RU2429973C2 - Laminar structure with low moisture permeability - Google Patents

Abstract

FIELD: construction.

SUBSTANCE: laminar structure for use in products includes three layers, one of which is a layer that prevents penetration of fluid medium, having the upper and lower surfaces, and containing a polymer composition that consists of a thermoplastic component and an elastomer component, which in the vulcanised form is dispersed as a discrete phase in the matrix of the thermoplastic polymer component. The second layer of the laminar structure is a thermoplastic layer, which forms a laminar structure with the lower surface of the layer, which prevents penetration of fluid medium and contains a film-forming semicrystalline polymer with a carbon chain with glass transition temperature T_g of less than approximately -20°C. The structure also comprises a layer including rubber with high content of diene, forming a laminar structure with the upper surface of the layer, which prevents penetration of fluid medium.

EFFECT: invention makes it possible to increase strength of product with low permeability of fluid medium.

19 cl, 5 dwg, 3 tbl, 1 ex

Description

FIELD OF THE INVENTION

The present invention relates to compositions of thermoplastic elastomers, especially suitable for use in tires and other rubber products, and to a method for the production of such compositions. Disclosed herein are compositions useful in multilayer or layered structures, for example, in a tire structure, especially as an air- and moisture-proof layer inside a tire carcass, which is often referred to as a tire sealant. Alternatively, such structures are applicable in the structure of hoses, in particular, as the inner layer of such structures. At least one of the layers includes nylon and a halogenated isobutylene-containing elastomer. In one aspect, the present invention relates to an improved composition of a thermoplastic elastomer having good heat resistance, wear resistance and flexibility and at the same time excellent air and moisture resistance from the point of view of use in the composition of the tire sealing layer and the barrier layer. In particular, the present invention relates to a composition of a soft thermoplastic elastomer having the form of one or more thin hydrophobic flexible thermoplastic layers.

State of the art

EP722850B1 describes a low permeability thermoplastic elastomer composition unsurpassed in terms of use as a gas barrier layer in pneumatic tires. This thermoplastic elastomer composition includes a low-permeable thermoplastic matrix, for example, a polyamide or a mixture of polyamides, in which low-permeable rubber is dispersed, such as brominated poly (isobutylene-co-p-methylstyrene) (brominated poly (isobutylene-co-paramethylstyrene), hereinafter - BIMS In the documents EP857761A1 and EP969039A1, the relative viscosity of the thermoplastic matrix and the phase of the dispersed rubber is described both as a function of the ratio of volume fractions and, independently, as close to unity in order to obtain a high concentration of small particles cured rubber dispersed in the thermoplastic phase EP969039A1 also indicates the importance of the small size of the rubber particles dispersed in the matrix of the thermoplastic polymer in terms of achieving acceptable wear resistance of the final composition, especially if this composition is intended to be used as a sealing layer pneumatic tires.

Compositions characterized by low gas permeability (i.e., acting as a gas barrier) and consisting of a thermoplastic polymer / mixtures based on a thermoplastic polymer, for example, high density polyethylene and nylon 6 or nylon 66 (HDPE / PA6.66), polyethylene terephthalate and aromatic nylon ( PET / MXD6), a polyethylene terephthalate and a copolymer of vinyl alcohol and ethylene (PET / EVOH), where one thermoplastic polymer is layered onto another layer during formation to form multiple layers, and methods for their production are described e.g. I. Hata, Kobunshi (Polymers), 40 (4), 244 (1991). In addition, the option of using such a composition as a tire sealing layer is described in Japanese Patent Application No. 7-55929. However, since these materials are thermoplastic polymers / mixtures based on a thermoplastic polymer, although having unsurpassed properties of a gas barrier, they are not flexible enough and, therefore, films made from them will inevitably collapse during tire operation.

Thus, nylon may be useful in polymer compositions from the point of view of reducing the permeability to air and other fluids of the tire sealant layer and the like, for example, for penetration from the inner to the outer surface of the tire or hose. However, it is also known that nylon may be moisture sensitive or hygroscopic, the latter term generally implying that nylon absorbs moisture from the air. Therefore, moisture that may be present in the air contained in the air chamber of the pneumatic tire can be absorbed by nylon contained in the structure of the tire sealing layer. Then, the absorbed moisture can penetrate through the various layers of the tire structure and possibly lead to the formation of bubbles or bloats inside or between the layers, thereby making them more susceptible to destruction due to separation of the layers from each other. In order to avoid such destruction, it is necessary to find a way to reduce the rate of movement of moisture vapor through the sealing layer and other layers passable for air or liquid.

US Pat. No. 5,768,158 describes a pneumatic tire provided with an air penetration preventing layer or a sealing layer consisting of a thin film of a polymer composition comprising at least 20% by weight. a thermoplastic polyester elastomer formed by a block copolymer of polybutylene terephthalate and polyoxyalkylene diimide diacid in a weight ratio of polybutylene terephthalate to polyoxyalkylene diimide diacid 85/15 or less. This polymer composition may further include dispersed rubber particles, which rubber particles have undergone dynamic vulcanization. The concept of using polymer compositions as a sealing layer was further developed, for example, in US Pat. No. 6,079,465, which describes a pneumatic tire including such a layer and the use of various thermoplastic polymers in this composition. This patent also describes the presence of a bonding layer or another layer that strengthens the bond or adhesive strength of the connection of the sealing layer to the structure as a whole. Further improvement of this technology in terms of improving adhesion to the sealing layer in the structure is described in US patent No. 6062283, where the parameters of the melt viscosity and solubility of the components of the thermoplastic polymer and the components of the elastomer are controlled in accordance with a specific mathematical formula. This patent also discloses a pneumatic tire provided with an air penetration preventing layer including a thermoplastic low permeable elastomer composition comprising a thermoplastic elastomer in which the thermoplastic polymer composition is a continuous phase and the rubber composition is a dispersed phase in which there is a polymer composition with barrier properties, which thermoplastic low permeable elastomer composition has a phase structure in which the polymer composition with a barrier polar properties, dispersed in the thermoplastic elastomer, has a flat shape, has a more than sufficient flexibility, excellent gas barrier property parameters and reduces the weight of the tire. This patent also describes the use of a polymer film layer for coloring the deepest inner and / or outermost surfaces of a tire.

US Pat. No. 6,136,123 (and the corresponding highlighted patent No. 6402867) describes a method for manufacturing pneumatic tires in which a single-layer or multi-layer thermoplastic film in the form of a tape or cylinder is used as an anti-air penetration layer, comprising: applying to at least a portion of a joined portion a thermoplastic film or a tire element facing the thermoplastic film, an adhesive composition containing a polymer component with an absolute value of the difference of the critical surface tension relative to the rubber component of the tire element and relative to the polymer component of the surface layer of the thermoplastic film is not more than 6 mN / m, respectively.

Other references of interest include: WO 2004/081107, WO 2004/081106, WO 2004/081108, WO 2004/081116, WO 2004/081099, US patents Nos. 4480074; 4,873,288; 5,073,597; 5,157,081; 5,910,544; 6,079,465; 6346571; 6538066 and 6814118.

SUMMARY OF THE INVENTION

One of the embodiments of the present invention relates to a layered structure comprising at least three layers, one of which is a layer that prevents the penetration of a fluid having upper and lower surfaces, at least one thermoplastic layer forming a layered structure with at least the lower surface of the specified layer preventing the penetration of a fluid, where the thermoplastic layer contains a film-forming semi-crystalline polymer with a carbon chain, character having a glass transition temperature, Tg, of less than about −20 ° C., said third layer contains at least one rubber with a high diene content; where the specified fluid penetration preventing layer contains a polymer composition characterized by a coefficient of breathability of 25 × 10 ^-12 cm ³ · cm / cm ² · sec cmHg (at 30 ° C) or less and Young's modulus from 1 to 500 MPa, where the layer of the specified polymer composition contains : (A) at least 10% weight. relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a coefficient of breathability of 25 × 10 ^-12 cm ³ · cm / cm ² · sec cmHg (at 30 ° C) or less and Young's modulus of more than 500 MPa, where the polymer component is selected from a group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers and imides, and (B) at least 10% by weight. relative to the total weight of the polymer composition of at least one elastomeric component with a coefficient of breathability of more than 25 × 10 ^-12 cm ³ · cm / cm ² · sec cmHg (at 30 ° C) and Young's modulus of not more than 500 MPa, where the elastomeric component is selected from the group consisting of diene rubbers and their hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, with the total amount of (A) + (B) component (A) and component (B) ) sosta at least 30% by weight. relative to the total weight of the polymer composition, where the elastomeric component (B) in the vulcanized state is dispersed as a discrete phase in the matrix of the thermoplastic polymer component (A) of the polymer composition. Adhesion or adhesion of the hydrophobic thermoplastic layer (s) to the layer (s) on which it is applied or with which it forms a layered structure can be achieved using an adhesive composition or a layer that enhances the adhesion of such layers, including adhesion of the thermoplastic layer to the penetration-preventing layer fluid and / or carcass ply of a pneumatic tire.

In a preferred aspect, the present invention relates to a tire having a carcass, a sealing layer and a thermoplastic film layer on the surface of the sealing layer facing the air chamber, where the sealing layer contains a dynamically vulcanized alloy of a structural polymer and a halogenated copolymer of isoolefin and para-alkyl styrene, and a thermoplastic film contains a polymer selected from the group consisting of homopolymers and copolymers of ethylene, for example, low density polyethylene. In another aspect, the present invention relates to a hose with an improved, vulcanizable layered structure.

Brief Description of the Drawings

Figure 1 is a simplified partial cross-section of a tire showing the arrangement of various layers in a tire, including a carcass ply, a sealing layer, and a substantially hydrophobic or moisture-impervious layer.

Fig. 1a is a simplified partial cross-section of a tire showing the arrangement of various layers in a tire, including a carcass ply, a sealing layer, a substantially hydrophobic or moisture-impervious layer and an adhesive layer located between the last of these and the carcass ply.

Figure 2 is a simplified partial cross-section of a tire showing the arrangement of various layers in a tire, including two substantially hydrophobic or moisture-impermeable layers.

Fig. 2a is a simplified partial cross-section of a tire showing the arrangement of various layers in a tire, including two substantially hydrophobic or moisture-impermeable layers and an adhesive layer between each of the substantially hydrophobic layers and the surface of the next adjacent layer with which it forms a layered structure.

FIG. 2b is a simplified partial cross-section of a tire showing the arrangement of various layers in a tire, including two substantially hydrophobic or moisture-impermeable layers and an adhesive layer between each of the substantially hydrophobic layers and the surface of the next adjacent layer with which it forms a layered structure, as well as an additional adhesive layer, located so that both sides of the thermoplastic layer between the frame and the sealing layer have an adhesive layer.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention provides a solution to the problem of moisture vapor penetration by using at least one layer of a substantially moisture-impermeable film as a surface layer on one or more surfaces of a nylon-containing layer. In another aspect, the present invention can be applied to tires made using conventional sealant layer compositions comprising halogenated isobutylene-containing elastomer as components, in particular in combination with thermoplastic elastomeric tire sealant compositions based on vulcanized mixtures of structural polymers, for example polyamides and brominated isobutylene-parameter styrene (BIMS) elastomers produced, for example, by dynamic vulcanization tion as described in document EP722850B1. In yet another aspect, the present invention is applicable to other products, where the layer that traps air or fluid includes nylon and, usually, where such a layer is used in combination with one or more other layers, for example, in hoses used for transportation of various fluids, including gases and liquids, as well as mixtures thereof.

In the context of the present invention, the term “hydrophobic” is a qualitative characteristic meaning the water-repellent nature of a material, compound or substance; lack or low affinity for water or attraction of water; tendency to repel or not absorb water; low degree of moisture absorption, tendency to not dissolve in water, not to mix with water or not to be moistened with water; lack of property is easy to mix with water; hydrophobic compounds are usually non-polar, do not have charged or electronegative atoms, often contain many CH bonds. Thus, the phrase “essentially hydrophobic” should be understood as indicating the degree, tendency to more than less hydrophobicity, usually towards the complete repulsion of water or the absorption of a very small amount of water. Such a description should be understood as referring to a material, compound, composition, mixture or substance, so that it will be clear to a person skilled in the art from this description that both the polyolefin film and the glass surface are hydrophobic, even though measurable amounts of moisture may be present in polyolefin and cannot be present in glass. Nylon, by contrast, is generally considered hydrophilic.

In this document, the new group numbering system of the Periodic System is as set forth in Chemical and Engineering News, 63 (5), 27 (1985). All molecular weight values are weighted average, unless otherwise indicated.

Throughout the description, including the claims, the word “contain” and its forms, such as “comprising” or “contains”, as well as “possesses”, “possessing”, “includes”, “include” and “including” and their forms mean that the named stages, elements or materials to which they relate are essential, however, other stages, elements or materials can be added, and at the same time, a structure is obtained that does not go beyond the scope of the claims or description. Used in the description of the invention and in the claim, they mean that the invention covers what is indicated, and, potentially, more. These terms, in particular in the claims, are encompassing, non-final and do not exclude additional, unnamed elements or process steps.

In the context of this document, “consisting essentially of” means that any other element or combination of elements is excluded, as well as any number of any element or combination of elements that would alter the basic and new features of the invention. Thus, for example, a layered structure is excluded which uses a substantially hydrophilic polymer or a combination of substantially hydrophilic polymers, with the exception of a combination of hydrophobic or substantially hydrophobic polymers in any layer, a hydrophobic layer adjacent to the layer preventing the penetration of the fluid, and in which the layer preventing the penetration of the fluid is made of any composition other than by dynamic vulcanization containing a structural polymer of the composition . Similarly, and, again only by way of example, a hydrophobic layer containing an amount of an additive or a mixture of polymers that change the rate of penetration of moisture vapor through the resulting hydrophobic layer or the layered structure as a whole to a level not contemplated by the present invention is excluded.

In the context of the present invention, unless otherwise specified in relation to a particular property, characteristic or variable, the term "essentially", applied to any criterion, such as a property, characteristic or variable, means the implementation of this criterion to such an extent that specialists in this It is clear to the field that the desired advantage or condition or the desired value of the property is achieved.

The term "polymer" can be used in relation to homopolymers, copolymers, interpolymers, terpolymers, etc. Similarly, the term “copolymer” may refer to a polymer containing at least two monomers, optionally with other monomers. When a polymer is described as containing any monomer, this monomer is present in the polymer in the form of a polymerized monomer or in derivative form. However, for brevity, the phrase “containing (corresponding) monomer” or the like is used. The term "isoolefin" means any monomer with two or more double bonds. In a preferred embodiment, a “multiolefin” is any monomer containing two conjugated double bonds, such as a conjugated diene, for example, isoprene.

As used herein, the term “elastomer” means any polymer or combination of polymers that meets the definition given in ASTM D1566. This term may be used interchangeably with the term "rubber (s)".

“Alkyl” means a paraffinic hydrocarbon group that can be obtained from an alkane by removing one or more hydrogen atoms from its formula, for example, a methyl group (CH ₃ ) or an ethyl group (CH ₃ CH ₂ ), etc.

“Aryl” means a hydrocarbon group with a ring structure characteristic of aromatic compounds, such as, for example, benzene, naphthalene, phenanthrene, anthracene, etc., which usually has alternating double bonds (“unsaturated”). That is, an aryl group is a derivative of an aromatic compound from which one or more hydrogen atoms, for example phenyl or C ₆ H _{5, are} removed.

The term "substitution" means the replacement of at least one hydrogen atom in a group with at least one substituent, which is, for example, halogen (chlorine, bromine, fluorine and iodine), an amino group, a nitro group, a sulfoxy group, (sulfonate or alkyl sulfonate), thiol, alkylthiol and hydroxy group; straight or branched chain alkyl containing from 1 to 20 carbon atoms, including methyl, ethyl, propyl, tert-butyl, isopropyl, isobutyl, etc .; a straight or branched chain alkoxy group containing from 1 to 20 carbon atoms, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy nonyloxy and decyloxy; haloalkyl, i.e., straight or branched chain alkyl containing from 1 to 20 carbon atoms, substituted with at least one halogen, 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, 2,3,3-trifluoropropyl, 1 1,2,2-t etrafluoroethyl and 2,2,3,3-tetrafluoropropyl. So, for example, a “substituted styrene unit” may be p-methylstyrene, p-ethylstyrene, etc.

In various preferred embodiments, the present invention relates to a layered structure comprising at least one layer comprising a structural thermoplastic polymer in the form of a continuous phase and a vulcanized elastomer in the form of a discrete phase. Such a composition is prepared, for example, using a technique known as dynamic vulcanization, and the resulting composition is known as a dynamically vulcanized alloy; details regarding such a composition and a method for its preparation are described below. This structure further includes a layer of an elastomeric composition comprising a high diene rubber, for example natural rubber and / or a styrene butadiene copolymer, which is described in detail below. Each of these layers usually contains additional components, such as reinforcing agents and processing aids, for example, soot and / or layered, intercalated or simply dispersed clay and processing oil, respectively. A layer of an elastomeric composition or a rubber layer with a high content of diene, usually obtained by standard methods of rubber composition, contain crosslinking agents or vulcanizing agents, often referred to as a vulcanizing system comprising a mixture of two or more individual components so that the final composition is suitable for vulcanization. On the surface of the layer of the structural thermoplastic polymer facing the fluid, which the layered structure must hold, there is a layer of a hydrophobic film. The second layer of hydrophobic film, optionally, forms a layer between the layer of the elastomeric composition and the other surface of the layer of structural thermoplastic polymer. If such an optional second hydrophobic layer is used, usually an adhesive composition or an adhesive layer located between this hydrophobic layer and the elastomeric composition layer is also used to increase the adhesion of these two layers. An adhesive composition or adhesive layer is also optionally present between the first hydrophobic layer and the structural thermoplastic polymer layer to improve the adhesion of these two layers. Typically, the compositions of these two adhesive layers, if both layers are present, are the same, although it is not necessary that they be the same. The structural polymer layer of the present invention may contain at least one reinforcing filler and other components so that they prevent the penetration of fluids. In the context of use in pneumatic tires, the structural polymer layer serves as a lining, usually the deepest inner surface of the tire structure, and is known in the tire industry as a sealing layer. Its composition and production method were developed by specialists in the field of rubber compounding in such a way as to slow down the penetration of air or oxygen through this layer to maintain tire pressure for a long time. Avoiding air penetration also reduces the likelihood of an increase in gas pressure between the layers, which can lead to premature failure or delamination. The use of at least one layer of a hydrophobic film, usually a thermoplastic film, and, optionally, two such layers of a hydrophobic film, significantly complicates the penetration of both a fluid medium such as air and a fluid such as moisture vapor from the deepest inner surface of the layered structure to the outermost surface of the layered structure and, for example, into the atmosphere. Thus, the high airtightness of a structural polymer, such as polyamide or nylon, can be supplemented by the use of a hydrophobic film to substantially impede the passage or penetration of moisture vapor through the structure and, thereby, reduce the likelihood of interlayer destruction caused by volume expansion of such vapor.

If the structural polymer layer is used as the deepest inner layer of the hose structure, it also makes it difficult for fluids to pass through the structure. Fluids in this case include air, oxygen, and other gases, as well as liquids such as water, fluorocarbons, or industrial fluids. The nature of the fluid within the layered structure dictates the choice of the components of the layer containing the structural polymer, including the choice of vulcanizable rubber used to produce a dynamically vulcanized alloy composition. The procedures of this choice are well known to those skilled in the art of blending for the production of hoses.

If the structural polymer-containing layer is used as a tire sealing layer, the tire sealing layer composition of the present invention can be used in the manufacture of a tire sealing layer for automobiles such as trucks, buses, cars, motorcycles, mopeds, all land vehicles, etc. .P. In addition, such a layer can be used in tires intended for non-motorized vehicles such as bicycles.

The first layer is usually a composition comprising rubber with a high content of diene, in the form of a film or sheet or frame layer. Alternatively, such a first layer may be a tubular layer of a hose structure. This layer may also contain reinforcing fibers, for example, tire cord or other reinforcing components suitable for use in tires or hoses.

If an optional second hydrophobic layer is not used, then the second layer is usually a dynamically vulcanized alloy composition, described in detail below, and usually is in the form of a sheet or film, however, it can also be in the form of a tubular layer of a hose structure. If an optional second hydrophobic layer is used, then the dynamically vulcanized alloy layer is the third layer.

The hydrophobic layer is usually present in the form of a sheet or film obtained, for example, by extrusion or calendering, and is formed when several layers are formed in a single extrusion or calendering operation.

Halogenated rubber is a rubber with a content of at least about 0.1 mol%. halogen, where halogen is selected from the group consisting of bromine, chlorine and iodine. Preferred halogenated rubbers useful in the context of the present invention include halogenated isobutylene-based homopolymers or copolymers. These polymers can be described as random copolymers comprising units derived from a C ₄ -C ₇ isomonoolefin, for example, units derived from isobutylene, and at least one other type of polymerizable units. In one embodiment of the invention, the isobutylene-based halogenated copolymer is butyl or branched butyl based rubber, especially brominated versions of these elastomers. (Suitable unsaturated butyl rubbers, such as homopolymers and copolymers of olefins or isoolefins, and other types of elastomers applicable in the context of the present invention are well known and described in Rubber Technology 209-581 (edited by Maurice Morton ed., Chapman & Hall 1995) , The Vanderbilt Rubber Handbook 105-122 (edited by Robert F. Ohm, RT Vanderbilt Co., Inc. 1990) and Edward Kresge and HC Wang at 8 Kirk-Othmer Encyclopedia of Chemical Technology 934-955 (John Wiley & Sons, Inc. 4th ed. 1993)).

Butyl rubbers are usually prepared by reacting a mixture of monomers, which mixture contains at least (1) a C ₄ -C ₁₂ isoolefin monomer, such as isobutylene, and (2) a multiolefin monomer. In one embodiment, the isoolefin is present in an amount of from 70 to 99.5% by weight. relative to the total weight of the mixture of monomers, in another embodiment, from 85 to 99.5% by weight. The multiolefin component is present in the mixture of monomers in an amount of 30 to 0.5% by weight. in one embodiment, and from 15 to 0.5% weight. - in another. In another embodiment, from 8 to 0.5% weight. a mixture of monomers is a multiolefin. The isoolefin is preferably a C ₄ -C ₁₂ compound, examples of which are not restrictive, such as isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl- 2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene and 4-methyl-1-pentene. A multiolefin is a C ₄ -C ₁₄ multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene, as well as other monomers similar to those described in European patent EP No. 0279456 and US patent No. 5506316 and No. 5162425. Other polymerizable monomers, such as styrene and dichlorostyrene, are also suitable for homopolymerization or copolymerization to produce butyl rubbers. In one of the embodiments of the invention, butyl polymer, applicable in the context of the invention, receive by the reaction of 95-88.5% by weight. isobutylene with 0.5-8% weight. isoprene or, in another embodiment, 0.5-5.0% by weight. isoprene. Butyl rubbers and methods for their production are described in detail, for example, in US patent No. 2356128, 3968076, 4474924, 4068051 and 5532312.

Halogenated butyl rubber is obtained by halogenating butyl rubber, the product described above. Halogenation can be carried out by any method, and the present invention 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. Further processing of the halogenated butyl rubber may also be carried out as described in US Pat. No. 4,288,575. The halogenated butyl rubber typically has a Mooney viscosity of about 20 to about 70 (ML 1 + 8 at 125 ° C); for example, from about 25 to about 55 in another embodiment of the invention. The halogen content is usually about 0.1-10% by weight. relative to the weight of halogenated butyl rubber; for example, about 0.5-5% weight .; alternatively, from about 0.8 to about 2.5% weight .; for example, from about 1 to about 2% weight.

Halogenated butyl rubber useful in the context of the present invention is commercially available; this is Bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney viscosity is usually about 27-37 (ML 1 + 8 at 125 ° C, ASTM 1646), and the bromine content is about 1.8-2.2% by weight. relative to the weight of Bromobutyl 2222. In addition, Bromobutyl 2222 has the following vulcanization parameters as reported by the manufacturer: MN, approximately 28-40 dN · m, ML, approximately 7-18 dN · m (ASTM D2084). Another commercially available version of the halogenated butyl rubber useful in the context of the present invention is Bromobutyl 2255 (ExxonMobil Chemical Company). Its Mooney viscosity is approximately 41-51 (ML 1 + 8 at 125 ° C, ASTM D1646), the bromine content is approximately 1.8-2.2% by weight. In addition, the manufacturer reports the following vulcanization parameters: MN from 34 to 48 dN · m, ML from 11 to 21 dN · m (ASTM D2084).

Another applicable embodiment of halogenated butyl rubber is halogenated, branched or “star branched” butyl rubber. Such rubbers are described, for example, in European patent EP No. 0678529 B1, US patent No. 5182333 and 5071913, each of which is incorporated into this description by reference. In one embodiment, star-branched butyl rubber (SBB) is a composition comprising butyl rubber and a polydiene or block copolymer. In the context of the present invention, the method for producing SBB is not a limitation. Polydienes, block copolymers or branching agents (hereinafter “polydienes") usually have cationic reactivity and are present during the polymerization of butyl or halogenated butyl rubber, or may be mixed with butyl rubber to form SBB. The branching agent or polydiene may be any suitable branching agent, and the present invention is not limited to the type of polydiene or branching agent used to produce SBB.

In one embodiment, the SBB is a composition of butyl or halogenated butyl rubber described above and a copolymer of polydiene and partially halogenated polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene ethylene butadiene copolymer diene rubber (EPDM), ethylene propylene rubber (EPM), block copolymers styrene-butadiene-styrene and styrene-isoprene-styrene. Polydienes may be present in an amount expressed in weight percent of the total monomer content, typically more than 0.3% by weight .; alternatively, from about 0.3 to about 3% weight .; or from about 0.4 to about 2.7% by weight.

The branched or star-branched butyl rubber used in the present invention is preferably halogenated. In one embodiment, the halogenated star-branched butyl rubber (HSBB) comprises butyl rubber, halogenated or non-halogenated, and a polydiene or block copolymer, halogenated or non-halogenated. The halogenation process is described in detail in US Pat. Polydien / block copolymers or branching agents (hereinafter “polydienes") typically have cationic reactivity and are present during the polymerization of butyl or halogenated butyl rubber, or may be mixed with butyl or halogenated butyl rubber to form HSBB. The branching agent or polydiene may be any suitable branching agent, and the present invention is not limited to the type of polydiene used to produce HSBB.

In one embodiment, the HSBB is a composition comprising the halogenated butyl rubber described above and a copolymer of polydiene and partially halogenated polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene and butadiene copolymer, ethylene, butadiene diene rubber, block copolymers styrene-butadiene-styrene and styrene-isoprene-styrene. Polydienes may be present in an amount expressed in weight percent of the total monomer content, typically more than 0.3% by weight .; alternatively, from about 0.3 to about 3% weight. or about 0.4-2.7% by weight.

A commercially available HSBB variant useful in the context of the present invention is Bromobutyl 6222 (ExxonMobil Chemical Company) having a Mooney viscosity (ML 1 + 8 at 125 ° C, ASTM D1646) of about 27-37 and a bromine content of about 2.2 -2.6% weight. In addition, the manufacturer reports the following Bromobutyl 6222 vulcanization parameters: MN from 24 to 38 dN · m, ML from 6 to 16 dN · m (ASTM D2084).

Preferred isoolefin / p-alkyl styrene copolymers include random copolymers comprising a C ₄ -C ₇ isoolefin such as isobutylene and halomethyl styrene. Halomethylstyrene may be styrene substituted with alkyl halide in the ortho, meta or para position. In one embodiment, halomethylstyrene is p-halomethylstyrene containing at least 80%, more preferably at least 90% by weight. para isomer. Halogen may be any halogen, preferably chlorine or bromine. The copolymer may also include functionally substituted interpolymers in which at least some of the alkyl substituents of the styrene monomer units contain benzyl halogen or another functional group, further described below. These interpolymers are referred to herein as “isoolefin copolymers containing halomethylstyrene” or simply “isoolefin copolymers”.

Preferred isoolefin copolymers may include monomers selected from the group consisting of isobutylene or isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, vinyl methyl ether, indene, vinyltrimethylsilane, hexene and 4-methyl-1-pentene. Preferred isoolefin copolymers may also further include multiolefins, preferably a C ₄ -C ₁₄ multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene, as well as other monomers, such as described in European patent EP No. 279456 and US patent No. 5506316 and No. 5162425. The desired styrene monomers of the isoolefin copolymer include styrene, methylstyrene, chlorostyrene, methoxystyrene, indene and indene derivatives and combinations thereof.

Preferred isoolefin copolymers can be described as interpolymers containing the following monomer units irregularly distributed along the polymer chain:

where R and R ¹ independently of one another are hydrogen, lower alkyl, preferably C ₁ -C ₇ alkyl and primary and secondary alkyl halides, X is a functional group such as halogen. Desirable halogens include chlorine, bromine, or combinations thereof. Preferably, each of R and R ¹ is hydrogen. The groups —CRR ₁ H and —CRR ₁ X can replace the styrene ring in ortho, meta or para positions, preferably in the para position. In one embodiment, up to 60 mol%. para-substituted styrene present in the structure of the interpolymer may have a structure with a functional substituent (2) described above, and in another embodiment, from 0.1 to 5 mol%. In another embodiment, the proportion of the structure with a functional substituent (2) is from 0.4 to 1 mol%. Functional group X may be a halogen or other functional group introduced by nucleophilic substitution of halogen benzyl halogen by other groups, such as carboxylic acid groups; salts of carboxylic acids; esters of carboxylic acids, amides and imides; hydroxy groups; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; cyanate; amino groups and mixtures thereof. Such functionally substituted isomonoolefin copolymers, the process for their preparation, methods for introducing functional substituents and vulcanization are described in more detail in US Pat. No. 5,162,445.

Of these copolymers of isobutylene and p-methylstyrene, copolymers containing from 0.5 to 20 mol% are best suited. p-methylstyrene, where up to 60 mol%. methyl substituents of the benzene ring contain a bromine or chlorine atom, preferably a bromine atom (p-bromomethylstyrene), as well as variants with an acid or ester functional group in which the halogen atom is replaced by a functional group of maleic anhydride or acrylic or methacrylic acid. Such interpolymers are called "halogenated poly (isobutylene-co-p-methylstyrene)" or "brominated poly (isobutylene-co-p-methylstyrene)"; they are commercially available under the EXXPRO ™ Elastomers brand name (ExxonMobil Chemical Company, Houston, TX). It should be understood that the use of the terms “halogenated” or “brominated” is not limited to the method of halogenation of the copolymer, and is intended only to describe the copolymer containing units derived from isobutylene, units derived from p-methylstyrene and units derived from p-halomethylstyrene.

Functionally substituted polymers preferably have a substantially homogeneous distribution of the composition, that is, at least 95% by weight. polymer is characterized by the content of p-alkylstyrene in the range of 10% of the average content of p-alkylstyrene in the polymer. More preferred polymers are also characterized by a narrow molecular weight distribution (Mw / Mn) of less than 5, more preferably less than 2.5, a preferred viscometric average 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, determined by gel permeation chromatography.

Preferred halogenated poly (isobutylene-co-p-methylstyrenes) are brominated polymers, which typically contain from about 0.1 to about 5% by weight. bromomethyl groups. In yet another embodiment, the amount of bromomethyl groups is from about 0.2 to about 2.5% weight. In other words, preferred copolymers contain from about 0.05 to about 2.5 mol%. bromine relative to the weight of the polymer, more preferably, from about 0.1 to about 1.25 mol%. bromine and, essentially, do not contain halogen-substituted rings or halogen atoms in the main polymer chain. In one embodiment, the interpolymer is a copolymer of units derived from C ₄ to C ₇ isomonoolefin, units derived from p-methyl styrene and units derived from p-halomethyl styrene, where p-halomethyl styrene units are present in the interpolymer in an amount of from about , 0.4 to about 1 mol%. relative to the amount of interpolymer. In another embodiment, p-halomethylstyrene is p-bromomethylstyrene. Mooney viscosity (1 + 8, 125 ° C, ASTM D1646, quoted) is from about 30 to about 60 Mooney units.

In another embodiment, the ratio between the ternary fraction of isoolefin and p-alkylstyrene and the mole fraction of p-alkylstyrene incorporated in the copolymer is described by the distribution equation for the units in the copolymer given below and is characterized by the distribution parameter of the units in the copolymer m.

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

where m is the parameter of the distribution of units in the copolymer,

And the molar ratio of p-alkylstyrene to isoolefin in the copolymer,

F is the proportion of the ternary fraction of p-alkylstyrene-isoolefin-p-alkylstyrene in the copolymer.

The m value for the copolymerization of an isoolefin and p-alkylstyrene in a specific diluent is best consistent with this equation. In some embodiments, m is from less than 38; alternatively, from less than 36; alternatively, from less than 35; alternatively, from less than 30. In other embodiments, m is from 1-38; alternatively, from 1-36; alternatively, from 1-35; alternatively from 1-30. Copolymers with such characteristics are described in documents WO 2004058825 and WO 2004058835.

In another embodiment, the isoolefin / p-alkylstyrene copolymer is substantially non-branched. In the context of the present invention, a polymer having substantially no long chain branching is defined as a polymer for which g ' _vis.avg. (average viscometric) greater than or equal to 0.978, alternatively greater than or equal to 0.980, alternatively greater than or equal to 0.985, alternatively greater than or equal to 0.990, alternatively greater than or equal to 0.995, alternatively greater than or equal to 0.998, in the alternative, greater than or equal to 0.999 when determined by size exclusion chromatography (SEC) with double frequency conversion, as described below. Such polymers are also described in WO2004058825 and WO2004058835.

In another embodiment, the ratio between the ternary fraction of the isoolefin and the multiolefin and the mole fraction of the multiolefin incorporated in the halogenated copolymer is described by the distribution equation for the units in the copolymer given below and is characterized by the distribution parameter of the units in the copolymer m.

F = mA / (1 + mA) ² ,

where m is the parameter of the distribution of units in the copolymer,

A is the molar ratio of multiolefin to isoolefin in the copolymer,

F is the proportion of the ternary fraction of the isoolefin-multiolefin-multiolefin in the copolymer.

The measurement of the proportion of the ternary fraction of the isoolefin and multiolefin in the copolymer and the molar fraction of the multiolefin incorporated in the copolymer is described below. The best fit to this equation is given by m for the copolymerization of the isoolefin and multiolefin in each diluent. In some embodiments, m is from more than 1.5; alternatively, from more than 2.0; alternatively, from more than 2.5; alternatively, from more than 3.0; alternatively, from more than 3.5. In other embodiments, m is from 1.10 to 1.25; alternatively, from 1.15 to 1.20; alternatively, from 1.15 to 1.25; alternatively, m is approximately 1.20. Halogenated rubbers with such characteristics are described in WO2004058825 and WO2004058835.

In another embodiment, the halogenated rubber does not substantially have a long chain branching. In the context of the present invention, a polymer having substantially no long chain branching is defined as a polymer for which g ' _vis.avg. greater than or equal to 0.978, alternatively greater than or equal to 0.980, alternatively greater than or equal to 0.985, alternatively greater than or equal to 0.990, alternatively greater than or equal to 0.995, alternatively greater than or equal to 0.998, alternatively, greater than or equal to 0.999 when determined by the SEC method with double frequency conversion, as described below. The presence or absence of long chain branching of polymers is determined by double frequency conversion SEC. Double frequency conversion SEC is carried out using a Waters chromatograph (Milford, Massachusetts) 150C, operating at 40 ° C and equipped with a light scattering detector Precision Detectors (Bellingham, Massachusetts) PD2040, a viscometric detector Viskotek (Houston, Texas) model 150R and differential reflectance with 150C). These detectors are connected in series: first, a light scattering detector, then a viscometric detector, and a third differential differential refractometric detector. As a diluent, tetrahydrofuran (0.5 ml / min) was used with a set of three columns of mixed-B type 10 microns manufactured by Polymer Laboratories, Ltd. (Shropshire, UK) for gel permeation chromatography with a light scattering detector. This instrument is calibrated to 16 narrow polystyrene standards (Polymer Laboratories, Ltd.). Data is collected using TriSEC software (Viscotek) and imported into WaveMetric's Igor Pro program (Lake Osuigo, Oregon) for analysis. To establish the relationship between the intrinsic viscosity ([η] _linear determined by the viscometric detector) and the molecular weight (M _w determined by the light scattering detector), linear polyisobutylene is used. The ratio of [η] _linear and M _w is expressed by the Mark-Houwink equation.

[η] _linear = KM _w ^α

The parameters K and α are obtained from the graph with a logarithmic scale on both axes of the dependence of the characteristic viscosity on M _w , where α and K are the angular coefficients. Significant deviations from the ratio established for linear standards indicate the presence of long chain branching. As a rule, samples with a more significant deviation from the linear dependence are characterized by a greater long-chain branching. The scale factor g 'also indicates a deviation from the established linear relationship.

[η] _sample = g '[η] _linear ([η] _samples = g' [η] _linear )

The value of g 'is defined as less than or equal to unity and greater than or equal to zero. When g 'is equal to or almost equal to unity, the polymer is considered linear. When g 'is significantly less than unity, the sample is characterized by the presence of long chain branching. 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 SEC with double frequency conversion g 'is calculated for each data layer of the chromatographic curve. Viscometric g 'or g' _vis.avg. calculated for the entire molecular weight distribution. The scale factor is calculated based on the average intrinsic viscosity of the sample.

g ' _vis.avg. = [η] _avg. / KM _w ^α

Other preferred halogenated rubbers comprise the halogenated isobutylene-p-methylstyrene-isoprene copolymer described in WO 01 / 21672A1.

Halogenated rubbers applicable in the layer preventing the penetration of the fluid and the binder layer may be the same or different.

In the context of the present invention, a structural polymer is defined as any thermoplastic polymer, copolymer or mixture thereof, characterized by a Young's modulus of more than 500 MPa and, preferably, a coefficient of breathability of less than 60x10 ^-12 cm ³ · cm / cm ² · sec cmHg (at 30 ° C), including, inter alia, one or more of the following:

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

b) polyester polymers: polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyacrylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, other polyoxyalkylene dihydrate dihydrate acid copolymer;

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

d) polymethacrylate polymers: polymethyl methacrylate, polyethyl acrylate;

e) polyvinyl polymers (non-limiting examples): vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl / polyvinylidene copolymer, copolymer / methacrylate;

f) cellulosic polymers: cellulose acetate, cellulose acetate butyrate;

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

h) polyimide polymers: aromatic polyimides;

i) polysulfones;

j) polyacetals;

k) polyactones;

l) polyphenylene oxide and polyphenylene sulfide;

m) styrene maleic anhydride;

n) aromatic polyketones;

o) mixtures of any or all of the polymers described in paragraphs a) to n), including also mixtures of any of the structural polymers shown by way of illustration or example in each of paragraphs a) to n) inclusive.

In the context of the present invention, this definition of a structural polymer excludes olefin polymers such as polyethylene and polypropylene.

Preferred structural polymers include polyamide polymers and mixtures thereof; particularly preferred are nylon 6, nylon 66, copolymer nylon 6/66, nylon 11 and nylon 12, and mixtures thereof.

A high diene rubber or elastomer, also referred to as a high diene monomer rubber, is a rubber containing, as a rule, at least 50 mol%. diene monomer C ₄ -C ₁₂ , usually at least from about 60 mol%. up to about 100 mol%; more preferably, from about 70 mol%. up to about 100 mol%; even more preferably, from about 80 mol%. up to about 100 mol%.

Suitable rubbers with a high content of diene monomer include homopolymers and copolymers of olefins or isoolefins and multiolefins or homopolymers of multiolefins. They are well known and described in Rubber Technology 179-374 (edited by Maurice Morton ed., Chapman & Hall 1995) and The Vanderbilt Rubber Handbook 22-80 (edited by Robert F. Ohm, RT Vanderbilt Co., Inc. 1990 ) Preferred examples of rubbers with a high content of diene monomer include polyisoprene, polybutadiene, styrene-butadiene, natural rubber, chloroprene, acrylonitrile-butadiene and the like, which can be used individually or in combination and mixtures.

Another group of useful rubbers with a high content of diene monomer includes block copolymers of styrene, similar to those in which the styrene content is from 5% by weight. up to 95% by weight, preferably from 10% by weight. up to 85% by weight, more preferably from 15% by weight. up to 70% weight. Preferred styrene block copolymers (SBCs) include those that typically contain part A of thermoplastic blocks and part B of elastomeric blocks. Part of blocks A is hard blocks, which are derivatives of materials with a sufficiently high glass transition temperature to form crystalline or glassy domains at the temperature of use of the polymer. Such rigid blocks, as a rule, form strong cross-links of a physical nature or clusters with other hard blocks of the copolymer. Part A of the rigid blocks typically contains polyvinylarene derived from monomers such as styrene, alpha-methylstyrene, other styrene derivatives or mixtures thereof. Part A of the rigid blocks may also be a copolymer derived from styrene monomers such as those described above and olefin monomers such as ethylene, propylene, butene, isoprene, butadiene, and mixtures thereof. Of the present invention, of these polymers, usually those that contain less than about 50% of the glassy phase are usable, that is, their glass transition temperature Tg should be less than about -50 ° C.

In one embodiment, the hard block part A is polystyrene with a number average molecular weight of from about 1000 to about 200000, preferably from about 2000 to about 100000, more preferably from about 5000 to about 60,000. Typically, part A of the rigid blocks is from about 5% to about 80%, preferably from about 10% to about 70%, more preferably from about 10% to, approximately 50% of the total weight of the copolymer.

The material forming blocks B preferably has a rather low glass transition temperature in the range of operating polymer operating temperatures, so that crystalline or glassy domains are not formed at these temperatures. Blocks B are generally considered soft blocks. This part B of soft blocks, as a rule, is an olefin polymer derived from aliphatic diene monomers with conjugated double bonds in a chain of 4-6 carbon atoms or linear alkene monomers consisting of 2-6 carbon atoms. Suitable diene monomers include butadiene, isoprene and the like, while suitable alkene monomers include ethylene, propylene, butene and the like. and, in each case, mixtures thereof. The soft block portion B preferably contains a substantially amorphous polyolefin, such as ethylene-propylene copolymers, ethylene-butene copolymers, polyisoprene, polybutadiene and the like. and mixtures thereof. The number average molecular weight of soft blocks B is typically from about 1000 to about 300,000, preferably from about 10,000 to about 200,000, more preferably from about 20,000 to about 100,000.

Typically, the soft block portion B is from about 20% to about 90%, preferably from about 30% to about 80%, more preferably from about 40% to about 80 % of the total weight of the copolymer.

Suitable for use in the SBC compositions described herein comprise at least one part A of substantially thermoplastic blocks and at least one portion B of substantially elastomeric blocks. SBCs can contain many blocks.

In one embodiment, the SBCs may be an AB diblock copolymer. In another embodiment, the block copolymer may be triblock copolymer ABA. In other embodiments, SBCs may be ABABA tetrablock copolymers or ABA-ABA pentabloxopolymers.

In another embodiment, SBCs are triblock copolymers with intermediate elastomeric blocks B and end thermoplastic blocks A and A ′, where A and A ′ may be derivatives of various vinylarene monomers. In other embodiments, SBCs include more than one block A and / or more than one block B, where each of blocks A can be derived from the same or different vinylarene monomers, and each of blocks B can be derived from the same or different olefin monomers.

SBCs can also have a star-shaped structure with three or more rays, where each of the rays is a BA, BA-A-BA-A or a similar type of copolymer, and blocks B are located near the central part or in the center of the star polymer. In other embodiments, SBCs may have four, five, or six beams.

In one embodiment, the olefin block of the polymer is at least about 50% by weight. block copolymer. Unsaturated olefin double bonds can be selectively hydrogenated to reduce sensitivity to oxidative degradation, hydrogenation can also positively affect elastic properties. For example, a polyisoprene block can be selectively hydrogenated or reduced to form an ethylene-propylene block. In one embodiment, the vinylarene block typically comprises at least about 10% by weight. SBC weights. However, a higher vinylarene content may be used to increase elasticity and stress relaxation.

Examples of suitable SBC polymer compositions for use in the composition described herein include styrene-olefin-styrene triblock copolymers such as styrene-butadiene-styrene (SBS), styrene-ethylene / butylene-styrene (S-EB-S), styrene- ethylene / propylene-styrene (S-EP-S), styrene-isoprene-styrene (SIS) and mixtures thereof. SBC can be a separate SBC or a mixture of SBC.

In one embodiment, the SBCs used in the polymer compositions described herein are polystyrene-ethylene / butylene-polystyrene block copolymers with a styrene content of more than about 10% by weight. Due to the high styrene content, the part formed by polystyrene blocks, as a rule, has a relatively large molecular weight.

In one embodiment, the SBC is characterized by a melt flow rate of from about 0.01 to about 150 dg / min. In another embodiment, the SBC is characterized by a melt flow rate of from about 0.1 to about 100 dg / min. In yet another embodiment, the SBC is characterized by a melt flow rate of from about 1 to about 75 dg / min (in each case, the melt flow rate is measured according to ASTM 1238 at 2.16 kg and 230 ° C.).

In one embodiment, the composition comprises an SBC formed by three-block segments consisting of units derived from styrene and at least one other unit selected from the group consisting of units derived from ethylene, units derived from butadiene, units derived from isoprene, units derived from isobutylene, and where less than 20% by weight is included in the copolymer containing styrene blocks. segments of two blocks. In another embodiment, the composition comprises SBC formed by segments selected from the group consisting of SIS, SBS, SEBS and SIBS (styrene-isoprene-butadiene-styrene), and where from about 5% to about 95% diene units of styrene block copolymer are hydrogenated.

An example of suitable SBC polymer compositions for use herein are the commercially available Dexco Polymer LP product under the Vector ™ name and the Kraton Polymers (Houston, Texas) Kraton ™ name.

Typically, polymer compositions, for example, used for tire manufacturing, are crosslinked in the finished product. Crosslinking, or vulcanization, is carried out by introducing vulcanizing agents and / or a vulcanization accelerator; a mixture of such agents is generally referred to as a vulcanizing system. It is known that the physical properties, performance, and wear resistance of vulcanized rubber are directly related to the amount (crosslink density) and type of cross-linking formed during the vulcanization reaction (see, for example, Helt et al., The Post Vulcanization Stabilization for NR, Rubber World 18-23 (1991)). Vulcanizing agents contain those components described above that facilitate or influence the vulcanization of elastomers; these are typically metals, vulcanization accelerators, sulfur, peroxides and other agents known in the art, as described above. Crosslinking agents or vulcanizing agents contain at least one of the following components, for example: sulfur, zinc oxide, fatty acids and mixtures thereof. Can also be used curing systems containing peroxide. Typically, polymer compositions can be crosslinked by the addition of vulcanizing agents, for example, sulfur, metal oxides (i.e., zinc oxide, ZnO), organometallic compounds, radical chain initiators, etc. and heating this composition or mixture. If a method known as “dynamic vulcanization” is used, the process is changed so that substantially simultaneous mixing and vulcanization, or crosslinking of at least one of the vulcanizable components of the composition containing at least one capable of vulcanizing rubber, elastomer or polymer, and at least one non-vulcanizable elastomer or polymer using the vulcanizing agent (s) for at least one vulcanizable component. (See, for example, US patent No. 6079465 and documents referred to in it). In particular, the following vulcanizing agents suitable for use in the present invention are well known: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ and NiO. These metal oxides can be used in conjunction with complexes of the corresponding metal stearates (for example, Zn, Ca, Mg and Al stearates) or with stearic acid, or a sulfur compound or alkyl peroxide. (See also Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber World 25-30 (1993)). The vulcanizing agent (s) often add vulcanization accelerators to the elastomeric compositions. The vulcanizing agent (s), with or without the addition of at least one vulcanization accelerator, is often referred to in the art as a vulcanizing system for elastomer (s). The vulcanizing system is used because, usually, to achieve a positive result, especially in the case of a mixture of rubber with a high content of diene monomer and less reactive elastomer, more than one vulcanizing agent is used.

For the implementation of dynamic vulcanization in the presence of a structural polymer with the formation of a substantially impermeable layer, any conventional vulcanizing system suitable for vulcanizing saturated halogenated polymers can be used, which is used to vulcanize at least the elastomeric halogenated copolymer of isomonoolefin C ₄ -C ₇ and p -alkylstyrene, except that vulcanizing substances, which are peroxides, are specifically excluded when carried out on of the present invention, when the thermoplastic structural polymer (s) is selected so that the peroxide self-crosslinks such polymers when the structural polymer cross-links with itself, resulting in a too vulcanized non-thermoplastic composition. Suitable vulcanizing systems for the elastomeric halogenated copolymer — a component of the composition of the present invention — include zinc oxide in combination with zinc stearate or stearic acid and optionally one or more of the following vulcanization accelerators or vulcanizing agents: Permalux, di-o-tolylguanidine salt of dicatecholborate; HVA-2, m-phenylene-bis-maleimide; Zisnet, 2,4,6-trimercapto-5-triazine; ZDEDC, zinc diethyldithiocarbamate, as well as other dithiocarbamates, included for the purposes of the present invention; Tetrone A, dipentamethylene diiuramhexasulfide; Vultac 5, an alkylated phenol disulfide; SP1045, phenol formaldehyde resin; SP1056, brominated alkyl phenol formaldehyde resin; DPPD, diphenylphenylenediamine; salicylic acid, o-hydroxybenzoic acid; rosin, abietic acid; TMTDS, tetramethylthiuram disulfide used in combination with sulfur.

Dynamic vulcanization is carried out under such conditions as to vulcanize, at least partially, preferably completely, an elastomeric halogen-containing copolymer of an air penetration-preventing layer.

With reference to the polymers and / or elastomers referred to herein, the terms “vulcanized” or “crosslinked” refer to a chemical reaction consisting in the formation of bonds, such as during chain growth, or cross-links between polymer chains involving a polymer or elastomer to such an extent that the elastomer treated in this way during operation of the tire exhibits the necessary functional properties resulting from the vulcanization reaction. For the purposes of the present invention, the complete completion of the vulcanization reactions in relation to the composition containing the elastomer, considered as "vulcanized" or "crosslinked", is not required. For example, for the purposes of the present invention, a tire containing a bonding layer is sufficiently vulcanized when its components have passed the necessary tests in accordance with the technical requirements for products during and after production, and this tire meets the performance requirements when used in a vehicle. In addition, the composition is satisfactory, sufficiently or substantially vulcanized or cross-linked, if the tire can be used even when further vulcanization leads to the formation of additional cross-links. After conducting a small experimental work using well-known tools and standard techniques, a person skilled in the art can easily determine the appropriate or optimal vulcanization time for the elastomer (s) and polymer (s) bonded layer to be used in the composition, as well as the amount and type of crosslinking agent (s) ) and the vulcanization accelerator (s) and vulcanization temperature to be used in the manufacture of the tire.

Vulcanization accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, etc. Acceleration of the vulcanization process can be achieved by introducing into the composition a certain amount of accelerator. The mechanism of accelerated vulcanization of natural rubber includes a complex of interactions between the vulcanizing substance, the vulcanization accelerator, activators and polymers. In the ideal case, all available vulcanizing agent is spent on the formation of effective cross-linking, connecting two polymer chains to each other and increasing the strength of the polymer matrix as a whole. Many vulcanization accelerators are known in the art, including, but not limited to, stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2,2'-benzothidiazide MBTS), disodium hexamethylene-1,6-bistiosulfate dihydrate, 2- (morpholinothio) benzothiazole (MBS or MOR), compositions of 90% MOR and 10% MBTS (MOR 90), N-tertarylbutyl-2-benzothiazolsulfenamide (TBBS), N-oxide-diethylethiocarbamyl-n-oxide-diethylene sulfonamide (OTOS), Zinc 2-ethylhexanoate (ZEN), N, N'-diethylthiourea. Vulcanizing agents, vulcanization accelerators and vulcanizing systems suitable for one or more crosslinkable polymer are well known in the art.

In one embodiment of the present invention, at least one curing agent is typically present in an amount of from about 0.1 phr (parts per hundred parts of rubber) to about 15 phr; alternatively, from about 0.5 phr to about 10 phr.

The described composition may contain one or more fillers, such as calcium carbonate, clay, mica, silica and silicates, talc, titanium dioxide, starch and other organic fillers, such as wood flour, and soot. Suitable filler materials include carbon black, such as channel gas black, furnace black, thermal black, acetylene black, lamp black, and the like. Most preferred is carbon black of reinforcing grades. The filler may also include other reinforcing and non-reinforcing materials, such as silica, clay, calcium carbonate, talc, wollastonite, titanium dioxide, and the like. Typically, the filler is present in the sealing layer in an amount of from about 20 to about 50% by weight. the total weight of the composition, more preferably, from about 25 to about 40% weight. In one embodiment, the filler is carbon black or modified carbon black. A preferred filler is carbon black of semi-reinforcing grades, typically used in an amount of from about 10 to about 150 weight. parts per hundred parts of rubber (phr), more preferably from about 30 to about 120 phr. Applicable carbon black grades as described in Rubber Technology 59-85 (1995) include grades N110 to N990. It is more desirable to use soot grades in the context of the present invention, for example for treadmills such as N229, N351, N339, N220, N234 and N110 in accordance with ASTM (D3037, D1510 and D3765). Particularly desirable is the use in the context of the present invention of carbon black variants used, for example, in the manufacture of a tire sidewall, such as N330, N351, N550, N650, N660 and N762. It is also particularly desirable to use, in the context of the present invention, carbon black variants useful, for example, in a tire sealant or chamber, such as N550, N650, N660, N762, N990 and Regal 85 (Cabot Corporation, Alpharetta, GA).

Layered, intercalated, or dispersed clay may also be present in the composition described. Such clay, also called "nanoclay", is well known, its distinguishing features, methods for producing and mixing with polymers are described, for example, in documents JP 2000109635, JP 2000109605, JP 11310643; DE 19726278; WO 098/53000 and US Pat. Nos. 5,091,462, 4,431,755, 4,472,538 and 5,910,523. Swellable layered clay materials suitable for the purposes of the present invention include natural or synthetic filosilicates, especially smectic clays such as montmorillonite, nontronite, beidellite, volconite, hectorite, saponite, saukonite, magadite, keniaite, stevensite, etc., as well as vermiculite, galloisite, alumina oxides, hydrotalcite, etc. These layered clays typically contain particles with a plurality of silicate plates, typically from about 4 to about 20 Å in one embodiment, and from about 8 to about 12 Å in another embodiment, linked to each other another, on the interlayer surface of which there are exchange cations, such as Na ⁺ , Ca ²⁺ , K ⁺ or Mg ²⁺ .

Layered clay can be intercalated or stratified as a result of treatment with organic molecules (swelling agents) capable of undergoing ion exchange reactions with cations present on the interlayer surfaces of the layered silicate. Suitable swelling agents include cationic surfactants such as ammonium, alkylamines or alkylammonium (primary, secondary, tertiary or quaternary), phosphonic or sulfonic derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides. Desirable amino compounds (or corresponding ammonium ions) include amines of 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 in which at least R ₁ is C ₁₂ -C ₂₀ alkyl or alkene.

Another class of swelling agents includes substances that can form covalent bonds with interlayer surfaces. These include polysilanes with the structure —Si (R ′) ₂ R ² , where R ′ is in each case the same or different, selected as an alkyl, alkoxy group or oxysilane; R ² is an organic radical compatible with the polymer matrix of the composite. Other suitable swelling agents include protonated amino acids and their salts containing 2-30 carbon atoms, such as 12-aminododecanoic acid, epsilon-caprolactam and the like. Suitable swelling agents and methods for intercalating layered silicates are described in US Pat. Nos. 4,472,538, 4,810,734, 4,889,885 and in WO92 / 02582.

In a preferred embodiment of the present invention, a layering 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; their multifunctional options. Desirable additives include: long chain tertiary amines such as N, N-dimethyloctadecylamine, N, N-dioctadecylmethylamine, dihydrotallowalkylmethylamine and the like. and amino terminated polytetrahydrofuran; long chain compounds of thiols and thiosulfates, such as sodium hexamethylene thiosulfate. In another embodiment of the present invention, an increase in the impermeability of the interpolymer is achieved through the use of polyfunctional vulcanizing agents such as hexamethylene bis (sodium thiosulfate) and hexamethylene bis (cinnamaldehyde).

The amount of layered, intercalated, or dispersed clay included in the composition of the present invention is an amount that is sufficient to give the composition improved mechanical properties or barrier properties, such as tensile strength or permeability to air / oxygen. This amount can usually be from about 0.5% weight. up to about 15% weight. in one embodiment, or from about 1% weight. up to about 10% weight. in another embodiment, and from about 1% weight. up to about 5% weight. in yet another embodiment, regarding the polymer content of the composition. When expressed in parts per hundred parts of rubber, layered, intercalated, or dispersed clay may be present in an amount of from about 1 phr to about 30 phr in one embodiment and from about 3 phr to about 20 phr in another embodiment. In one embodiment, the layered clay is an alkylamine layered clay.

In the context of this document, the term "process oil" means both process oils derived from oil, and synthetic and active plasticizers. Technological or plasticizing oil may be present in compositions with air-barrier properties, however, the amount of such materials is limited, as they contribute to the deterioration of the ability of the composition to prevent the penetration of a fluid. Oils or plasticizers are used mainly to increase the manufacturability of the composition during the manufacturing process of the layer, for example, by mixing, calendaring, etc. Suitable typically plasticizing oils include aliphatic acid esters or hydrocarbon plasticizing oils, such as paraffinic or naphthenic oils derived from petroleum. In addition, plasticizers such as organic esters and other synthetic plasticizers can be used. It is particularly preferable to use plasticizers such as N-butylsulfonamide or other plasticizers suitable for polyamides in the dynamically vulcanized alloy composition. In another embodiment of the invention, rubber process oils such as naphthenic, aromatic, or paraffin oil diluent may be present in an amount of from about 1 phr to about 5 phr. Alternatively, the dynamically vulcanized fluid penetration preventing composition of the present invention may contain an active emollient or plasticizer. Typically, the basis of such materials is maleated ethylene ethyl acrylate (EEA); copolymers of maleated ethylene oxide (EO) and maleated ethylene propylene (EP) (for example, Exxelor brands sold by ExxonMobil Chemical Company); terpolymers of ethylene, an acrylic ester based on methyl, ethyl or butyl acrylate and the third monomer maleic anhydride or glycidyl methacrylate (Lotader brand from Arkema, Inc.); and other epoxidized polymers such as epoxidized natural rubber and epoxidized styrene-butadiene-styrene terpolymers (SBS). In yet another embodiment of the invention, naphthenic, aliphatic, paraffinic and other aromatic oils are essentially absent in the composition. The expression “substantially absent” means that naphthenic, aliphatic, paraffinic and other aromatic oils may be present, if any, in the composition in an amount not exceeding 2 phr.

As used herein, the term “dynamic vulcanization” means a vulcanization process in which a structural polymer and rubber are mixed with high shear at an elevated temperature in the presence of a vulcanizing agent. As a result, cross-linking and the formation of fine particles, for example, in the form of a microgel distributed in a structural polymer forming a continuous matrix, occur simultaneously in rubber; the final composition is known in the art as a “dynamically vulcanized alloy” (DVA). Dynamic vulcanization is enhanced by mixing the ingredients at a temperature equal to or higher than the vulcanization temperature of the rubber using equipment such as rollers, Banbury® mixers, continuous mixers, kneading machines or mixing extruders (e.g. twin screw extruders). A unique feature of a dynamically vulcanized composition is that although the rubber is vulcanized, the composition can be processed and reprocessed by conventional thermoplastics processing methods such as extrusion, injection molding, injection molding, etc. Waste and / or waste can also be used or recycled.

Dynamic vulcanization is carried out under such conditions as to at least partially, preferably completely vulcanize the elastomeric halogen-containing copolymer. For this, a thermoplastic structural polymer, an elastomeric copolymer and, optionally, other polymers are mixed with each other at a temperature sufficient to soften the polymer or, more often, at a temperature above the melting temperature of the polymer, if the polymer is crystalline. The vulcanizing system is preferably pre-mixed with the elastomeric component. Heating and kneading at the vulcanization temperature is usually sufficient to complete the vulcanization in about 0.5 to about 10 minutes. The vulcanization time can be reduced by increasing the vulcanization temperature. A suitable range of vulcanization temperatures generally extends from the melting point of a given polymer to about 300 ° C; for example, this temperature may correspond to a range from about the melting temperature of the polymer matrix to about 275 ° C. Preferably, the vulcanization is carried out in a temperature range exceeding the melting temperature of the matrix polymer by a value of from about 10 ° C to about 50 ° C.

It is preferable to continue mixing until the desired degree of vulcanization or crosslinking is achieved. If vulcanization continues after mixing is stopped, the composition may become unsuitable for re-processing as a thermoplastic. However, dynamic vulcanization can be carried out in stages. For example, vulcanization can be started in a twin-screw extruder, and the granules are formed from a dynamically vulcanized alloy material using an underwater granulation device, then quenching stops vulcanization before it is completed. Later, the vulcanization process can be completed under dynamic vulcanization conditions. Those skilled in the art will understand how much and type of vulcanizing agents and mixing time are required for rubber vulcanization. If it is necessary or desirable to determine the appropriate concentrations and conditions, only rubber can be vulcanized using various amounts of a vulcanizing agent, which may contain one or more vulcanizing agents and / or vulcanization accelerators, in order to determine the optimal vulcanizing system and the appropriate vulcanization conditions that should be use to achieve substantially complete vulcanization. Although it is preferred that all components are present in the mixture before the dynamic vulcanization process begins, this is not a necessary condition. For example, in one embodiment of the invention, the elastomer to be cured can be dynamically cured in the presence of a part or all of the thermoplastic structural polymer. Then this mixture can be diluted or dispersed under appropriate conditions in an additional amount of thermoplastic structural polymer. Similarly, it is not necessary to add all fillers and oils, if used, prior to the dynamic vulcanization step. Part or all of the fillers or oils may be added after vulcanization is complete. Some ingredients, such as stabilizers and processing aids, are more effective if they are introduced after vulcanization.

In an alternative embodiment of the invention, the dynamic vulcanization process is carried out in accordance with the technology and method described in document PCT / US2005 / 38824, filed October 27, 2005, “Thermoplastic Elastomer Compositions and Process for Producing Same” (“Thermoplastic elastomer composition and method thereof production ”), which is incorporated into this description by reference. Using this technology, it is possible to obtain a dynamically vulcanized composition in which the small vulcanized particles formed during dynamic vulcanization comprise more than about 60% vol. relative to the volume of the composition of the elastomer and structural polymer. Such an unusually high concentration is achieved through the use of a fractional stepwise addition of the halogenated elastomer component (s) during the dynamic vulcanization process, as described in this application.

The degree of vulcanization of vulcanized rubber can be described in terms of gel content, crosslink density, amount of extractable components, or as the state of vulcanization that could be achieved by rubber during vulcanization in the absence of a polymer. For example, for the present invention, it is preferable that the halogenated elastomer be vulcanized from about 50% to about 85% of the total vulcanization relative to the rubber in its pure form, as measured, for example, by tensile strength or during testing using measuring instrument for determining the degree of vulcanization by measuring the viscosity of the attenuation of torsional vibrations of the disk (ASTM D 2084, Standard Test Method for Determining the Properties of Rubber Vulcanized by Using Rubber measuring device for determining the degree of vulcanization by measuring the viscosity by damping the torsional vibrations of the disk).

Typically, a hydrophobic or essentially hydrophobic layer contains a thermoplastic polymer or copolymer substantially non-absorbing water. For convenience, this document is also referred to as a thermoplastic layer. Suitable or applicable materials for this layer are also described as semi-crystalline or carbon chain polymers, including mixtures of such polymers and copolymers. Due to the semi-crystalline nature, this polymer can be shaped into a film, which is preferred for the described application. The presence of a carbon chain contributes to the fact that the polymer is essentially hydrophobic. Such carbon chain polymers include polymers and copolymers known to those skilled in the art, such as polyolefins, styrene, vinyl, acrylic polymers, fluorocarbons and diene polymers. Preferred polymers should have an equilibrium water content at 100% relative humidity of less than about 0.1 g per 100 g of polymer or a molar water content per unit under the same conditions of less than about 0.1. Various polymers, but especially polyolefins, such as ethylene homopolymers and copolymers, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene and alpha olefin copolymers, are applicable in the present invention. wherein the alpha olefin contains from one to about eight carbon atoms, including but not limited to ethylene styrene, ethylene propylene, ethylene butene, ethylene hexene, ethylene octene and the like. Applicable polymers are determined by a combination of their properties, as indicated, and, additionally, by the information set forth in DW Van Krevelen's “Properties of Polymers”, 3rd ed., Elsevier (1990), pp. 569-572, included in the present description by reference (referred to as "Van Krevelen"). As indicated in this paper, polymers described as hydrophobic usually obey Henry's law over the entire range of relative pressure and absorb only a small amount of water. The various applicable polymers and copolymers include those characterized by the presence of functional groups, individually or in combination, and molar water content, illustrated and shown in table 18.11 "Van Krevelen". In other words, the suitability of polymers with different structural groups can be judged on the basis of the data in this table. In addition, polymers suitable in the context of the present invention must have flexibility that matches the operating conditions of the product into which they are included, for example, tires, hoses, etc. Such polymers have a glass transition temperature (Tg) of less than about -20 ° C, preferably less than about -30 ° C, most preferably less than about -40 ° C. When selecting suitable polymers, a combination of a preferred level of water content as described above and Tg can be used. In another embodiment, the applicable polymers are characterized by a melt index (ASTM 1238, condition E) of 0.1-200 dg / min, preferably 0.5-150 dg / min. In another embodiment, the applicable polymers are characterized by elongation at break of more than 500%, preferably more than 600%, preferably more than 650%, measured in accordance with ASTM D-882. In yet another embodiment, preferred polymers include homo- and copolymers of polyethylene with a density of 0.900-0.96 g / cm ³ , preferably

0.910-0.95 g / cm ³ measured in accordance with ASTM D-1505. In another embodiment, preferred polymers include homo- and copolymers of polyethylene with a melt strength of 2 cN or more, preferably 3-100 cN, preferably 4-50 cN, preferably 5 cN or more. Melt strength is measured using Goettfert Rheotens attached to an Instron capillary rheometer. The polymer melt is extruded through a capillary with a radius of 0.007633 cm and a geometric ratio (capillary length / capillary radius) of 33.531 at a constant plunger speed. Therefore, the polymer is affected with a constant apparent shear rate relative to the wall. Then the extruded melt is stretched by a pair of gears with a radius of 1.91 cm at a distance of (N) from the end of the capillary. The speed of rotation of these wheels in time is increased linearly, and the tensile force (F) is measured. The strength of the melt corresponds to the tensile force (SN) at the time of rupture of the thread. When measuring the melt strength, the following conditions are used: temperature 190 ° C, plunger speed 0.127 cm / s, wheel acceleration 2.4 cm / s / s, capillary radius 0.076327 cm, capillary length 2.5593 cm, cylinder radius 0.47625 cm, the radius of the wheel is 1.91 cm. The thickness of the thermoplastic, essentially hydrophobic layer, is usually from about 1 micron to about 100 microns; preferably from about 1 micron to about 50 microns; or from about 1 micron to about 40 microns; for example, from about 5 microns to about 35 microns, or about 25 microns. This layer is preferably as thin as technologically possible when the desired or desired properties of the finished tire structure are achieved. For the purposes of the present invention, suitable thermoplastic materials can be identified by the moisture vapor transmission rate (MVTR) for the thermoplastic material in question, and especially for a layered structure including such a thermoplastic material. A significant decrease in the MVTR for a structure comprising one or more layers of thermoplastic material in the composition or as one of the layers indicates the suitability of such a material. Naturally, a decrease in this indicator depends on the thickness of the thermoplastic material, and it is possible to achieve a balance between the optimization of MVTR and the preservation of other physical and dynamic properties necessary from the point of view of the reliability of the product in which such layer (s) are present, including, for example, adhesion strength with an intermediate layer, dynamic elastic modulus, thermal stability at high and low temperatures, etc. Typically, the MVTR is about 25% lower than for a structure without a similar layer; preferably about 30% lower; more preferably, about 35% lower; even more preferably, about 45% lower; for example, the MVTR may be lower by about 50% or more. In a multi-layer structure of a substantially hydrophobic thermoplastic film, the MVTR can be even lower; for example, about 50%, 60%, 70%, or even lower. A decrease in MVTR may also cover values in the range displayed by the given values as well as intermediate values; for example, 25% -70%; 25% -60%; 30% -50%; 35% -60%; 30% -65%; 33% -55%, etc. Moreover, a thermoplastic material, for example, low density polyethylene, optionally may contain other additives or fillers, preferably further reducing permeability, including, for example, carbon black, calcium carbonate, talc, clay and mixtures thereof. Adequate amounts of such additional additives are typically from about 5 phr to about 60 phr; preferably from about 10 phr to about 50 phr; however, in each case of the use of such optional materials, their concentration is limited by the amount that does not adversely affect the elongation at break of the finished mixture. In other words, the resulting modified thermoplastic material must meet technological requirements and have acceptable or adequate properties from the point of view of use in the composite structure.

Other optional additives useful in the fluid barrier layer, typically introduced in amounts of less than about 10 phr, may be selected from the group consisting of pigments, antioxidants, antiozonants, processing aids, tackifier, and so on. .P. and mixtures thereof. Such optional additives may be administered at the discretion of the blender to provide specific useful characteristics, for example, using a tackifier to enhance contact adhesion during tire assembly or using an antioxidant to improve the thermal aging characteristics of the vulcanized composition, provided that the basic properties compositions, for example, impermeability, while not unnecessarily affected.

As is known, various alternative methods can be used to form and overlay the plastic layer (s) and the adhesive layer (s) on other layers. For example, numerous suitable methods for molding plastics are described in S. Middleman, “Fundamentals of Polymer Processing”, especially Chapters 6-8 and 10, ed. McGraw-Hill, New York, 1977; Z. Tadmor and C.G. Gogos, “Principles of Polymer Processing”, John Wiley & Sons, New York, 1979, Part IV (Shaping), incorporated herein by reference. In particular, hydrophobic compositions can be shaped into a layer suitable for further use by, for example, an extruder or calender. If convenient or applicable, extrusion may include the use of equipment that allows extrusion in two or more layers, preventing the penetration of a fluid, a hydrophobic layer or a plurality of hydrophobic layers, as described herein, an adhesive layer, if used, and a rubber layer with high content of dienes, for example, the tire carcass layer. In a preferred embodiment, the hydrophobic layer for use in the tire structure has a thickness of typically about 5 mm or less; preferably about 2.5 mm or less; more preferably, from about 0.2 to about 2.0 mm; most preferably, from about 0.2 to about 1.5 mm; for example, from about 0.3 to about 0.9 mm. The thickness of the hydrophobic layer intended for use in the structure of the hose may be the same or different, depending on the purpose of the hose. For example, the specifications for an unreinforced low pressure hose may differ from the requirements for a reinforced high pressure hose and, likewise, a hose designed for liquids may differ from a hose designed for gas. Thickness adjustment is the responsibility of the product developer, engineer or chemist, and, if necessary, can be selected experimentally.

A dynamically vulcanized layer that prevents the penetration of a fluid, or a hydrophobic layer, which in the product will come into contact with the inner surface of the tire carcass layer or with the inner surface of the tubular structure of the hose, must have sufficient adhesion to avoid delamination or destruction of the bond between the layers. The same is true for a hydrophobic layer deposited on a layer that prevents the penetration of a fluid, or intended to be in contact with it. Whereas a dynamically vulcanized fluid barrier layer composition may typically have sufficient bond strength with the carcass layer or the inner surface of the hose, the hydrophobic layer (s) is less likely to have sufficient adhesion to the layers with which it is in contact. Thus, it is useful, although not necessary, but as an alternative it is preferable to use a layer or composition that improves adhesion between the components. Such an optional layer or composition, referred to as an adhesive layer, in a pneumatic tire, for example, is usually located between the sealing layer, with or without a hydrophobic layer, and the inner surface of the carcass layer. One or more adhesive layers may be used to further enhance adhesion between the various layers, as described herein. The adhesive layer, if present on the inner surface of the tire carcass or the inner surface of the tubular structure of the hose, typically has a thickness of from about 1 micron to about 100 microns; preferably from about 5 microns to about 50 microns; or from about 10 microns to about 40 microns; for example, from about 20 microns to about 35 microns, or about 25 microns. If an adhesive layer is used between the layer preventing the penetration of the fluid and the hydrophobic layer closest to the fluid, its thickness may be the same as described above, or, alternatively, slightly less; typically from about 0.5 microns to about 15 microns; alternatively, from about 0.5 microns to about 5 microns. The adhesive layer is easily formed by coextrusion with a sealing layer so that these two layers can then be brought into contact with the frame layer; if two adhesive layers are used, both of these layers can be coextruded with a sealing layer. Alternatively, the adhesive layer can be prepared independently, stored between the release sheets and used as necessary, or it can be in the form of a liquid composition that is sprayed or applied with a brush to the appropriate surface (s), when necessary; these techniques can be used in combination. The adhesive layer contains at least one polymer, copolymer, chemically modified polymers or copolymers and mixtures thereof, as well as other additives commonly introduced into adhesive compositions. Typical components of the adhesive compositions include one or more tackifiers, vulcanizing agents, an elastomeric component capable of simultaneously curing with diene rubbers, an elastomeric component capable of curing with nylon or other thermoplastic matrix material used in the sealant composition, and other components well known to those skilled in the art of rubber composition, especially for tires. Particularly well-suited polymers include styrene-butadiene-styrene (SBS) copolymers and epoxidized SBS, for example, Daicel Chemical's Epofriend line of copolymers. Alternatively, the adhesive composition contains a copolymer of maleated ethylene, polymers of epoxidized ethylene, such as terpolymers of ethylene, an acrylic ester based on methyl, ethyl or butyl acrylate and a third monomer, such as maleic anhydride or glycidyl methacrylate (Lotader from Arkema, Inc. ; polymers of this type are particularly applicable between a hydrophobic layer containing a homopolymer or copolymer of ethylene, such as LDPE, and a dynamically vulcanized layer that prevents the penetration of a fluid containing eylon since epoxidized ethylene polymer comprises terpolymer comprising maleic anhydride or epoxy groups and ethylene groups). Such a polymer is used in the adhesive layer between homopolymers or copolymers of ethylene, such as polyethylene, and polar polymers, such as nylon and polyester. Ethylene-based ionomers (such as ethylene acrylic acid and various metal counterions), ethylene acrylate copolymers and ethylene vinyl acetate copolymers are also useful. Applicable adhesive compositions can be prepared as described, for example, in international publication WO 96/34736 or US patent No. 6402867, included in their entirety in the present description.

The compositions of the present invention and layered structures made using such compositions can be used in tires; vulcanized tire chambers; air duct sleeves, such as shock absorbers with a pneumatic chamber, diaphragms; in hoses, including hoses for transporting gases and liquids. These compositions, the hydrophobic layer (s) containing such compositions, and structures are particularly suitable for pneumatic tires, where they prevent the penetration of water vapor, increase the ability of the entire structure of the sealing layer of the tire to retain air and increase the stability of the final multilayer structure of the tire. Particularly applicable is such a structure in which a layer of a hydrophobic film is connected to the tire sealing layer, and this hydrophobic layer forms the deepest inner surface of the tire, and the back surface of the sealing layer is in contact with and firmly adhered to the tire carcass inner surface. Alternatively, if a second hydrophobic layer is used on the back surface of the sealing layer, an adhesive layer can be placed between this second hydrophobic layer and the inner tire carcass layer to further enhance the adhesion of these two dissimilar components. It is well known that the carcass ply typically contains a reinforcing tire cord. As described in detail above, the sealing layer has advantageously low permeability and preferably contains a dynamically vulcanized composition, which includes a structural polymer, especially polyamide, and a halogenated isobutylene-p-methylstyrene copolymer. In addition, due to the unique physical properties of the hydrophobic layer, it can be very thin, so the structure of the tire as a whole (as well as other structures that include the air or liquid retaining layer and the hydrophobic layer) is lighter. Such weight reduction, especially for a tire or hose structure of considerable length, can be significant.

Creating a tire is a complex, multi-stage process that involves several different components or layers. Typically, a sealing layer or “mixture” is prepared by calendering the rubber composition for the sealing layer, as described above, to form sheets from about 0.5 mm to about 2 mm thick and cutting these sheets into strips of the desired width and length in accordance with the parameters of the sealing layer of a specific size or type of tire. After that, the sealing layer is ready for use as an element of the structure of the pneumatic tire. A pneumatic tire is a multilayer structure that includes an outer surface including a tread and sidewall of a tire, an intermediate carcass layer formed by several layers containing reinforcing fibers (e.g., viscose, polyester, nylon or metal fibers) included in the rubber matrix and sealing a layer deposited on the inner surface of the frame layer. Typically, tires are made on a forming drum using the layers described above. When the unvulcanized tire is ready, it is removed from the drum and placed in a heated mold. In the form there is a pneumatic diaphragm located in the inner circumference of an unvulcanized tire. The mold is closed, after which the diaphragm is inflated, which gives the tire a shape, pressing it to the inner surfaces of the closed mold at the initial stages of the vulcanization process. As a result of heating the diaphragm and shape, the tire temperature rises to the vulcanization temperature. The vulcanization temperature is usually from about 100 ° C to about 250 ° C; preferably from about 150 ° C. to about 200 ° C. The vulcanization time can vary from about one minute to several hours; preferably from about 5 to 30 minutes. The time and temperature of vulcanization depend on many variables well known to those skilled in the art, including the composition of the tire components, including the vulcanizing system of each layer, the overall size and thickness of the tire, etc. Vulcanization parameters can be determined using various well-known laboratory test methods, including the test method described in ASTM D 2084 (Standard Test Method for Rubber-Determined Vulcanization Properties Using a Measuring Instrument to Determine Vulcanization Degree by Measuring Viscosity by Attenuation of Torsional Disk Vibration), and also tensile-compression test, adhesion test, bend test, etc. The result of vulcanization of the tire assembly is complete or substantially complete vulcanization or crosslinking of all elements or layers of the tire, i.e., the sealing layer, carcass layer, as well as the tread and sidewall of the tire. In addition to giving each layer and structure as a whole the required strength parameters, vulcanization improves the adhesion of the elements, as a result of which many individual layers are converted into a vulcanized, solid tire.

FIG. 1 is a partial cross-sectional view of a tire along a meridian, showing a typical example of the location of an air-tight or sealant layer and a substantially hydrophobic layer in a pneumatic tire. In FIG. The tread part 1 is indicated by the number 1, the carcass layer by the number 2, the sidewall of the tire by the number 4. On the inner surface of the tire, inside the carcass layer 2 there is a sealing layer 3. On the deepest inner surface of the sealing layer is a substantially hydrophobic thermoplastic layer 5 of the present invention . FIG. 1a illustrates the same structure as FIG. 1, except that between the layer 3, the sealing, and the layer 2, the frame, is an adhesive layer 6.

FIG. 2 is a similar partial cross section of the tire along the meridian, showing a typical example of the location in the pneumatic tire of an air barrier or a sealing layer, further illustrating an alternative embodiment of the present invention. In FIG. 2, the tread 1, the carcass ply 2 and the sidewall 4 correspond to those shown in FIG. 1. Again, on the inner surface of the tire, inside the carcass ply 2 there is a sealing layer 3. On the deepest inner surface of the sealing layer, as well as on the back surface of the sealing layer, are essentially hydrophobic thermoplastic layers 5 and 5 ′ of the present invention. FIG. 2a illustrates the introduction of an optional adhesive layer 6 between layer 5 and layer 3, as well as an optional adhesive layer 6 'between layer 5' and layer 2 (frame). As shown in FIG. 2b, illustrating another alternative embodiment of the invention, the adhesive layer 6 is located between the layer 5 and the layer 3, the adhesive layer 7 is located between the layer 5 'and the layer 3, the adhesive layer 8 is located between the layer 5' and the layer 2. In other words, the adhesive layer is present on both surfaces of the essentially hydrophobic layer 5 ', therefore, it is firmly adhered to both surfaces with which it contacts, that is, to the sealing layer 3 and the carcass layer 2.

In the present description and claims, including the described embodiments of the invention, the singular (as referred to in the English version with the articles “a”, “an”, “the”) mean plural interpretation, unless otherwise clearly defined by context. For example, the reference to “thermoplastic polymer intended for use in the hydrophobic layer” includes a separate thermoplastic, as well as two or more different thermoplastics in combination or mixture, and the like.

In the present description and the claims, the term “about”, used to define a variable, parameter or condition or in connection with them, implies that these disclosed numbers, ranges, parameters and conditions are not strictly defined, and that the implementation of the present invention by specialists in this area using temperatures, concentrations, quantities, contents, number of carbon atoms, such parameters as purity, particle size, surface area, bulk density, etc., that go beyond the range zones or differing from a single value, leads to the desired result, namely, a multilayer structure including a hydrophobic layer, which multilayer structure is suitable for use in industrial products suitable for holding fluid, including, for example, pneumatic tires, hoses and etc.

The following examples are specific illustrations of embodiments of the invention described herein. However, it should be understood that the present invention is not limited to the particular details set forth in the examples. All proportions and percentages in these examples, as well as in the description, are given by weight, unless otherwise indicated. Any numerical range given in the description or claims that reflects a specific set of properties, units of measure, conditions, physical condition or percentage, implies the literal unambiguous inclusion in it by reference or otherwise of any number belonging to such a range, including any subset of numbers in any range specified in this way. For example, whenever a numerical range with a lower limit, R _L , and an upper limit, R _U , is disclosed, any number R belonging to this range is specifically indicated. In particular, the following R values in this range are specifically indicated: R = R _L + k (R _U - R _L ), where k is a variable from 1% to 100% in increments of 1%, for example, k means 1%, 2 %, 3%, 4%, 5%, ... 50%, 51%, 52%, ... 95%, 96%, 97%, 98%, 99% or 100%. In addition, any numerical range specified by any two values of R, as expected above, is also specifically indicated.

Various aspects or embodiments of the present invention are set forth in the following numbered paragraphs.

1. A layered structure comprising at least three layers, one of which is

1) a layer that prevents the penetration of a fluid having upper and lower surfaces;

2) at least one thermoplastic layer forming a layered structure with a lower surface of the layer preventing the penetration of a fluid, where the specified thermoplastic layer contains a film-forming semi-crystalline polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C;

3) a layer comprising at least one rubber with a high content of diene;

where the specified preventing the penetration of the fluid layer contains a polymer composition characterized by a coefficient of breathability of 25x10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) or less and Young's modulus from 1 to 500 MPa, where the specified polymer composition contains:

(A) at least 10% weight. relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a coefficient of breathability of 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) or less and Young's modulus of more than 500 MPa, where the polymer component is a structural polymer and / or selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers and imides, and

(B) at least 10% weight. relative to the total weight of the polymer composition of at least one elastomeric component with a coefficient of breathability of more than 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) and Young's modulus of not more than 500 MPa, where the elastomeric component is selected from the group consisting of diene rubber and its hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers,

wherein the total amount (A) + (B) of component (A) and component (B) is at least 30% by weight. relative to the total weight of the polymer composition, where the elastomeric component (B) in the vulcanized state is dispersed as a discrete phase in the matrix of the thermoplastic polymer component (A) of the polymer composition.

2. The structure according to claim 1, wherein said thermoplastic polymer has an equilibrium water content at 100% relative humidity of less than about 0.1 g per 100 g of polymer or a molar water content per polymer unit under the same conditions of less than about 0, one.

3. The structure according to claim 1 or 2, further comprising a second thermoplastic layer, where the thermoplastic of said second thermoplastic layer is identical to or different from said first thermoplastic layer, and where said second thermoplastic layer forms a layered structure with another of said upper and tender surfaces of said layer preventing the penetration of fluid.

4. The structure according to claim 1, 2 or 3, in which: (1) when the specified structure includes one thermoplastic layer, the specified surface of the specified layer, preventing the penetration of a fluid that is not in contact with the specified thermoplastic layer, further comprises an adhesive composition; and (2) when the specified structure includes two thermoplastic layers with their own surfaces, the surface of one of these thermoplastic layers, not in contact with the specified layer, preventing the penetration of the fluid, is in contact with or additionally contains an adhesive composition or adhesive layer.

5. The structure according to claim 4, in which the specified adhesive composition provides such adhesion to the base, which is sufficient to ensure proper functioning of the combination of the specified structure and the specified basis.

6. The structure according to claim 5, in which the specified effective adhesion is achieved due to the vulcanization of the adhesive composition.

7. The structure according to claim 4 or 5, in which the specified adhesive composition contains an epoxidized block copolymer of styrene-butadiene-styrene.

8. The structure according to any one of claims 1 to 7, in which said thermoplastic layer contains a polymer selected from the group consisting of homopolymers and copolymers of polyolefins, styrene, vinyl, acrylic polymers, fluorocarbons, diene polymers and mixtures thereof.

9. The structure according to any one of claims 1 to 8, wherein said at least one filler is selected from the group consisting of carbon black, clay, layered clay, calcium carbonate, mica, silicon oxide, silicates, talc, dioxide titanium, wood flour and mixtures thereof.

10. The structure of claim 9, wherein said at least one filler is selected from the group consisting of carbon black, layered clay, and mixtures thereof.

11. The structure according to any one of claims 1 to 10, wherein said at least one vulcanizing system comprises at least one vulcanizing agent and at least one vulcanization accelerator.

12. The structure according to any one of claims 1 to 11, wherein said fluid penetration preventing layer further comprises an additive selected from the group consisting of pigments, plasticizers, active softeners, antioxidants, antiozonants, processing aids, tackifiers and mixtures thereof.

13. The structure according to any one of claims 1 to 12, suitable for use in tires, in which the specified layer containing at least one structural polymer, is a sealing layer, and the specified layer containing the specified rubber with a high content of dienes is a skeleton layer or a side layer, or both.

14. The structure according to any one of claims 1 to 13, in which the thermoplastic polymer component is selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers, imides and mixtures thereof.

15. The structure according to claims 1 to 13, in which the thermoplastic polymer component is a structural polymer selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, copolymer nylon 6/66, copolymer of nylon 6/66/610, nylon MXD6, nylon 6T, copolymer of nylon 6 / 6T, copolymer of nylon 66 / PPS, copolymer of nylon 66 / PPS, polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, copolymer of polyethylene terephthalate / polyethylene isofth polybutylene naphthalate complex fluid ristallicheskogo polyester copolymer polioksialkilendiimidat / polibutirattereftalat, polyacrylonitrile, polymethacrylonitrile, acrylonitrile / styrene copolymer, methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene, polymethylmethacrylate, polyethylmethacrylate, ethylene vinyl acetate, polyvinyl alcohol copolymer, vinyl alcohol / ethylene copolymer, polyvinylidene chloride, polyvinyl chloride copolymer, vinyl chloride / vinylidene chloride, vinylidene chloride / methyl acrylate copolymer, cellulose acetate, cellulose butyrate acetate, livinylidene fluoride, polyvinyl fluoride, polychlorofluoroethylene, tetrafluoroethylene / ethylene copolymer, aromatic polyimides and mixtures thereof.

16. The structure according to any one of claims 1 to 15, wherein said at least one elastomeric component (B) is selected from the group consisting of natural rubber, synthetic polyisoprene rubber, epoxylated natural rubber, styrene-butadiene rubber ( SBR), polybutadiene rubber (BR), nitrile butadiene rubber (NBR), hydrogenated NBR, hydrogenated SBR; ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), maleic acid modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene and aromatic vinyl copolymers or diene brominated monomers IIR, chlorinated copolymer IIR, chlorinated copolymer IIR methyl styrene, chloroprene rubber, epichlorohydrin homopolymers, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymers, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymers, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone, polysulfide rubber, vinylidene fluoride rubbers, elastomer rubber based tetrafluoroethylene propylene rubber, elastomer rubber, tetrafluoroethylene propylene rubber, elastomer rubber, , polyester-based elastomers, urea and elastomer-based elastomers Stomer based on polyamide.

17. The structure according to any one of claims 1 to 16, wherein said at least one elastomeric component (B) is selected from the group consisting of a C ₄ -C ₇ isomonoolefin halide copolymer and p-alkyl styrene, a brominated isobutylene copolymer p-methyl styrene, hydrogenated nitrile butadiene rubber, acrylonitrile butadiene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, chlorinated butyl rubber and brominated butyl rubber.

18. The structure according to any one of claims 1 to 17, in which the specified elastomeric component of the specified layer, preventing the penetration of a fluid, is essentially completely vulcanized.

19. The structure of claim 8, wherein said thermoplastic is selected from the group consisting of ethylene homopolymers, ethylene copolymers, low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene-styrene copolymer, ethylene-propylene copolymer, ethylene- copolymer butene, ethylene-hexene copolymer, ethylene-octene copolymer and mixtures thereof.

20. The structure according to any one of claims 2-19, wherein said thermoplastic polymer has a glass transition temperature, Tg, of less than about -20 ° C.

21. The structure according to any one of claims 1 to 20, further comprising an adhesive layer or adhesive composition between the specified thermoplastic layer and the specified layer, preventing the penetration of the fluid.

22. A product including:

(A) a first layer containing an elastomer;

(B) a second layer containing a dynamically vulcanized alloy of a structural polymer and a copolymer of isoolefin and p-alkylstyrene, where the second layer has the property of preventing the penetration of a fluid;

(C) a substantially hydrophobic thermoplastic layer having upper and lower surfaces and comprising a film-forming semi-crystalline, essentially hydrophobic carbon chain polymer, characterized by a glass transition temperature, Tg, of less than about -20 ° C;

wherein said upper or said lower surface of said second layer is adjacent to said first layer, and the other of said upper or lower surfaces of said thermoplastic layer is adjacent to the fluid.

23. The product of claim 22, wherein said structural polymer is selected from the group consisting of polyamides, polyesters, polynitriles, poly (meth) acrylates, polyvinyls, cellulose, fluoropolymers, imides, and mixtures thereof.

24. The article of claim 22 or 23, wherein said first layer elastomer is selected from the group consisting of at least one halogenated elastomer and at least one high diene rubber.

25. The product according to paragraph 24, wherein said first layer elastomer is selected from the group consisting of a halogen-containing random copolymer of isomonoolefin C ₄ -C ₇ and p-alkyl styrene, where p-alkyl styrene is from about 0.5% weight. up to about 20% weight. the specified copolymer, a halogen-containing random copolymer of isomonoolefin C ₄ -C ₁₂ and multiolefin C ₄ -C ₁₄ , where the halogen is selected from the group consisting of chlorine, bromine and mixtures thereof; natural or synthetic rubber containing at least 50 mol%. diene monomer and selected from the group consisting of polyisoprene, polybutadiene, poly (styrene-co-butadiene), block copolymer of poly (styrene-butadiene-styrene), natural rubber and mixtures thereof.

26. The product according to item 23, wherein said structural polymer is selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, nylon 6 / copolymer 66/610, nylon MXD6, nylon 6T, copolymer of nylon 6 / 6T, copolymer of nylon 66 / PP, copolymer of nylon 66 / PPS, polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, copolymer of polyethylene terephthalate / polyethylene isophthalate, polyacrylate polyethylene polyethylene iimiddikislota / polibutirattereftalat, polyacrylonitrile, polymethacrylonitrile, acrylonitrile / styrene copolymer, methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene, polymethylmethacrylate, polyethylmethacrylate, ethylene vinyl acetate, polyvinyl alcohol copolymer, vinyl alcohol / ethylene copolymer, polyvinylidene chloride, polyvinyl chloride copolymer, polyvinyl / polyvinylidene, vinylidene chloride / methyl acrylate copolymer, cellulose acetate, cellulose butyrate acetate, polyvinylidene fluoride, polyvinyl fluoride, polychlorofluoride ethylene, tetrafluoroethylene / ethylene copolymer, aromatic polyimides and mixtures thereof.

27. The product according to any one of paragraphs.22-26, wherein said thermoplastic polymer has an equilibrium water content at 100% relative humidity of less than about 0.1 g per 100 g of polymer or a molar water content of less than about, 0.1.

28. The product according to any one of paragraphs.22-27, wherein said thermoplastic layer contains a polymer selected from the group consisting of homopolymers and copolymers of polyolefins, ethylene homopolymers, copolymers of ethylene, styrene, vinyl, acrylic polymers, fluorocarbons, diene polymers and mixtures thereof.

29. The product according to p, in which the specified thermoplastic layer contains low density polyethylene.

30. The product according to any one of paragraphs.22-29, further comprising an adhesive composition or an adhesive layer located between the specified essentially hydrophobic thermoplastic layer and the specified layer, preventing the penetration of the fluid.

31. The product of claim 30, wherein said adhesive composition or adhesive layer comprises at least one polymer or copolymer selected from the group consisting of copolymers of maleated ethylene, copolymers of epoxidized ethylene, ethylene ionomers, ethylene acrylate copolymers, ethylene vinyl acetate copolymers and their mixtures.

32. The product according to item 30, in which the thickness of the specified adhesive layer or adhesive composition is from about 1 micron to about 15 microns.

33. The product according to any one of paragraphs.22-32, further comprising a second, essentially hydrophobic thermoplastic layer between the specified layer that prevents the penetration of a fluid, and the specified first layer containing an elastomer.

34. The product according to p. 33, further comprising an adhesive composition or adhesive layer located between the specified essentially hydrophobic thermoplastic layer and the specified first layer containing an elastomer.

35. The product according to any one of paragraphs.22-34, having essentially a hose shape.

36. A pneumatic tire including an inner air chamber, a portion of the outer tread and sidewalls, an inner carcass portion having an upper surface adhered to or glued to the indicated portion of the outer tread and sidewalls, and a lower surface, a laminate sealing layer having an upper surface and a lower surface, where the upper surface of the specified sealing layer is bonded or glued to the lower surface of the specified frame layer, and the lower surface of the specified sealing layer is itself a deep inner surface in contact with air located in said air chamber, where the sealing layer contains a structural polymer and at least one thermoplastic layer forming a layered structure with at least said lower surface of the sealing layer, where the thermoplastic layer contains a film-forming a semi-crystalline, essentially hydrophobic carbon chain polymer, characterized by a glass transition temperature, Tg, of less than about -20 ° C.

37. The pneumatic tire according to claim 36, wherein said sealing layer comprises a dynamically vulcanized alloy of a structural polymer and a halogen-containing random elastomeric copolymer of isomonoolefin C ₄ -C ₇ and p-alkyl styrene, where p-alkyl styrene is from about 0.5% weight . up to about 20% weight. the specified copolymer, where the specified elastomeric copolymer in a vulcanized state is dispersed as a discrete phase in the matrix of the specified structural polymer.

38. The pneumatic tire according to claim 36, wherein said sealing layer comprises a dynamically vulcanized alloy of a structural polymer and a halogen-containing statistical elastomeric copolymer of isomonoolefin C ₄ -C ₁₂ and multiolefin C ₄ -C ₁₄ , where the specified elastomeric copolymer in the vulcanized state is dispersed in the form of a discrete phase in the matrix of the specified structural polymer.

39. The pneumatic tire according to clause 37, where the tire is vulcanized.

40. A method of obtaining a pneumatic tire, comprising a carcass element containing rubber with a high content of dienes, and a sealing layer, which is the deepest inner layer of the specified tire, where the method includes the following steps:

(A) providing a sealing layer comprising a substantially vulcanized halogenated isomonoolefin-containing elastomer dispersed in particulate form in a structural polymer, wherein the sealing layer has upper and lower surfaces;

(B) providing a first thermoplastic layer forming a layered structure with at least a specified lower surface of said sealing layer, where the thermoplastic layer comprises a film-forming semi-crystalline, essentially hydrophobic carbon chain polymer having a glass transition temperature, Tg, of less than about -20ºС;

(C) bringing into contact the upper surface of the specified sealing layer with the specified frame element with the formation of an additional layered structure;

(D) heating and molding the specified layered structure under pressure to obtain the desired tire shape at a temperature of from about 100 ° C to about 250 ° C for a period of time that is sufficient for substantially complete vulcanization of the specified structure.

41. The method according to clause 40, further comprising using a second thermoplastic layer forming a layered structure with a specified upper surface of the specified sealing layer, where the second thermoplastic layer contains a film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less approximately -20ºС; where said first thermoplastic layer, said second thermoplastic layer or both of these layers are in contact with an adhesive composition or an adhesive layer located between said thermoplastic layer and said layer preventing the penetration of a fluid between said thermoplastic layer and said frame or both.

42. The method according to paragraph 41, wherein said adhesive layer contains an epoxidized block copolymer of styrene.

43. The tire according to clause 36, selected from the group consisting of a tire suitable for use on cars, trucks, construction vehicles, recreational vehicles and agricultural vehicles.

44. Pneumatic tire, including the outer tread layer, the intermediate layers of the sidewall and the carcass and the deepest inner layer, preventing the penetration of air:

(i) the layer preventing the penetration of air has upper and lower surfaces, where the layer contains a polymer composition characterized by a coefficient of breathability of 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) or less and Young's modulus of 1 MPa to about 500 MPa, where the specified polymer composition contains:

(A) at least 10% weight. relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a coefficient of breathability of approximately 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) or less and Young's modulus of more than 500 MPa, where the polymer component selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers and imides, and

C) at least 10% weight. relative to the total weight of the polymer composition of at least one elastomeric component with an air permeability coefficient of more than about 25 × 10 ^-12 cm ³ · cm / cm ² · sec cmHg (at 30 ° C) and Young's modulus not more than 500 MPa, where the elastomeric component is selected from the group consisting of diene rubbers and their hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, with the total amount of (A) + (B) component (A) ) and comp ponent (B) is at least about 30% by weight. relative to the total weight of the specified polymer composition, where the elastomeric component (B) in the vulcanized state is dispersed as a discrete phase in the matrix of the thermoplastic polymer component (A) of the specified polymer composition.

(ii) at least one thermoplastic layer forming a layered structure with at least a specified lower surface of the specified layer preventing the penetration of air, where the thermoplastic layer contains a film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C.

45. The pneumatic tire according to item 44, further comprising an adhesive composition or adhesive layer located between the specified thermoplastic layer and the specified layer, preventing the penetration of the fluid.

46. The pneumatic tire according to claims 44 or 45, further comprising a second thermoplastic layer forming a layered structure with a specified upper surface of the specified sealing layer, where the thermoplastic layer contains a film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C; and further comprising an adhesive layer located between the thermoplastic layer forming a layered structure with the upper surface of the specified sealing layer, and the specified frame layer.

47. The pneumatic tire according to claim 46, wherein said adhesive layer comprises an epoxidized styrene block copolymer.

48. The pneumatic tire according to claim 44, wherein said component (i) (A) is at least one polyamide and said component (i) (B) is at least one bromine-containing random elastomeric copolymer C ₄ -C ₇ isomonoolefin; and p-alkylstyrene.

49. The pneumatic tire according to claim 45, wherein said adhesive layer comprises at least one polymer selected from the group consisting of ethylene terpolymers and acrylic ester terpolymers containing at least one methyl acrylate, ethyl acrylate or butyl acrylate; and at least one maleic anhydride or glycidyl methacrylate.

50. A vulcanizable layered structure comprising at least two layers containing an elastomer and at least one layer of a thermoplastic film, the first of these two layers containing an elastomer is characterized as a layer that prevents the penetration of a fluid, the second of these, according to at least two layers containing elastomer includes at least one rubber with a high content of diene; the specified layer of thermoplastic film contains at least one thermoplastic film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C;

wherein said layers are arranged in an order selected from the following: (1) said at least one thermoplastic film layer, said fluid barrier layer, and said layer comprising high diene rubber; or (2) said fluid barrier layer, said layer comprising high diene rubber, and said at least one layer of thermoplastic film; and said fluid barrier layer comprises a composition having a Young's modulus of from about 1 MPa to about 500 MPa, where the composition includes:

(A) at least 10% weight. relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a Young's modulus of more than 500 MPa, where the polymer component is selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers and imides, and

(B) at least 10% weight. relative to the total weight of the polymer composition of at least one elastomeric component with a Young's modulus of not more than 500 MPa, where the elastomeric component is selected from the group consisting of diene rubbers and their hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, while the total amount (A) + (B) of component (A) and component (B) is at least 30% by weight. relative to the total weight of the polymer composition, where the specified elastomeric component (B) in a substantially vulcanized state is dispersed as a discrete phase in the matrix of the thermoplastic polymer component (A) of the polymer composition.

51. The structure according to item 50, in which these layers are arranged in order (1), further comprising a second thermoplastic layer located between the specified layer that prevents the penetration of the fluid, and the specified layer comprising rubber with a high content of diene, where the second thermoplastic layer contains a film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C.

52. The structure according to § 51, further comprising at least one adhesive layer located between (1) the specified layer of the thermoplastic film and the specified layer preventing the penetration of the fluid, (2) between the specified second layer of the thermoplastic film and the specified layer, including rubber with a high content of diene, or between and (1) and (2).

53. The structure of claim 50, 51, or 52, further comprising an additive selected from the group consisting of pigments, antioxidants, antiozonants, processing aids, tackifiers, and mixtures thereof.

54. A structure according to any one of claims 50-53, suitable for use in tires, wherein said layer containing at least one structural polymer is a sealing layer, and said layer comprising said high diene rubber is a skeleton layer or a side layer, or both.

55. The structure according to any one of claims 50-54, wherein said structural polymer is selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers, imides and mixtures thereof.

56. The structure according to any one of pp 50-54, wherein said structural polymer is selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6 / copolymer 66, copolymer of nylon 6/66/610, nylon MXD6, nylon 6T, copolymer of nylon 6 / 6T, copolymer of nylon 66 / PPS, copolymer of nylon 66 / PPS, polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene terephthalate / polyethylene isophthalate copolymer, polyethylene isophthalate, polyethylene liquid polyester copolymer according lioksialkilendiimidat / polibutirattereftalat, polyacrylonitrile, polymethacrylonitrile, acrylonitrile / styrene copolymer, methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene, polymethylmethacrylate, polyethylmethacrylate, ethylene vinyl acetate, polyvinyl alcohol copolymer, vinyl alcohol / ethylene copolymer, polyvinylidene chloride, polyvinyl chloride copolymer, vinyl chloride / vinylidene chloride, vinylidene chloride / methyl acrylate copolymer, cellulose acetate, cellulose acetate butyrate, polyvinylidene fluoride, polyvinyl fluoride, lichlorofluoroethylene, tetrafluoroethylene / ethylene copolymer, aromatic polyimides and mixtures thereof.

57. The structure according to any one of claims 50 to 56, wherein said at least one elastomeric component (B) is selected from the group consisting of natural rubber, synthetic polyisoprene rubber, epoxylated natural rubber, styrene-butadiene rubber ( SBR), polybutadiene rubber (BR), nitrile butadiene rubber (NBR), hydrogenated NBR, hydrogenated SBR; ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), maleic acid-modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene-aromatic vinyl copolymers or diene brominated with IIR, chlorinated bromide, IIR, bromo, bromo, and chloroprene rubber, epichlorohydrin homopolymers, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymers, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymers, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene propylene rubber, fluorinated elastomer rubber-based elastomer rubber polyester based, urea-based elastomers and base elastomers ve polyamide.

58. The structure according to any one of claims 50-57, wherein said at least one elastomeric component (B) is selected from the group consisting of a copolymer of a C ₄ -C ₇ isomonoolefin halide and p-alkyl styrene, a brominated isobutylene copolymer p-methyl styrene, hydrogenated nitrile butadiene rubber, acrylonitrile butadiene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, chlorinated butyl rubber and brominated butyl rubber.

59. The structure according to any one of p. 50-58, in which the specified elastomeric component of the specified layer, preventing the penetration of a fluid, is essentially completely vulcanized.

60. The vulcanized structure according to any one of paragraphs.50-59.

61. An article comprising a vulcanizable structure according to any one of claims 50-60.

62. The product according to item 61, selected from the group consisting of hoses and components of pneumatic tires.

63. Pneumatic tire, including the outer tread layer, the intermediate layers of the sidewall and the carcass and the deepest inner layer, preventing the penetration of air:

(i) the specified layer preventing the penetration of air, has upper and lower surfaces, where the layer contains a polymer composition characterized by a coefficient of breathability of approximately 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) or less and the module Jung from about 1 MPa to about 500 MPa, where the specified polymer composition contains:

(A) at least 10% weight. relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a coefficient of breathability of approximately 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) or less and Young's modulus of more than 500 MPa, where the polymer component selected from the group consisting of polyamide, polyester, polynitrile, polymethacrylate, polyvinyl, cellulose, fluoropolymer and imide, and

(B) at least 10% weight. relative to the total weight of the polymer composition of at least one elastomeric component with a coefficient of breathability of more than about 25 × 10 ^-12 cm ³ · cm / cm ² sec cmHg (at 30 ° C) and Young's modulus of not more than 500 MPa, where elastomeric the component is selected from the group consisting of diene rubber and its hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, with the total amount of (A) + (B) component (A) and comp ponent (B) is at least about 30% by weight. relative to the total weight of the specified polymer composition, where the elastomeric component (B) in the vulcanized state is dispersed as a discrete phase in the matrix of the thermoplastic polymer component (A) of the specified polymer composition; and

(ii) at least one thermoplastic layer forming a layered structure with at least a specified lower surface of the specified layer preventing the penetration of air, where the thermoplastic layer contains a film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C.

EXAMPLES

Compositions were prepared in accordance with the following examples. The amount of each component used is expressed in parts per hundred parts of rubber (phr) present in the composition. The following commercially available products were used as components of the compositions of these examples:

Fluid Prevention Polymer Components Description N11 (Nylon 11) Rilsan BMN O (Atochem) N6 / 66 (copolymer nylon 6/66) Ube 5033B (Ube) P1 Plasticizer, BM4, N-butylsulfonamide (Daihachi Chemical Ind.) R1 Active emollient, AR201, maleated copolymer of ethylene / ethyl acrylate (EEA) (Mitsui-Dupont) Tg = -35ºС S1 Stabilizer kit includes Irganox, Tinuvin, Copper Iodide (CuI) Rubber component Description Bims Brominated isobutylene / p-methylstyrene copolymer, 0.75% Br, 5% PMS, (ExxonMobil Chemical) Vulcanizing system components Function Description Zno Zinc oxide is a component of the vulcanizing system St-acid Stearic acid is a component of the vulcanizing system Znst Zinc stearate - component of the vulcanizing system Hydrophobic Thermoplastic Components Function Description PE-1 Low Density Polyethylene (LDPE), LD-150BW (0.75 MI, density 0.923, elastic modulus 240 MPa, ExxonMobil Chemical) PE-2 Low Density Polyethylene (LDPE), Novatec LD LJ603 (7MFR, Density 0.917, Japan Polyethylene Corp.)

In accordance with the compositions or formulations shown in table 1, examples 1 and 2 were performed by dynamic vulcanization using a two-screw extruder at 220 ° C. The elastomeric component and the curing system were loaded into the mixer, mixed for about 3.5 minutes and unloaded at a temperature of about 90 ° C. The mixture was then granulated using a rubber granulator. Premixing of nylon components with plasticizer and stabilizers was performed using a Japan Steel Works, Ltd. twin-screw extruder. models (JSW-44) at 210ºС. Then, all pre-mixed nylon components, including plasticizer and stabilizer, pre-prepared rubber granules and active softener, were metered into a double-screw extruder JSW-44 at 220 ° C for extrusion mixing and dynamic vulcanization. The extrudates were cooled in a water bath, granulated and dried.

Table 1 Example (phr) one 2 Bims one hundred one hundred Zno 0.15 0.15 St-acid 0.60 0.60 Znst 0.30 0.30 N11 40,4 0 N6 / 66 27.8 66.5 P1 11.0 23,4 R1 10.1 10.0 S1 0.51 0.50 Permeability* twenty 21 M50, RT ** 4.1 6.0 EB (%), RT ** 380 400 * Permeability test: permeability to oxygen at 30 ° C, measured in accordance with JIS K7126 standard with a dimension of 10 ^-12 cm ³ · cm / cm ² · sec · cmHg
** M50 - 50% modulus of elasticity in MPa, measured at room temperature (RT) (in accordance with ASTM D412-92);
EB - elongation at break, measured at room temperature (in accordance with ASTM D412-92).

A layered A / B / A structure was made in which layer A was PE1 and layer B was the composition of Example 1. The layered structure was formed using a W&H blown coextrusion line (Windmoeller & Hoelscher Corp., Lincoln, Rhode Island, USA) with a 250 mm head and three extruders 60/90/60 mm. The line speed was about 65 kg / h for PE1 and about 70 kg / h for the composition of Example 1 with a blow ratio of 2. A / B layered structure was made using a Brampton blown coextrusion line (Brampton Engineering, Brampton, Ontario California) with a head 100 mm and two extruders 50/75 mm, layer A was PE2 and layer B was the composition of example 2. The line speed was about 0.5 kg / h for PE2 and 1 kg / h for the composition of example 2 with a degree of blowing 4. Comparative moisture permeability data for the composition of example 1 and the layered structure PE1 / example 1 / PE1 are shown in table 2, and for the composition of example 2 and the layered structure PE2 / example 2 in table 3.

table 2 Example one 3 Layered material Example 1 PE1 / example 1 / PE1 Thickness (micron) one hundred 52/106/52 MVTR * 8 2.5 * MVTR - the rate of penetration of water vapor in units g / m ² · day, measured at 38 ° C using a Permatran-W measuring device model 3/61 (Mocon, Inc., Minneapolis, Minnesota)

Table 3 Example 2 four Layered material Example 2 PE2 / example 2 Thickness (micron) 170 70/171 MVTR 16 8 E '(-40ºС) 370 280 E '(-20ºС) 294 225 E '(20ºС) 140 192 MVTR — water vapor penetration rate in units of g / m ² · day, measured at 38 ° C using a Permatran-W Model 3/61 measuring instrument (Mocon, Inc., Minneapolis, Minnesota)
E '- dynamic elastic modulus in MPa, measured using rheometric dynamic mechanical analysis (DMTA), temperature scanning at 1 Hz (TA Instruments, Inc., formerly Rheometric Scientific)

As can be seen from tables 2 and 3, during the formation of a layered structure from a polyethylene film, in these examples — LDPE, and a thermoplastic elastomeric composition, the value of the rate of penetration of water vapor for the resulting layered structure was significantly reduced. In addition, the use of a soft or flexible LDPE layer did not adversely affect the modulus of elasticity of the thermoplastic elastomer at room temperature and low temperature.

All documents described are incorporated herein by reference, including any priority documents and / or test procedures, to the extent that they do not contradict the present description. The principles, preferred embodiments and operating modes of the present invention are set forth above. Although the present invention has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and possible uses of the present invention. Therefore, it should be understood that numerous modifications of illustrative embodiments of the invention are possible, and that other options may be offered without departing from the spirit and scope of the present invention defined in the claims.

Claims (19)

1. A layered structure for use in products, comprising at least three layers, one of which is a layer that prevents the penetration of a fluid having upper and lower surfaces; at least one thermoplastic layer forming a layered structure with a lower surface of the layer preventing the penetration of a fluid, where the specified thermoplastic layer contains a film-forming semi-crystalline polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about -20 ° C; and a layer comprising at least one rubber with a high content of diene, forming a layered structure with at least the upper surface of the layer, preventing the penetration of the fluid;
where the specified preventing penetration of the fluid layer contains a polymer composition characterized by a coefficient of breathability of 25 · 10 ^-12 cm ³ · cm / cm ² · with cmHg (at 30 ° C) or less and Young's modulus from 1 to 500 MPa, where the specified layer specified The polymer composition contains:
(A) at least 10 wt.% Relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a coefficient of breathability of 25 · 10 ^-12 cm ³ · cm / cm ² · s cmHg (at 30 ° C) or less and Young's modulus of more than 500 MPa, where the polymer component is selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers and imides, and
(B) at least 10 wt.% Relative to the total weight of the polymer composition of at least one elastomeric component with a coefficient of breathability of more than 25 · 10 ^-12 cm ³ · cm / cm ² · s cmHg (at 30 ° C) and Young's modulus is not more than 500 MPa, where the elastomeric component is selected from the group consisting of diene rubber and its hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, with the total amount (A ) + (B) component (A) and component (B) is at least 30% by weight relative to the total weight of the polymer composition, where the elastomeric component (B) is dispersed in the vulcanized state as a discrete phase in the matrix of the thermoplastic polymer component (A) of the polymer composition. 2. The structure according to claim 1, wherein said thermoplastic polymer has an equilibrium water content at 100% relative humidity of less than about 0.1 g per 100 g of polymer, or a molar water content per polymer unit of less than about 0.1. 3. The structure according to claim 1, further comprising a second thermoplastic layer, where the thermoplastic of said second thermoplastic layer is identical to or different from said first thermoplastic layer, and where said second thermoplastic layer forms a layered structure with another of said upper and tender surfaces of said layer, preventing fluid penetration. 4. The structure according to claim 1, in which: (1) when the specified structure includes one thermoplastic layer, the specified surface of the specified layer, preventing the penetration of a fluid that is not in contact with the specified thermoplastic layer, further comprises an adhesive composition; and (2) when the specified structure includes two thermoplastic layers with their own surfaces, the surface of one of these thermoplastic layers, not in contact with the specified layer, preventing the penetration of the fluid, is in contact with or additionally contains an adhesive composition or adhesive layer. 5. The structure according to claim 1, wherein said thermoplastic layer contains a polymer selected from the group consisting of homopolymers and copolymers of polyolefins, styrene, vinyl, acrylic polymers, fluorocarbons, diene polymers and mixtures thereof. 6. The structure according to claim 1, suitable for use in tires, in which the specified layer containing at least one layer that prevents the penetration of the fluid is a sealing layer, and the specified layer containing the specified rubber with a high content of dienes is a frame layer or a side layer, or both. 7. The structure according to claim 1, in which the thermoplastic polymer component is selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers, imides and mixtures thereof. 8. The structure according to claim 1, wherein said at least one elastomeric component (B) is selected from the group consisting of natural rubber, synthetic polyisoprene rubber, epoxylated natural rubber, styrene-butadiene rubber (SBR), polybutadiene rubber ( BR), nitrile butadiene rubber (NBR), hydrogenated NBR, hydrogenated SBR; ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), maleic acid-modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene and aromatic vinyl copolymers or diene monomers, brominated IIR, chlorinated brominated IIR, chlorinated brominated IIR, chlorinated brominated IIR methyl styrene, chloroprene rubber, epichlorohydrin homopolymers, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymers, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymers, chlorosulfonyl polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone, polysulfide rubber, vinylidene fluoride rubbers, elastomer rubber based tetrafluoroethylene propylene rubber, elastomer rubber, tetrafluoroethylene propylene rubber, elastomer rubber, polyester-based elastomers, urea-based elastomers and polyamide based elastomers. 9. The structure of claim 5, wherein said thermoplastic is selected from the group consisting of ethylene homopolymers, ethylene copolymers, low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene-styrene copolymer, ethylene-propylene copolymer, ethylene- copolymer butene, ethylene-hexene copolymer, ethylene-octene copolymer and mixtures thereof. 10. Product including:
(A) a first layer containing an elastomer;
(B) a second layer containing a dynamically vulcanized alloy of a structural polymer and a copolymer of isoolefin and p-alkylstyrene, where the second layer has the property of preventing the penetration of a fluid;
(C) a substantially hydrophobic thermoplastic layer having upper and lower surfaces and comprising a film-forming semi-crystalline, essentially hydrophobic carbon chain polymer having a glass transition temperature, Tg, of less than about -20 ° C;
wherein said upper or said lower surface of said second layer is adjacent to said first layer, and the other of said upper or lower surfaces of said thermoplastic layer is adjacent to the fluid. 11. The product of claim 10, wherein said thermoplastic polymer has an equilibrium water content at 100% relative humidity of less than about 0.1 g per 100 g of polymer or a molar water content per polymer unit of less than about 0.1. 12. The product of claim 10, wherein said thermoplastic layer contains a polymer selected from the group consisting of homopolymers and copolymers of polyolefins, ethylene homopolymers, ethylene copolymers, styrene, vinyl, acrylic polymers, fluorocarbons, diene polymers and mixtures thereof. 13. The product of claim 10, further comprising an adhesive composition or an adhesive layer located between the specified essentially hydrophobic thermoplastic layer and the specified layer, preventing the penetration of the fluid. 14. The product of claim 13, wherein said adhesive composition or adhesive layer comprises at least one polymer or copolymer selected from the group consisting of copolymers of maleated ethylene, copolymers of epoxidized ethylene, ethylene ionomers, ethylene acrylate copolymers, ethylene vinyl acetate copolymers and their mixtures. 15. The product according to item 13, in which the thickness of the specified adhesive layer or adhesive composition is from about 1 μm to about 15 μm. 16. The product of claim 10, where the product is a hose. 17. Pneumatic tire, including the outer tread layer, the intermediate layers of the sidewall and the carcass and the deepest inner layer, preventing the penetration of air:
(i) the specified layer preventing the penetration of air has upper and lower surfaces, where the layer contains a polymer composition characterized by a coefficient of breathability of 25 · 10 ^-12 cm ³ · cm / cm ² · s cmHg (at 30 ° C) or less and the module Young's from 1 MPa to about 500 MPa, where the specified polymer composition contains:
(A) at least 10 wt.% Relative to the total weight of the polymer composition of at least one thermoplastic polymer component with a coefficient of breathability of about 25 · 10 ^-12 cm ³ · cm / cm ² · s cmHg (at 30 ° C) or less and a Young's modulus of more than 500 MPa, where the polymer component is selected from the group consisting of polyamides, polyesters, polynitriles, polymethacrylates, polyvinyls, cellulose, fluoropolymers and imides, and
(B) at least 10 wt.% With respect to the total weight of the polymer composition of at least one elastomeric component with a coefficient of breathability of more than about 25 · 10 ^-12 cm ³ · cm / cm ² · s cmHg (at 30 ° C ) and Young's modulus of not more than 500 MPa, where the elastomeric component is selected from the group consisting of diene rubbers and their hydrogenates, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluorine rubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, with the total amount (A) + (B) component (A) and component (B) is not less than about 30% by weight relative to the total weight of said polymer composition, where the elastomeric component (B) in the vulcanized state is dispersed as a discrete phase in the matrix of the thermoplastic polymer component (A) of said polymer composition,
(ii) at least one thermoplastic layer forming a layered structure with at least a specified lower surface of the specified layer preventing the penetration of air, where the thermoplastic layer contains a film-forming semi-crystalline, essentially hydrophobic polymer with a carbon chain, characterized by a glass transition temperature, Tg, less than about −20 ° C., and
where at least one of the layers of the frame or the intermediate layer of the sidewall includes at least one rubber with a high content of diene. 18. The pneumatic tire according to claim 17, further comprising an adhesive composition or an adhesive layer located between said thermoplastic layer and said layer preventing the penetration of a fluid. 19. The pneumatic tire according to claim 18, wherein said adhesive layer comprises at least one polymer selected from the group consisting of ethylene terpolymers and acrylic ester terpolymers containing at least one methyl acrylate, ethyl acrylate or butyl acrylate; and at least one maleic anhydride or glycidyl methacrylate.

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