than or equal to approximately 95% of the previously described maximum degree of cure to which they will be capable.

For the purpose of dynamic vulcanization in the presence of a structural resin, prior to obtaining, for example, a highly impermeable layer or film, any conventional curing system can be used that is capable of curing saturated or unsaturated halogenated polymers and curing at least an elastomeric halogenated C ₄ -C copolymer ₇ isomonoolefin and para-alkylstyrene, except that peroxide hardeners are specifically excluded from the practice of this invention when One or more thermoplastic structural resins are present such that the peroxide will crosslink the resins themselves. If, in these circumstances, the structural resin itself began to cure or crosslink, this would result in an overly cured, non-thermoplastic composition. Curing systems suitable for use in the elastomeric halogenated copolymer component of the present invention include zinc oxide in combination with zinc stearate or stearic acid and optionally with one or more of the following accelerators or vulcanizing agents: Permalux - di-ortho-toluylguanidine salt of dicatechinboric acid; HVA-2 - meta-phenylenebismaleimide; Zisnet - 2,4,6-trimercapto-5-triazine; DEDCC - zinc diethyldithiocarbamate, and also with the inclusion for the purposes of the present invention and other dithiocarbamates; Tetrone A - dipentamethylenetiuramhexasulfide; Vultac 5 - alkylated phenol disulfide, SP1045 - phenol-formaldehyde resin; SP1056 - brominated alkyl phenol formaldehyde resin; DFFD - diphenylphenylenediamine; salicylic acid - ortho-hydroxybenzoic acid; extraction rosin - abietic acid and TMTDS - tetramethylthiuram disulfide used in combination with sulfur.

Curing accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates and the like. The acceleration of the curing process can be achieved by adding a certain amount of accelerator to the composition. The mechanism of accelerated vulcanization of rubber involves complex interactions between the hardener, accelerator, activators and polymers. In the ideal case, the entire amount of available hardener is spent on the formation of effective crosslinkings that connect individual polymer chains to each other and improve the overall strength of the polymer matrix. Many accelerators are known in the art that include, but are not limited to, the following: stearic acid, diphenylguanidine (DFG), tetramethylthiuramdisulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuramdisulfide (TBTD, 2,2) -benzothiazyl disulfide (MBTS), hexamethylene-1,6-bistiosulfuric acid disodium dihydrate, 2- (morpholintio) benzothiazole (MBS or MOR), compositions containing 90% MOR and 10% MBTS, (MOR 90), N- (tertiary butyl) -2-benzothiazolsulfenamide (TBBS) and N-oxide-diethylene thiocarbamyl-N-oxide-diethylene sulfonamide (HSE), Zinc 2-ethylhexanoate (EHC), N, N'-diethylthiourea. Hardeners, accelerators and curing systems, of which they are a part and which are suitable for use in one or several crosslinkable polymers, are well known in the art.

The curing system can be dispersed in a rubber component with a suitable concentration, and the rubber component will optionally contain one or more fillers, cheapeners and / or plasticizers as a result of, for example, mixing the rubber and components of the curing system in the manufacturing step prior to adding the rubber containing composition , to thermoplastic using any mixing equipment commonly used in the rubber industry for such a purpose, for example, two alkovyh rolls, Banbury mixer, kneading extruder and the like. Such mixing is commonly called the “acceleration” of the rubber composition. Alternatively, the rubber composition may be accelerated in the mixing extruder step prior to dynamic vulcanization, although this is difficult to control in a commercial, practical, integrated way and is less desirable. The curing system is particularly preferred to disperse in the rubber phase or in the rubber composition, also optionally containing one or more fillers, cheapeners and other ingredients common to the intended use of the intended use, before adding rubber to the thermoplastic resin (s) using mixing equipment, which is supposed to conduct dynamic vulcanization. In such an operation, the preformed rubber composition can be granulated for more efficient and effective feeding into dynamic vulcanization equipment, preferably a mixing extruder, as described below.

In one embodiment of the invention, at least one hardener is usually present in an amount in the range of from about 0.1 to about 15 parts per hundred parts of rubber; alternatively, from about 0.5 to about 10 parts per hundred parts of rubber.

Suitable combinations of hardeners, modifiers and curing accelerators can be illustrated as follows: as a general purpose rubber vulcanizer, for example, sulfur vulcanizer, powdered sulfur, precipitated sulfur, finely dispersed sulfur, surface treated sulfur, insoluble sulfur, dimorpholisulfide sulfide and sulfide . Such compounds can be used in an amount in the range of from about 0.5 parts per hundred parts of rubber to about 4 parts per hundred parts of rubber (parts by weight per 100 parts by weight of the elastomeric component). Alternatively, an organic peroxide vulcanizer, benzoyl peroxide, tert-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, 2,5-dimethylhexane-2,5-di ( peroxybenzoate) and mixtures thereof, if it is possible to use such a material, taking into account other components present in the form of polymers and resins. If used, such hardeners may be present at levels in the range of from about 1 part per hundred parts of rubber to about 20 parts per hundred parts of rubber. Other suitable hardeners include phenolic resin vulcanizers, such as alkyl phenol resin bromide, or a mixed crosslinker system including tin chloride, chloroprene or other halogen donor and alkyl phenol resin, and mixtures thereof. Such agents may be used at levels ranging from about 1 part per hundred parts of rubber to about 20 parts per hundred parts of rubber. Alternatively, other suitable hardeners, cure modifiers, and suitable levels include zinc oxide and / or zinc stearate (from about 0.05 parts per hundred parts of rubber to about 5 parts per hundred parts of rubber), stearic acid (from about 0.1 parts per hundred parts of rubber to about 5 parts per hundred parts of rubber), magnesium oxide (from about 0.5 parts per hundred parts of rubber to about 4 parts per hundred parts of rubber), lyserg (from 10 to 20 hours / one hundred hours of rubber or so), para-quinondioxime, para-dibenzoylquinone dioxime, tetrachloro-para-benzoquinone, poly-p ara-dinitrosobenzene (from about 0.5 hours / one hundred hours of rubber to about 10 hours / one hundred hours of rubber), methylenedianiline (from about 0.05 hours / one hundred hours of rubber to about 10 hours / one hundred hours rubber) and mixtures thereof. In addition, if desired or necessary, one or more vulcanization accelerators can be added in combination with a vulcanizing agent, including, for example, aldehyde ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioic acid salt, thiourea, and mixtures thereof, for example, in quantities in the range of from about 0.1 parts per hundred parts of rubber to about 5 parts per hundred parts of rubber and more.

Preferred polymer components comprise, as a vulcanizable component (s), halogenated copolymers containing isobutylene, for example, halogenated butyl rubber, such as chlorinated butyl rubber or brominated butyl rubber and a brominated isobutylene-para-methyl styrene copolymer (BIMS copolymer), and a thermoplastic or a mixture of various nylon polymers. It is particularly preferred that the dynamically vulcanized compositions of the present invention contain a halogenated rubber component (s) in the form of dispersed substantially fully cured small particles in a continuous thermoplastic matrix. The dynamically vulcanized halogenated rubber component is preferably dispersed in a polyamide matrix in the form of small particles having an average particle size in the range of about 0.1 microns to about 1 micron; for example, from about 0.1 microns to 0.75 microns, or from about 0.1 microns to about 0.5 microns. Particle size can be determined by methods well known in the art and including atomic force microscopy (AFM) in the tapping phase described in published patent application US 2006/0223941 (October 5, 2006) by reference incorporated herein.

For the purposes of the present invention, the component in the form of BIMS is also called an elastomer characterized by low vaccination efficiency, and the second rubbers are called rubbers, characterized by high vaccination efficiency. In each case, grafting refers to grafting onto the polyamide (s) that is present in the composition. This difference in efficiency and the method for measuring the operational characteristics of polymers are further described below.

The compositions described herein may contain one or more excipients, such as calcium carbonate, clay, mica, silica and silicates, talc, titanium dioxide, starch and other organic fillers, such as wood flour, and carbon black . Suitable filler materials include carbon black, such as channel black, furnace black, thermal black, acetylene black, lamp black, modified carbon black such as carbon black treated with or coated with silicon dioxide (described, for example, in patent US No. 5916934, by reference incorporated herein) and the like. Preferred is carbon black reinforcing grades. The filler may also include other reinforcing or non-reinforcing materials, such as silicon dioxide, clay, calcium carbonate, talc, titanium dioxide and the like. A filler may be present at a content level in the range of 0 to about 30 weight percent.

Layered, intercalated or dispersed clays may also be present in the composition. These clays, also called "nano-clays", are well known, and their nature, methods for producing and mixing with polymers are described, for example, in documents JP 2000109635, JP 2000109605, JP 11310643; DE 19726278; WO 98/53000 and US Patent Nos. 5091462, 4431755, 4472538 and 5910523. Swellable layered clay materials suitable for use in the present invention include natural or synthetic phyllosilicates, in particular smectite clays such as montmorillonite, nontronite, beidellite, volcon , laponite, hectorite, saponite, saukonite, magadite, kenyaite, stevensite and the like, as well as vermiculite, halloysite, aluminum oxides, hydrotalcite and the like. In general, these layered clays include particles containing a plurality of silicate plates having a thickness typically in the range of from about 4 to about 20 U in one embodiment and from about 8 to about 12 U in another embodiment, interconnected and containing exchanged cations, such as Na ⁺ , Ca ^{+ 2} , K ⁺ or Mg ^{+ 2} , present on the interlayer surfaces.

Layered clay can be intercalated and delaminated by treatment with organic molecules (swelling agents) capable of undergoing ion exchange reactions involving cations present on the interlayer surfaces of the layered silicate. Suitable swelling agents include cationic surfactants such as ammonium, alkylamino or alkylammonium (primary, secondary, tertiary and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides. The desired amine compounds (or the corresponding ammonium ion) are those that include the structure R ₁ R ₂ R ₃ N, where R ₁ , R ₂ and R ₃ are C ₁ -C ₃₀ alkyls or alkenes that may be identical or different. In one embodiment, the exfoliating agent is a so-called long chain tertiary amine, wherein at least R ₁ is C ₁₂ -C ₂₀ alkyl or alkene.

Another class of swelling agents includes those that can covalently bind to interlayer surfaces. These include polysilanes described by the structure —Si (R ′) ₂ R ² , where R ′ is identical or different in each case, and is selected from alkyl, alkoxy or oxysilane, and R ² is an organic radical compatible with the matrix polymer of the composite . Other suitable swelling agents include protonated amino acids and their salts containing 2-30 carbon atoms, such as 12-aminododecanoic acid, epsilon-caprolactam and the like. Suitable swelling agents and methods for intercalating layered silicates are described in US Pat. Nos. 4,472,538, 4,810,734, 4,889,885 and WO 92/02582.

In one preferred embodiment of the invention, an exfoliating or swelling agent is combined with a halogenated polymer. In one embodiment, the agent includes all primary, secondary, and tertiary amines and phosphines; alkyl and aryl sulfides and thiols and their multifunctional variants. Desirable additives include: long chain tertiary amines such as N, N-dimethyl octadecylamine, N, N-dioctadecylmethylamine, di (alkyl radical of hydrogenated animal fat) methylamine and the like, and amino terminal polytetrahydrofuran; long chain thiol and thiosulfate compounds, such as sodium hexamethylenetiosulfate. In another embodiment, improved interpolymer impermeability is obtained by using polyfunctional hardeners such as hexamethylene bis (sodium thiosulfate) and hexamethylene bis (cinnamaldehyde).

The amount of layered, intercalated or dispersed clay incorporated into the composition of the invention is an amount sufficient to provide improved mechanical properties or impermeability characteristics of the composition, for example, tensile strength or air / oxygen permeability. Amounts can usually be in the range from about 0.5 to about 15% of the mass. in one embodiment, or from about 1 to about 10% of the mass. in another embodiment, and from about 1 to about 5% of the mass. in yet another embodiment, based on the level of polymer in the composition. When expressed in parts per hundred parts of rubber, layered, intercalated or dispersed clay may be present in an amount in the range of from about 1 to about 30 parts per hundred parts of rubber in one embodiment and from about 3 to about 20 parts per hundred parts. rubber in another embodiment. In one embodiment, the exfoliating clay is clay exfoliating by the action of an alkylamine.

As used herein, the term “process oil” means both process oils made from petroleum and synthetic plasticizers. Technological or plasticizing oil may be present in airtight compositions. Such oils are mainly used to improve the processing of the composition during the preparation of the layer, for example, mixing, calendaring and the like. Suitable plasticizing oils, in particular for the elastomeric component (s), include aliphatic acid esters or hydrocarbon plasticizing oils, such as paraffinic or naphthenic petroleum oils. A plasticizing oil, preferred for use in standard compositions of the internal sealing layer containing a non-internal combustion engine, non-structural resin, is paraffin oil; hydrocarbon plasticizing oils suitable for use in such inner liners include oils that demonstrate the following general characteristics.

Property Preferably Minimum As much as possible Density in degrees ANI at 60 ° F (15.5 ° C) 15-30 10 35 Flash point (open crucible detection method), ° F (° C) 330-450
(165-232 ° C) 300
(148 ° C) 700
(371 ° C) The pour point, ° F (° C) 30 to +30
(-34 to
-1 ° C) -35
(-37 ° C) 60
(15 ° C) Sebolt Viscosity in Seconds at 100 ° F (38 ° C) 100-7000 fifty 20000

In general, the process oil may be selected from paraffin oils, aromatic oils, naphthenic oils, and polybutene oils. Polybutene processing oil is a low molecular weight (Mn value less than 15,000) homopolymer or copolymer consisting of units derived from olefins containing from about 3 to about 8 carbon atoms, more preferably from about 4 to about 6 carbon atoms. In another embodiment, the polybutene oil is a C ₄ raffinate homopolymer or copolymer. 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 referred to as "polybutene technological oil "or" polybutene "). Suitable examples of polybutene oils are PARAPOL ™ Process Oils (ExxonMobil Chemical Company, Houston, Texas), including grades designated PARAPOL ™ 450, 700, 950, 1300, 2400 and 2500. PARAPOL ™ Polybutene Process Oils are typically synthetic liquid polybutenes having a specific molecular weight. The molecular weights of PARAPOL ™ oils range from a Mn value of approximately 420 (PARAPOL ™ 450) to a Mn value of approximately 2700 (PARAPOL ™ 2500). The molecular weight distribution ("MMP") for PARAPOL ™ oils is usually in the range of from about 1.8 to about 3, preferably from about 2 to about 2.8. The density (g / ml) of PARAPOL ™ process oils ranges from approximately 0.85 (PARAPOL ™ 450) to approximately 0.91 (PARAPOL ™ 2500). The bromine number (g / g) for PARAPOL ™ oils ranges from about 40 for a process oil with a Mn value of 450 to about 8 for a process oil with a Mn value of 2700.

Rubber process oils also have ASTM designations, depending on whether they fall into the class of paraffinic, naphthenic, or aromatic hydrocarbon process oils. The type of process oil used will be that which is usually used in combination with the type of elastomeric component, and those skilled in the art of rubber chemistry will need to understand what type of oil will need to be used with the particular rubber in a particular application. In the case of a thermoplastic elastomeric composition, the oil may be present at a level in the range from 0 to about 20% of the mass. from the total composition; to maximize the impermeability of the composition, the oil is preferably not included.

Minimizing the viscosity difference between the rubber or SIMS component and the thermoplastic or nylon components during mixing and / or processing improves uniform mixing and fine morphology of the mixture, in other words, small dispersed particles of vulcanized rubber, which greatly improves good mechanical properties as well as the desired permeability characteristics of the mixture. However, due to the presence of flow activation properties and a decrease in shear viscosity typical of BIMS polymers, lower viscosity values of BIMS polymers at elevated temperatures and shear rates encountered during mixing are much more pronounced in comparison with decreases in viscosity of the thermoplastic component with which the polymer Beams are mixed. Thus, if it is necessary to choose the viscosity of the nylon component to ensure its similarity with the viscosity of the rubber, taking into account the low SIMS viscosity at high shear rates and temperatures, in order to further reduce the viscosity, it is necessary to use either low molecular weight nylon with lower viscosity or nylon in combination with a plasticizer , or a combination of both approaches. Matching the viscosity of the nylon resin phase with the viscosity of the SIMS polymer phase or the approximation of the first to second can improve the size of the dispersed particles and the combined morphology of dynamically vulcanized mixtures of SIMS and nylon, such as those described in EP 857761 A1 and EP 969039 A1. However, depending on the nature of the modifications, these alternatives may result in undesirable mechanical properties, for example, due to the use of nylons having a reduced molecular weight and / or increased permeability due to the use of a typical nylon plasticizer depending on the amount and type of plasticizer used.

One alternative approach to reducing the viscosity of the nylon phase, described in WO 2007050076, published May 3, 2007 and incorporated by reference herein, is based on the use of low molecular weight polymeric polyamides as plasticizers. Thus, it is possible to use medium and high molecular weight nylons and, thus, preserve the mechanical properties of the resulting dynamically vulcanized mixtures of vulcanized BIMS and nylon, and, in addition, due to the demonstration of relatively low permeability by low molecular weight polyamides, the resulting dynamically vulcanized mixtures do not show significant reduce its permeability characteristics. Suitable plasticizers include those sold under various trademarks, including Sunmide (Sanwa Chemical Industry Co., Ltd.) and Uni-Rez® (Arizona Chemical). Such materials are usually characterized by a molecular weight of less than about 20,000 daltons; such as in the range of from about 1000 to about 18000 daltons; preferably from about 3,000 to about 17,000 daltons, and flash points greater than about 250 ° C, brittleness temperatures less than about -20 ° C, and a softening temperature less than about 180 ° C. In addition, suitable low molecular weight amides are characterized by a viscosity at 200 ° C. of less than about 15 pascal second (Pa-sec); alternatively, in the range of from about 0.05 to about 12 Pa-sec; preferably from about 0.2 to about 10 Pa-sec. Suitable products are commercially available, covering the full range of the above viscosities, including: Sunmide product codes 15, 15K-5, 52 and 72; 300; 500; 550; NT-110, 130K, 180D, 140E, 140PK-20 and 100G, characterized by viscosities in the range from about 0.25 Pa-sec to about 0.60 Pa-sec as measured at 190 ° C; and from about 0.4 Pa-s to about 15 Pa-s as measured at 200 ° C; as well as Uni-Rez grades 2611-2722 and, specifically, including grades 2614 having a viscosity of approximately 1.1, grades 2633 having a viscosity of approximately 4.3 and grades 2653 having a viscosity of approximately 7.5, where all measurements are carried out at 200 ° C.

In addition to this, plasticizers such as organic esters and other synthetic plasticizers can be used. Plasticizers, particularly preferred for use in an ICE composition, are N-butylsulfonamide or other plasticizers suitable for polyamides. Nylon plasticizers include, but are not limited to: lactams such as caprolactam and laurillactam; and sulfonamides such as ortho, para-toluenesulfonamide, N-ethyl (ortho, para-toluenesulfonamide), trimellitates, phthalates, adipates, phosphates and glycolates. Other plasticizers include those described in US Pat. No. 4,197,379, by reference incorporated herein. Examples of plasticizers can be selected from the group consisting of phthalate plasticizers, adipate plasticizers, phosphate plasticizers, glycolate plasticizers, sulfonamide plasticizers, trimellitate plasticizers and polymer plasticizers, in particular low molecular weight nylon. Preferred plasticizers are selected from the group consisting of phthalate plasticizers, adipate plasticizers and sulfonamide plasticizers. Examples of suitable plasticizers include dibutyl phthalate, ditsikglogeksilftalat, diethyl phthalate, diisodecyl phthalate, dimethyl phthalate, di (2-ethylhexyl) phthalate, diphenyl phthalate, diundetsilftalat mixed C ₇ -C ₁₁ dialkyl phthalate, butyl benzyl phthalate, benzilftalat, di (2-ethylhexyl) adipate, mixed C ₇ - C ₉ dialkiladipinat, tributoxyethyl phosphate, tributyl phosphate, tricresyl phosphate, triphenyl phosphate, krezildifenilfosfat, 2-etilgeksildifenilfosfat, izodetsildifenilfosfat, butilftalilbutilglikolyat, methyl phthalyl ethyl and mixed C ₇ -C ₉ alkiltrimellit t. Sulfonamide plasticizers include a preferred class of plasticizers for polyamides, including, for example, N-butylbenzylsulfonamide, N-cyclohexyl-para-toluenesulfonamide, ortho, para-toluenesulfonamide, N-ethyl-ortho, para-toluenesulfonamide and-to-ethylamide . In another embodiment, rubber process oils, such as naphthenic, aromatic, or paraffin filling oils, may be present in an amount in the range of from about 1 to about 5 parts per hundred parts of rubber. In yet another embodiment, naphthenic, aliphatic, paraffinic and other aromatic oils are substantially absent from the composition. By the term “substantially absent” is meant that naphthenic, aliphatic, paraffinic and other aromatic oils may be present, if at all, in an amount not exceeding 2 parts per hundred parts of rubber.

The degree of cure of vulcanized rubber can be described when expressed in terms of gel content, crosslink density, amount of extractable components, or it can be based on the cure state that would be achieved in the rubber if it cured in the absence of resin. For example, in the present description, it is preferable that the halogenated elastomer achieves from about 50 to about 85% of the total cure when calculated on the elastomer per se as measured, for example, tensile strength or measured using a device test to determine the degree of cure with an oscillating Disc (ASTM D 2084, Standard Test Method for Rubber Property-Vulcanization Using Oscillating Disc Cure Meter).

After describing each of the components suitable for use in the thermoplastic elastomeric composition of the present invention, the following paragraphs describe effective and novel methods for preparing such compositions.

Dynamic vulcanization can be carried out in various types of commercial equipment, generally available in the rubber and plastics industry, including Banbury® enclosed rubber mixers, roller mixers and mixing extruders. One preferred mixing device is a twin screw extruder extruder with worms meshed. Stirring is generally carried out under such conditions in time and temperature so that the dispersed rubber particles, in particular the first rubber component, a halogenated elastomer containing isobutylene, are dispersed and cured and / or interact with the polyamide to the extent necessary to preserve them stability, that is, preventing coalescence of such particles upon completion of mixing of the composition. A suitable range of vulcanization temperatures typically ranges from about the melting temperature of the resin (s) to less than about 300 ° C; for example, the temperature may range from about the melting temperature of the matrix resin (s) to about 275 ° C; preferably from about 230 ° C to about 265 ° C; alternatively, from about 235 ° C to about 260 ° C; since from about 240 ° C to about 260 ° C; for example, from about 230 ° C to about 250 ° C. Alternatively, dynamic vulcanization can be carried out in a temperature range exceeding the melting temperature of the matrix resin by a value in the range from about 10 ° C to about 50 ° C; more preferably exceeding the melting temperature of the polyamide or mixed polyamide thermoplastic matrix by an amount in the range of from about 20 ° C to about 40 ° C. A mixing extruder usually consists of several sections of a cylinder, each of which may have temperature control, and the function of each of which may vary, for example, a feed section, a mixing section, a cooling section, a melt section and the like. Therefore, the temperature in each section can be adjusted to implement the most suitable conditions for melting, mixing, dispersing and curing the components that are supplied along the process stream to or within each section. For example, temperatures in the earliest sections of the process stream may be raised to promote the heating, melting, and dispersion of the polyamide (s) and stabilizers and plasticizers of the polyamide that are typically fed to the first section (s) of the extruder, for example, to a value in the range of from about 230 ° C to about 250 ° C. This can be followed by temperatures suitable for mixing, dispersing and dynamically vulcanizing a component containing SIMS, for example in the range of from about 200 ° C to about 230 ° C, and then temperatures suitable for mixing and dispersing the second elastomer and for release a mixed composition from a mixing extruder, for example, in the range of from about 190 ° C to about 220 ° C. The temperature data are presented for illustrative purposes only, since specific values can be selected based on the specific type (s) and brand (s) of polyamide, the specific curing system used for the dynamic vulcanization of BIMS or another halogenated component containing isobutylene, as well as a specific the type of second rubber, its activity and whether it will be dynamically vulcanized or dispersed without dynamic vulcanization.

In one embodiment of the present invention, the necessary or suitable amount of a crosslinker (s) or curing system is dispersed in the elastomeric component (s) by admixture to an elastomeric component of a crosslinker capable of crosslinking the elastomeric component (s) that is desirable to form a vulcanized dispersed phase at temperature in the range from low to moderate, essentially insufficient to activate the curing system, before the introduction of the thus prepared sludge and accelerated composition of the elastomeric component (s) in contact with the component (s) in the form of a resin for the purpose of conducting dynamic vulcanization of the mixture. According to this method, the crosslinker essentially does not react with rubber, nor does it have the ability to partially react with a thermoplastic resin, leading either to a decrease in molecular weight or to crosslinking of the resin. In addition, it is easier to control the crosslinking speed and the degree of crosslinking of the elastomeric component. Therefore, the compositions of the present invention have improved properties.

For example, to pre-mix or pre-formulate an elastomeric component with a predetermined amount of a crosslinker or “system”, the latter being a multicomponent hardener mixture, a mixing device, such as a Banbury® mixer, twin roll rollers, is used in the flesh until a substantially uniform dispersion is obtained. rubber industry and the like, in particular, in the case of using a combination of a stapler and an accelerator. At the moment, an elastomeric component may be added here, if desired, suitable amounts of optional fillers, such as carbon black or modified carbon black, clay or modified clay, oil and / or plasticizer. As noted earlier, during this phase of mixing, the temperature is controlled at a sufficiently low level for the particular selected elastomer (s) and taking into account the activity of the curing system, which ensures effective dispersion of the rubber phase components and prevents premature crosslinking of the elastomers. A suitable temperature during the mixing step for dispersing the hardeners or the curing system may be less than about 120 ° C.

Having ensured the presence in the thermoplastic elastomeric composition of several components, including one or more polyamides, a vulcanizable BIMS elastomer and at least one secondary rubber, for sufficient distribution and dispersion mixing, as well as dynamic vulcanization, it will usually be necessary to include several stages or stages of mixing. Typically, by introducing hardeners, the SIMS rubber composition is preliminarily prepared using a closed rubber mixer, such as Banbury®, or rollers for the rubber industry, and granulation is carried out. In the prior art method, each individual polyamide component is premixed with a plasticizer and stabilizers using a two-screw extruder and granulated. In conclusion, the granules of the pre-compounded SIMS rubber composition, the pre-mixed polyamide granules and the secondary rubber granules are metered or fed into a twin-screw extruder for extrusion mixing and dynamic vulcanization. Such stages of multi-stage mixing and intermediate cooling and granulation are expensive, prone to manufacturing errors and during production lead to the emergence of significant reserves in the intermediate stages.

In contrast, the dynamic vulcanization method of the present invention is modified in comparison with what is a typical prior art method. Improved methods of the present invention provide a reduction in the number of mixing steps required to obtain a thermoplastic elastomeric composition having excellent morphology for applications such as in the case of internal sealing layers of tires and other industrial applications using impermeable films. In particular, when mixing, it is preferable to use double-screw extrusion mixing methods, in particular, a single-stage double-screw mixing method, to obtain a thermoplastic elastomeric composition based on mixtures of polyamides with reaction combined elastomers, including the previously described SIMS elastomer and secondary elastomers. A particularly preferred one-step method of dynamic vulcanization with two-screw extrusion mixing involves the sequential addition of components, the first to add one or more polyamides in combination with their respective stabilizer (s) and plasticizer (s), if any, followed by the addition of one or more elastomers, characterized by low vaccination efficacy (such as BIMS, hardener or crosslinker containing it) agents) and in granular form), and then one or more elastomers characterized by high grafting efficiency (previously described secondary elastomers) are added last. Ensuring the effectiveness of mixing and processing is achieved by spacing the addition of elements of the composition along the length of the cylinder of a twin-screw extruder using several feed holes. In particular, the spacing between the feed holes for elastomers characterized by low grafting efficiency and characterized by high grafting efficiency is selected to provide the proper opportunity to undergo a reaction with polyamide (s) in order to obtain and stabilize an elastomer characterized by small particle size and dispersed in a continuous polyamide matrix . In one embodiment, this result is achieved by spacing the feeding holes for the elastomers from each other along the length of the extruder barrel by an L / D value (the ratio between the length of the extruder screw and the diameter of the extruder screw), greater than about 6. The length L is usually the length of the threaded parts of the worm, in other words, the length of the part of the worm that has a threaded thread. The diameter of the worm indicates the maximum width of the worm in its threaded part, in other words, where there is a threaded cut of the worm, since extruder worms usually have sections of variable width depending on the function of a particular part of the worm, for example, transportation, dispersion, mixing, melting, heating, cooling and the like. If there is a threaded thread on the worm in that part that is not in contact with the components of the compositions, for example, thermoplastic resin and / or elastomer, such parts will not be included in the determination of the length or diameter of the worm. The calculation of the L / D value for the twin-screw extruder is identical and is based on one of the two screws, since each usually has the same diameter and length.

In the methods of the present invention, mixing and dynamic vulcanization is preferably carried out in a twin-screw mixing extruder, commercial examples of which are readily available and well known in the art. The shear rate during mixing usually exceeds about 500 sec ^-1 ; preferably in the range of from about 500 to about 7500 sec ^-1 ; alternatively, from about 1000 to about 7500 sec ^-1 ; for example, from about 2000 to about 7500 sec ^-1 . Such extruders should be provided only with the presence of several feed holes corresponding to the various components of the overall composition and the limitations described in detail later in this document. In addition, the mixing worms should only be adapted to ensure that there is a mixing area after each of the supply openings and an appropriate length after the introduction of all the ingredients, so that when using the selected polymer components and vulcanizing agents or the BIMS curing system, dynamic vulcanization can be carried out and completed in the desired degrees. Such features can easily be determined by a person skilled in the art with limited experimentation based on the provisions of this document. Alternatively, mixing and dynamic vulcanization can be carried out in any suitable mixing equipment in which various components can be introduced and mixed and in which dynamic vulcanization can be carried out. For example, to receive each of the components or mixtures of components so that they can be mixed and dispersed, a closed Banbury® rubber mixer can be used, and such a mixing device can be used to conduct dynamic vulcanization at elevated temperatures. To ensure convenient and efficient processing, it is preferable to use an extruder, more preferably a two-screw displacement extruder mixing extruder with two co-rotating worms engaged, including suitable feeding, mixing, cooling and discharging zones consistent with the provisions of this document.

In one preferred mixing sequence, the polyamide component (s), their stabilizers and plasticizers can be introduced into the feed openings of the extruder located downstream of the process stream; these components do not need to be premixed or premixed. To ensure the mixing and dispersion of the stabilizer and plasticizer in the polyamide phase, it is necessary to provide for the presence of a sufficient length along the worm. Mixing variations are possible, such as adding a stabilizer (s) with nylon or dispersing a stabilizer (s) with a nylon plasticizer (if used) and adding a mixture of stabilizers plus a plasticizer to the nylon after it is mixed. If necessary, a cooling zone may be provided in order to avoid excessive heating of the polyamide, such that its viscosity would become undesirably low before being mixed with BIMS. In other words, as previously discussed, for effective mixing and dispersing the SIMS in the polyamide, it is preferred that the viscosities of the polyamide and its stabilizer and plasticizer and SIMS and its hardeners and fillers and plasticizers, if any, are approximately identical (essentially “consistent”) in the moment they are mixed with each other and the initiation of dynamic vulcanization. As previously described, a SIMS rubber composition is usually preliminarily formulated by introducing hardeners, also referred to as “acceleration”, when using a closed rubber mixer such as Banbury® or rollers for the rubber industry, and granulation is usually carried out to facilitate feeding or dosing. As previously discussed, the temperature must be controlled to avoid an excessively low temperature and the resulting high viscosity polymer blends and the associated power consumption. Similarly, an excessively high temperature will result in an excessively low viscosity, in particular of the polyamide mixture, and possibly decomposition, as well as poor mixing with the SIMS composition. A suitable temperature range is from about 230 ° C to about 250 ° C; preferably not inferior to approximately 210 ° C or not exceeding approximately 275 ° C.

In the course of the process stream, after the feed opening for the SIMS, a feed opening for the secondary rubber in granular form is provided, while the secondary rubber is also called rubber, characterized by a high grafting efficiency. Two rubber components are particularly preferred not to be fed into the mixing extruder together to avoid inadvertent coalescence of the rubber particles formed in the extruder. In addition, since the SIMS rubber is characterized by reduced grafting efficiency, it is fed first to ensure that there is additional grafting time on the polyamide simultaneously with the dispersion and curing reaction during dynamic vulcanization. In contrast, secondary rubber, characterized by increased grafting efficiency, can be fed at a point further down the process stream and closer to the exit of the extruder, since it reacts faster and grafts onto polyamide more easily.

In addition, since grafting is usually accompanied by an increase in the viscosity of the grafted polymer and may also be accompanied by viscous heating, if necessary, suitable cooling zones can be introduced between the feed holes for two rubbers to adjust the temperature and viscosity of the composition, and, if necessary, a zone can be introduced cooling after the feed hole for the second rubber in order to control the viscosity and temperature of the total composition at a given point to obtain the desired orfologii and particle size of the dispersed rubber components.

The specific characteristics of the extruder and the worms (for the worm, the design or configuration, diameter, relationship between volume and surface area, etc.) will determine the specific aggregate L / D value for the system. However, for any given extruder, the overall position on the cylinder can be designated as the position located earlier or further along the process flow as a result of taking the aggregate L / D value and dividing it in half. In this case, it is preferable that the elastomer, characterized by reduced grafting efficiency, be added or fed into the first half of the extruder or half of the extruder, located earlier in the process flow, and the elastomer, characterized by increased grafting efficiency, should be added or fed into the extruder into the second half of the extruder or half of the extruder, located along the process stream further. As described, the polyamide components and their stabilizers and plasticizers, if any, are added first. Typically a twin-screw extruder mixing extruder with meshes in mesh, suitable for use in the present invention, will have an L / D value in the range of at least about 25 to less than about 60; more preferably from about 30 to about 55; alternatively, from about 35 to about 50; for example, from about 38 to about 48.

The total agitation time for dynamic vulcanization can range from about 30 seconds to about 8 minutes; for example, from about 45 seconds to about 6 minutes; since from about 1 minute to about 4 minutes. However, the mixing time can, and preferably must be adjusted as necessary to obtain a dynamically vulcanized composition, which is characterized by a suitable small and stable particle size (s) of the elastomer, and the total composition, which demonstrates the target physical properties and / or permeability characteristics based on the first and second rubber, and also taking into account whether or not the second rubber will be dynamically vulcanized, as discussed previously. A specialist in the relevant field of polymer mixing technology, in particular extrusion mixing, based on the principles and detailed information presented in this document, will easily select the mixing time, cumulative in either every part or at every stage of the method, in combination with the addition of various previously described components.

The thermoplastic elastomeric composition thus obtained is structured with an elastomeric component forming a discrete phase dispersed as a dispersed phase (domain) in a nylon resin matrix that forms a continuous phase. As a result of dynamic vulcanization, the composition remains thermoplastic, and using conventional molding, extruding, or calendering, a structure similar to a film, layer or sheet can be obtained from the composition.

By molding the thermoplastic elastomeric composition obtained in the form of a sheet, film, or sleeve using a T-shaped extrusion head to produce sheets, an extrusion head with a straight-through or lateral structure to produce sleeves, a cylindrical extrusion head for blow molding, and the like at the end of a single screw extruder, or due to calendaring, the composition becomes possible to use as a layer preventing the penetration of air, for example, internal metiziruyuschego layer, the pneumatic tire and as a component or layer of the hose, and the like. The thermoplastic elastomeric compositions of the present invention immediately after selection in the form of strands can be granulated and then molded using a single screw extruder, which is usually used for resin.

Thus, the obtained molded product in the form of a sheet or sleeve can be effectively used for the manufacture of the inner sealing layer of the pneumatic tire or the inner layer of the hose or the outer shell of the hose for low-permeable hose. In addition, the low permeability characteristics of the composition are suitable for use in the case of fluids other than gases, for example, fluids such as water, hydraulic fluid, brake fluid, heat transfer medium and the like, provided that the layer located in direct contact with the fluid, will exhibit suitable resistance to the effects of the working fluid.

Any range of numerical values presented in the preceding description of the invention herein or in the paragraphs and claims of the present document hereinafter related to various aspects of the invention, such as those that represent a specific set of properties, units of measure, conditions, physical conditions or percentages, it is assumed by reference or otherwise unambiguously literally including in this document any numerical value falling within the limits of such range azone, including any subset of numerical values or ranges within any of the ranges so mentioned. In addition, the term “approximately” when used as a modifier of a variable, characteristic or condition or in connection with them implies a message that the numerical values, ranges, characteristics and conditions described in this document are flexible, and that that the practical implementation of the present invention by specialists in the relevant field of technology when using temperatures, times, concentrations, quantities, levels, levels of carbon atoms, properties such as particle size, pl schad surface, bulk density and the like, which are located outside the range or different from a single value, will result in the achievement of the desired result, namely preparation of a dynamically vulcanized composition having a high content of elastomer. containing at least one elastomer containing isobutylene, and at least one thermoplastic and suitable for use, for example, in a pneumatic tire or hose or as an internal sealing layer of a tire.

EXAMPLES

The following commercially available products were used for the components used in the examples.

1. Resin Components

N11 (nylon 11): Rilsan BMN O TL (Atochem).

N6 / N66 (copolymer of nylon 6/66): Ube 5033B (Ube).

P: plasticizer, BBSA, N-butylsulfonamide.

C: stabilizer package, includes Irganox, Tinuvin and CuI.

2, Rubber components

BIMS-1: Exxpro 89-4 (ExxonMobil Chemical).

ZnO: hardener zinc oxide.

St-acid: hardener stearic acid.

ZnSt: hardener of zinc stearate.

AR201: maleated ethylene-ethyl acrylate (EEA) copolymer (Mitsui-DuPont).

Exxelor VA 1840: maleated (0.2-0.5% by weight) ethylene-octene copolymer (ExxonMobil Chemical).

To study the efficacy of grafting elastomers onto nylon using a closed Brabender rubber mixer at 220 ° C and 60 rpm for three minutes, mixtures of elastomers with N6 / 66 were obtained. Before adding 40 parts of elastomer, 60 parts of nylon were first added within 2 minutes; after that, the combination was stirred for 1 minute. After stirring, the nylon-elastomer mixture was extracted with a solvent (s) to determine the amount of elastomer grafted onto nylon. The solvents used were hot toluene and xylene for BIMS, hot xylene for AR201 and hot toluene and xylene for Exxelor 1840. The mixtures were extracted for 12 hours and the solvents were regenerated every four hours. After extracting the mixture for 24 hours, it was dried in a vacuum oven at 60 ° C. Based on the results of solvent extraction, the mass percentage of elastomer was determined for each elastomer, which was grafted onto nylon after 1 minute at 220 ° C in a Brabender mixer; the results are shown in Table 1. Of the three Exxelor 1840 elastomers tested on N6 / 66, it appears that they are vaccinated the most and are called an elastomer characterized by "high vaccination efficiency." The effectiveness of the AR201 vaccine on N6 / 66 is much lower and similar to that of the BIMS; these elastomers will be characterized as elastomers characterized by “low grafting efficiency”.

Table 1
Vaccination Effectiveness for Graded Elastomers Nylon N6 / 66 Vaccination (% wt.) * BEAM 40 Ar201 43 Exxelor 1840 86 * Mass percentage of unextracted rubber.

A dynamically vulcanizable alloy (ICE) mixture, designated F1 and having the composition shown in Table 2, was prepared according to alternative methods using a JSW-44 twin-screw extruder (TEX44, Japan Steel Work).

table 2
Formulation F1 Recipe F1 Elastomers Exxpro 89-4 one hundred Zno 0.15 Stearic acid 0.60 Zinc stearate 0.30 AR201 10.1 Plastics Ube 5033B (N6 / 66) 27.8 Atochem BESN (N11) 40,4 Plasticizer Bbsa 11.0 Stabilizer Irganox 1098 0.34 Tinuvin 622 LD 0.14 Cui 0,03

In the comparative example shown in Table 3, the SIMS rubber composition was preliminarily prepared by introducing hardeners using a kneading machine (closed rubber mixer) at 40 rpm for 3.5 minutes at 90 ° C, and granulation was performed. For a comparative example, each individual nylon component was pre-mixed with plasticizer and stabilizers using a JSW-44 twin-screw extruder at 210 ° C and 100 rpm and granulated. Therefore, in the comparative example, there are two additional stages of double-screw mixing (one for N6 / 66 and one for N11), intended for the preparation of nylon masterbatches (nylon compositions containing plasticizer and stabilizers) before their use in the stage of two-screw extrusion mixing and dynamic vulcanization. In this three-stage comparative example of mixing, all the granules selected from the granules of the preformed rubber composition, the granules of the AR201 elastomer and the granules of the pre-mixed N6 / 66 and N11 were metered and added to the first feed hopper of the first section of the cylinder, in other words, at the position along the way process flow first of all.

As previously discussed, an extruder is typically formed from connected sections of a cylinder, each of which has a length equivalent to an L / D value in the range of from about 2 to about 3, and each of which usually has an independent cooling section, optionally with independent thermocouple and pressure sensors. The JSW-44 twin-screw extruder, used in this and other examples of twin-screw mixing described in this document, had 14 segments in total and had a combined L / D value of 49. The temperatures in the cylinder segments along the length of the extruder were set in accordance with thermocouples, reflecting temperatures metal. Temperatures ranged from approximately 190 ° C to approximately 250 ° C in the following typical figure (thermocouple temperatures in ° C from zone 1 — supply — to zone 14 — exit; the actual temperature of the polymer composition at the exit of the extruder — in section 14, was in the range from about 260 ° C to about 270 ° C): 250/250/250/250/230/200/200/200/200/200/200/195/190/220. The component in the form of BIMS was usually introduced into zone 5, and the secondary rubber into zone 10; mixing zones were in zones 4, 9 and 12.

As shown in table 3, to obtain the internal combustion engine compositions designated as F1, used alternative single-stage methods of two-screw mixing. Liquid nylon plasticizer was pumped to extruder position 2, corresponding to position at L / D = 7. Two additional feed positions were located along the process stream further under number 3, L / D = 24.5, and under number 4, L / D = 35. As the results obtained for example 1 demonstrate, by feeding the first nylons together with stabilizers, followed by feeding the nylon plasticizer and, finally, adding two elastomeric components, good quality granules can be obtained that have good rubber dispersion morphology (fine rubber dispersions in continuous nylon matrix). However, when an elastomer characterized by low grafting efficiency (BIMS) was fed before nylon first, as demonstrated in Example 2, unsatisfactorily mixed granules having mutually continuous morphology were obtained. For triggering a one-step method of mixing, nylon (nylons) must be fed to the rubber component (s); preferably, nylon is fed together with a stabilizer and a plasticizer, although stabilizers and a plasticizer are not required to be supplied at the same feed point, provided that these components are fed to the rubber (s).

Table 3
ICE F1, obtained by various methods of double-screw mixing Comparative Example 1 Example 1 Example 2 Precomposed Beams Composition Yes Yes Yes Premixed Nylon Yes (N / A / S) No No Three-stage mixing Yes No No Single stage mixing No Method 1 Method 2 Added component (s) *
The sequence of adding 1-2-3 ** Not applicable N / S-P-K / A K-P-A / N / S Pellet quality *** Good Good Bad Morphology**** Good Good Intercontinuity * N: nylons, C: stabilizers, P: plasticizer, A: AR201, K: rubber (BIMS).
** Add position in the extruder: 1-2-3, where 1 at L / D = 3.5, 2 at L / D = 7, and 3 at L / D = 24.5 along the length of the cylinder of the extruder.
*** The quality of the granules was judged by the smoothness of the surface of the extruded polymer strands.
**** Morphology was evaluated using the AFM method in the tapping phase (atomic force microscopy).

Received additional formulations shown in table 4. In the plastic phase in F1 and F2 used two nylons and only one nylon N6 / 66 was used in formulations F3, F4 and F5, Therefore, comparative examples corresponding to compositions F3, F4 and F5 are two-stage methods of double-screw extrusion mixing, since only one additional step of obtaining with preliminary mixing of nylon is required. As for the single-stage two-screw mixing methods used for formulations F3, F4 and F5, as well as F1, four different feed positions were used: where at position 1 L / D = 3.5, at position 2 L / D = 7, at position 3 L / D = 24.5 and at position 4 L / D = 35, again when using an extruder JSW-44, characterized in the aggregate value of L / D 49.

Table 4
Formulations ICE F2-F5 Recipe F2 F3 F4 F5 Elastomers Exxpro 89-4 one hundred one hundred one hundred one hundred Zno 0.15 0.15 0.15 0.15 Stearic acid 0.60 0.60 0.60 0.60 Zinc stearate 0.30 0.30 0.30 0.30 AR201 9.2 0 0 10.1 Exxelor 1840 0 10.0 10.0 0 Plastics Ube 5033B (N6 / 66) 29.5 69.2 62,4 63.0 Atochem BESN (N11) 44.3 0 0 0 Plasticizer Bbsa 8.2 20.7 26.8 27.0 Stabilizer Irganox 1098 0.37 0.37 0.31 0.32 Tinuvin 622 LD 0.15 0.15 0.13 0.13 Cui 0.04 0.04 0,03 0,03

As shown in tables 5 to 8, it is preferable to either add two elastomers together, or first add an elastomer characterized by reduced grafting efficiency (BIMS, as shown in table 1). If BIMS was added, the latter received an unsatisfactory morphology (see method 4). In method 5, the BIMS rubber was added together with nylon stabilizers prior to the introduction of nylon plasticizer. Given the desirability of reducing the viscosity of nylon as a result of plasticization in order to ensure that its viscosity is consistent with the viscosity of the elastomeric components, the addition of elastomeric components prior to the introduction of the plasticizer is undesirable. Using Method 3 with the latter, either AR201 or Exxelor 1840 added excellent morphology. In formulations F1 and F2 containing AR201, which was characterized by a similar but somewhat higher vaccination efficiency compared to the case of SIMS, good morphologies could be obtained by adding AR201 together with SIMS, as in method 1. However, with a much higher vaccination efficiency, observed for Exxelor 1840 in comparison with the case of BIMS, later it is preferable to add a polymer characterized by increased vaccination efficiency, such as Exxelor 1840, which was added last in method 3.

Table 5
ICE F1, obtained by various methods of double-screw mixing Comparative Example 1 Example 3 Example 1 Example 4 Example 5 Recipe F1 F1 F1 F1 F1 Precomposed Beams Composition Yes Yes Yes Yes Yes Premixed Nylon Yes (N / A / S) No No No No Three-stage mixing Yes No No No No Single stage mixing No Method 3 Method 1 Method 4 Method 5 The sequence of adding 1-2-3-4 Not applicable N / S-P-K-A N / S-P-K / A N / S-P-A-K N / S / K-P-A Pellet quality Good Good Good HX (IF) HX (IF) Morphology Good Good Good Hx Hx The quality of the cast film Good Good Good Hx Hx

Addition items: 1-2-3-4, where 1 with L / D = 3.5, 2 with L / D = 7, 3 with L / D = 24.5, and 4 with L / D = 35.

N: nylons, C: stabilizers, P: plasticizer, A: AR201, K: BIMS rubber.

Poor morphology demonstrated the presence of large nylon domains (grains), aggregation of dispersions of elastomers and / or occasionally intermittent phases of nylon and rubber.

The quality of the cast film was judged by the uniformity and smoothness of the cast film.

HX = "not good"; IF = phase inversion, in the sense that the rubber phase is either intercontinuous with nylon or is a continuous phase.

Table 6
ICE F2 obtained by various methods of double-worm mixing Reference Example 2 Example 6 Example 7 Example 8 Example 9 Recipe F2 F2 F2 F2 F2 Precomposed Beams Composition Yes Yes Yes Yes Yes Premixed Nylon Yes (N / A / S) No No No No Three-stage mixing Yes No No No No Single stage mixing No Method 3 Method 1 Method 4 Method 5 The sequence of adding 1-2-3-4 Not applicable N / S-P-K-A N / S-P-K / A N / S-P-A-K N / S / K-P-A Pellet quality Good Good Good HX (IF) HX (IF) Morphology Good Good Good Hx Hx The quality of the cast film Good Good Good Hx Hx

Addition items: 1-2-3-4, where 1 with L / D = 3.5, 2 with L / D = 7, 3 with L / D = 24.5, and 4 with L / D = 35.

N: nylons, C: stabilizers, P: plasticizer, A: AR201, K: BIMS rubber.

Table 7
ICE F3 obtained by various methods of double-worm mixing Reference Example 3 Example 10 Example 11 Example 12 Example 13 Recipe F3 F3 F3 F3 F3 Precomposed Beams Composition Yes Yes Yes Yes Yes Premixed Nylon Yes (N / A / S) No No No No Two-stage mixing Yes No No No No Single stage mixing No Method 3 Method 1 Method 4 Method 5 The sequence of adding 1-2-3-4 Not applicable N / S-P-K-E N / S-P-K / E N / S-P-E-K N / S / K-P-E Pellet quality Good Good Good HX (IF) HX (IF) Morphology Good Good Good Hx Hx The quality of the cast film Good Good Good Hx Hx

Addition items: 1-2-3-4, where 1 with L / D = 3.5, 2 with L / D = 7, 3 with L / D = 24.5, and 4 with L / D = 35.

N: nylons, C: stabilizers, P: plasticizer, E: Exxelor 1840, K: BIMS rubber.

Addition items: 1-2-3-4, where 1 with L / D = 3.5, 2 with L / D = 7, 3 with L / D = 24.5, and 4 with L / D = 35.

N: nylons, C: stabilizers, P: plasticizer, E: Exxelor 1840, K: BIMS rubber.

In addition to this, it is possible to further reduce the distance between the positions of the addition of BIMS and either AR201 or Exxelor 1840. As shown in Table 9, excellent morphologies could be obtained with thermoplastic elastomeric compositions containing either AR201 or Exxelor 1840, with the addition of BIMS only with L / D 7 along the process flow prior to adding either AR201 or Exxelor 1840. Therefore, for the production of excellent dispersion morphologies for these ICEs, using single-stage two-screw extrusion mixing, nylon will be preferred they are added first, most preferably together with stabilizers and a plasticizer for nylon. Among the elastomers, the elastomer characterized by the lowest vaccination efficiency is preferably added first, and the elastomer characterized by the increased vaccination efficiency is preferably added last. To ensure good mixing and morphology, it is preferable to sufficiently spaced the positions of addition of these elastomers characterized by low and high grafting efficiencies. The spacing of the additions of such elastomers is preferably greater than approximately L / D = 6.

Table 9
ICE F4 obtained by various methods of double-worm mixing Reference Example 5 Example 19 Example 20 Recipe F5 F5 F4 Precomposed Beams Composition Yes Yes Yes Premixed Nylon Yes (N / A / S) No No Two-stage mixing Yes No No Single stage mixing No Method 6 Method 6 The sequence of adding 1-2-3 * -4 Not applicable N / S-P-K-A N / S-P-K-E Pellet quality Good Good Good Morphology Good Good Good The quality of the cast film Good Good Good

N: nylons, C: stabilizers, P: plasticizer, E: Exxelor 1840, K: BIMS rubber.

Addition items: 1-2-3 * -4, where 1 with L / D = 3.5, 2 with L / D = 7, 3 * with L / D = 28, and 4 with L / D = 35.

Any range of numerical values presented in the preceding description of the invention herein or in the paragraphs and claims of the present document hereinafter related to various aspects of the invention, such as those that represent a specific set of properties, units of measure, conditions, physical conditions or percentages, it is assumed by reference or otherwise unambiguously literally including in this document any numerical value falling within the limits of such range azone, including any subset of numerical values or ranges within any of the ranges so mentioned. In addition, the term “approximately” when used as a modifier of a variable, characteristic or condition or in connection with them implies a message that the numerical values, ranges, characteristics and conditions described in this document are flexible, and that that the practical implementation of the present invention by specialists in the relevant field of technology using temperatures, concentrations, quantities, levels, levels of carbon atoms and properties that fall outside the range if it differs from a single value, it will lead to the achievement of the desired result, namely, the production of a thermoplastic elastomeric composition demonstrating the desired morphology, including one or more dispersed elastomers in a thermoplastic matrix, preferably obtained by an effective, more preferably one-stage, extruder mixing method.

All documents described herein are incorporated by reference into this document, including any priority documents and / or test procedures. In the preceding description of the invention, the principles, preferred embodiments and procedures of the present invention have been described. Despite the description of the invention herein with reference to specific embodiments, it should be understood that these embodiments are merely illustrations of the principles and applications of the present invention. Therefore, it is necessary to understand that in the illustrative embodiments, many modifications can be made, and that other schemes can be developed without deviating from the scope and essence of the present invention defined in the attached claims.

Claims (20)

1. The method of dynamic vulcanization to obtain a thermoplastic elastomeric composition, which is carried out in a mixer capable of shear the polymer components at elevated temperatures, said composition comprising dispersed particles of at least one first elastomer comprising a halogenated elastomer containing isobutylene, and dispersed particles of at least one second elastomer having at least one functional group capable of entering into p a reaction with the polyamide and grafted onto it, wherein said particles of the at least one first and at least one second elastomers are dispersed in a continuous thermoplastic polyamide matrix containing at least one polyamide selected from the group consisting of polyamide homopolymers and polyamide copolymers, wherein said method comprises the steps of:
(1) dispersing in said halogenated elastomer at least one representative selected from a hardener or curing system suitable for crosslinking said halogenated elastomer in order to obtain a pre-formulated halogenated elastomer composition using shear conditions, mixing time and temperature sufficient essentially for uniformly dispersing said hardener or curing system, but not sufficient to stimulate, essentially crosslinking said elastomer, which would prevent its subsequent flow and dispersion when added to the polyamide under conditions of elevated temperature and shear;
(2) introducing said at least one polyamide and optionally at least one heat stabilizer of a polyamide, or an oxidizing stabilizer, or a light stabilizer, or a combination thereof, into said mixer and shear and heat enough to stimulate the melting of the polyamide and dispersing said optional stabilizer in said polyamide and producing a polyamide mixture;
(3) the introduction of at least one polyamide plasticizer in an amount sufficient to stimulate obtaining, essentially, a correspondence between the viscosity of said polyamide mixture and the viscosity of said previously prepared halogenated elastomer composition at temperature and under shear conditions present in said mixer;
(4) introducing said preformed halogenated elastomer composition into said mixer and conducting heating and shear, sufficient in magnitude to initiate dynamic vulcanization of said halogenated elastomer; and
(5) introducing said second elastomer and continuing to heat and shear substantially to disperse said second elastomer and essentially to complete said dynamic vulcanization of said halogenated elastomer; and
the release of said dynamically vulcanized thermoplastic elastomeric composition from said mixer. 2. The method according to claim 1, where the said mixer is a mixing extruder having at least one extruder screw, described by a characteristic value of L / D, where L is the length of the threaded part of at least one extruder screw, a D represents the maximum diameter of said at least one extruder screw in its threaded portion. 3. The method according to claim 2, where the said extruder is a twin-screw extruder. 4. The method according to claim 3, where said extruder is characterized by an L / D value in the range from about 25 to about 60. 5. The method according to claim 4, where the aforementioned preformed halogenated elastomer composition is supplied to said extruder in a position located upstream of the process stream equal to or less than half the total L / D value of said extruder, and said second elastomer is fed to said extruder in the course of the process stream beyond a position equal to or greater than half the total L / D value of said extruder, provided that the feed position of the previously mentioned lennoy halogenated elastomer composition and said second elastomer separated from each other along the length of said extruder, is at least about L / D = 6. 6. The method according to claim 1, further comprising granulating and cooling the granules obtained from the previously prepared halogenated elastomer composition in step 1. 7. The method according to claim 1, where said halogenated elastomer in said polyamide matrix is dispersed in the form of particles having an average size in the range from about 0.1 μm to about 1.0 μm, and said second elastomer in said polyamide matrix is dispersed in the form particles having an average size in the range from about 0.1 microns to about 1.0 microns. 8. The method according to claim 1, where the said second elastomer or rubber is selected from the group consisting of ethylenically unsaturated highly saturated copolymer rubbers based on nitrile conjugated diene (HNBR), epoxidized natural rubbers (ENC), butadiene nitrile rubbers (BNK), hydrin rubbers, acrylic rubbers grafted with maleic anhydride, acrylonitrile-butadiene-styrene rubbers (ABS), grafted with maleic anhydride, ethylene-propylene-diene rubbers (grafted with maleic anhydride, styrene-ethylene / butadiene rubbers in (SEBS), maleated ethylene-propylene copolymer rubbers (EPM), maleated ethylene-butene rubbers, maleated ethylene-hexene rubbers, maleated ethylene-octene rubbers, maleated ethylene-decene rubbers, maleated vinyl acetate-copolymers of ethylene-ethylene-copolymers of ethylene-ethylene-copolymers maleated ethylene-ethyl acrylate copolymers, maleated ethylene-acrylic acid copolymers, EPDM / styrene copolymers, maleic acid-modified EPDM / styrene copolymers , Graft copolymers of EPDM / acrylonitrile modified with maleic acid graft copolymers of EPDM / acrylonitrile copolymers, styrene / maleic acid; reactive thermoplastic phenoxysmols, maleated isobutylene-isoprene copolymers, maleated isobutylene-para-methyl styrene copolymers, maleated halogenated isobutylene-isoprene copolymers, maleated star-branched butyl rubbers (ZRB), maleated maleated copolymers. 9. The method of claim 8, wherein said second elastomer or rubber comprises maleic anhydride present in an amount selected from the group consisting of less than about: 50 wt.%, 45 wt.%, 40 wt.%, 35 wt. %, 30 wt.%, 25 wt.%, 20 wt.%, 15 wt.%, 10 wt.%, 9 wt.%, 8 wt.%, 7 wt.%, 6 wt.%, 5 wt. %, 4 wt.%, 3 wt.% And 2 wt.% Maleic anhydride. 10. The method according to claim 1, where the aforementioned essentially complete dynamic vulcanization corresponds to the degree of curing selected from the group consisting of values in the range from about 60% to more than about 95%; from about 65% to about 95%; from about 70% to about 95%; from 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%. 11. The method of claim 10, wherein said curing degree is at least about 80%. 12. The method according to claim 1, where the aforementioned composition containing an elastomer further comprises at least one component selected from the group consisting of fillers and plasticizers. 13. The method according to claim 1, where the aforementioned polyamide is selected from the group consisting of nylon 11, nylon 12, a copolymer of nylon 6/66 and mixtures thereof. 14. The method according to claim 1, where the aforementioned at least one halogenated elastomer or rubber containing isobutylene is selected from the group consisting of halogenated butyl rubber, a halogenated isoolefin / para-alkylstyrene copolymer, a halogenated isobutylene-para-methylstyrene-isoprene copolymer halogenated branched butyl rubber; and halogenated star-branched butyl rubber. 15. The method according to item 13, where the aforementioned halogenated butyl rubber is characterized by a high content of the following halogenated structure, where X is a halogen

16. The method according to 14 or 15, where the halogen is selected from the group consisting of bromine and chlorine. 17. The method according to 14, where the aforementioned halogenated isoolefin / para-alkylstyrene copolymer contains a C ₄ -C ₇ isoolefin. 18. The method of claim 17, wherein said halogenated isoolefin / para-alkyl styrene copolymer comprises a isobutylene-para-methyl styrene halogenated copolymer. 19. The method of claim 18, wherein said halogen is bromine. 20. The method of dynamic vulcanization to obtain a thermoplastic elastomeric composition, which is carried out in a twin-screw extruder mixer, characterized by the ratio between the total length and diameter (L / D) of the worm 49, where the worm is provided with threaded parts, and L is the total length of the threaded parts of the worm, and D is the maximum width of the worm in its threaded part, and the worm is capable of shear, heat and cool the polymer and other components to produce a thermoplastic elastome the composition, said composition comprising dynamically vulcanized rubber particles of brominated isobutylene-para-methylstyrene copolymer (BIMS) and particles of maleated ethylene-octene copolymer rubber, each of which is dispersed in a continuous thermoplastic matrix of nylon 6/66 copolymer resin, wherein said method includes the steps of:
(1) dispersing in 100 parts by mass of the BIMS rubber a curing system containing a mixture of 0.15 parts of zinc oxide, 0.60 parts of stearic acid and 0.30 parts of zinc stearate, in order to thereby obtain a pre-compiled composition of BIMS and mixing in a closed rubber mixer at 40 rpm, 90 ° C. for 3.5 minutes, sufficient essentially to uniformly disperse said curing system, but insufficient to stimulate essentially crosslinking of said SIMS, which would prevent its subsequent flow during conditions of elevated temperature and shear, and granulation and cooling of said previously prepared composition BIMS;
(2) introducing into the aforementioned extruder at L / D = 3.5, 62.4 parts of a copolymer of nylon 6/66 and a mixture of 0.47 parts of heat stabilizers, oxidizing stabilizers, light stabilizers of polyamide and providing shear and heating sufficient to stimulate the melting of nylon and dispersing stabilizers in said nylon, and producing a polyamide mixture;
(3) the introduction at L / D = 7 of 26.8 parts of the plasticizer of the polyamide N-butylsulfonamide;
(4) introducing at L / D = 28 granules containing the previously prepared halogenated elastomer composition corresponding to the composition shown previously in position (1), and heating and shear, sufficient to initiate dynamic vulcanization of the halogenated elastomer; and
(5) introducing at L / D = 35 10 parts of maleated ethylene-octene copolymer rubber and continuing to heat and shear substantially to disperse said second elastomer and essentially to complete said dynamic vulcanization of said SIMS; and
the release of said dynamically vulcanized thermoplastic elastomeric composition from said mixer.