RU2412055C2 - Laminar material based on thermoplastic polymer composition with low air permeability and air tire with inner layer made thereof - Google Patents

Abstract

FIELD: process engineering.

SUBSTANCE: invention relates to laminar material base on thermoplastic polymer composition to be sued for production of air tire inner layer, to method of its production and to air tire incorporating said material. Laminar material comprises, at least, one layer A made from thermoplastic resin that features coefficient of air permeability making 10×10^-12 cub. cm·cm/cm²·sec·cm Hg and less whereon applied is, at least, one layer B made from thermoplastic polymer composition formed from composition of modified polymer (E) dispersed in matrix of thermoplastic resin D. Thermoplastic polymer composition of layer B features melt viscosity of 500-2000 Pa·s and Young modulus of 1-400 MPa at room temperature. Thickness of layer A makes 0.05-10 mcm. Coefficient of air permeability of laminar material C makes 20×10^-12 cub. cm·cm/cm²·sec·cm Hg and less.

EFFECT: high-elasticity gas-proof laminar material for air tire inner layer.

20 cl, 13 ex, 7 tbl

Description

FIELD OF TECHNOLOGY

The present invention relates to a low breathable laminate based on a thermoplastic polymer composition and to a method for its manufacture, as well as to a pneumatic tire using the aforementioned laminate as an inner layer.

BACKGROUND

Reducing fuel consumption is one of the most significant technical problems in automobiles. Part of this problem is the reduction in weight of pneumatic tires.

In order to maintain a constant air pressure in the tire, the inner surface of the pneumatic tire typically has an inner layer containing a low permeable rubber such as butyl rubber or halogenated butyl rubber. However, halogenated butyl rubber is characterized by large hysteresis losses, and therefore, if a rubber warps after curing the rubber tire, the inner surface between the carcass layer and the inner layer in between the carcass cords, the rubber layer of the inner layer will deform together with the deformation of the carcass layer, and therefore a problem will appear consisting in increasing the rolling resistance. Accordingly, in the general case, in the gap between the inner layer (usually halogenated butyl rubber) and the rubber of the inner surface of the carcass ply, a layer of rubber is called a bonding rubber and has a small hysteresis loss. Therefore, in addition to the thickness of the inner layer of halogenated butyl rubber, the thickness of the connecting layer is added, and the thickness of the layers generally exceeds 1 mm (i.e., 1000 μm), which ultimately leads to an increase in the mass of the product.

Techniques have been proposed for using various materials as the inner layer of a pneumatic tire instead of a low-permeable rubber such as butyl rubber. For example, Japanese Patent Publication (Kokoku) No. 47-31761, for example, describes the application of a coating of a solution or dispersion of synthetic resins, such as polyvinylidene chloride, a saturated polyester resin, a polyamide resin having a breathability coefficient (cm ³ (standard condition), onto the inner surface of a vulcanized tire. ) / cm · sec · mm of mercury), not more than 10 × 10 ^-13 at 30 ° С and not more than 50 × 10 ^-13 at 70 ° С, with a thickness of 0.1 mm or less.

The methodology disclosed in Japanese Patent Publication (Kokoku) No. 47-31761 disclosed describes the preparation of a synthetic resin coating layer having a specific air permeability coefficient on the inner peripheral surface of the carcass or the inner peripheral surface of the vulcanized tire inner layer and maintaining the thickness of the synthetic coating layer. resin equal to 0.1 mm or less, but the pneumatic tire described in this publication has problems with stickiness in a pair of rubber-synthetic resin. In addition, there is a disadvantage in that the inner layer is characterized by poor moisture resistance (or water resistance).

Japanese Unexamined Patent Publication (Kokai) No. 5-330307 describes the halogenation of an inner surface of a tire (using a conventional known chlorinating solution, bromine solution or iodine solution), and then producing a polymer film on the inner surface (thickness in the range of 10 to 200 μm ) from methoxymethylated nylon, copolymerized nylon, a mixture of polyurethane and polyvinylidene chloride or a mixture of polyurethane and polyvinylidene fluoride.

In addition, Japanese Unexamined Patent Publication (Kokai) No. 5-318618 describes a pneumatic tire incorporating a thin film of methoxymethylated nylon as an inner layer. In accordance with this methodology, to obtain a pneumatic tire, a solution or emulsion of methoxymethylated nylon is sprayed on or coated on the inner surface of the unvulcanized tire, and then the tire is vulcanized, or a solution or emulsion of methoxymethylated nylon is sprayed on the inner surface of the tire after vulcanization, or a coating of them. In addition to the disadvantage of poor water resistance of thin films, there is also a disadvantage in these publications in the difficulty of maintaining uniformity of film thickness.

In addition, Japanese Unexamined Patent Publication (Kokai) No. 6-40207 provides an example of using a multilayer film as a tire layer to prevent air penetration, including a low breathable layer including a polyvinylidene chloride film or an ethylene-vinyl alcohol copolymer film, and an adhesive layer formed from a polyolefin film, an aliphatic polyamide film or a polyurethane film. However, in this system, the low breathability layer has insufficient flexibility, and the film cannot track the expansion or contraction of the material during operation of the tire, and thus the tire splits.

In addition, Japanese Unexamined Patent Publication (Kokai) No. 5-508435 proposes the use of a composition formed from a halogen-containing copolymer of C ₄ -C ₇ isomonoolefin and p-alkyl styrene and containing carbon black plasticizing oil as a tire inner layer for a tire inner composition. and a vulcanizer, but the inner layer is characterized by an insufficient coefficient of breathability and, in addition, is not suitable for use when reducing the weight of the tire.

Thus, a material intended to obtain a gas insulating layer used in the inner layer of a pneumatic tire and the like is required to have flexibility and gas insulating ability, but so far no material has been proposed that possesses both of these properties.

In general, a thermoplastic elastomeric composition, which is formed from a component in the form of a thermoplastic resin as a continuous phase and an elastomeric component as a dispersed phase, and in which at least part of the elastomeric component is crosslinked (vulcanized), demonstrates the presence of highly elastic characteristics due to the presence of elastomeric component, which in the past was generally crosslinked, and due to the formation of a continuous phase component in the form of a thermoplastic resin, it can be subjected to uta thermoplastic molded at a high temperature at which it melts and becomes fluid. Therefore, a thermoplastic elastomeric composition having this dispersed structure, demonstrates the presence of characteristics that make it possible to molding by processing methods similar to those used for plastics, while maintaining the properties of vulcanized rubber.

Therefore, when compared with vulcanized rubber, the thermoplastic elastomeric composition demonstrates the following main advantages:

(1) no separate vulcanization process is required,

(2) recycling of products and defects obtained during processing is possible,

(3) weight reduction is possible.

Among them, in particular, a thermoplastic elastomeric composition (in which part or all of the elastomeric component forming the dispersed phase is crosslinked (vulcanized) during mixing with a thermoplastic resin that forms a continuous phase and undergoes dynamic crosslinking (vulcanization)) can a product that has especially outstanding properties - mechanical physical properties of a rubbery elastomer, resistance to shrinkage under compression and oil resistance, and instead of ordinary rubber It can be used for the manufacture of automotive parts, building materials, medical equipment, general industrial materials, and the like.

With regard to this thermoplastic elastomeric composition, the authors of the present invention previously proposed and filed an application (Japanese Patent Application No. 7-150353 (i.e., Japanese Unexamined Patent Publication No. 8-259741)) for a polymer composition for making a tire having a breathability coefficient not larger than 25 × 10 ^-12 cubic cm · cm / cm ² · sec · cm mercury, and Young's modulus in the range from 1 to 500 MPa, which as a polymer composition for the manufacture of tires demonstrates an excellent balance between the ability to prevent air penetration and the flexibility that can be used to reduce weight tires, and which is formed from a mixture of a specific amount of thermoplastic resin, characterized by a coefficient of breathability not greater than 25 × 10 ^-12 cubic meters. cm · cm / cm ² · sec · cm mercury, and Young's modulus, greater than 500 MPa, and a specific amount of elastomeric component, characterized by a coefficient of air permeability greater than 25 × 10 ^-12 cubic cm · cm / cm ² · sec · cm mercury, and Young's modulus not greater than 500 MPa.

This proposed composition demonstrates the presence of excellent functionality as a polymer composition for the manufacture of tires, but when used as an inner layer or other layer preventing the penetration of air, the pneumatic tire detects the problem of insufficient adhesion in the pair of rubber layer - thermoplastic elastomeric composition, taken individually .

In addition, the authors of the present invention, being engaged in research to make the aforementioned polymer composition for making a tire even more effective in preventing air penetration, have proposed and filed an application (Japanese Patent Application No. 7-55929) (i.e., Japanese Unexamined Patent Publication No. 8- 244402) on the composition of a thermoplastic resin for the manufacture of tires, forming a built-in layer that prevents the penetration of air, as a result of extruding a mixture of at least two types of ness of thermoplastic resins, during which one component in the form of a thermoplastic resin among the components in the form of thermoplastic resins is not completely dispersed, but dispersed oriented in a flat form due to shear stress during extrusion, since it is incompatible.

In the case of using this thermoplastic resin composition as a layer of a pneumatic tire preventing air penetration, sufficient ability to prevent air penetration can be obtained, since the composition is a thermoplastic resin composition, but the composition was unsatisfactory from the point of view of sufficient control of flexibility and durability with respect to fatigue bending, and there was also a problem consisting in insufficient stickiness in a pair of rubber-composition layer thermoplastic resin taken individually.

Thus, as explained previously, there is a known thermoplastic elastomeric composition comprising a component in the form of a thermoplastic resin as a continuous phase and an elastomeric component as a dispersed phase, which exhibits high elasticity, is flexible, can be processed like a thermoplastic, and makes it possible to control the air insulating ability or gas-insulating ability. In addition, there is a known thermoplastic resin composition which makes it possible to obtain a layer interposed between the layers having the ability to prevent gas penetration. A thermoplastic elastomeric composition that exhibits high elasticity and can be processed like a thermoplastic, and which makes it possible to obtain an embedded layer on the outside of the layers demonstrating the presence of adhesiveness and other necessary functions, has not yet been developed.

Other references of interest include: documents WO 2004/081107, WO 2004/081106, WO 2004/081108, WO 2004/081116 and WO 2004/081099.

SUMMARY OF THE INVENTION

The purpose of the present invention is to propose a layered material based on a thermoplastic polymer composition, characterized by a coefficient of breathability equal to 20 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less, and suitable for use as the inner layer of a pneumatic tire, thereby eliminating the above-mentioned disadvantages of the prior art.

The present invention provides a laminate (C) based on at least one thermoplastic polymer composition, comprising: a thermoplastic resin composition (A), characterized by an air permeability coefficient of 10 × 10 ⁻¹² cc. cm · cm / cm ² · sec · cm mercury or less, on which a thermoplastic polymer composition (B) is layered, characterized by a melt viscosity of 500-2000 Pa · sec and Young's modulus at room temperature of 1-400 MPa, where the layer thickness of the composition is thermoplastic resin (A) is 0.5-10 microns, and the coefficient of breathability of the layered material (C) is 20 × 10 ^-12 cubic cm · cm / cm ² · sec · cm mercury or less.

DETAILED DESCRIPTION OF THE INVENTION

In this specification and in the claims that follow, singular forms include the plural, unless the context clearly requires otherwise.

As used herein, all molecular weights are weight average molecular weights unless otherwise indicated.

Throughout the description of the invention in its entirety, including the claims, 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 steps, elements or materials to which they relate are essential, but other steps, elements or materials may be added and a structure corresponding to the scope of the claims will still be obtained or description of the invention. 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, not mentioned elements or process steps.

In the present context, “essentially consisting of” means the exclusion of any element or combination of elements, as well as any amount of any element or combination of elements, which would change the basic and new features of the invention.

For the purposes of the present invention, unless otherwise defined in relation 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 the extent that the 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 "essentially" is also used to rationally describe the essence of an object so that its scope would be understood by specialists in the relevant field of technology that meets the invention, and to distinguish the claimed essence of the object from the prior art.

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 is 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 is a form that 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 double bonds, preferably two conjugated double bonds, such as a conjugated diene, like isoprene.

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

The term “alkyl” means a paraffinic hydrocarbon group that can be obtained 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 the exclusion of one or more hydrogen atoms from the formula, 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, nitro, sulfoxy (sulfonate or alkyl sulfonate) thiol, alkylthiol and hydroxy; straight or branched chain alkyl containing from 1 to 20 carbon atoms, which includes methyl, ethyl, propyl, tert-butyl, isopropyl, isobutyl and the like; alkoxy, straight or branched chain alkoxy 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 contains 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-trifluoroethyl l, 2,3,3-trifluoropropyl, 1,1,2,2-tetrafluoroethyl and 2,2,3,3-tetrafluoropropyl. Thus, for example, a “substituted styrene unit” includes p-methylstyrene, p-ethylstyrene and the like.

As a material having excellent gas insulating ability, a polyamide thermoplastic resin (hereinafter referred to as polyamide resin) was known. In addition, butyl rubber was known as a material with excellent flexibility. Applicants have found that instead of using butyl rubber to realize a material that demonstrates a good balance of gas insulating ability and flexibility, layered material (C) based on the indicated thermoplastic materials (A) and (B) could be used.

The thermoplastic resin composition used as component (A) in the laminate (C) of the present invention may be any thermoplastic resin composition having a low air permeability coefficient, preferably 25 × 10 ⁻¹² cc. cm · cm / cm ² · sec · cm mercury or less, more preferably 10 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less, more preferably 1 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less, more preferably in the range from 0.1 × 10 ⁻¹² to 10 × 10 ⁻¹² cc. cm · cm / cm ² · sec · cm mercury. In the case of an excessively large value of the coefficient of breathability of the thermoplastic resin, the desired balance of gas insulating ability and flexibility cannot be obtained.

Common examples of thermoplastic resin (A) are ethylene-vinyl alcohol copolymers, polyamide resins, polyvinylidene chloride and its copolymers, acrylonitrile copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene terephthalate, polyester resins and the like. EVOH resins suitable for use in the present invention as the thermoplastic resin (A) include thermoplastic and crystalline ethylene-vinyl alcohol copolymers containing at least 35 mol% of vinyl alcohol.

Polyamide resins suitable for use in the present invention as a thermoplastic resin (A) include thermoplastic polyamides (nylons) including crystalline or resinous high molecular weight solid polymers, including copolymers and terpolymers containing repeating amide units in the polymer chain. Polyamides can be obtained by polymerizing one or more ε-lactams, such as caprolactam, pyrrolidion, laurillactam and aminoundecane lactam, or amino acids, or by condensation of dibasic acids and diamines. Suitable for use as a thermoplastic resin (A) are both fiber-forming nylons and brand nylons used for molding. Examples of such polyamides are polycaprolactam (Nylon 6), polylauryl lactam (Nylon 12), polyhexamethylene adipamide (Nylon 66), polyhexamethylene azelamide (Nylon 69), polyhexamethylene sebacamide (Nylon 610), polyhexamethylene isophthalamide (Nylon 6IP), ND6, N66, and a condensation product of 11-aminoundecanoic acid (Nylon 11). You can also use Nylon 6 (N6), Nylon 11 (N11), Nylon 12 (N12), copolymer Nylon 6/66 (N6 / 66), Nylon 610 (N610), Nylon 46, Nylon MXD6, Nylon 69 and Nylon 612 ( N612). You can also use their copolymers and mixtures thereof. Further examples of satisfactory polyamides (especially those having a softening point of less than 275 ° C.) are described in Kirk-Othmer, Encyclopedia of Chemical Technology, v. 10, page 919 and Encyclopedia of Polymer Science and Technology, Vol. 10, pages 392-414. In the practice of this invention, commercially available thermoplastic polyamides can advantageously be used as thermoplastic resins (A), linear crystalline polyamides having a softening point or a melting point in the range of 160-230 ° C. are preferred.

A thermoplastic polymer composition suitable for use as component (B) in the laminate (C) of the present invention is one that has a melt viscosity in the range of 50 to 2000 Pa · sec, preferably from 700 to 1500 Pa · sec and Young's modulus at room temperature in the range from 1 to 400 MPa, preferably from 1 to 200 MPa. In the case of an excessively small or excessively large magnitude of the melt viscosity of the thermoplastic polymer (B), the desired molding of the cylindrical product (extrusion) becomes difficult, and thus the film becomes difficult. In addition to this, in the case of an excessively large Young's modulus of the thermoplastic polymer (B), the film will not be able to control the deformation, and therefore, cracks or breaks may appear.

Typical examples of a thermoplastic composition suitable for use as component (B) of the present invention are those formed from modified polymers (E) dispersed in a matrix of a thermoplastic resin composition (D). Despite the absence of any specific restrictions imposed on the ratio between the amounts of the modified polymer (E) and the matrix (D), the preferred ratio (D) :( E), for example, is in the range from 60:40 to 30:70 mass. Examples of the modified polymer (E) are brominated isobutylene-p-methylstyrene copolymers, maleic anhydride, ethylene-α-olefin copolymers, ethylene-glycidyl methacrylate (EGMA) copolymer, maleic anhydride-modified ethylene-ethyl acrylate copolymer (Mal-EEA). Examples of matrix (D) are polyamide resins such as Nylon 11, Nylon 12, Nylon 666, Nylon 610, Nylon 612, Nylon 6, Nylon 66.

The components (A), (B), (D) and (E) of the present invention, in addition to the aforementioned main ingredients, may contain conventional additives commonly used in them, such as a vulcanizer or a crosslinker, a vulcanization or crosslinking accelerator, various types oils, antioxidant, reinforcing filler, plasticizer, emollient, in an amount that will not adversely affect the objectives of the present invention.

Laminates (C) of the present invention are formed from a layer of a thermoplastic resin composition (A) having a thickness in the range from 0.05 to 10 μm, preferably from 0.05 to 3 μm, onto which a layer or layers of a thermoplastic polymer composition (B) are layered . Preferably, the laminate (C) is enclosed in a sandwich structure formed using the same or different layers of thermoplastic polymer compositions (B). The thermoplastic polymer composition (B) may be formed from a modified polymer composition (E) dispersed in the matrix (D) of the thermoplastic polymer composition mentioned previously.

Layered material (C) is characterized by a coefficient of breathability equal to 20 × 10 ^-12 cubic meters. cm · cm / cm ² · sec · cm mercury or less, preferably 10 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less.

The layered material (C) of the present invention can be of any shape through the use of any known layering technique. For example, the layered material (C) in the form of a sheet can be obtained by multilayer coextrusion, multilayer blow molding, and the like. Alternatively, the cylindrical layered material (C) can be obtained by multilayer extrusion molding of a thermoplastic resin composition (A) and a thermoplastic polymer composition (B), which is well known in the art.

The laminate (C) of the present invention can advantageously be used as the inner layer of a pneumatic tire, since the laminate (C) exhibits a good balance of excellent gas insulating ability and excellent flexibility.

The layered material (C) of the present invention, containing the adhesive (F), can be of any shape using any known layering technique. For example, a laminate (C) containing adhesive (F) in the form of a sheet can be obtained by multilayer coextrusion, multilayer blow molding, and the like. Alternatively, a cylindrical laminate (C) containing adhesive (F) can be obtained by multilayer extrusion molding of a thermoplastic resin composition (A), a thermoplastic polymer composition (B) and an adhesive composition (F), which is well known at the present level technicians.

The laminate (C) of the present invention containing glue (F) can advantageously be used as the inner layer of a pneumatic tire, since the laminate (C) containing glue (F) exhibits a good balance of excellent gas insulating ability and excellent flexibility.

Adhesives (F) have been proposed using various formulations instead of the composition of Table V, such as conventional adhesives. For example, European Patent No. 0774340 describes the difference in critical surface tension in the case of a rubber-like component of a tire element and a polymer component of a surface layer of a thermoplastic film.

Preferred modified polymer compositions suitable for use as the dispersed phase of the thermoplastic polymer composition (B) comprise functionalized polymer (s) (having one or more functional groups). The term "functionalized polymer (s)" means that the polymer is contacted with a functional group and optionally a catalyst, heat, initiator and / or source of free radicals to stimulate incorporation into the polymer, grafting onto the polymer, binding to the polymer, physical bonding and / or chemical addition to the polymer of an entire amount or part of a functional group. Accordingly, in one aspect, a functionalized polymer suitable for use in the present invention includes a contact product of a polymer, a functional group, and a functionalization catalyst (such as a catalyst, heat, initiator, or free radical source). Such functionality is also referred to herein as vaccination. Similarly, a functional group is also referred to herein as a graft monomer. In addition, a “functionalized polymer” is also defined as including a polymer obtained by direct polymerization of monomers including olefin monomers and a monomer having a functional group (or using initiators having a functional group) to obtain a polymer having a functional group.

By “maleated” polymer is meant a polymer that has been contacted with maleic acid or maleic anhydride and optionally a catalyst, heat, initiator and / or free radical source to stimulate incorporation into the polymer, grafting onto the polymer, binding to the polymer, physical bonding and / or chemically adding to the polymer all or part of maleic acid or maleic anhydride.

By “functional group” is meant any compound having a weight average molecular weight of 1000 g / mol or less that contains a heteroatom and / or unsaturation. Preferred functional groups include any compound having a weight average molecular weight of 750 or less that contains one or more heteroatoms and one or more centers of unsaturation. Preferably, the functional group is a compound containing a heteroatom and unsaturation, such as maleic anhydride or maleic acid. Preferred functional groups include organic acids and their salts, organic amides, organic imides, organic amines, organic esters, organic anhydrides, organic alcohols, organic acid halides (such as acid chlorides, acid bromides and the like), organic peroxides, organic silanes etc.

Examples of preferred functional groups include compounds containing a carbonyl bond, such as carboxylic acids, esters of carboxylic acids, 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-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic 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-dicar acid, 1,2,3,4,5,8,9,9-octahydronaphthalene-2,3-dicarboxylic anhydride, 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 a preferred embodiment, maleic anhydride is grafted onto the 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.

At the present level of technology there are several methods 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. The functionalized polymer can be prepared by solution or suspension methods (i.e., using a solvent) or by a melting method (i.e., without using a solvent). Functionalized polymer can also be obtained in a high shear mixer, a fluidized bed reactor and / or the like.

Typically, the polymer is combined with a free radical initiator and grafting monomer at a temperature and for a period of time sufficient to stimulate grafting of the monomer onto the polymer until a functionalized polymer is obtained. In such an embodiment, the functionalized polymer can be obtained by heating the polymer and a functional group polymerized by a radical mechanism (for example, maleic anhydride) in the presence of a catalyst in the form of a radical initiator, such as an organic peroxide. This combination is preferably heated at a temperature equal to approximately equal to or greater than the decomposition temperature of the catalyst in the form of a radical initiator.

Suitable radical initiator catalysts include: diacyl peroxides, peroxy esters, peroxyketals, dialkyl peroxides and the like. Specific examples include benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy acetate, tert-butyl-O- (2-ethylhexyl) monoperoxycarbonate, n-butyl (4,4-di (tert-butylperoxy) valerate), 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (tert-butylperoxy) butane, dicumyl peroxide, tert-butyl cumyl peroxide, a, a'-bis (tert-butylperoxyisopropyl) benzene, di-tert-butylperoxide (DTBP), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, cyclohexanone oxide, tert-butyl peroxyisopropyl carbonate, di-tert-butylperphthalate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexene-3, di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, hydroperoxides, dilauryl peroxide, dicumyl peroxide and the like. In a preferred embodiment, the functionalization is carried out at a temperature higher than the melting temperature of the polymer, but lower than the decomposition temperature of the initiator. Suitable temperature ranges are from 35 ° C to 350 ° C, preferably from 40 ° C to 250 ° C, preferably from 45 ° C to 200 ° C.

The radical initiator catalyst is preferably used with a concentration in the range of from 0.00001 to 100% by mass, more preferably from 0.1 to 10% by mass, based on the weight of the functional group. The heating temperature depends on whether or not the reaction is carried out in the presence of a solvent, but usually it is in the range from about 50 ° C to 350 ° C.

In a method using a solvent, the reaction can be carried out using a polymer in the form of a solution or suspension having a concentration in the range from 0.1 to 50 wt.%, In the presence of a halogenated hydrocarbon compound containing from 2 to 20 carbon atoms, an aromatic compound, a halogenated aromatic compounds, alkyl substituted aromatic hydrocarbons, cyclic hydrocarbons and / or hydrocarbon compounds containing from 6 to 20 carbon atoms, which are stable against exposure to radical at. Preferred solvents include hexane and cyclohexane.

Various techniques can be used to characterize functionalized polymers, some of which are described in “Structure Characterization” of The Science and Technology of Elastomers, F. Eirich, editor, Academic Press 1978, Chapter 3 by G. Ver Strate, which is incorporated by reference in this document.

Preferably, the functionalized polymer contains maleic anhydride in an amount of less than about 50% by weight, preferably less than about 45% by weight, preferably less than about 40% by weight, preferably less than about 35% by weight, preferably less than about 30% mass., preferably less than about 25% of the mass., preferably less than about 20% of the mass., preferably less than about 15% of the mass., preferably less than about 10% of the mass ss., preferably less than about 9% by weight, preferably less than about 8% by weight, preferably less than about 7% by weight, preferably less than about 6% by weight, preferably less than about 5% by weight, preferably less more than about 4% by weight, preferably less than about 3% by weight, preferably less than about 2% by weight, maleic anhydride. In addition, preferably the level of maleic anhydride 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 a preferred embodiment, the functionalized polymer may contain from 0.1 to about 10% of the mass. maleic anhydride, more preferably from 0.25 to about 5% by weight, more preferably from 0.5 to 4% by weight, more preferably from 0.75 to 3.5% by weight, more preferably from 1.5 to 2 , 5% wt., Maleic anhydride.

The level of functional group content in the grafted polymer can be determined by the method of infrared spectroscopy with Fourier transform based on calibration using standards in which the absolute level of content of functional groups was determined. Specifically, the level of maleic anhydride in the grafted polymer can be determined by infrared spectroscopy with Fourier transform based on calibration using standards, the absolute content of maleic anhydride in which was determined in accordance with the method described in M. Sclavons et al. (M. Sclavons, P. Franquinet, V. Carlier, G. Verfaillie, I. Fallais, R. Legras, M. Laurent, and FC Thyrion, Polymer , 41, 1989 (2000)), where the sample is a functionalized polymer (polymer g-MA) is first purified from residual monomer by complete solubilization in xylene followed by reprecipitation in acetone. This precipitated polymer is then dried. Approximately 0.5 g of the reprecipitated polymer is dissolved in 150 ml of toluene at boiling point. For a heated solution in which polymers do not precipitate during titration, potentiometric titration is carried out using TBAOH (tetra-butylammonium hydroxide) using bromothymol blue as a color indicator. In order to verify that all diacid formed by hydrolysis of maleic anhydride under the influence of environmental moisture is converted back to anhydride, the polymers are preferably preheated to 200 ° C. for 1 hour before dissolution.

Polymers suitable for use in the present invention in the preparation of functionalized polymers 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 modified polymers includes polymers of a C ₄ -C ₇ isoolefin (such as isobutylene) copolymerized with one or more compounds selected from isoprene, isobutylene, 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 IOMB methylstyrene).

In yet another embodiment, maleic anhydride grafted rubbers suitable for use as modified polymers (E) herein could be modified or maleic anhydride grafted copolymers of ABS (acrylonitrile butadiene styrene), EPDM (ethylene propylene diene) SEBS (styrene-ethylene / butadiene-styrene) and the like. Other maleated ethylene copolymer rubbers suitable for use as modified polymers (E) include maleated ethylene-propylene copolymer, maleated ethylene-hexene copolymer, maleated ethylene-hexene copolymer, maleated ethylene-decene copolymer, maleated ethylene-decene copolymer, ethylene propylene diene, maleated ethylene vinyl acetate copolymer, maleated ethylene methyl acrylate copolymer, maleated ethylene copolymer ene-ethyl acrylate, ethylene-acrylic acid copolymer, maleated, and the like. Suitable maleated copolymer rubbers also include copolymers of maleic anhydride or derivatives thereof and one or more comonomers such as ethylene, methacrylate, butyl acrylate and the like.

Preferred modified polymer compositions suitable for use as the dispersed phase of the thermoplastic polymer composition (B) comprise functionalized polymer (s), such as isobutylene-based halogenated rubbers, including halogenated butyl rubber. Halogenated butyl rubber is obtained by halogenating butyl rubber. Halogenation can be carried out by any method, and the invention herein is not limited to the halogenation method. Methods for halogenating polymers, such as butyl polymers, are described in US Pat. 4 to 60 ° C. using bromine (Br ₂ ) or chlorine (Cl ₂ ) as a halogenating agent. Post-processed halogenated butyl rubber, which is described in US Pat. No. 4,288,575, can also be used. Halogenated butyl rubber suitable for use is typically characterized by a Mooney viscosity in the range of about 20 to about 70 (ML _{1 + 8} at 125 ° C. ); for example, from about 25 to about 55 in another embodiment. The preferred level of halogen is usually in the range from about 0.1 to 10% of the mass. when calculating the mass of halogenated 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. A particularly preferred form of halogenated butyl rubber is characterized by a high level of the following halogenated structure (preferably from 60 to 95% as measured by NMR), where X is halogen, and in a 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 content is in the range of about 1.8 to 2.2% by weight. In addition, its curing characteristics 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 RN Webb, TD Shaffer and AH Tsou, Commercial Isobutylene Polymers, Encyclopedia of Polymer Science and Technology, 2002, John Wiley & Sons, by reference incorporated herein.

Another suitable embodiment of the implementation of halogenated butyl rubber is halogenated, branched or “star branched” butyl rubber. These rubbers are described, for example, in EP 0678529 B1, U.S. 5182333 and 5071913, each of which is incorporated herein by reference. 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 “polydienes”) are typically cationic reactive and present during the polymerization of butyl rubber or halogenated butyl rubber, or can be mixed with butyl rubber until Obtaining an ADS. 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, styrene butadiene rubber ethylene-propylene-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, expressed in wt%, in an amount usually greater than 0.3 wt% .; 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 present during the polymerization of butyl rubber or halogenated butyl rubber, or may be mixed with butyl rubber or halogenated butyl rubber to obtain GBRS. The branching agent or polydiene can 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, butadiene-styrene rubber, these -propylene-diene rubber, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. Polydienes may be present, based on the total level of monomer content, expressed in wt%, in an amount typically greater than about 0.3 wt%, alternatively in the range of about 0.3 to 3 wt%. 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 levels of a range of from about 2.2 to 2.6% of the mass. In addition, the curing characteristics of Bromobutyl 6222 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 halogenated isoolefin / para-alkyl styrene copolymers suitable for use in the present invention as isobutylene-based halogenated rubber (suitable for use as the dispersed phase of the thermoplastic polymer composition (B)) include random copolymers containing isobutylene and halogenmethyl styrene. Halogenmethyl styrene may be ortho-, meta- or para-alkyl-substituted styrene. In one embodiment, the implementation of halogenmethylstyrene is p-halogenomethylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer. A “halogen” group can be any halogen, preferably chlorine or 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. Preferred isobutylene-based rubbers can be characterized as interpolymers containing the following monomer units randomly distributed over 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 chloro, bromo, or combinations thereof, preferably bromo. 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 p-substituted styrene present in the copolymer structure, 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 another functional group that can be introduced as a result of nucleophilic substitution of benzyl halogen by other groups, such as carboxylic acid groups; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; simple thioether; xanthate; cyanide; cyanate; amino and mixtures thereof. These functionalized isomonoolefin copolymers, the method for their preparation, methods for their functionalization and curing are more specifically described in US Pat. No. 5,162,445.

Particularly suitable for use with such copolymers of isobutylene and p-methylstyrene are those containing from 0.5 to 20 mol.% P-methylstyrene, where up to 60 mol.% Groups of methyl substituents present in the benzyl ring contain a bromine atom or chlorine, preferably a bromine atom (p-bromomethylstyrene), as well as their variants functionalized with an acid or ester, where the halogen atom has been replaced by the functionality of maleic anhydride or acrylic or methacrylic acid. These interpolymers are called “halogenated poly (isobutylene-p-methylstyrene) copolymer” or “poly (isobutylene-p-methylstyrene) brominated copolymer” and are commercially available under the name EXXPRO ™ Elastomers (ExxonMobil Chemical Company, Houston, Texas). You must understand that the use of the terms “halogenated” or “brominated” is not limited to the method of halogenating the copolymer, but simply describes a copolymer that contains units derived from isobutylene, units derived from p-methylstyrene, and units derived from p-halogenmethylstyrene.

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 p-alkylstyrene in the range of 10% of the average level of p-alkylstyrene in the polymer as measured by gel permeation chromatography (as demonstrated in US 5162445). 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 poly (isobutylene-p-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% of bromine, based on the weight of the polymer, more preferably from about 0.1 to about 1.25 mol% of bromine and are substantially free of halogen in the ring or halogen in the polymer backbone. In one embodiment, the interpolymer is a copolymer consisting of units derived from C ₄ -C ₇ isomonoolefin, units derived from p-methylstyrene, and units derived from p-halogenmethylstyrene, where the units of p-halogenmethylstyrene in the interpolymer are present in an amount in a range of from about 0.4 to about 1 mol%, based on the amount of interpolymer. In yet another embodiment, p-halogenmethylstyrene is p-bromomethylstyrene. Mooney viscosity (ML _{1 + 8} , 125 ° C, ASTM D1646) ranges from about 30 to about 60 Mooney viscosity units.

In another embodiment, the ratio between the proportion of triads of isoolefin and p-alkylstyrene and the mol% of p-alkylstyrene introduced into the copolymer 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 = 1- {mA / (1 + mA)},

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

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

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

The best approximation method for this equation yields the m value for the copolymerization of isoolefin and p-alkylstyrene in a particular diluent. In certain embodiments, m is 38 or less; alternatively 36 or less; in an alternative embodiment, 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; in an alternative embodiment 1-35; and alternatively 1-30. Copolymers having such characteristics are described in documents WO 2004058825 and WO 2004058835.

In yet another embodiment, the isoolefin / para-alkyl styrene copolymer is substantially free of long chain branches. For the purposes of this invention, a polymer that is substantially free of long chain branches is defined as a polymer for which the parameter g ' _avg . _Binding is greater than or equal to 0.978, alternatively greater than or equal to 0.980, alternatively greater than or equal to 0.985, in alternative 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 than or equal to 0.999, as determined by the exclusion method described below sizes chromatography (SEC) with triple detection. Such polymers are also described in WO2004058825 and WO2004058835.

In another embodiment, the ratio between the fraction of triads of isoolefin and multiolefin and the mol% of the 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 the multiolefin introduced into the copolymer are described below. The best approximation method for this equation yields the m value for the copolymerization of the 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; alternatively, from 1.15 to 1.25; and alternatively, m is about 1.20. Halogenated rubbers that have these characteristics are described in documents WO 2004058825 and WO 2004058835.

In yet another embodiment, the halogenated rubber is substantially free of long chain branches. For the purposes of this invention, a polymer that is substantially free of long chain branches is defined as a polymer for which the parameter g ' _avg . _Binding is greater than or equal to 0.978, alternatively greater than or equal to 0.980, alternatively greater than or equal to 0.985, in alternative 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 than or equal to 0.999, as determined by triple detection ECR leduyuschim way. 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. A linear polyisobutylene is used to establish a relationship between the intrinsic viscosity ([η] _linear determined using a viscometer detector) and the molecular weight (M _w determined using a light scattering detector). 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 ratio for a 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 has 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. With triple detection ECR, the g 'value is calculated for each cross section of the chromatographic curve from the experimental point. The _{viscosity average} g 'or g' _avg . _{Bindings are} calculated over the entire molecular weight distribution. The scaling coefficient g ' _{cf. binding is} calculated from the average characteristic viscosity of the sample:

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

Other preferred halogenated elastomers or rubbers suitable for use as the dispersed phase of the thermoplastic polymer composition (B) include the halogenated isobutylene-p-methylstyrene-isoprene copolymer described in WO 01 / 21672A1.

Preferred polyamides suitable for use as matrix (D) in the thermoplastic polymer composition (B) include thermoplastic polyamides (nylons) including crystalline or resinous high molecular weight solid polymers, including copolymers and terpolymers containing repeating amide units in the polymer chain. Polyamides can be obtained by polymerizing one or more epsilon-lactams, such as caprolactam, pyrrolidion, laurillactam and aminoundecane lactam, or amino acids, or by condensation of dibasic acids and diamines. Suitable for use as a matrix (D) in a thermoplastic polymer composition (B) are both fiber-forming nylons and brand nylons used for molding.

Examples of such polyamides are polycaprolactam (Nylon 6), polylaurillactam (Nylon 12), polyhexamethylene adipamide (Nylon 66), polyhexamethylene azelamide (Nylon 69), polyhexamethylene sebaceamide (Nylon 610), polyhexamethylene isophthalamide (Nylon 6IP), ND6, N66, and a condensation product of 11-aminoundecanoic acid (Nylon 11). You can also use Nylon 6 (N6), Nylon 11 (N11), Nylon 12 (N12), copolymer Nylon 6/66 (N6 / 66), Nylon 610 (N610), Nylon 46, Nylon MXD6, Nylon 69 and Nylon 612 ( N612). You can also use their copolymers and mixtures thereof. Further examples of satisfactory polyamides (especially those having a softening point of less than 275 ° C.) are described in Kirk-Othmer, Encyclopedia of Chemical Technology, v. 10, page 919 and Encyclopedia of Polymer Science and Technology, Vol. 10, pages 392-414. In the practice of this invention, commercially available thermoplastic polyamides can advantageously be used as a matrix (D) in a thermoplastic polymer composition (B), linear crystalline polyamides having a softening point or a melting point in the range of 160-230 ° C. are preferred.

In an alternative embodiment, the amounts of the modified polymer (E) (preferably a halogenated copolymer of isobutylene and para-methyl styrene) and a thermoplastic resin matrix (D) (preferably polyamide) suitable for use in the present invention are preferably in the range of from 95 to 25 parts by weight and from 5 to 75 parts by mass, more preferably from 90 to 25 parts by mass and from 10 to 75 parts by mass, respectively, provided that their total amount is 100 parts by mass.

In a preferred embodiment, the thermoplastic polymer composition (B) of the present invention (which includes a component in the form of a modified polymer (such as modified rubber) dispersed in a matrix of a thermoplastic resin (such as polyamide)) is subjected to dynamic vulcanization.

The term “dynamic vulcanization” is used herein to mean a vulcanization process in which a polyamide resin and a first rubber-like component are vulcanized under high shear. As a result, the first vulcanizable rubber-like component is simultaneously vulcanized and dispersed in the form of fine “microgel” particles in a polyamide resin matrix.

Dynamic vulcanization is carried out by mixing the ingredients at a temperature equal to or higher than the rubber curing temperature using equipment such as rollers, a Banbury® mixer, a continuous mixer, a kneading machine, or a mixing extruder, for example a twin screw extruder. A unique characteristic of a dynamically vulcanized composition is that despite the possibility of partial or complete vulcanization of the rubber-like component, the composition can be processed and processed using conventional rubber processing techniques such as extrusion, injection molding, direct compression and the like. Waste or spray can be disposed of and recycled.

The method for producing the thermoplastic polymer composition (B) in the present invention typically involves mixing the first rubber-like component, a polyamide and an optional dispersion aid using a biaxial kneading machine / extruder and the like to disperse the rubber in a continuous phase polyamide. During the vulcanization of the modified polymer (E) with stirring, you can add a vulcanizer and subject the modified polymer (E) to dynamic vulcanization. In addition, during the aforementioned kneading, it is possible to add various formulating additives (with the exception of the vulcanizer) used for the modified polymer (E) and thermoplastic resin (E) (e.g. polyamide), but they are preferably mixed in advance before kneading. On the kneading machine used for mixing, special restrictions are not imposed. Examples thereof are a screw extruder, a kneading machine, a Banbury mixer, a biaxial kneading machine / extruder, and the like. Among them, a biaxial kneading machine / extruder is preferred for mixing the thermoplastic resin (E) and the modified polymer (D) and dynamically vulcanizing the modified polymer (D). In addition, two or more types of kneading machines can be used for sequential kneading. As a condition for melting and kneading, the temperature should be at least equal to the temperature at which the thermoplastic resin (D) (e.g. polyamide) will melt. In addition, the shear rate during kneading is preferably in the range from 1000 to 7500 sec ^-1 . The total kneading time is in the range from 30 seconds to 10 minutes. In addition, when adding the vulcanizer, the vulcanization time after addition is preferably in the range from 30 seconds to 5 minutes. After that, the thermoplastic polymer composition (B) obtained by the above method is usually extruded or calendared to obtain a film. A method for producing a film may be a conventional method for producing a film from a thermoplastic resin or a thermoplastic elastomer.

The thermoplastic polymer composition (B) according to the present invention may comprise a vulcanizing agent or a crosslinker, a vulcanization or crosslinking accelerator, a plasticizer, softener or various other additives, generally mixed with general purpose rubbers. The formulations are mixed and vulcanized by conventional methods for preparing a composition, which can then be used for vulcanization or crosslinking. The amounts of these added additives can be made equal to the amounts generally added in the past, until they are contrary to the purpose of the present invention.

In yet another embodiment, the composition of the present invention comprises a laminate comprising three or more layers. In a preferred embodiment, the laminate comprises a first layer of a dynamically vulcanized alloy (including a polyamide matrix and a dispersed phase of a modified polymer, preferably a dispersed phase of halogenated rubber based on isobutylene), a second layer of an EVOH copolymer and a third layer of another dynamically vulcanized alloy (including a polyamide a matrix and a dispersed phase of a modified polymer, preferably a dispersed phase of halogenated rubber based on isobutylene), tory can be the same or different compared to a dynamically vulcanized alloy in the first layer. In some embodiments, the second layer is sandwiched between the first and third layers, and optionally the third layer is in contact with the tire, typically the tire carcass, or an adhesive layer applied to the tire carcass. Preferably, the thickness of the first layer is in the range from 10 to 100 μm, preferably from 30 to 60 μm, preferably from 35 to 45 μm. Preferably, the thickness of the second layer is in the range from 0.1 to 100 μm, preferably from 0.5 to 25 μm, preferably from 0.5 to 10 μm. Preferably, the thickness of the third layer is in the range from 10 to 100 μm, preferably from 30 to 60 μm, preferably from 35 to 45 μm. In other embodiments, the thickness of the first layer is in the range from 10 to 100 μm, preferably from 10 to 80 μm, preferably from 10 to 60 μm. In other embodiments, the thickness of the second layer is in the range from 0.1 to 100 μm, preferably from 0.3 to 25 μm, preferably from 0.5 to 5 μm. In other embodiments, the thickness of the third layer is in the range from 10 to 100 μm, preferably from 10 to 80 μm, preferably from 10 to 60 μm. In some embodiments, the first and third layers have the same thickness. In alternative embodiments, the first and third layers have different thicknesses. In a preferred embodiment, the thickness of the first layer is in the range of 10 to 60 μm, the thickness of the second layer is in the range of 0.5 to 5 μm, and the thickness of the third layer is in the range of 10 to 60 μm.

In a suitable embodiment, the dynamically vulcanized alloy ("DIC") present in the first or third layer contains the previously described polyamide matrix, preferably selected from the group consisting of polycaprolactam (Nylon 6), polylauryl lactam (Nylon 12), polyhexamethylene adipamide (Nylon 66), polyhexamethylene azelamide (Nylon 69), polyhexamethylene sebacamide (Nylon 610), polyhexamethylene isophthalamide (Nylon 6IP), Nylon 46, Nylon MXD6, Nylon 6/66, the condensation product of 11-aminoundecanoic acid (Nylon 11) and Nylon 612 (N612).

In a suitable embodiment, the dynamically vulcanized alloy ("DIC") present in the first or third layer contains the previously described modified polymer present in the form of a dispersed phase, preferably the previously described isobutylene-based halogenated rubber present in the form of a dispersed phase.

Other internal combustion engines suitable for use as the first and / or third layers are those described in documents WO 2004/081107, WO 2004/081106, WO 2004/081108, WO 2004/081116 and WO 2004/081099.

ICE, preferred for use in the present invention, are usually characterized by a melt viscosity in the range from 500 to 2000 Pa · s and / or Young's modulus at room temperature in the range from 1 to 400 MPa and / or elongation at break greater than 150% at room temperature.

Preferred modified polymers (E) suitable for use in the first and / or third layer include polymers having a melt viscosity of 500-2000 Pa · sec, preferably 600-1800 Pa · sec, more preferably 700-1700 Pa · sec, and a modulus Jung at room temperature 1-400 MPa, preferably 5-350 PA, more preferably 10-300 MPa.

A preferred thermoplastic resin (A) (preferably EVOH copolymers) suitable for use in the second layer typically includes EVOH copolymers containing from 15 to 60 mol% of ethylene, preferably from 20 to 55 mol% of ethylene, preferably from 25 to 50 mol .% ethylene.

A preferred thermoplastic resin (A) (preferably EVOH copolymers) suitable for use in the second layer typically includes EVOH copolymers having a melting point in the range of 145 to 250 ° C., preferably from 150 to 240 ° C., more preferably from 155 to 230 ° C.

A preferred thermoplastic resin (A) (preferably EVOH copolymers) suitable for use in the second layer typically includes EVOH copolymers having an air permeability of 0.05 × 10 ⁻¹² cc. cm · cm / cm ² · sec · cm mercury or less, preferably 0.03 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less, preferably 0.01 × 10 ⁻¹² cc. cm · cm / cm ² · sec · cm mercury or less.

Layered material (preferably the previously described three-layer structure) is usually characterized by a coefficient of breathability equal to 20 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less, preferably 10 × 10 ^-12 cc. cm · cm / cm ² · sec · cm mercury or less, and is preferably characterized by Young's modulus in the range from 1 to 500 MPa and / or elongation at break, greater than 150% at room temperature.

Since the thermoplastic resin matrix (D) (e.g., polyamide) and the modified polymer (E) (e.g., halogenated rubber) usually vary significantly in solubility, an additional optional compatibilizing ingredient may be suitable for use in order to improve the compatibility of these polymers. Such compatibilizers include highly saturated nitrile-based copolymer rubbers with an unsaturation of ethylene-type conjugated diene (HNBR), epoxylated natural rubbers (ENC), BNC, hydrin rubbers, acrylic rubbers and mixtures thereof. The compatibilizers appear to fulfill their function by modifying, in particular reducing, the surface tension between the rubber-like and resin-like components. Other compatibilizers include copolymers, such as those having the structure of both or one representative selected from polyamide and polymer rubber, or the structure of a copolymer having an epoxy group, a carbonyl group, a halogen group, an amine group, a maleated group, an oxazoline group, a hydroxy a group and the like, capable of reacting with polyamide or polymer rubber. They can be selected based on the type of polyamide and polymer rubber being mixed, but suitable copolymers typically include, for example, a styrene / ethylene-butylene / styrene block copolymer (SEBS) and its form modified with maleic acid; EPDM, grafted copolymer EPDM / styrene or EPDM / acrylonitrile and their forms modified with maleic acid; styrene / maleic acid copolymer; reactive thermoplastic phenoxy resin; and mixtures thereof. No specific restrictions are imposed on the amount of compatibilizer to be mixed, but when used, it is usually in the range of about 0.5 to about 10 parts by weight, based on 100 parts by weight of the polymer component, in other words, the total amount of polyamide and polymer rubber.

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, for example, during chain extension, or crosslinking between polymer chains, constituting the polymer or elastomer, to such an extent that the elastomer exposed to this method, when using the tire, could 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, a tire containing an inner layer composition based on the present invention is in a sufficiently cured state when the tire of which it is a component successfully passes the necessary tests to determine product specifications during and after manufacture and demonstrate satisfactory performance characteristics when used on 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 crosslinks.

In general, polymer compositions, for example, those used to make tires, are crosslinked in the final product — the tire. 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 a "cure" system. It is known that the physical properties, performance, and durability of vulcanized rubber formulations 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 the curing of, or influence the elastomers, and generally include metals, metal oxides, accelerators, sulfur, peroxides and other agents commonly used in the art and as previously described. Crosslinkers or hardeners include at least one representative selected, for example, from sulfur, zinc oxide and fatty acids and mixtures thereof. You can also use peroxide-containing curing systems. 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 structural or technical resin (ie, polyamide) and at least one vulcanizable rubber are mixed under conditions of high shear and elevated temperature 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 polyamide, which 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 point of polyamide, 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 processed 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 vulcanizer (s) for at least one vulcanizable component (See, for example, US 6079465 and the references cited therein).

The following are conventional hardeners that can 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 of elastomer compositions are often added to the hardener (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, since the ICE method is used in the present invention, the properties of the curing system need to be adapted to the mixing method. Usually, in the first stage or in the case of more than two stages of adding rubber, then in the previous stage, the rubber (s) are cured to a level of approximately 50% of the maximum degree of cure that the particular rubber (s) and the curing system can achieve with the curing temperature during the measurement, regardless of the method of dynamic vulcanization for a period of time that is less than the approximate residence time in the mixer. 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 mixing extruder. An example of a mixture, often called an “accelerated” formulation, 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. Thereafter, accelerated formulations 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 cure state (as described in detail in the American Society for Testing and Materials , Standard ASTM D412). Alternatively, an accelerated formulation 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). Having set the maximum degree of cure, for the rubber (s) of the first or previous step added to the dynamically vulcanizable mixture, it is preferable to conduct dynamic vulcanization in such a way that the degree of cure of such rubber (rubbers) is selected from the group consisting of a value in the range from approximately 50%, for example, 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 90%; for a period of time shorter or substantially equivalent to the approximate residence time in the mixer used for dynamic vulcanization. Therefore, upon completion of the dynamic vulcanization process, the vulcanizable rubbers added to the composition will be sufficiently cured to achieve the desired properties of the thermoplastic composition, of which they are, for example, insulating in terms of inhibiting the penetration of a fluid (air or liquid), such as in the case of inner layer for 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 the vulcanizable rubbers will cure at least up to 50% of the maximum cure state that they will be able to, based on the system, time and temperature of cure, and usually the cure state of such rubbers will exceed 50% of the maximum degree curing. In addition, it may be desirable to cure the rubber particles to a degree less than the maximum curing state that the rubber will be capable of, so that the flexibility, as measured, for example, by the Young modulus, of the rubber-like component is at a level suitable for the final use case for which the composition is intended, for example, for the inner layer of the tire or component of the 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 technical 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 There are one or more thermoplastic structural resins, such that the peroxide crosslinkes the resins themselves. If, in the circumstances, the polyamide 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 (m-phenylenebismaleimide); Zisnet (2,4,6-trimercapto-5-triazine); DEDCC (zinc diethyldithiocarbamate), as well as including 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 with a concentration suitable for use in the desired portion of the rubber-like component, the rubber-like component optionally containing one or more fillers, cheapeners and / or plasticizers, for example, by mixing the rubber and components of the curing system in the step prior to adding the composition containing rubber to thermoplastics using any mixing equipment commonly used in the rubber industry To this purpose, for example two-roll mill, Banbury mixer, kneading extruder and the like. Such mixing is commonly called the “acceleration” of the rubber composition. Alternatively, the rubber composition can be accelerated at the stage of the mixing extruder prior to dynamic vulcanization. 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 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 phr; alternatively, from about 0.25 to about 10 phr.

Suitable combinations of hardeners, modifiers and curing accelerators can be illustrated as follows: suitable for use as a general vulcanizing rubber for rubber are, for example, sulfur vulcanizer, powdered sulfur, precipitated sulfur, highly dispersed sulfur, sulfur treated surface, insoluble sulfide sulfide, dimorph alkylphenol disulfide and mixtures thereof. Such compounds can be used in amounts ranging from about 0.5 phr to about 4 phr (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 polymer and resin-like components present. If used, such hardeners may be present at levels ranging from about 1 phr to about 20 phr. Other suitable hardeners include phenolic resin vulcanizers, such as alkyl phenol resin bromide, or a mixed crosslinker system including stannous chloride, chloroprene or other halogen donor and alkyl phenol resin, and mixtures thereof. Such additives can be used at levels ranging from about 1 phr to about 20 phr. Alternatively, other suitable hardeners, curing modifiers and suitable levels of use include zinc oxide and / or zinc stearate (from about 0.05 phr to about 5 phr), stearic acid (from about 0.1 phr to about 5 phr), magnesium oxide (from about 0.5 phr to about 4 phr), lyserg (from 10 to 20 phr or so), p-quinondioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene ( from about 0.5 phr to about 10 phr), methylene dianiline (from about 0.05 phr to about 10 phr) and mixtures thereof. In addition, if desired or necessary, in combination with a vulcanizing agent, one or more vulcanization accelerators can be added, including, for example, ammonium aldehyde, guanidine, thiazole, sulfenamide, thiuram, dithic acid salt, thiourea, and mixtures thereof, for example, in amounts in a range of from about 0.1 phr to about 5 phr or more.

The layered compositions described herein (including each layer) may also contain one or more components in the form of fillers, 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 (which is described, for example, in US patent No. 5916934, by reference incorporated herein) and the like. Most 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. The filler may be present at a content level in the range from about 0 to about 30% of the mass. by weight of rubber present in the composition.

In the composition of the layered material or in one or in all of its layers, layered, intercalated or dispersed clays may also be present. These clays, also called "nano-clays", are well known, and their nature, methods for preparing and mixing with polymers are described, for example, in JP 2000109635, JP 2000109605, JP 11310643; DE 19726278; WO98 / 53000; and US Pat. Nos. 5,091,462, 4,431,755, 4,472,538 and 5,910,523. 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, volconcoite gaponite , 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 comprising a plurality of silicate plates having a thickness typically in the range of from about 4 to about 20 Å in one embodiment and from about 8 to about 12 Å 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 aids 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 having 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, which may be the same 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. They include polysilanes described by the structure —Si (R ′) ₂ R ² , where R ′ is the same or different in each case, and is selected from alkyl, alkoxy or oxysilane, and R ² is an organic radical compatible with matrix polymer 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 WO92 / 02582.

In a preferred embodiment, the 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 options. 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 yet 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 insulating ability 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, when calculating the level of polymer content 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 phr in one embodiment and from about 3 to about 20 phr 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 derived from oil and synthetic plasticizers. Process or plasticizing oil may be present in air-insulating 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 include aliphatic acid esters or hydrocarbon plasticizing oils such as paraffinic or naphthenic petroleum oils. A plasticizing oil, preferred for use in standard non-internal combustion engine based non-ICE internal layer compositions, is paraffin oil; hydrocarbon plasticizing oils suitable for use in such inner layers include oils that exhibit 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
(from -34 to -1 ° C) -35
(-37 ° C) 60
(15 ° C)

In general, the process oil may be selected from paraffin oils, aromatic oils, naphthenic oils, and polybutene oils. Polybutene process oils are low molecular weight (Mn, less than 15,000) homopolymers or copolymers 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 yet 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, “polybutene process oil” "Or" polybutene "). Suitable examples of polybutene oils are the PARAPOL ™ Process Oils (previously available from ExxonMobil Chemical Company, Houston, Texas, currently available from Infineum International Limited, Milton Hill, England under the trade name "INFINEUM c, d, f or g), including grades previously identified as PARAPOL ™ 450, 700, 950, 1300, 2400 and 2500. In addition, preferred polybutene oils are SUNTEX ™ polybutene oils available from Sun Chemicals. Preferred polybutene process oils are typically synthetic liquid polybutene having a specific molecular weight, preferably in the range of Mn of about 420 to Mn of about 2700. Molecular weight distribution of -Mw / Mn- (“MMP”) for preferred polybutene oils typically range from about 1.8 to about 3, preferably from about 2 to about 2.8. The preferred density (g / ml) of suitable polybutene processing oils is in the range of about 0.85 to about 0.91. The bromine number (g / g) for preferred polybutene oils ranges from about 40 for a process oil with Mn 450 to about 8 for a process oil with Mn 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 the composition of the inner layer, oil is usually present at a level in the range from 0 to about 25% by weight .; preferably from about 5 to 20% of the mass. from the total composition. 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; preferably, oil is not included in order to maximize the impermeability of the composition.

In addition to this, plasticizers such as organic esters and other synthetic plasticizers can be used. A plasticizer, particularly preferred for use in an ICE composition, is N-butylsulfonamide or other plasticizers suitable for use in the case of polyamides. In yet 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 phr. In yet another embodiment, naphthenic, aliphatic, paraffinic and other aromatic oils are substantially absent from the composition. The term "essentially absent" means that naphthenic, aliphatic, paraffinic and other aromatic oils in the composition may be present, if any, in an amount not greater than 2 phr.

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 have been 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).

By molding the thermoplastic polymer composition 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, and then layering on the thermoplastic resin (A), the composition becomes possible to use as a layer, preventing its air penetration, for example, the inner layer of the tire and as a component or layer of the hose, and the like.

Thus obtained molded product in the form of a sheet of laminated material or a sleeve of laminated material can be effectively used for the manufacture of the inner 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 in direct contact with the fluid will demonstrate suitable resistance to the effects of the working fluid.

Any range of numerical values given in the description of the invention herein before or in the paragraphs and claims of the present document hereinafter with respect to various aspects of the invention, such as those representing a specific set of properties, units of measure, conditions, physical conditions or percentages , is assumed to be by reference or otherwise unambiguously literally including any numerical value falling within this range, including any a subset of numerical values or ranges within any range so mentioned.

EXAMPLES

Now, the present invention will be further illustrated by the following examples, but not by way of limitation.

In the following examples and comparative examples, the following starting materials were used.

1. Low breathable thermoplastic resin (A)

See table I below.

2. Thermoplastic polymer (B)

See table II below.

3. Glue composition (F)

See table V below.

Table I
Low breathable thermoplastic resin (A) Resin Source material Air permeability coefficient (× 10 ^-12 cubic cm · cm / cm ² · sec · cm mercury) EVOH Ethylene Vinyl Alcohol Copolymer (Eval L17B, Kuraray) 0.002 PA6 Nylon 6 (Amiran CM1041, Toray) 0.42 PA11 * Nylon 11 (Rilsan BESNOTL, Atochem) 10 *: Comparative sample Table II
Thermoplastic polymer (B) Source polymer Source material Young's modulus (MPa) RA6.66 Nylon 6.66 Copolymer (UBE 5033B, Ube Ind.) 1100 RA6.66 Nylon 6.66 Copolymer (UBE 5013B, Ube Ind.) 1100 RA11 Nylon 11 (Rilsan BESNOTL, Atochem) 620 RA11 Nylon 11 (Rilsan BMNO, Atochem) 630 RA12 Nylon 12 (UBESTA 3030XA, Ube Ind.) 940 ESBS Epoxidized styrene-butadiene-styrene copolymer, styrene content 40% wt., Oxiran content 1.5% wt. (Epofriend AT501, Daicel Chemical Ind.) 720 SBS Styrene-butadiene-styrene copolymer (Tufprene 315, Asahi Chemical), according to Asahi Kasei, the styrene / butadiene ratio is approximately 20/80 wt.%, MFR (melt flow rate) (ASTM 1238, 190 ° C, 2.16 kg ) 3.5 g / 10 min 74 Br-IPMS Brominated isobutylene-p-methylstyrene copolymer, 0.75% Br, 5% PMS (Exxpro ™ MDX89-4, Exxon Mobil Chemical) 4.2 Mah-EP The copolymer of ethylene-propylene modified with maleic anhydride, characterized by a content of maleic anhydride of 1.0% by weight. (MP0610, Mitsui Chemical) eleven Mah-eb The copolymer of ethylene-1-butene, modified with maleic anhydride, characterized by a content of maleic anhydride of 0.5% by weight. (MA8510, Mitsui Chemical) 38 Mah-e01 Maleic anhydride-modified ethylene-1-octene copolymer, Tg = -47 ° C, maleic anhydride content in the range from 0.2 to 0.5 wt%, MFI (melt flow index) (ASTM 1238, 5 kg / 230 ° C) 8.0 dg / min (Exxelor VA1840, Exxon Mobil Chemical) thirty Mah-e02 Maleic anhydride-modified ethylene-1-octene copolymer, Tg = -57 ° C, maleic anhydride content in the range from 0.5 to 1.0 wt%, MFR (ASTM 1238, 2.16 kg / 230 ° C) 3 dg / min (Exxelor VA1803, Exxon Mobil Chemical) 7.1 EPDM Ethylene Propylene Diene Rubber (ESPRENE 305, Sumitomo Chemical) 3,1 Carbon black FEF (SEAST 116, Tokai Carbon) - St-acid Stearic Acid (Bead Stearic Acid, NOF) - Tackifier YS Resin D105 having a softening point of 105 ° C (Yasuhara Chemical) - Plasticizer n-butylbenzenesulfonamide (BM-4, Daihachi Chemical Ind.) -

3. The matrix of the composition of thermoplastic resin (D)

Two types of matrices of thermoplastic resin compositions were obtained (i.e., BESNOTL B14 and 5033B B14) (see Table III).

Table III
Matrix Material BESNOTL B14 5033B B14 Composition (mass parts) BESNOTL ^{* one} one hundred - 5033B ^{* 2} - one hundred Softener ^{* 3} 16.3 16.3 Total (phr) 116.3 116.3 * 1: see PA11 (see table II)
* 2: RA6-66 (see table II)
* 3: see table II

4. Obtaining formulations 1 and 2

Formulations 1 and 2 were obtained by mixing the components listed in table IV for 10 minutes using a Banbury mixer at 120 ° C.

Table IV Material Recipe 1 Recipe 2 Composition (mass parts) Br-IPMS ^{* 1} one hundred - Carbon black ^{* 1} 80 - St-acid ^{* 1} one - ESBS ^{* 1} - fifty SBS ^{* 1} - fifty Tackifier ^{* 1} - thirty Total (phr) 183.5 130 * 1: See table II

Table v
Glue (F) Material Glue Composition (mass parts) ESBS ^{* 1} one hundred Tackifier ^{* 1} thirty St-acid ^{* 1} one Peroxide ^{* 1} 2 ZnO ^{* 1} 0.5 Total (phr) 133.5 * 1: See table II

Adhesive Formulation (F)

The adhesive formulation shown in Table V below was mixed for 3 minutes using a double-screw kneading machine at 100 ° C. The resulting mixture was granulated using a conventional rubber granulator to obtain granules of a thermoplastic adhesive composition (F).

Examples 1-13 and comparative examples 1-6

The components shown in the following tables VI and VII were mixed for 3 minutes using a double-screw kneading machine at 230 ° C. The resulting mixture was granulated using a conventional rubber granulator to obtain granules of the thermoplastic polymer composition (B). Young's modulus and melt viscosity were determined as follows. The results are shown in tables VI and VII.

Young's modulus: Young's modulus was determined by the method corresponding to JIS K6251 Test Method for Tensile Properties of Vulcanized Rubber. Used samples of the film obtained by extrusion in the examples from which the shapes of JIS No. 3 vanes were carved in the direction of flow of the thermoplastic resin during extrusion.

We plotted a tangent to the curve in the region of the initial strain on the obtained stress-strain curve, and Young's modulus was determined from the angle of inclination of the tangent.

Melt viscosity : Melt viscosity refers to the melt viscosity for any temperature or component during mixing. The melt viscosity of each polymer material depends on the temperature, shear rate (sec ^-1 ) and shear stress, thus measuring the shear stress and shear rate for the polymer material at any temperature in the molten state, allowing flow through the capillary, in particular in the temperature range mixing time and melt viscosity are measured using the following formula:

,η = σ /

,

представляет собой скорость сдвига.where σ is the shear stress, and

represents shear rate.

Note that melt viscosity was measured using a Capillary Rheometer Capillograph 1C manufactured by Toyo Seiki using the outlet portion of the forming channel having a diameter of 1 mm and a length of 10 mm.

The granules of the previously prepared thermoplastic polymer composition (B) were used for layering for polymer (A), as shown in Table VI using the melt blown extrusion method using a four-layer blow molding machine to produce four cylindrical layers (B) / (A) / (B) / glue (F), and as shown in Table VII, using the melt blown extrusion process using a three-layer blow molding machine to produce four cylindrical layers (B) / (A) / glue (F). The overall caliber of the film of the laminate is preferably controlled to be approximately 100 microns. The gauge (or thickness) of the layer (A) of the resulting laminate was determined by considering the cross section of the film of the laminate using the SEM method. The results are shown in tables VI and VII. The evaluation of the resulting laminate materials, if used as the inner layer of a pneumatic tire, was done as follows.

Resistance to air permeability of the resin and laminate composition: In this case, they are in accordance with JIS K7126 Test Method of Gas Permeation Degree of Plastic Films and Sheets (Method A).

Sample: Used samples of layered materials obtained in the examples.

Test gas: Air (N ₂ : O ₂ = 8: 2).

Test temperature: 30 ° C.

The results are shown in tables VI and VII.

Laboratory performance tests: A tire with a steel radial cord 165SR13 was made, which was assembled on a rim with a size of 13CH41 / 2-J, filled with air to a pressure of 200 kPa, installed on a passenger car of class 1500 cc. cm, and then operated on a real road for 20,000 km with a load corresponding to four passengers (65 kg / passenger).

At the end of this operation, the tire was separated from the rim and visual inspection of the sealing layer on the inner surface of the tire was performed. Evaluation for tires exhibiting cracking in the sealant layer was given in Tables VI and VII.

Breathability test (pressure drop)

The tire was left for 3 months at an initial pressure of 200 kPa, room temperature of 21 ° C and no load. The internal pressure was measured at four-day intervals and the value of α was determined, repeatedly referring to the formula:

Pt / Po = exp (-αt),

where Pt is the measured pressure, Po is the initial pressure, and t is the number of days elapsed.

The results were evaluated as follows.

X (good) ... <2.5% / month

Y (satisfactory) ... 2.5% / month <air leak <4.0% / month

N (unsatisfactory) ...> 4.0% / month

Table VI (continued) Example 7 Example 8 Example 9 Example 10 Composition (mass parts) BESNOTL (PA11) 40 40 - - 3030XA (RA12) - - 45 - MA510 (Mah-EB) 60 - - - VA1840 (Mah-EO) - 60 - - VA1803 (Mah-EO) - - 55 - Formulation 2 (see table IV) - - - one hundred Result of evaluation for polymer (B) Young's modulus (MPa) 135 128 215 45 Melt viscosity (Pa · sec) 930 870 1120 1215 Polymer Layer (A) EVOH EVOH PA6 EVOH Layer gauge (A) (μm) 1,5 2.2 1,1 2.1 The evaluation result for the layered material (C) Lab tire test No cracking No cracking No cracking No cracking Durability test X X X X Air permeability coefficient (× 10 ^-12 cubic cm · cm / cm ² · sec · cm mercury) <1 <1 15.9 <1 Breathability test X X X X

Table VII
Grade for three-layer film (B) / (A) / adhesive (F) Example 11 Example 12 Example 13 Composition (mass parts) BESNOTL (PA11) thirty thirty 35 5033V (RA6.66) 10 10 10 VA1840 (Mah-EO) 60 - - VA1803 (Mah-EO) - 60 55 Result of evaluation for polymer (B) Young's modulus (MPa) 140 132 230 Melt viscosity (Pa · sec) 960 910 1220 Polymer Layer (A) EVOH EVOH EVOH Layer gauge (A) (μm) 1,6 2.5 2.1 The evaluation result for the layered material (C) Laboratory performance tests No cracking No cracking No cracking Air permeability coefficient (× 10 ^-12 cubic cm · cm / cm ² · sec · cm mercury) <1 <1 <1 Air leak X X X

Claims (20)

1. A layered material (C) based on a thermoplastic polymer composition for use in the inner layer of a pneumatic tire, containing at least one layer (A) obtained from a thermoplastic resin composition, where layer (A) is characterized by an air permeability coefficient of 10 · 10 ^-12 cc cm · cm / cm ² · s · cm of mercury column and less, on which at least one layer (B) is obtained, obtained from a thermoplastic polymer composition formed from a modified polymer composition (E) dispersed in a matrix of a thermoplastic resin composition (D), where the thermoplastic polymer composition of layer (B) is characterized by a melt viscosity of 500-2000 Pa · s and Young's modulus at room temperature of 1-400 MPa, where the thickness of layer (A) is 0.05-10 μm, and the air permeability coefficient is layered material (C) is equal to 20 · 10 ^-12 cubic cm · cm / cm ² · s · cm mercury or less. 2. The layered material (C) according to claim 1, further comprising at least one layer (F) of glue. 3. The layered material (C) according to claim 1 or 2, where one layer (A) of the thermoplastic resin composition is enclosed in a sandwich structure, between layers (B), the sandwich layers (B) can include the same or different thermoplastic polymer compositions . 4. The layered material (C) according to claim 1 or 2, where the coefficient of breathability of the composition of the thermoplastic resin layer (A) is 2.5 · 10 ^-12 cc. cm · cm / cm ² · s · cm mercury or less. 5. The layered material (C) according to claim 1 or 2, wherein the thermoplastic resin composition of layer (A) contains one or more representatives selected from copolymers of ethylene-vinyl alcohol and / or polyamide resins. 6. The layered material (C) according to claims 1 or 2, wherein the thermoplastic resin composition (D) is at least one representative selected from the group consisting of Nylon 11, Nylon 12, Nylon 666, Nylon 610, Nylon 612 , Nylon 6, Nylon 66. 7. The layered material (C) according to claim 6, wherein the modified polymer composition (E) is at least one representative selected from the group consisting of brominated isobutylene-p-methylstyrene copolymers and maleic anhydride ethylene-α- copolymers olefin. 8. The layered material (C) according to claim 7, where the mass ratio of the modified polymer composition (E) to the composition of the thermoplastic resin (D) is in the range from 60/40 to 30/70. 9. The layered material (C) according to claim 1 or 2, where the thermoplastic polymer composition of the layer (B) is at least partially dynamically vulcanized mixture. 10. The layered material (C) according to claim 1 or 2, where the layered material includes at least three layers: the first layer contains a layer (B), where the thermoplastic polymer composition is at least partially dynamically vulcanized, the second layer (A), where the composition of the thermoplastic resin contains a copolymer of ethylene-vinyl alcohol containing from 15 to 60 mol.% Ethylene, characterized by a melting point in the range from 145 ° to 250 ° C and a permeability of 0.05 · 10 ^-12 cubic meters. cm · cm / cm ² · s · cm mercury, and the third layer contains the same or different layer (B), where the thermoplastic polymer composition can be at least partially dynamically vulcanized. 11. The layered material (C) according to claim 10, where at least partially dynamically vulcanized thermoplastic polymer compositions present in the first and third layers (B) independently contain a polyamide matrix. 12. The layered material (C) of claim 10, wherein the at least partially dynamically vulcanized thermoplastic polymer compositions present in the first and third layers (B) independently comprise a polyamide matrix (D) and a dispersed phase of the functionalized polymer. 13. The layered material (C) according to item 12, where the functionalized polymer includes maleated rubber. 14. The layered material (C) according to claim 12, wherein the functionalized polymer comprises isobutylene-based halogenated rubber. 15. The layered material (C) according to claim 10, where the thickness of the first layer is in the range from 10 to 100 μm, the thickness of the second layer is in the range from 0.05 to 10 μm, and the thickness of the third layer is in the range from 10 to 100 microns. 16. The layered material (C) according to clause 15, where the first and third layers have different thicknesses. 17. The layered material (C) according to clause 15, where the first and third layers have the same thickness. 18. The layered material (C) according to claim 10, where at least partially dynamically vulcanized thermoplastic polymer compositions (B) present in the first and / or third layers further comprise nanoclay. 19. A method of producing a layered material (C) based on a thermoplastic polymer composition for use in the inner layer of a pneumatic tire according to claim 1 or 2, where the layered material is obtained by multilayer extrusion molding of a layer (A) obtained from a thermoplastic resin composition and a layer (B ) obtained from a thermoplastic polymer composition, giving a cylindrical shape. 20. A pneumatic tire using the laminate (C) as an inner layer according to claim 1 or 2.