RU2421484C2 - Substance for improving processing properties of elastomeric mixtures - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of preparing elastomeric mixtures involving bringing at least one elastomer derived from isomonoolefin C₄-C₇ into contact with a substance for improving processing parameters, which contains at least one functionalised polymer, having at least one succinic anhydride group and having number-average molecular weight 800-2500 and viscosity 35-1000 cS at 100°C. The invention also describes articles such as tyre tubes, made from said elastomeric mixtures.

EFFECT: obtaining substances which improve processing.

12 cl, 14 tbl

Description

FIELD OF THE INVENTION

The invention relates to substances for improving technological properties for use in the preparation of elastomeric mixtures. So, in particular, the invention relates to substances for improving technological properties, including functionalized polymers, for use in the preparation of elastomeric mixtures

BACKGROUND OF THE INVENTION

In the tire industry, manufacturers of tires and tire components, when they manufacture such products, have an endless choice. So, for example, the choice of components for technical rubber compounds for tires and tire components depends on the balance of the target properties and such an end use as tires with a diagonal or radial arrangement of cord threads in the carcass, as well as the end use of the product (for example, for airplanes, trucks / buses or cars).

An equally important consideration in selecting components may be the ability to efficiently process individual components in a batch rubber composition, and then to subsequently process these unvulcanized rubber compounds. For example, dry solids, in particular dust-free particles such as fillers, can be easily pneumatically transported and automatically weighed in the required quantities to prepare a batch in closed rubber mixers such as Banbury ™ mixers. Bulk powder materials, such as packaged polymers, may require grinding to smaller, more convenient to handle particles, so as to accurately add the quantities required to prepare the batch. Liquids have the same problems of transportation, weighing, but they can also create additional concerns in view of their volatility and the need for flow without loss due to leakage. For example, a viscous liquid may require heating to help achieve the required flow rates for accurate weighing and loading when preparing a batch in a closed rubber mixer without emitting volatile gaseous emissions.

Moreover, the additional subsequent processing of these unvulcanized rubber compounds may highly depend on the particular plant equipment used. Thus, the properties of unvulcanized rubber compounds, such as Mooney viscosity and Mooney vulcanization, can be important variables and parameters in order to provide assistance in optimizing production efficiency, especially since post-mixing rubber processing equipment such as rollers, rolls clamping jaws, calendars, syringe machines, etc., at enterprises around the world can vary significantly in technological volumes, speeds and operating temperatures. Thus, the need for any component for such mixtures is due to its ability to facilitate the ease of processing of unvulcanized rubber compounds. So, in particular, in the manufacturing process of the part of the tire that is responsible for air tightness, such as the inner shell of the tire, manufacturers turn to a variety of techniques, including the widespread use of "butyl" rubbers or elastomers in various ways.

Butyl rubbers, generally copolymers of isobutylene and isoprene, optionally halogenated, find widespread use due to their ability to impart targeted air tightness to the tire. Halobutyl rubbers (halogenated butyl rubbers) are polymers that are selected to retain air in the inner shells of tires for applications in cars, trucks / buses, airplanes (see, for example, US No. 5922153, US No. 5491196, EP 0102844 and EP 0127998 ) Bromobutyl rubber, chlorobutyl rubbers and branched ("star") halogenated butyl rubbers are isobutylene-based elastomers that can be prepared for these specific applications. EXXPRO ™ elastomers (ExxonMobil Chemical Company, Houston, TX), generally halogenated random copolymers of isobutylene and para-methyl styrene (see, for example, US No. 6293327, US No. 5386864) are also of particular interest due to their improvements over traditional butyl rubbers. published patent application US No. 2002/151636; JP 2003170438 and JP 2003192854; application of various techniques for mixtures of industrial EXXPRO ™ elastomers with other polymers).

Of the many choices made by a specialist in the processing of the aforementioned elastomeric mixtures, the choice of a substance for improving technological properties is of increasing importance. Substances for improving technological properties are an important factor in the processing of elastomers for tire inner shells, as they can affect the permeability of the vulcanized tire, the ability of the components of the molded but unvulcanized tire to adhere to each other, called "stickiness in the unvulcanized state", and / or efficiency subsequent processing of unvulcanized rubber compounds. By selecting the appropriate substance to improve technological properties, the manufacturer can influence the conditions in which elastomers are processed and many of the properties of end-use products made from these elastomers. Thus, for example, an unvulcanized low Mooney viscosity rubber compound can increase productivity values. However, an excessively low Mooney viscosity can lead to stretching or tearing of the unvulcanized rubber composition, potentially increasing the amount of waste. Similarly, an increase in Mooney vulcanization of an unvulcanized rubber composition may allow the use of higher operating temperatures of rollers, roll jaws, calendars, syringe machines, and the like.

Recently, to facilitate the processing of elastomeric mixtures in industry, the use of distillate “fractions” from the oil distillation process or oils for filling rubber in the latex stage such as aromatic, paraffin, naphthenic oils and mixtures thereof has gained widespread acceptance (see, for example, US No. 5162409 and US No. 5631316). However, the use of these components can increase the permeability of a pneumatic membrane, such as the inner shell of a tire. Later, polybutene substances were of great interest for improving technological properties due to their ability to reduce the permeability of the pneumatic membrane component while preserving other target properties of a tire that is in the process of maintenance and / or in the manufacture of a tire (see, for example, US No. 6710116, published US patent application No. 2005/0027062, WO 2002/32995, WO 2002/32992, WO 2002/32993, WO 2002/48257 and WO 2004/009700). The use of polybutene substances to improve technological properties is a radical deviation from recent aspirations, since these substances to improve technological properties are obtained by polymerization of non-distillate "fractions" of the oil distillation process.

References to descriptions of other known technical solutions include WO 2004/058874 and JP 2003292705.

However, even greater improvements are needed to give the balance of properties more substantial choices and flexibility that manufacturers must consider when deciding how elastomers should be recycled in light of the targeted properties of specific end-use products. So, for example, it is still necessary to further reduce the permeability of the pneumatic membrane component of the tire or to maintain the permeability of the pneumatic membrane component and / or to reduce obstacles in the processing of unvulcanized rubber compounds. The present invention satisfies this requirement by providing greater choices in this regard through the use of process enhancing materials, including the functionalized polymers described herein.

SUMMARY OF THE INVENTION

The invention provides methods for preparing elastomeric mixtures, comprising contacting at least one elastomer with a substance for improving technological properties, where this substance for improving technological properties includes at least one functionalized polymer having at least one anhydride group.

In another embodiment, products such as inner shells of tires made from the aforementioned elastomeric blends are also provided.

DETAILED DESCRIPTION OF THE INVENTION

The following describes various specific options, versions and examples of carrying out the invention, including preferred options and definitions that are adopted in the present description in order to understand the essence of the claimed invention.

In the present description of the link to the "groups" of the Periodic Table of Elements, a new numbering scheme for the groups of the Periodic Table of Elements is used, which is presented in the Hawley's Condensed Chemical Dictionary 852 (13th edition, 1997).

The term "suspension" refers to the volume of the diluent, including polymers that precipitated from the diluent, monomers, Lewis acid and initiator. The concentration of the suspension is expressed in volume percent of partially or completely precipitated polymers in terms of the total volume of the suspension.

The term "polymer" can be used to refer to homopolymers, copolymers, ternary copolymers, etc. Similarly, the term "copolymer" may refer to a polymer comprising units of at least two monomers, optionally with units of other monomers.

When a polymer is referred to as comprising a monomer, this monomer is contained in the polymer in a polymerized form or in the form of a derivative of this monomer. However, for simplicity of reference, the abbreviated expression “including (appropriate) monomer” or the like is used. Similarly, when the catalytic components are described as including components in neutral stable forms, it will be readily apparent to those skilled in the art that the ionic form of the component is a form that reacts with monomers to form polymers.

The term "rubber" refers to any polymer or composition of polymers that meets the following definition according to ASTM D 1566: "a material that is capable of recovering after large deformations and can or is already modified to a state in which it is essentially insoluble (but can swell) in boiling solvent ... " The term “elastomer” and the term “rubber” can be used interchangeably.

The term "elastomeric mixture" refers to any mixture comprising at least one elastomer, as presented above.

The term "vulcanized rubber compound" as defined by ASTM D1566 refers to a "structured elastic material compounded from an elastomer that is sensitive to high deformations under the action of weak force, capable of quickly recovering the deformation force to approximately restore its original size and shape." The terms "vulcanized elastomeric mixture" with the term "cured rubber compound", referring to any elastomeric mixture that is pre-treated during the vulcanization process and / or which includes or which is obtained using an effective amount of a vulcanizing agent or vulcanizing group, are used interchangeably.

The thermoplastic elastomer, as defined by ASTM D1566, refers to a rubber-like material, "which can be re-softened by heating and cured by cooling due to the temperature range characteristic of the polymer and can be molded into articles in a softened state." Thermoplastic elastomers are systems of separated microphases of at least two polymers. One phase is a solid polymer that does not flow at room temperature, but becomes fluid when it is heated, which gives the thermoplastic elastomers their strength. The other phase is a soft, rubbery polymer that gives thermoplastic elastomers their elasticity. The solid phase is, as a rule, the main or continuous phase.

Thermoplastic vulcanizate as defined by ASTM D1566 refers to a “thermoplastic elastomer with a chemically structured rubber-like phase obtained by dynamic vulcanization”. Dynamic vulcanization is "a process of homogeneous melt mixing of a thermoplastic polymer and an acceptable reactive rubber-like polymer to produce a thermoplastic elastomer with a chemically structured rubber-like phase ...". The rubbery phase, whether structured or not, is typically a small or dispersed phase.

The term "part. / 100" represents the number of parts per hundred parts of rubber or "parts" and indicates the generally accepted in the art content of the components of the mixture, determined relative to the total number of all elastomeric components. In total part / 100 or parts of all rubber components, whether one, two, three or more different rubber components are contained in a given recipe, is always expressed as 100 parts / 100. The content of all other non-rubber components set relative to 100 frequent. rubber and expressed in frequent./100. This way you can easily compare, for example, the concentration of vulcanizing substances or the content of the filler, etc. in different mixtures, based on the same relative proportion of rubber, without the need to recalculate the percentages for each component after adjusting the concentrations of only one or more components.

The term "isomonoolefin" refers to any olefin monomer containing at least one carbon atom having two substituents on the carbon atom.

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

The terms "elastomer" or "polymer" based on isobutylene refers to elastomers or polymers comprising at least 70 mol% of repeating units of isobutylene.

The term "hydrocarbon" refers to molecules or segments of molecules containing mainly hydrogen and carbon atoms. In some embodiments, the term “hydrocarbon” also encompasses halogenated hydrocarbon analogues and analogues containing heteroatoms, as discussed in more detail below.

The term “alkyl” refers to a paraffinic hydrocarbon group that can be derivatized from an alkane by removing one or more hydrogen atoms from this compound, in particular, such as, for example, a methyl group (CH ₃ ) or an ethyl group (CH ₃ CH ₂ ) and etc.

The term “aryl” refers to a hydrocarbon group that forms a ring structure characteristic of aromatic compounds such as, for example, benzene, naphthalene, phenanthrene, anthracene, etc., and, as a rule, has an alternating double bond inside its structure ( "unsaturated group"). Thus, an aryl group is a group derivatized from an aromatic compound by removing one or more hydrogen atoms from this compound, in particular, such as phenyl or (C ₆ H ₅ ).

By the term “substituted” is meant the substitution of at least one hydrogen group with at least one substituent selected, for example, from a halogen atom (chlorine, bromine, fluorine or iodine), an amino group, nitro, sulfoxy (sulfonate or alkyl sulfonate), thiol, alkylthiol and hydroxyl; alkyl, straight or branched, containing from 1 to 20 carbon atoms, examples of which include methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, etc .; alkoxy, straight or branched alkoxy containing from 1 to 20 carbon atoms, examples of which include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; haloalkyl, which is straight chain or branched alkyl containing from 1 to 20 carbon atoms, which is substituted by at least one halogen atom, examples of which include 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, tr fluoromethyl, 2,2,2-trifluoroethyl, 2,3,3-trifluoropropyl, 1,1,2,2-tetrafluoroethyl, and 2,2,3,3-tetrafluoropropyl. Thus, in particular, examples of the “substituted styrene unit” include n-methyl styrene, n-ethyl styrene, etc.

Butyl rubber

Preferred elastomers that may be used in the practice of the present invention include isobutylene-based homopolymers and copolymers. As stated above, the term “isobutylene-based elastomer or polymer” refers to an elastomer or polymer containing at least 70 mol% of repeating isobutylene units. Such polymers can be described as a random copolymer of a C ₄ to C ₇ isomonoolefin derivatized unit, such as an isobutylene derivatized unit, and at least one of the other polymerizable units. The isobutylene-based copolymer may or may not be halogenated.

In one embodiment, the elastomer is butyl rubber or branched butyl rubber, predominantly halogenated versions of these elastomers. Suitable elastomers are unsaturated butyl rubbers, such as homopolymers and copolymers of olefins or isoolefins and multiolefins or homopolymers of multiolefins. Elastomers of these and other types suitable for carrying out the invention are well known and described in Rubber Thechnology 209-581 (ed. Morton, Chapman & Hall 1995), The Vanderbilt Rubber Handbook 105-122 (ed. Ohm., RT Vanderbilt Co., Inc. 1990) and Kresge and Wang in 8 KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL THECHNOLOGY 934-955 (John Wiley & Sons, Inc. 4th edition, 1993). Non-limiting examples of unsaturated elastomers that can be used in the method and composition of the present invention are isobutylene-isoprene copolymer, polyisoprene, polybutadiene, polyisobutylene, butadiene-styrene copolymer, natural rubber, star butyl rubber and mixtures thereof. Elastomers suitable for carrying out the present invention may be prepared by any suitable method known in the art, and the scope of the invention by any particular elastomer production method described herein is not limited.

Elastomeric mixtures may include at least one butyl rubber. Butyl rubbers are prepared by reaction in a mixture of monomers, the mixture comprising at least (1) a C ₄ to C ₇ isoolefin monomer component, such as isobutylene, and (2) a multiolefin monomer component. The isoolefin comprises from 70 to 99.5 wt.% Of the total weight of the mixture of monomers in one embodiment and from 85 to 99.5 wt.% In another embodiment. The multiolefin component is contained in the monomer mixture in an amount of from 30 to 0.5 wt.% In one embodiment and from 15 to 0.5 wt.% In another embodiment. Nevertheless, in yet another embodiment, from 8 to 0.5 wt.% Of the monomer mixture are multiolefin.

An isoolefin is a compound with C ₄ no C ₇ , non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene , 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene and 4-methyl-1-pentene. A multiolefin is a C ₄ to C ₁₄ multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl fulvene, hexadiene, cyclopentadiene and piperylene, as well as other monomers such as described in EP 0279456 and US 5506316 and US 5162425. For homopolymerization or copolymerization to produce butyl rubbers, other polymerizable monomers such as styrene and dichlorostyrene are also acceptable. One embodiment of the butyl rubber polymer of the invention is prepared by reacting from 95 to 99.5% by weight of isobutylene and from 0.5 to 8% by weight of isoprene, or in another embodiment, from 0.5 to 5.0% by weight of isoprene. Butyl rubbers and methods for their preparation are described, for example, in US 2356128, US 3968076, US 4474924, US 4068051 and US 5532312 (see, in addition, WO 2004/058828, WO 2004/058827, WO 2004/058835, WO 2004 / 058836, WO 2004/058825, WO 2004/067577, a WO 2004/058829).

Industrial examples of useful butyl rubbers are EXXON ™ isobutylene-isoprene copolymers of butyl grades having a Mooney viscosity of 30 to 56 (ML 1 + 8 at 125 ° C.) (ExxonMobil Chemical Company, Houston, TX). Another industrial example of a suitable butyl rubber is VISTANEX ™ isobutylene rubber having a viscosity average molecular weight of 0.75 to 2.34 × 10 (ExxonMobil Chemical Company, Houston, TX).

Star-Butyl Rubber

Another embodiment of butyl rubber that can be used in carrying out the invention is branched or “star-shaped” butyl rubber. These rubbers are described, for example, in EP 0678529 B1, US 5182333 and US 5071913. In one embodiment, the star-shaped butyl rubber ("GOITER") is a composition of butyl rubber (either halogenated or non-halogenated) and a polydiene or block copolymer (either halogenated or non-halogenated ) The scope of the invention is not limited to a specific method for producing SCA. Polydienes / block copolymers or branching agents (hereinafter referred to as "polydienes") are typically cationic reactive and are present during polymerization to produce butyl or halogenated butyl rubber or can be mixed with butyl rubber to produce goiter. Any suitable branching agent may be used as the branching agent or polydiene, and the scope of the invention is not limited to the particular type of polydiene used to produce the SCA.

In one embodiment, the SCA is typically a composition of butyl or halogenated butyl rubber, as described above, and a copolymer of polydiene and partially hydrogenated polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, butadiene-styrene rubber -propylene-diene rubber (TEPD), ethylene-propylene rubber (BEP), styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. These polydienes are present in terms of the mass percentage of monomer in an amount of more than 0.3 wt.% In one embodiment, from 0.3 to 3 wt.% In another embodiment, and yet in another embodiment, from 0.4 to 2, 7 wt.%.

An industrial embodiment of the SCA of the present invention is SB Butyl 4266 (ExxonMobil Chemical Company, Houston, TX) having a Mooney viscosity (ML 1 + 8 at 125 ° C, ASTM D1646) of 34 to 44. Moreover SB Butyl 4266 product has the following vulcanization characteristics: MN is 69 ± 6 dN · m, and ML is 11.5 ± 4.5 dN · m (ASTM D2084 standard).

Halogenated Butyl Rubber

In a suitable embodiment, the elastomer is halogenated. Halogenated butyl rubber is prepared by halogenating the butyl rubber product described above. Halogenation can be carried out in any way, and the scope of the invention by any particular halogenation method is not limited. Methods for halogenation of polymers, such as butyl polymers, are described in US 2631984, US 3099644, US 4554326, US 4681921, US 4650831, US 4384072, US 4513116 and US 5681901. In one embodiment, butyl rubber is halogenated in a hexane diluent at a temperature of from 4 to 60 ° C using bromine (Br ₂ ) or chlorine (Cl ₂ ) as a halogenating agent. Such halogenated butyl rubber has a Mooney viscosity of from 20 to 70 (ML 1 + 8 at 125 ° C.) in one embodiment and from 25 to 55 in another embodiment. The mass percentage of halogen atoms is from 0.1 to 10 wt.% In terms of the mass of halogenated butyl rubber in one embodiment and from 0.5 to 5 wt.% In another embodiment. Nevertheless, in yet another embodiment, the mass percentage of halogen atoms in the halogenated butyl rubber is from 1 to 2.5 wt.%.

An industrial embodiment of a suitable halogenated butyl rubber of the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company, Houston, TX). Its Mooney viscosity is from 27 to 37 (ML 1 + 8 at 125 ° C, ASTM 1646, modified method), and the bromine content is from 1.8 to 2.2 wt.% In terms of the product Bromobutyl 2222. Further , Bromobutyl 2222 product has the following vulcanization characteristics: MN is from 28 to 40 da · m, ML is from 7 to 18 da · m (according to ASTM D2084). Another industrial embodiment of halogenated butyl rubber is Bromobutyl 2255 (ExxonMobil Chemical Company, Houston, TX). Its Mooney viscosity is from 41 to 51 (ML 1 + 8 at 125 ° C, according to ASTM D1646), and the bromine content is from 1.8 to 2.2 wt.%. Moreover, the product Bromobutyl 2255 has the following vulcanization characteristics: MN is from 34 to 48 dN · m, ML is from 11 to 21 dN · m (according to ASTM D2084).

Star halogenated butyl rubber

As another embodiment of the elastomer of the invention, branched or “star” halogenated butyl rubber is used. In one embodiment, this halogenated star-shaped butyl rubber is a composition of butyl rubber (either halogenated or non-halogenated) and a polydiene or block copolymer (either halogenated or non-halogenated). Halogenation methods are described in detail in US 4074035, US 5071913, US 5286804, US 5182333 and US 6228978. The scope of the invention by any specific method for producing halogenated star-shaped butyl rubber is not limited. To obtain a halogenated star-shaped butyl rubber during polymerization to form butyl or halogenated butyl rubber, polydienes / block copolymers or branching agents (below "polydienes") are present, which are generally cationic reactive or can be mixed with butyl or halogenated butyl. As a branching agent or polydiene, any suitable branching agent and the particular type of polydiene used to produce the halogenated star-shaped butyl rubber can be used, the scope of the invention is not limited.

In one embodiment, the halogenated star-shaped butyl rubber is typically a composition of butyl or halogenated butyl rubber as described above and a copolymer of polydiene and partially hydrogenated polydiene selected from the group consisting of styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, butadiene rubber, ethylene-propylene-diene rubber, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. These polydiene are contained in terms of the mass percentage of monomer greater than 0.3 wt.% In one embodiment, from 0.3 to 3 wt.% In another embodiment, and yet in another embodiment, from 0.4 to 2.7 wt. .%.

An industrial embodiment of the halogenated star-shaped butyl rubber of the present invention is Bromobutyl 6222 (ExxonMobil Chemical Company, Houston, TX) having a Mooney viscosity (ML 1 + 8 at 125 ° C., ASTM D1646) of 27 to 37 and bromine content from 2.2 to 2.6 wt.% in terms of halogenated star-shaped butyl rubber. Moreover, the product Bromobutyl 6222 has the following vulcanization characteristics: MN is from 24 to 38 dN · m, ML is from 6 to 16 dN · m (ASTM D2084 standard).

Halogenated Isobutylene / Para-Methyl Styrene Rubber

The elastomeric mixtures of the present invention may also include at least one random copolymer containing C ₄ to C ₇ isomonoolefins such as isobutylene and an alkyl styrene comonomer such as para-methyl styrene containing at least 80%, more preferably at least 90 wt.%, para-isomers and optionally include functionalized copolymers in which at least one or more alkyl substituent groups present in styrene monomer units contain a benzyl halogen atom or some another functional group. In another embodiment, the polymer may be a statistical elastomeric copolymer of C ₃ to C ₆ ethylene or α-olefin and an alkyl styrene comonomer such as para-methyl styrene containing at least 80%, alternatively at least 90 wt.%, Steam -isomers, and optionally includes functionalized copolymers in which at least one or more alkyl substituent groups present in styrene monomer units contain a benzyl halogen atom or some other functional group. Illustrative materials can be characterized as polymers containing the following monomeric units disordered along the polymer chain:

in which each of R and R ¹ independently represents a hydrogen atom, lower alkyl, such as C ₁ to C ₇ alkyl, or primary or secondary alkyl halide, and X denotes a functional group such as a halogen atom. In one embodiment, each of R and R ¹ represents a hydrogen atom. Up to 60 mol% of para-substituted styrene units included in the structure of the functionalized copolymer can have the above functionalized structure (2) in one embodiment and from 0.1 to 5 mol% in another embodiment. However, in yet another embodiment, the content of the functionalized structure (2) is from 0.2 to 3 mol%.

Functional group X may be a halogen atom or some other functional group that can be introduced by nucleophilic substitution of a benzyl halogen atom by other groups, such as residues of carboxylic acids, salts of carboxylic acids, esters, amides and imides of carboxylic acids, hydroxyl, alkoxide, phenoxide , thiolate, thioether, xanthate, cyanide, cyanate, amino group and mixtures thereof. These functionalized isomonoolefin copolymers, the method for their preparation, methods of functionalization and vulcanization are more specifically presented in US 5162445.

In one embodiment, the elastomer comprises random polymers of isobutylene and para-methyl styrene, including from 0.5 to 20 mol% of para-methyl styrene, where up to 60 mol% of methyl substituent groups on the benzyl ring contain a bromine or chlorine atom, in particular an atom bromine (para-bromomethylstyrene), as well as their variants functionalized by residues of acids and esters.

In another embodiment, the functional group is selected so that it can interact or form polar bonds with functional groups contained in the matrix polymer, for example, such as acidic, amino, and hydroxyl functional groups, when the polymer components are mixed at high temperatures.

In some embodiments, random copolymers are characterized by a substantially homogeneous composition distribution, whereby the content of para-alkylstyrene units in at least 95 wt.% Of the polymer is in a 10% range of the average content of para-alkylstyrene in the polymer. Illustrative polymers are characterized by a narrow molecular weight distribution (Mw / Mn) of less than 5, more preferably less than 2.5, a preferred illustrative molecular weight is in the range of 200,000 to 2,000,000, and an illustrative number average molecular weight is in the range of 25,000 to 750,000. as determined by gel permeation chromatography.

In one embodiment, the brominated isobutylene / p-methylstyrene copolymers typically contain from 0.1 to 5 mol% of bromomethylstyrene groups, based on the total number of units derived from monomers in the copolymer. In another embodiment, the content of bromomethyl groups is from 0.2 to 3.0 mol%, from 0.3 to 2.8 mol% in another embodiment, from 0.4 to 2.5 mol% in another embodiment, and yet from 0.3 to 2.0 in another embodiment, where the target interval may be any combination of any upper limit with any lower limit. To put it differently, the illustrative copolymers contain from 0.2 to 10 wt.% Bromine atoms in terms of the weight of the polymer, from 0.4 to 6 wt.% Bromine atoms in another embodiment, and from 0.6 to 5.6 wt.% in another embodiment, and are essentially free of ring halogen atoms or halogen atoms in the main polymer chain. In one embodiment, the random polymer is a copolymer of units derived from an isoolefin with C ₄ no C ₇ (or isomonoolefin), units derived from para-methyl styrene, and units derived from para-halomethyl styrene, wherein the para-halomethyl styrene units are contained in this polymer in an amount of from 0.4 to 3.0 molar%, calculated on the total number of para-methylstyrene units, and para-methylstyrene derivatized units are contained in an amount of 3 to 15 wt.%, calculated on the total polymer weight in one var and those of 4 to 10 wt.% in another embodiment. In yet another embodiment, para-halomethylstyrene is para-bromomethylstyrene.

An industrial embodiment of the halogenated isobutylene / p-methyl styrene rubber of the present invention is EXXPRO ™ elastomers (ExxonMobil Chemical Company, Houston, TX) having a Mooney viscosity (ML 1 + 8 at 125 ° C, ASTM D1646) from 30 to 50, p-methylstyrene content from 4 to 8.5 wt.% And bromine content from 0.7 to 2.2 wt.% Relative to halogenated isobutylene / p-methylstyrene rubber.

An elastomer (s), such as that discussed above, can be prepared by suspension polymerization, typically in a diluent comprising halogenated hydrocarbon (s), such as chlorinated hydrocarbon and / or fluorinated hydrocarbon, including mixtures thereof (see, for example , WO 2004/058828, WO 2004/058827, WO 2004/058835, WO 2004/058836, WO 2004/058825, WO 2004/067577 and WO 2004/058829).

In some embodiments related to blends, an elastomer (s) as described above may be combined with at least one of the following materials.

General purpose rubber

General-purpose rubber, often referred to as commodity rubber, can be any rubber that typically provides high strength and good abrasion resistance combined with low hysteresis and high elasticity. These elastomers require antioxidants in the finished mixture, as they are usually characterized by poor heat resistance and resistance to oxygen, in particular ozone resistance. Often they are easily recognizable in the market due to their low selling prices in comparison with the prices of special elastomers and the large volumes of their consumption, as described by School in RUBBER TECHNOLOGY, COMPOUNDING AND TESTING FOR PERFORMANCE, c. 125 (Dick, ed., Hanser, 2001).

Examples of general purpose rubbers include natural rubbers (NR), isoprene rubber (IR), styrene butadiene rubber (BSK), butadiene rubber (BC), isoprene butadiene rubber (IBC), styrene-isoprene butadiene rubber (SIBC), and mixtures. Ethylene propylene rubber (EPD), ethylene propylene diene rubber (TEPD) and mixtures thereof are also often referred to as general purpose elastomers.

In another embodiment, the mixture may also include natural rubber. Natural rubbers are described in detail by Subramaniam in Rubber Technology, c. 179-208 (edited by Morton, Chapman & Hall 1995). The target natural rubber variants of the present invention are selected from Malaysian rubbers such as SMR CV, SMR 5, SMR 10, SMR 20, SMR 50 and mixtures thereof, and the Mooney viscosity of these natural rubbers at 100 ° C. (ML 1 + 4) is from 30 to 120, more preferably from 40 to 65. The Mooney viscosity test referred to in the present description is carried out in accordance with ASTM D-1646.

In another embodiment, the elastomeric mixture may also include butadiene rubber (BK). The Mooney viscosity of this butadiene rubber, as determined at 100 ° C (ML 1 + 4), can range from 35 to 70, from 40 to about 65 in another embodiment, and yet in another embodiment from 45 to 60 Some examples of industrial synthetic rubbers that can be used in carrying out the present invention are products marketed under the trademark BUDENE ™ (Goodyear Chemical Company, Akron, Ohio), BUNA ™ (Lanxess Inc., Sarnia, Ontario, Canada) and Diene ™ (Firestone Polymers LLC, Akron, Ohio). An example is polybutadiene with a high content of cis units (cis-BK). The term "cis-polybutadiene" or "high cis-linked polybutadiene" means that 1,4-cis-polybutadiene is used where the amount of cis component is at least 95%. A specific example of high cis-linked polybutadiene technical products used in the mixture is BUDENE ™ 1207 or BUNA ™ CB 23.

In another embodiment, the elastomeric mixture may also include isoprene rubber (IR). The Mooney viscosity of isoprene rubber, which is determined at 100 ° C (ML 1 + 4), can range from 35 to 70, from 40 to about 65 in another embodiment, and yet from 45 to 60 in another embodiment. An example of these industrial synthetic rubbers that may be used in the practice of the present invention is NATSYN ™ 2200 (Goodyear Chemical Company, Akron, Ohio).

In another embodiment, the elastomeric mixture may also include rubbers with units derived from ethylene and propylene, such as EPD and TEPD, acceptable as additional rubbers. Examples of comonomers acceptable in the preparation of TEPD are ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, and other compounds. These rubbers are described in Rubber Technology 260-283 (1995). Suitable ethylene-propylene rubber is technically available as a VISTALON ™ product (ExxonMobil Chemical Company, Houston, TX).

However, in another embodiment, the elastomeric mixture may include a triple copolymer of ethylene / alpha-olefin / diene. alpha-Olefin is selected from the group consisting of C ₃ to C ₃₀ alpha-olefin, propylene, butene and octene being preferred, and propylene being most preferred. The diene component is selected from the group consisting of C ₄ to C ₃₀ dienes. Examples of suitable dienes include a straight chain hydrocarbon diolefin and cycloalkenyl substituted alkenes containing from 6 to 15 carbon atoms. Specific examples include (a) straight chain acyclic dienes such as 1,4-hexadiene and 1,6-octadiene; (b) branched acyclic dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyrcene and dihydroocinene ; (c) monocyclic alicyclic dienes such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; (d) polycyclic alicyclic fused and bridged cyclic dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene (DCPD); bicyclo (2.2.1) hepta-2,5-diene, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene-norbornene such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene , 5-ethylidene-2-norbornene (ENB), 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene (VNB); (e) cycloalkenyl substituted alkenes, such as allylcyclohexene, vinylcyclooctene, allylcyclodecene, vinylcyclododecene. Examples also include dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene. Examples of diolefins are 5-ethylidene-2-norbornene, 1,4-hexadiene, dicyclopentadiene and 5-vinyl-2-norbornene. For further information and an example of how a person skilled in the art can use these ternary copolymers, please refer, in particular, to US No. 6245856.

Special Purpose Rubber

In one embodiment, the auxiliary elastomer is a special-purpose rubber containing a polar functional group such as butadiene-acryl-nitrile rubber (LHC or nitrile butadiene rubber), a copolymer of 2-propenitrile and 1,3-butadiene. Nitrile butadiene rubber may have an acrylonitrile content of from 10 to 50 wt.% In one embodiment, from 15 to 40 wt.% In another embodiment, and yet from 18 to 35 wt.% In another embodiment. Mooney viscosity can be in the range from 30 to 90 in one embodiment (1 + 4, 100 ° C, ASTM D1646) and from 30 to 75 in another embodiment. Such rubbers are common in the art and are described, for example, in Handbook of Plastics, Elastomers and Composites 1.41-1.49 (ed. Harper, McGraw-Hill, Inc. 1992). Examples of these industrial synthetic rubbers that can be used in carrying out the present invention are products marketed under the trade names BREON ™, NIPOL ™, SIVIC ™ and ZETPOL ™ (Zeon Chemicals, Louisville, Kentucky), EUROPRENE ™ N (Polimeri Europa Americas, Houston, TX); and KRYNAC ™, PERBUNAN ™ and THERBAN ™ (Lanxess Corporation, Akron, Ohio).

In another embodiment, the auxiliary elastomer is a derivative of the LHC, such as hydrogenated and carboxylated and styrene-containing butadiene-nitrile rubbers. Butadiene-acrylonitrile-styrene rubber (BASK or "ABS" rubber), a copolymer of 2-propenitrile, 1,3-butadiene and styrene, may have an acrylonitrile content of from 10 to 40 wt.% In one embodiment, from 15 to 30 wt.% in another embodiment, and yet from 18 to 30 wt.% in another embodiment. The styrene content in the BASK copolymer may range from 15 to 40 wt.% In one embodiment, from 18 to 30 wt.% In another embodiment, and yet from 20 to 25 wt.% In another embodiment. Mooney viscosity can be in the range from 30 to 60 in one embodiment (1 + 4, 100 ° C, ASTM D1646) and from 30 to 55 in another embodiment. These rubbers are common in the art and are described, for example, in Handbook of Plastics, Elastomers and Composites 1.41-1.49 (ed. Harper, McGraw-Hill, Inc. 1992). An industrial example of this synthetic rubber that can be used in the practice of the present invention is marketed under the trade name KRYNAC ™ (Lanxess Corporation, Akron, Ohio).

However, in yet another embodiment, the auxiliary elastomer is a special-purpose rubber containing a halogen group such as polychloroprene (HC or chloroprene rubber), a homopolymer of 2-chloro-1,3-butadiene. Mooney viscosity can be in the range from 30 to 110 in one embodiment (1 + 4, 100 ° C, ASTM D1646) and from 35 to 75 in another embodiment. These rubbers are common in the art and are described, for example, in Handbook of Plastics, Elastomers and Composites 1.41-1.49 (ed. Harper, McGraw-Hill, Inc. 1992). Industrial examples of these synthetic rubbers that may be used in carrying out the present invention are marketed under the trade names NEOPRENE ™ (DuPont Dow Elastomers, Wilmington, Delaware), BUTACLOR ™ (Polimeri Europa Americas, Houston, TX) and BAYPREN ™ (Lanxess Corporation, Akron, Ohio).

Semi-crystalline polymer

In one embodiment, the elastomeric mixture may include at least one semi-crystalline polymer, which is an elastic polymer with a moderate degree of crystallinity due to stereoregular propylene sequences. A semi-crystalline polymer may include (A) a propylene homopolymer in which the stereoregularity is to some extent disturbed, in particular by regioinversions; (B) a statistical propylene copolymer in which the propylene stereoregularity is at least partially disturbed by comonomers, or (C) a combination of (A) and (B).

In another embodiment, to facilitate vulcanization and other chemical modification of the blended composition, the semi-crystalline polymer further includes a non-conjugated diene monomer. The amount of diene contained in the polymer is preferably less than 10 wt.%, And more preferably less than 5 wt.%. The diene can be any non-conjugated diene that is commonly used for the vulcanization of ethylene-propylene rubbers, including, although not limited to, ethylidene norbornene, vinyl norbornene and dicyclopentadiene.

In one embodiment, the semi-crystalline polymer is a random copolymer of propylene and at least one comonomer selected from ethylene, C ₄ -C ₁₂ α-olefins, and combinations thereof. In the particular case of this embodiment, the copolymer comprises ethylene derivatized units in an amount ranging from the lower limit of 2, 5, 6, 8 or 10 wt.% To the upper limit of 20, 25 or 28 wt.%. This option may also include propylene derivatized units contained in the copolymer in an amount in the range from the lower limit of 72, 75 or 80 wt.% To the upper limit of 98, 95, 94, 92 or 90 wt.%. These mass percentages are calculated in terms of the total mass of units derivatized from propylene and ethylene, i.e. in terms of the mass percent of units derivatized from propylene and the mass percent of units derivatized from ethylene, which is 100%.

The ethylene composition of the polymer can be determined as follows. A thin uniform film is pressed at a temperature of about 150 ° C or higher, then it is fixed in a Perkin Elmer PE 1760 infrared spectrophotometer. A full spectrum of the sample is taken from 600 to 4000 cm ^-1 and the monomer percentage of ethylene can be calculated in accordance with the following equation: mass percentage of ethylene = 82.585-111.987X + 30.045X ² , where X denotes the ratio of peak height at 1155 cm ^-1 and peak height at either 722 or 732 cm ^-1 , depending on which peak is higher. Using this method, the concentrations of other monomers in the polymer can also be determined.

The comonomer content in the intervals of individual molecular weights can be determined by Fourier transform IR spectrometry (ICPF) in combination with samples collected by GPC. One such method is described by Wheeler and Willis in Applied Spectroscopy, Volume 47, cc. 1128-1130 (1993). Various, but similar, methods that are well known to those skilled in the art are equally suitable for this purpose.

The comonomer content and sequence distribution in the polymers can be determined by ¹³ C ( ¹³ C-NMR) nuclear magnetic resonance spectroscopy, and such a method is well known to those skilled in the art.

In one embodiment, the semi-crystalline polymer comprises a random propylene copolymer having a narrow compositional distribution. In another embodiment, the polymer is a random propylene copolymer having a narrow composition distribution and a melting point, which is determined by DSC, from 25 to 110 ° C. This copolymer is described as statistical, because for a polymer including propylene, comonomer and optionally diene, the amount and distribution of comonomer residues is consistent with the random, random polymerization of the monomers. In stereoblock structures, the number of block monomeric residues of any one kind adjacent to each other exceeds the predicted static distribution in statistical copolymers with a similar composition. Stereoblock ethylene-propylene copolymers traditionally have a distribution of ethylene residues that is more consistent with these block structures than with the disordered, statistical distribution of monomer residues in the polymer. The intramolecular compositional distribution (i.e., statistical) of the copolymer can be determined by ¹³ C-NMR analysis, which positions the comonomer residues relative to the neighboring propylene residues. The intermolecular compositional distribution of the copolymer is determined by thermal fractionation in a solvent. A typical solvent is a saturated hydrocarbon such as hexane and heptane. The thermal fractionation method is described below. Typically, approximately 75 wt.%, Preferably 85 wt.%, The copolymer is isolated in the form of one or two adjacent soluble fractions, and the rest of the copolymer in immediately processed or subsequent fractions. Each of these fractions has a composition (in mass percent of such a comonomer as ethylene and another α-olefin) that differs by no more than 20% (relative), preferably 10% (relative), from the average mass percent of the comonomer in the copolymer. This copolymer has a narrow compositional distribution if it meets the requirements of the fractionation test described above. To obtain a copolymer with a target static and narrow compositional distribution, it is advisable if (1) a metallocene catalyst with a single region is used, which determines only the only statistical variant of the attachment of the first and second monomer sequences, and (2) the copolymer is mixed well in a tank type polymerization reactor with a stirrer and a continuous supply of raw materials, which causes only one polymerization environment for essentially all polymeric x copolymer chains.

The crystallinity of the polymers can be expressed in heat of fusion data. Embodiments of the present invention include polymers having a heat of fusion, as determined by DSC, in the range from a lower limit of 1.0 or 3.0 J / g to an upper limit of 50 or 10 J / g. Without being based on any theory, it is believed that the polymers of the embodiments of the present invention typically have isotactic crystallizable propylene sequences, and higher values of the heat of fusion are believed to be due to the melting of these crystalline segments.

The crystallinity of the polymer can also be expressed in percent crystallinity data. The highest thermal energy for polypropylene is estimated at 189 J / g. In other words, 100% crystallinity corresponds to 189 J / g. Therefore, in accordance with the above-mentioned values of the heat of fusion, the polymer has polypropylene crystallinity in the range, the upper limit of which is 65, 40, 30, 25, or 20%, and the lower limit is 1, 3, 5, 7, or 8%.

The degree of crystallinity also reflects the melting point. The term "melting point" used in the present description refers to the highest peak among the primary and secondary melting peaks, as determined by the DSC discussed above. In one embodiment of the present invention, the polymer has a single melting point. Typically, a propylene copolymer sample exhibits secondary melting peaks adjacent to the main peak, which are considered together as a single melting point. The highest of these peaks is considered the melting point. A preferred polymer has a DSC melting point in the range from an upper limit of 110, 100, 90, 80, or 70 ° C to a lower limit of 0, 20, 25, 30, 35, 40, or 45 ° C. Typically, a sample of the alpha olefin copolymer component exhibits secondary melting peaks adjacent to the main peak; they are considered together as the only melting point. The highest of these peaks is considered the melting point.

The weight average molecular weight (Mw) of the semi-crystalline polymer may be in the range with an upper limit of 5,000,000, 1,000,000 or 500,000 g / mol, a lower limit of 10,000, 20,000 or 80,000 g / mol, and a molecular weight distribution of Mw / Mn (MMP), which is sometimes called the "polydispersity index" (PPD), is in the range from the lower limit of 1.5, 1.8 or 2.0 to the upper limit of 40, 20, 10, 5 or 4.5. The parameters Mw and MMP used in the present description can be determined by a wide variety of methods, including those presented in US No. 4540753 and the literature mentioned in the present description, or by those methods found in Verstrate et al., Macromolecules, volume 21, p.3360 (1988), the contents of which are incorporated into this description by reference in accordance with current US practice.

In one embodiment, the semi-crystalline polymer has a Mooney viscosity, ML (1 + 4) at 125 ° C., 100 or less, 75 or less, 60 or less, or 30 or less. The Mooney viscosity referred to in the present description can be defined as ML (1 + 4) at 125 ° C in accordance with ASTM D1646.

The semi-crystalline polymer used in embodiments of the present invention may have a molecular structure regularity index (m / p) ranging from a lower limit of 4 or 6 to an upper limit of 8, 10 or 12. The molecular structure regularity index, expressed as m / r, determined by nuclear magnetic resonance spectroscopy by ¹³ C ( ¹³ C-NMR), it is calculated as indicated by Cheng in Macromolecules, Volume 17, p. 1950 (1984). The designation “m” or “p” describes the stereochemistry of pairs of adjacent propylene groups, with “m” referring to “meso” and “p” to racemic. A ratio of m / p of 1.0 generally characterizes the syndiotactic polymer, and a ratio of m / p of 2.0 is an atactic material. Isotactic material can theoretically have a ratio approaching infinity, and many atactic polymers as by-products have a sufficient isotactic component so that it leads to ratios greater than 50.

In one embodiment, the semi-crystalline polymer has isotactic stereoregular propylene crystallinity. The term “stereoregular” as used herein means that the prevailing amount, i.e. more than 80% of the propylene residues in polypropylene or in the continuous polypropylene phase of the mixture, in particular in a high-impact copolymer, with the exception of any other monomer, such as ethylene, has the same 1,2-position incorporation, and the stereochemical orientation of the side methyl groups is the same, either meso- or racemic.

An auxiliary method for describing the regularity of the molecular structure of propylene units in embodiments of the present invention is the use of the triadic regularity of the molecular structure. The triadic regularity of the molecular structure of the polymer is the relative regularity of the molecular structure of the sequence of three adjacent propylene units, the chain consisting of head-to-tail bonds, expressed as a binary combination of the "m" and "p" sequences. For the copolymers of the present invention, this is usually expressed as the ratio of the number of units of special regularity of the molecular structure to all propylene triads in the copolymer.

The triadic regularity of the molecular structure (fraction mm) of the propylene copolymer can be determined by the ¹³ C-NMR spectrum of the propylene copolymer and the following formula:

where PPP (mm), PPP (mp) and PPP (pp) denote the areas under the peaks due to the methyl groups of the second units in the following three chains of propylene units, including head-to-tail bonds:

¹³ C-NMR spectrum of the propylene copolymer is determined as described in US No. 5504172. The spectrum related to the methyl carbon atom site (19-23 ppm (ppm)) can be divided into the first plot (21.2-21.9 ppm), the second plot (20.3- 21.0 ppm) and the third section (19.5-20.3 ppm). Each peak in the spectrum was attributed, citing an article in Polymer, Volume 30, p. 1350 (1989). In the first section, the methyl group of the second link in the chain of three propylene units is represented by PPP (mm) resonances. In the second section, the methyl group of the second unit in a chain of three propylene units is represented by PPP (mp) resonates and the methyl group (PPE-methyl group) of the propylene unit, whose adjacent units correspond to the resonances of the propylene unit and ethylene unit (near 20.7 ppm ) In the third section, the methyl group of the second link in the chain of three propylene units is represented by PPP (pp) resonates and the methyl group (EPE methyl group) of the propylene unit, whose adjacent units correspond to the resonances of ethylene units (near 19.8 ppm).

The calculation of the triadic regularity of the molecular structure is outlined in general in the methods presented in US No. 5504172. Subtracting the areas under the peaks due to the error in the penetrations of propylene (both 2.1 and 1.3) from the areas under the peaks from the total areas under the peaks of the second section and the third section make it possible to establish the areas under the peaks based on chains of 3 propylene units ( PPP (Mr) and PPP (PP)) containing head-to-tail connections. Thus, it is possible to estimate the areas under the peaks of PPP (mm), PPP (mp) and PPP (pp) and, therefore, it is possible to determine the triad regularity of the molecular structure of the chain of propylene units, including head-to-tail bonds.

A semi-crystalline polymer may have a triadic regularity of the molecular structure of three propylene units, as determined by the ¹³ C-NMR spectrum, in 75% or more, 80% or more, 82% or more, 85% or more, or 90% or more.

In embodiments of the present invention, the semi-crystalline polymer has a melt spreading rate (CPP) of 5000 dg / min or less, in another embodiment 300 dg / min or less, in another embodiment 200 dg / min or less, in another embodiment 100 dg / min or less , in another embodiment, 50 dg / min or less, in another embodiment, 20 dg / min or less, in another embodiment, 10 dg / min or less, or in another embodiment, 2 dg / min or less. The determination of polymer CPP is carried out in accordance with ASTM D1238 (230 ° C., 2.16 kg).

In some embodiments, the semi-crystalline polymer of the present invention is contained in the inventive mixed compositions in an amount of from a lower limit of 50, 70, 75, 80, 82 or 85 wt.%, Calculated on the total weight of the composition to an upper limit of 99, 95 or 90 wt.% in terms of the total weight of the composition.

In some embodiments, the semi-crystalline polymer used in carrying out the present invention is presented, for example, in WO 00/69963, WO 00/01766, WO 99/07788, WO 02/083753 and is described in more detail as "Propylene olefin copolymer" in WO 00 / 01745. Semicrystalline polymers are technically available as VISTAMAXX ™ special purpose elastomers (ExxonMobil Chemical Company, Houston, TX) and VERSIFY ™ elastomers (not prepared using methods described herein) (Dow Chemical Company, Midland, Michigan).

Thermoplastic resin

In another embodiment, the elastomeric blends may include at least one thermoplastic resin. Thermoplastic resins suitable for carrying out the present invention can be used alone or in combination, they are resins containing nitrogen, oxygen, halogen, sulfur atoms or other groups capable of interacting with aromatic functional groups, such as halogen atoms and acid groups. These resins are contained in the nanocomposite in an amount of from 30 to 90 wt.% Nanocomposite in one embodiment, from 40 to 80 wt.% In another embodiment, and yet from 50 to 70 wt.% In another embodiment. However, in yet another embodiment, the resin is contained in an amount of more than 40 wt.% Nanocomposite and more than 60 wt.% In another embodiment.

Suitable thermoplastic resins include those selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins (ABS), polyphenylene oxide (PFD), polyphenylene sulfide (PFS, polystyrene, polystyrene, polystyrene, acrylonitrile resins (SAN), resins of styrene / maleic anhydride copolymers (CMA), aromatic polyketones (PEEK, PED and RECK) and mixtures thereof.

Acceptable thermoplastic polyamides (nylons) include crystalline or resinous high molecular weight solid polymers, including copolymers and ternary copolymers containing repeating amide units in the polymer chain. Polyamides can be prepared by polymerization of one or more epsilon-lactams, such as caprolactam, pyrrolidion, laurillactam and aminoundecane lactam or amino acids, or by polycondensation of dibasic acids and diamines. Suitable nylons as fiber-forming and molding varieties. Examples of such polyamides are polycaprolactam (nylon-6), polylaurillactam (nylon-12), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene azelamide (nylon-6,9), polyhexamethylene sebacamide (nylon-6,10), polyhexamethylene isophthalamide (nylon 6 , IF) and the polycondensation product of 11-aminoundecanoic acid (nylon-11). Additional examples of acceptable polyamides (mainly those with a softening point of less than 275 ° C) are presented in 16 Encyclopedia of Chemical Technology, pp. 1-105 (John Wiley & Sons, 1968), Concise Encyclopedia of Polymer Science and Technology, c .748-761 (John Wiley & Sons, 1990) and 10 Encyclopedia of Polymer Science and Technology, c. 392-414 (John Wiley & Sons, 1969). When carrying out the present invention, technically available thermoplastic polyamides can be effectively used, linear crystalline polyamides having a softening point or melting point in the range of 160 to 260 ° C. are preferred.

Suitable thermoplastic polyesters that may be used include polymeric reaction products of one or a mixture of aliphatic or aromatic polycarboxylic acids, esters or anhydrides, and one or a mixture of diols. Examples of suitable polyesters include poly (trans-1,4-cyclohexylene), poly (C ₃ -C ₆ alkanedicarboxylates) such as poly (trans-1,4-cyclohexylene succinate) and poly (trans-1,4-cyclohexylene adipate); poly (cis- or trans-1,4-cyclohexanedimethylene) alkanedicarboxylates such as poly (cis-1,4-cyclohexanedimethylene) oxalate and poly (cis-1,4-cyclohexanedimethylene) succinate; poly (C ₂ -C ₄ alkylene terephthalates) such as polyethylene terephthalate and polytetramethylene terephthalate; poly (C ₂ -C ₄ alkylene isophthalates) such as polyethylene isophthalate and polytetramethylene isophthalate, and the like. materials. Preferred polyesters are derivatized from aromatic dicarboxylic acids, such as naphthalic and phthalic acids, and C ₂ to C ₄ diols, such as polyethylene terephthalate and polybutylene terephthalate. Preferred polyesters are usually characterized by a melting point in the range from 160 to 260 ° C.

Polyphenylene ether (PFE) thermoplastic resins that can be used in accordance with the present invention are well known technically available materials obtained by oxidative dehydrocondensation polymerization of alkyl substituted phenols. Usually they are linear amorphous polymers, the glass transition temperature of which is in the range from 190 to 235 ° C. These polymers, the process for their preparation, and polystyrene compositions are further described in US 3,334,435.

Other thermoplastic resins that can be used include polycarbonate analogues of the polyesters described above, such as segmented ether and phthalate copolymers; polycaprolactone polymers; styrene resins, such as styrene copolymers with less than 50 mol% acrylonitrile (SAN) and resin copolymers of styrene, acrylonitrile and butadiene (ABS); sulfonic polymers such as polyphenyl sulfone; copolymers and homopolymers of ethylene and α-olefins from C ₂ to C ₈ , in one embodiment, a homopolymer of units derived from propylene, and in another embodiment, a random copolymer or block copolymer of units derived from ethylene and units derived from propylene, etc. thermoplastic resins that are known in the art.

In another embodiment, the mixtures of the present invention, further comprising any of the thermoplastic resins (also called thermoplastic or thermoplastic polymer) described above, are processed into dynamically vulcanized mixtures of polymers and copolymers.

The term "dynamic vulcanization" is used herein to define a vulcanization process in which a structural resin and a vulcanizable elastomer are vulcanized under high shear conditions. As a result, a vulcanizable elastomer is simultaneously structured and dispersed within the matrix of structural resin in the form of fine particles of a "microgel".

Dynamic vulcanization is carried out by mixing the components at a temperature that is equal to or higher than the vulcanization temperature of the elastomer in a device such as rollers, Banbury ™ mixers, continuous rubber mixers, plasticizers and mixing worm presses, for example double worm presses. A unique characteristic of dynamically vulcanized compositions is that despite the possibility of complete vulcanization of the elastomeric component, such mixtures can be processed and recycled using conventional rubber processing technologies, such as extrusion, injection molding, direct compression, etc. You can recycle and recycle waste and squeezed from the vulcanization form.

Particularly preferred thermoplastic polymers that can be used in the ICE of the present invention include structural resins selected from the group consisting of polyamides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile butadiene-styrene resins (ABS), polyphenylene oxide (PFD), polyphenylene sulfide (PPS), styrene-acrylonitrile resins (SAN), polyimides, styrene / maleic anhydride copolymers (CMA), aromatic polyketones (PEEK, PEK and PEKK) and mixtures thereof. Preferred structural resins are polyamides. More preferred polyamides are nylon 6 and nylon 11. In a preferred embodiment, the structural resin (s) may be contained in an amount ranging from about 10 to 98 wt.%, More preferably from about 20 to 95 wt.%, The elastomer may be contained in an amount in the range from about 2 to 90 wt.%, preferably from about 5 to 80 wt.%, in terms of the polymer mixture. In a preferred embodiment, the elastomer is contained in said mixture in the form of particles dispersed in said structural resin.

In a preferred embodiment, the elastomer is selected from an isobutylene-alkylstyrene copolymer, preferably an isobutylene / p-methylstyrene copolymer, a halogenated isobutylene-alkylstyrene copolymer, preferably a halogenated isobutylene / p-methylstyrene copolymer, star-shaped butyl rubber, halogenated butyl butylobutyl butyl butylobutyl butylbutyl. In another preferred embodiment, the elastomer comprises bromobutyl rubber and / or chlorobutyl rubber.

The elastomer may be contained in the elastomeric mixture in the range of up to 90 ppm in one embodiment, up to 50 ppm in another embodiment, up to 40 ppm in another embodiment, and still up to 30 ppm in another variant, however, in yet another embodiment, the elastomer may be contained in an amount of at least 2 parts / 100, from at least 5 parts / 100 in another embodiment, from at least 5 parts / 100 in another embodiment and yet from at least 10 ppm / 100 in another embodiment. The target option may include any combination of any upper limit in part./100 and any lower limit in part./100.

In other embodiments, the elastomer, either alone or in the form of a mixture (i.e., reactor mixtures, physical mixtures, such as those prepared by melt mixing) of elastomers may be contained in the mixture in an amount of from 5 to 90 ppm in one embodiment, from 10 up to 80 ppm in another embodiment, however, in yet another embodiment, from 30 to 70 ppm / 100, however in yet another embodiment, from 40 to 60 ppm / 100, however, from 5 to 50 ppm / 100 in another embodiment, and yet from 5 to 40 ppm / 100 in another embodiment, however, from 20 to 60 ppm / 100 in another embodiment, and yet from 20 to 50 hours ./100 in yet another embodiment, the chosen embodiment depending upon the desired end use of the mixture.

Elastomeric mixtures may also contain at least one of the other elastomers or two or more elastomers. The elastomer (s) may also be combined with other materials or polymers.

In some embodiments, and when appropriate, the elastomers used in carrying out the invention may be linear, substantially linear, block, or branched.

Elastomeric mixtures may also include many other components, as discussed in more detail below, and may optionally be vulcanized to obtain vulcanized elastomeric mixtures from which end-use products are ultimately made as described in more detail below.

Plastomers

Plastomers that can be used in carrying out the present invention can be described as polyolefin copolymers having a density of from 0.85 to 0.915 g / cm ³ and a melt index (IR) in the range from 0.10 to 30 dg / min. In one embodiment, an acceptable plastomer is a copolymer of units derived from ethylene and derived from at least one C ₃ to C ₁₀ unit α-olefin, a copolymer having a density in the range of from less than 0.915 g / cm ³ . The number of comonomers (derivatized from α-olefin from C ₃ to C ₁₀ units) contained in the plastomer is in the range from 2 to 35 wt.% In one embodiment, from 5 to 30 wt.% In another embodiment, however, from 15 to 25 wt.% In another embodiment, and yet from 20 to 30 wt.% In another embodiment.

The plastomer, which can be used in carrying out the invention, has a melt index (IR) in the range from 0.1 to 20 dg / min (ASTM D1238, 190 ° C, 2.1 kg) in one embodiment, from 0.2 to 10 dg / min in another embodiment, and yet from 0.3 to 8 dg / min in another embodiment. The average molecular weight of suitable plastomers is in the range from 10,000 to 800,000 in one embodiment and from 20,000 to 700,000 in another embodiment. A 1% secant bending modulus (ASTM D790) of suitable plastomers is in the range of 10 to 150 MPa in one embodiment and 20 to 100 MPa in another. Further, the plastomer, which can be used in the mixtures of the present invention, has a melting point (T _PL ) of from 50 to 62 ° C (first melting peak), from 65 to 85 ° C (second melting peak) in one embodiment and from 52 up to 60 ° C (first melting peak) and from 70 to 80 ° C (second melting peak) in another embodiment.

Plastomers that can be used in carrying out the present invention are metallocene-catalyzed copolymers of ethylene derivatized units and units derived from higher molecular weight α-olefins, such as propylene, 1-butene, 1-hexene and 1-octene, which contain a sufficient amount of one or more of these comonomer units to achieve a density in the range from 0.860 to 0.900 g / cm ³ in one embodiment. The molecular weight distribution (Mw / Mn) of the target plastomers is in the range from 2 to 5 in one embodiment and from 2.2 to 4 in another embodiment. Examples of these technically accessible plastomers are EXACT 4150 products, a copolymer of ethylene and 1-hexene, wherein the units derived from 1-hexene comprise from 18 to 22 wt.% Plastomer, which has a density of 0.895 g / cm ³ and IR 3.5 dg / min (ExxonMobil Chemical Company, Houston, TX), and EXACT ™ 8201, a copolymer of ethylene and 1-octene, wherein the units derived from 1-octene comprise from 26 to 30 wt.% plastomer, which has a density of 0.882 g / cm ³ and IR 1.0 dg / min (ExxonMobil Chemical Company, Houston, TX).

Substances for improving technological properties

Functionalized polymer

The invention provides a method for preparing an elastomeric mixture comprising contacting at least one elastomer with a substance for improving technological properties, where the substance for improving technological properties includes at least one functionalized polymer having at least one anhydride group.

At least one functionalized polymer can be obtained by functionalizing at least one polymer with at least one anhydride. So, for example, the process of obtaining upon receipt of at least one functionalized polymer involves the functionalization of the polymer in solution with an anhydride either by means of a thermal "new" reaction or in the presence of chlorine.

In some embodiments, at least one polymer may be derivatized from a polymer obtained by polymerizing monomers including one or more olefins, alpha olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenes and / or substituted styrenes and vinyl ethers. For example, monomers may contain from 2 to 20 carbon atoms, in another embodiment from 2 to 12, and in another embodiment from 4 to 10 carbon atoms.

In one embodiment, the functionalized polymer comprises C ₂ -C ₁₂ -α-olefin derivatized units.

In another embodiment, the functionalized polymer comprises C ₄ -C ₁₀ isoolefin derivatized units.

However, in yet another embodiment, the functionalized polymer includes isobutylene derivatized units.

At least one anhydride group may be derivatized from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride, propenylate succinic anhydride, 2-pentenedicarboxylic acid anhydrides, and mixtures thereof. Illustrative examples can be represented by general formulas:

Such functionalized polymers are widely available and are usually used as lubricants. Examples of suppliers of such products include Infineum International Ltd., Linden, NJ and Chevron Oronite, Company, Houston, TX.

In one embodiment, the at least one functionalized polymer is succinic functionalized polyisobutylene (PIBNA). For example, the production process for the production of PIBNA may include functionalization in a solution of polyisobutylene or polybutene (PIB), such as low molecular weight PIB, with maleic anhydride either by thermal "ENA" reaction (thermal PIBPA) or in the presence of chlorine (chlorine-PIBPA). As with all polymers that need to be functionalized, when appropriate, the starting PIB can be obtained from pure isobutylene monomer or a mixture of butene isomers.

In some embodiments, the number average molecular weight (determined by gel permeation chromatography) of the parent polymer, such as PIB, is in the range of from about 400 (the mass of the molecule in units of atomic mass relative to the hydrogen atom, which is set to 1.0) to about 5000 or higher, in another embodiment, from about 500 to about 2500; in another embodiment, from about 800 to about 2500; and in another embodiment, from about 800 to about 1500.

In some embodiments, the anhydride functional group of the at least one functionalized polymer, such as PIBNA, may be from about 0.5 to about 2.0 mol%, alternatively from about 0.8 to about 1.7 mol%, and in another embodiment, from about 1.0 to about 1.5 mol%.

Technical examples include the functionalized PIBSA 48 polymer from Infineum, mentioned above and derivatized from PIB with Mn 2200 with an anhydride functional group in an amount of about 1.2 mol%, and the functionalized PIBSA 55 polymer derived from PIB with Mn 2200 with an anhydride functional group in an amount about 1.4 mol%. Other technical examples include PIBAA OLOA 15500 from Chevron Oronite, mentioned above, derived from PIB with Mn 1000, and PIBIAA OLOA 15667, derivatized from PIB with Mn 1300.

However, in other embodiments, the process improvement material as described above may have a number average molecular weight (Mn) as determined by gel permeation chromatography, less than 10,000 in one embodiment, less than 8,000 in another embodiment, and yet less than 6,000 in yet one option. In one embodiment, the substance for improving technological properties has a number average molecular weight of more than 400, more than 700 in another embodiment, and yet more than 900 in another embodiment. A preferred embodiment may be a combination of any lower molecular weight limit with any upper molecular weight limit described herein. So, for example, in one embodiment, a substance for improving technological properties may have a number average molecular weight of from 400 to 10,000, from 700 to 8,000 in another embodiment, and yet from 900 to 3,000 in another embodiment.

In some embodiments, the substance for improving technological properties may have a number average molecular weight (Mn) from 450 to 5000, in another embodiment from 500 to 2500, in another embodiment from 900 to 2500, in another embodiment about 1000, in another embodiment about 1300, and in another embodiment, about 2,300.

Illustrative viscosity values (ASTM D445) of a substance for improving technological properties can range from about 10 to about 6,000 cSt (centistokes) at 100 ° C in one embodiment; in another embodiment, from about 35 to about 1000 cSt at 100 ° C, in another embodiment, from about 75 to about 500 cSt at 100 ° C, in another embodiment from about 100 to about 300 cSt at 100 ° C, in another embodiment from about 100 to about 200 cSt at 100 ° C, nonetheless exceeds 35 cSt at 100 ° C in another embodiment, and nevertheless more than 100 cSt at 100 ° C in another embodiment .

Nevertheless, in other embodiments, the viscosity values of the substance to improve the technological properties may be in the range from 10 to 6000 cSt (centistokes) at 100 ° C (in one embodiment) and from 35 to 5000 cSt at 100 ° C (in another embodiment). However, in other embodiments, the viscosity exceeds 35 cSt at 100 ° C (in another embodiment) and exceeds 100 cSt at 100 ° C.

The elastomeric mixture includes or is prepared using from 1 to 60 ppm / 100 in one embodiment, from 2 to 40 ppm / 100 in another embodiment, from 3 to 35 ppm / 100 in another embodiment, however, from 4 to 30 part./100 in another embodiment, however, from 2 to 10 part./100 in another embodiment, however, from 3 to 25 part./100 in another embodiment, and nevertheless from 2 to 20 part ./100 in another embodiment of a substance for improving technological properties, as presented above, where the target interval of the amount of substance for improving technological properties may include any top s limit in portions. / 100 in combination with any lower limit in portions. / 100, described herein.

In one embodiment, the substance for improving technological properties or the elastomeric mixture does not contain aromatic groups or unsaturated bonds.

In another embodiment, the substance for improving technological properties or the elastomeric mixture is free or essentially free, or can only be characterized by concentrations at the level of impurities of aromatic, naphthenic, paraffin oils or mixtures thereof. As used herein, the term “substantially free” refers to a content of 1000 ppm or less, in another embodiment 800 ppm or less, in another embodiment 500 ppm or less, in another embodiment 250 ppm. / million or less, in another embodiment, 100 ppm or less, in another embodiment, 75 ppm or less, in another embodiment, 50 ppm or less, in another embodiment, 20 ppm or less, in another embodiment, 15 ppm or less, in another embodiment, 10 ppm or less, and in another embodiment, 5 ppm or less.

However, in other embodiments, the process improver or elastomeric mixture may include other components, such as the following.

Polybutene

According to one aspect of the invention, polybutene oil for filling rubber in a latex stage may be contained in mixtures for pneumatic diaphragms. In one embodiment of the invention, the polybutene oil for filling rubber in the latex stage is a low molecular weight (Mn less than 15,000) homopolymer or copolymer of olefin derivatized units, each of which contains from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms in another embodiment . Nevertheless, in yet another embodiment, the polybutene is a homopolymer or copolymer of C ₄ raffinate. A variant of such low molecular weight polymers called “polybutene” polymers is described, for example, in Synthetic Lubricants and High-Performance Functional Fluids, p. 357-392 (edited by Rudnick & Shubkin, Marcel Dekker 1999) (hereinafter referred to as “polybutene” oil for filling rubber in the latex stage "or" polybutene ").

In one embodiment of the invention, the polybutene oil for filling rubber in the latex stage is a copolymer of isobutylene derivatized units derived from 1-butene units and derived from 2-butene units. In one embodiment, this polybutene is a homopolymer, copolymer or ternary copolymer of three units in which the isobutylene derivatized units comprise from 40 to 100 wt.% Of the copolymer, the units derived from 1-butene comprise from 0 to 40 wt.% Of the copolymer, and the derivatized from 2-butene, the units comprise from 0 to 40 wt.% copolymer. In another embodiment, the polybutene is a copolymer or a triple copolymer of three units in which the isobutylene derivatized units comprise from 40 to 99 wt.% Of the copolymer, the units derived from 1-butene comprise from 2 to 40 wt.% Of the copolymer, and the derivatized from 2- butene units comprise from 0 to 30 wt.% copolymer. Nevertheless, in yet another embodiment, the polybutene is a triple copolymer of three units in which the isobutylene derivatized units comprise from 40 to 96 wt.% Of the copolymer, the units derived from 1-butene comprise from 2 to 40 wt.% Of the copolymer, and the derivatized from 2-butene, the units comprise from 2 to 20 wt.% copolymer. However, in another embodiment, the polybutene is a homopolymer or copolymer of isobutylene and 1-butene, in which the isobutylene derivatized units comprise from 65 to 100 wt.% Of the homopolymer or copolymer, and the 1-butene derivatized units comprise from 0 to 35 wt.% Of the copolymer .

Polybutene oil for filling rubber in the latex stage, which can be used in carrying out the invention, typically have a number average molecular weight (Mn) of less than 10,000 in one embodiment, less than 8,000 in another embodiment, and less than 6,000 in another embodiment. In one embodiment, the polybutene oil has a number average molecular weight of more than 400, more than 700 in another embodiment, and in another embodiment more than 900. A preferred embodiment may be a combination of any lower molecular weight limit with any upper molecular weight limit described herein. So, for example, in one embodiment of the polybutene according to the invention, this polybutene has a number average molecular weight of from 400 to 10,000, from 700 to 8,000 in another embodiment, and yet from 900 to 3,000 in another embodiment. Values of acceptable viscosity of polybutene oil for filling rubber in the latex stage are in the range from 10 to 6000 cSt (centistokes) at 100 ° C in one embodiment, from 35 to 5000 cSt at 100 ° C in another embodiment, however, exceed 35 cSt at 100 ° C. in yet another embodiment, however, exceed 100 cSt at 100 ° C. in yet another embodiment.

Industrial examples of such latex stage rubber filling oils are PARAPOL ™ Series latex rubber filling oils (ExxonMobil Chemical Company, Houston, TX), such as PARAPOL ™ 450, 700, 950, 1300, 2400 and 2500 ; ORONITE ™ (ChevronTexaco, New Orleans, Louisiana); DAELIM POLYBUTENE ™ (Daelim Industrial Co., Ltd., Korea); INDOPOL ™ (Innovene USA LLC, Lisl, Illinois); TRS PIB (Texas Petrochemicals, Houston, TX). Technically available polybutene oils for filling rubber in the latex stage of the PARAPOL ™ series are synthetic liquid polybutenes, each individual composition having a specific molecular weight and all compositions can be used in the mixture of the invention. The molecular weight of the rubber filling oils in the PARAPOL ™ latex stage is from 420 (PARAPOL ™ 450 product) to 2700 (Mn) (PARAPOL ™ 2500 product), as determined by gel permeation chromatography. The MMP values of PARAPOL ™ oils are in the range from 1.8 to 3 in one embodiment and from 2 to 2.8 in another embodiment.

The table below shows some of the properties of PARAPOL ™ oils that can be used in embodiments of the present invention, the viscosity of which was determined in accordance with ASTM D445, and the molecular weight - gel permeation chromatography.

Properties of substances to improve the technological properties of PARAPOL ^tm individual varieties

Grade Mn Viscosity at 100 ° С, cSt 450 420 10.6 700 700 78 950 950 230 1300 1300 630 2400 2350 3200 2500 2700 4400

PARAPOL ™ latex rubber filling oils have the following other properties: the density (g / ml) of PARAPOL ™ latex rubber filling oils ranges from about 0.85 (PARAPOL ™ 450) to 0.91 (PARAPOL ™ 2500). The bromine number (CG / G) of PARAPOL ™ oils is in the range of 40 for a rubber filling oil in a latex stage with Mn 450 to 8 for a rubber filling oil in a latex stage with Mn 2700.

The elastomeric mixture of the invention may include one or more types of polybutenes in the form of a mixture prepared by mixing either with each other before being added to the elastomer or with the elastomer. In this way, the amount and distinguishing properties (for example, viscosity, Mn, etc.) of a mixture of polybutene oils for filling rubber in the latex stage can be varied. For example, the PARAPOL ™ 450 product can be used when a lower viscosity of the mixture according to the invention is needed, while the PARAPOL ™ 2500 product can be used when a higher viscosity is required, or their compositions can be used to achieve any other viscosity or molecular weight . In this way, the physical properties of the mixture can be controlled. More specifically, the expression “polybutene oil for filling rubber in the latex stage” encompasses one oil or a composition of two or more oils used to achieve any desired viscosity or molecular weight (or other property) at the intervals indicated in the present description.

Polybutene oil or oils for filling rubber in the latex stage are contained in the elastomeric mixture according to the invention in an amount of from 1 to 60 parts / 100 in one embodiment, from 2 to 40 parts / 100 in another embodiment, from 4 to 35 parts / 100 in yet another embodiment, and yet from 5 to 30 ppm / 100 in yet another embodiment, however, from 2 to 10 ppm / 100 in yet another embodiment, however, from 5 to 25 ppm / 100 in still in one embodiment, but from 2 to 20 ppm / 100 in another embodiment, where the target interval for polybutene can be any upper limit in ppm / 100 in combination with any lower limit ohm in part./100 presented in the present description. In a preferred embodiment, the polybutene oil for filling rubber in the latex stage does not contain aromatic groups or an unsaturated bond.

The polyolefin blends of the present invention include a non-functionalized plasticizer (“NFP”). The NFP of the present invention is a compound containing carbon and hydrogen atoms and substantially not containing functional groups selected from hydroxide, aryl and substituted aryl, halogen, alkoxy groups, carboxylates, esters, unsaturated carbon atoms, acrylates, oxygen atoms, nitrogen and carboxyl. The term “to a significant degree” means that these groups and compounds containing these groups are not intentionally introduced into NFP, and if they are present at all, they contain less than 5 wt.% Of NFP in one embodiment, less than 1 wt.% in another embodiment, and yet less than 0.5 wt.% in another embodiment.

In one embodiment, the NFP consists of C ₆ to C ₂₀₀ paraffins and C ₈ to C ₁₀₀ paraffins in another embodiment. In another embodiment, the NFP consists essentially of C ₆ to C ₂₀₀ paraffins and consists essentially of C ₈ to C ₁₀₀ paraffins in yet another embodiment. Taking into account the objectives of the present invention and its description, the term "paraffin" embraces all isomers, such as n-paraffins, branched paraffins, isoparaffins, and may encompass cyclic aliphatic materials and mixtures thereof, they can be derivatized synthetically using means known in the art or from refined crude oil in such a way as to satisfy the requirements presented for the target NFP described in this description. It should be clearly understood that in order to achieve the necessary properties, materials of the classes presented in the present description, which can be used as NFPs, can be used alone or mixed with other NFPs described in the present description.

NFP can be in the polyolefin mixtures according to the invention in an amount of from 0.1 to 60 wt.% In one embodiment, from 0.5 to 40 wt.% In another embodiment, however, from 1 to 20 wt.% In another embodiment and yet in another embodiment, from 2 to 10 wt.%, where the target range may include any upper limit in mass percent with any lower limit in mass percent presented in the present description.

NFP can also be described by any number or any combination of parameters presented in the present description. In one embodiment, the NFP of the present invention has a pour point of below 0 ° C in one embodiment and below -5 ° C in another embodiment, below -10 ° C in another embodiment, however, below -20 ° C in another embodiment nevertheless below -40 ° C in yet another embodiment, nevertheless below -50 ° C in yet another embodiment, and yet below -60 ° C in yet another embodiment, nevertheless above -120 ° C in still in one embodiment and still higher than -200 ° C in another embodiment, where the target range may include any upper limit for the temperature of the yield stress with any lower limit pour point described in the present description. In one embodiment, the NFP is a paraffinic or other compound having a pour point below -30 ° C and in the range from -30 to -90 ° C in another embodiment, in the viscosity range from 0.5 to 200 cSt at 40 ° C (ASTM D445). Most mineral oils, which, as a rule, contain aromatic residues and other functional groups, have a pour point of 10 to -20 ° C in a similar viscosity range.

NFP can have a dielectric constant at 20 ° C less than 3.0 in one embodiment, less than 2.8 in another embodiment, less than 2.5 in another embodiment, however less than 2.3 in another embodiment, and yet less than 2 , 1 in another embodiment. Polyethylene and polypropylene each have a dielectric constant (1 kHz, 23 ° C.) of at least 2.3 (CRC Handbook of Chemistry and Physics (Lide, ed. 82 ^d ed. CRC Press 2001).

NFP has a viscosity (ASTM D445) from 0.1 to 3000 cSt at 100 ° C, from 0.5 to 1000 cSt at 100 ° C in another embodiment, from 1 to 250 cSt at 100 ° C in another embodiment, however from 1 to 200 cSt at 100 ° C in another embodiment, and yet from 10 to 500 cSt at 100 ° C in another embodiment, where the target range may include any upper viscosity limit with any lower viscosity limit presented in the present description.

NFP has a specific gravity (ASTM D4052, 15.5 / 15.6 ° C) of less than 0.920 g / cm ³ in one embodiment, less than 0.910 g / cm ³ in another embodiment, from 0.650 to 0.900 g / cm ³ in another embodiment, from 0.700 to 0.860 g / cm ³ in another embodiment and from 0.750 to 0.855 g / cm ³ in another embodiment, from 0.790 to 0.850 g / cm ³ in another embodiment and nevertheless from 0.800 to 0.840 g / cm ³ in another an embodiment where the target range may include any upper specific gravity with any lower specific gravity presented herein. NFP has a boiling point of from 100 to 800 ° C in one embodiment, from 200 to 600 ° C in another embodiment, and yet from 250 to 500 ° C in another embodiment. Further, NFP has a weight average molecular weight (GPC or GC) of less than 20,000 g / mol in one embodiment, however less than 10,000 g / mol in another embodiment, however less than 5,000 g / mol in yet another embodiment, however less than 4000 g / mol in yet another embodiment, however less than 2000 g / mol in yet another embodiment, however less than 500 g / mol in yet another embodiment, and yet greater than 100 g / mol in yet another embodiment, where the target molecular weight range can be any combination of any upper molecular weight limit with any lower molecular weight limit the masses presented in the present description.

A compound suitable as an NFP for the polyolefins of the present invention may be selected from commercially available compounds such as so-called "isoparaffins", "poly-alpha-olefins" (P-a-O) and "polybutenes" (sub-group P- aO). Compounds of these three classes can be defined as paraffins, which can span branched, cyclic, normal structures and mixtures thereof. These NFPs can be described as spanning C ₆ to C ₂₀₀ paraffins in one embodiment and C ₈ to C ₁₀₀ paraffins in another embodiment.

Isoparaffins

The so-called "isoparaffins" are defined as follows. These paraffins, suitably isoparaffins, are paraffin chains that have a C ₁ to C ₁₀ alkyl branch along at least a portion of each paraffin chain. C ₆ to C ₂₀₀ paraffins may include C ₆ to C ₂₅ isoparaffins in one embodiment and C ₈ to C ₂₀ isoparaffins in another embodiment.

More specifically, isoparaffins are saturated aliphatic hydrocarbons whose molecules have at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e., the molecule has one or more tertiary or quaternary carbon atoms), and preferably in which the total number of carbon atoms per molecule is in the range from 6 to 50, in the range from 10 and 24 in another embodiment, and yet from 10 to 15 in another embodiment. As a rule, various isomers with each number of carbon atoms are contained. These isoparaffins may also include branched side chain cycloparaffins, usually as a small component of isoparaffins. The density (ASTM D4052, 15.6 / 15.6 ° C) of these isoparaffins is in the range from 0.70 to 0.83 g / cm ³ , the pour point is below -40 ° C in one embodiment and below -50 ° C in another embodiment, the viscosity (ASTM 445, 25 ° C) is from 0.5 to 20 cSt at 25 ° C, and the average molecular weights are in the range from 100 to 300 g / mol. Isoparaffins are technically available under the trademark ISOPAR (ExxonMobil Chemical Company, Houston, TX), they are described, for example, in US No. 6197285, US No. 3818105 and US No. 3439088 and are marketed as isoparaffins of the ISOPAR ™ series.

Isoparaffins of the ISOPAR series

Title Boiling range (° C) Pour point (° C) The average specific gravity (g / cm ³ ) Viscosity at 25 ° C (cSt) Saturated and aromatic compounds (wt.%) ISOPAR E 117-136 -63 0.72 0.85 <0.01 ISOPAR G 161-176 -57 0.75 1.46 <0.01 ISOPAR H 178-188 -63 0.76 1.8 <0.01 ISOPAR K 179-196 -60 0.76 1.85 <0.01 ISOPAR L 188-207 -57 0.77 1.99 <0.01 ISOPAR M 223-254 -57 0.79 3.8 <0.01 ISOPAR N 272-311 -63 0.82 14.8 <0.01

In another embodiment, isoparaffins are a mixture of branched and normal paraffins containing from 6 to 50 carbon atoms in the molecule and from 10 to 24 carbon atoms in another embodiment. The isoparaffin composition has a branched paraffin / n-paraffin ratio ranging from 0.5: 1 to 9: 1 in one embodiment and from 1: 1 to 4: 1 in another embodiment. The isoparaffins of the mixture in this embodiment contain more than 50 wt.% (Of the total weight of the isoparaffin composition) of monomethyl materials, for example 2-methyl, 3-methyl, 4-methyl, 5-methyl or the like, with minimal branch formation with substituent groups with the number of carbon atoms is greater than 1, such as, for example, ethyl, propyl, butyl or the like, in terms of the total mass of isoparaffins in the mixture. In one embodiment, the isoparaffins of the mixture contain more than 70 wt.% Monomethyl materials, calculated on the total weight of the isoparaffins in the mixture. The isoparaffin mixture boils in the range from 100 to 350 ° C. in one embodiment and in the range from 110 to 320 ° C. in another embodiment. In the preparation of materials of different varieties, the paraffin mixture is usually divided into fractions having narrow boiling ranges, for example, a boiling range of 35 ° C. These branched paraffin / n-paraffin mixtures are described, for example, in US Pat. No. 5,906,727.

Other suitable isoparaffins are also technically available under the trade names SHELLSOL ™ (Royal Dutch / Shell Group of Companies), SOLTROL ™ (Chevron Phillips Chemical Co. LP) and SASOL ™ (Sasol Limited, Johannesburg, South Africa). Industrial examples are SHELLSOL ™ products (boiling point: from 215 to 260 ° C), SOLTROL 220 (boiling point: from 233 to 280 ° C), SASOL LPA-210 and SASOL-47 (boiling point: from 238 to 274 ° FROM).

Poly alpha olefins

Paraffins suitable as NFP according to the invention also include the so-called poly-alpha-olefins (P-a-O), which are defined as follows. P-a-O, which can be used in carrying out the present invention, include C ₆ to C ₂₀₀ paraffins and C ₁₀ to C ₁₀₀ n-paraffins in another embodiment. P-a-O are dimers, trimers, tetramers, pentamers, etc. C ₄ to C ₁₂ α-olefins in one embodiment and C ₅ to C ₁₂ α-olefins in another embodiment. Suitable olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. In one embodiment, the olefin is 1-decene, and the NFP is a mixture of dimers, trimers, tetramers and pentamers (and higher molecular weight variants) of 1-decene. P-a-O are more specifically defined, for example, in US No. 5171908 and US No. 5783531 and in the work of Synthetic Lubricants and High-Performance Functional Fluids, p.1-52 (edited by Rudnick & Shubkin, Marcel Dekker, Inc. 1999) .

P-a-O of the present invention have a weight average molecular weight of from 100 to 20,000 in one embodiment, from 200 to 10,000 in another embodiment, however, from 200 to 7000 in another embodiment, however, from 200 to 2000 in another variant and nevertheless from 200 to 500 in another embodiment. Typically, P-a-O have viscosity values ranging from 0.1 to 150 cSt at 100 ° C. in one embodiment and from 0.1 to 3000 cSt at 100 ° C. in another embodiment (ASTM D445). P-a-O, which can be used in carrying out the present invention, have pour points below 0 ° C in one embodiment, below -10 ° C in another embodiment, however below -20 ° C in another embodiment, and not less than -40 ° C in another embodiment. Target P-a-O are technically available as P-a-O SHF and SuperSyn (ExxonMobil Chemical Company, Houston, TX).

Poly alpha olefins of the SHF and SuperSyn series

P-a-o Specific Gravity (g / cm ³ , 15.6 / 15.6 ° C) Viscosity at 100 ° С, cSt IW The temperature loss of fluidity, ° C SHF-20 0.798 1.68 - -63 SHF-21 0,800 1.70 - -57 SHF-23 0.802 1.80 - -54 SHF-41 0.818 4.00 123 -57 SHF-61/63 0.826 5.80 133 -57 SHF-82/83 0.833 7.90 135 -54 SHF-101 0.835 10.0 136 -54 SHF-403 0.850 40,0 152 -39 SHF-1003 0.855 107 179 -33 SuperSyn 2150 0.850 150 214 -42 SuperSyn 2300 0.852 300 235 -thirty SuperSyn 21000 0.856 1000 305 -eighteen SuperSyn 23000 0.857 3000 388 -9

Other substances for improving technological properties include esters, polyethers and polyalkylene glycols.

In the preparation of the elastomeric mixtures according to the invention, other substances may be contained or used to improve technological properties. Substances for improving technological properties include, although not limited to, plasticizers, tackifiers, dry diluents, chemical conditioning agents, homogenization aids and peptizing agents such as mercaptans, petroleum and vulcanized vegetable oils, mineral oils, paraffin oils polybutene oils, naphthenic oils, aromatic oils, waxes, resins, rosins, etc.

Some mineral oils that differ in their viscosity index and the amount of saturated products and sulfur they contain are classified by the American Petroleum Institute (ANI) into groups I, II and III of hydrocarbon base components. The basic components of group I are solvent refined mineral oils. They contain the largest portion of unsaturated foods and sulfur and have the lowest viscosity indexes.

The materials of groups II and III are mineral oils with high viscosity indices and very high viscosity indices. They are hydrotreated mineral oils. Group III oils contain less unsaturated products and sulfur than group I oils and have higher viscosity indices than group II oils. Rudnick and Shubkin in Synthetic Lubricants and High-Performance Functional Fluids, second edition edited by Rudnick & Shubkin, Marcel Dekker, Inc. New York, 1999, describes mineral oils as typically representing the following.

Group I mineral oils are refined using solvent extraction of aromatic compounds, solvent dewaxing, hydrotreating in order to reduce the sulfur content to obtain mineral oils with sulfur concentrations above 0.03 wt.%, Saturated product concentrations from 60 to 80% and a viscosity index of about 90.

Group II mineral oils were subjected to moderate hydrocracking with conventional solvent extraction of aromatic compounds, dewaxing with a solvent and more stringent hydrotreating in order to lower sulfur concentrations to below or equal to 0.03 wt.%, As well as to remove double bonds in some olefinic and aromatic compounds; the concentration of saturated products is more than 95-98%, and the IW is approximately 80-120.

Mineral oils of group III are severely hydro-processed, with virtually 100% concentrations of saturated products in some oils, sulfur concentrations are less than or reach 0.03 wt.% (Preferably in the range of 0.001 to 0.01%), and VI exceeds 120.

A substance for improving technological properties, as a rule, is contained or is used in the production process in an amount of from 1 to 70 parts / 100 in one embodiment, from 3 to 60 parts / 100 in another embodiment, and nevertheless from 5 to 50 parts ./100 in another embodiment.

In one embodiment of the invention, paraffinic, naphthenic and / or aromatic oils are essentially absent, which means that they are not intentionally added to the mixture or, if in an alternative embodiment, they are contained only in an amount of up to 0.2 wt.% from mixtures used for the manufacture of pneumatic diaphragms.

Fillers

The elastomeric mixture may have one or more filler components, such as, for example, calcium carbonate, silicon dioxide, clay and other silicates, which may or may not be exfoliated, mica, talc, titanium dioxide and carbon black.

The fillers of the present invention can be characterized by any particle size, which is usually in the range, in particular from about 0.0001 to about 100 microns. Used in the present description, the term "silicon dioxide" is used to denote silicon dioxide with particles of any type or size or another derivative of silicic acid, or silicic acid itself after processing by solution, pyrogen or similar methods, and these particles are characterized by specific surface area, including untreated precipitated silica, crystalline silica, colloidal silicon dioxide, aluminum and calcium silicates, colloidal silicon dioxide, and the like.

In one embodiment, the filler is carbon black or a modified carbon black and combinations of any of them. In another embodiment, the filler is a mixture of carbon black and silica. A preferred filler for products such as tire treads and sidewalls is a semi-reinforcing carbon black contained in an amount of 10 to 100 ppm of the mixture, more preferably 30 to 80 ppm of 100 in another embodiment and yet 50 to 80 ppm / 100 in another embodiment. Carbon black acceptable grades, as set forth in Rubber Technology, c. 59-85 (1995), covered by a range of products from N110 to N990. More suitable carbon blacks that can be used, for example, in tire tread material, are N229, N351, N339, N220, N234 and N110 products meeting ASTM D3037, D1510 and D3765 standards. Variants of carbon black, which can be used, for example, in the material of the sidewalls of tires, are products N330, N351, N550, N650, N660 and N762. Options for carbon black that can be used in tire liners and other pneumatic diaphragms are N550, N660, N650, N762, N990 and Regal 85.

The layered filler may include layered clay, optionally treated or pretreated with a modifying agent, such as organic matter. Elastomeric mixtures may include clay, optionally treated or pre-treated with a modifying agent to form a nanocomposite or nanocomposite mixture.

Nanocomposites may include at least one elastomer, as described above, and at least one modified layered filler. The modified layered filler may be prepared by a method comprising contacting at least one layered filler, such as at least one layered clay, with at least one modifying agent.

Modified layered filler can be prepared by methods and using equipment well known to specialists in this field of technology (see, for example, US No. 4569923, US 5663111, US 6036765 and US 6787592). Illustrations of such methods are presented in the examples section. However, their list is by no means exhausted.

In one embodiment, a layered filler, such as layered clay, may include at least one silicate.

In some embodiments, the silicate may include at least one “smectite” or “smectic type clay”, belonging to the general class of clay minerals with expanding crystal lattices. So, for example, dioctahedral smectites, which consist of montmorillonite, beidellite, and nontronite, and trioctahedral smectites, which include saponite, hectorite, and coconite, can be attributed to them. Smectic clays obtained by synthetic means, for example, by hydrothermal methods, as described in US 3252757, 3586468, 3666407, 3671190, 3844978, 3844979, 3852405 and 3855147 are also covered.

However, in other embodiments, at least one silicate may include natural or synthetic phyllosilicates, such as montmorillonite, nontronite, beidellite, bentonite, volkonskoit, laponite, hectorite, saponite, coconite, magadite, kenyaite, stevensite, etc., and also vermiculite, halloysite, aluminate oxides, hydrotalcite, etc. Combinations of any of the previous options are also contemplated.

A layered filler, such as layered clays described above, can be modified, in particular intercalated, or separated by treatment with at least one modifying agent or a swelling agent, or an exfoliating agent, or an additive capable of undergoing ion exchange reactions with cations located on interlayer surfaces of the layered filler.

Modifying agents are also known as swelling or delaminating agents. Usually they are additives capable of entering into ion-exchange reactions with cations located on the interlayer surfaces of the layered silicate. Suitable exfoliating agents include cationic surfactants such as ammonium, alkyl amines and alkyl ammonium (primary, secondary, tertiary and quaternary), phosphonium and sulfonium derivatives of aliphatic, aromatic and arylaliphatic amines, phosphines and sulfides.

For example, amine compounds (or having the corresponding ammonium ion) are compounds of the formula R ² R ³ R ⁴ N, in which R ² , R ³ and R ⁴ , which may be the same or different, are C ₁ to C ₃₀ alkyls or alkenes in one embodiment, C ₁ to C ₂₀ alkyls or alkenes in another embodiment. In one embodiment, the exfoliating agent is a so-called long chain tertiary amine in which at least R ² is C ₁₄ to C ₂₀ alkyl or alkene.

In other embodiments, the class of exfoliating agents includes those that can be covalently bonded to interlayer surfaces. These include polysilanes of the structure —Si (R ⁵ ) ₂ R ⁶ , where R ⁵ is the same or different in each case, and their values are selected from alkyl, alkoxy, and oxysilane, and R ⁶ is an organic radical compatible with the matrix polymer of the composite.

Other suitable delaminating agents include protonated amino acids and their salts containing from 2 to 30 carbon atoms, such as 12-aminododecanoic acid, epsilon-caprolactam and the like. materials. Suitable swelling agents and methods for intercalating layered silicates are described in US 4,472,538, 4,810,734, 4,889,885, and also WO 92/02582.

In one embodiment, the exfoliating agent or additives are capable of interacting with the halogen portions of the halogenated elastomer to form complexes that facilitate the exfoliation of the clay. In some embodiments, these additives include all primary, secondary, and tertiary amines and phosphines, alkyl and aryl sulfides, and thiols, as well as multifunctional variants thereof. Suitable additives include long chain tertiary amines, such as N, N-dimethyl octadecylamine and N, N-dioctadecyl methylamine, the so-called dihydrogenated tall oil alkylmethyl amines and the like, and polytetrahydrofuran with an amino terminal group, long chain thiol and thiosulfate sulfate compounds.

However, in other embodiments, the modifying agents include a polymer chain comprising a carbon chain of length C ₂₅ to C ₅₀₀ , where this polymer chain also includes an ammonium functionalized group represented by the following group, suspended from polymer chain E:

in which the values of each R, R ¹ and R ² , which are the same or different, are independently selected from hydrogen atom, C ₁ to C ₂₆ alkenes and aryls, C ₁ to C ₂₆ substituted alkyls, alkenes and C ₁ to C ₂₆ aryls, aliphatic alcohols and C ₁ to C ₂₆ ethers, carboxylic acids, nitriles, ethoxylated amines, acrylates and C ₁ to C ₂₆ esters; and wherein X is an ammonium counterion such as Br ^- , Cl ^- and PF ₆ ^- .

A modifying agent, such as that provided herein, is contained in the mixture in an amount necessary to achieve optimal air retention, as determined by the permeability test presented herein. So, for example, although this should not be limited, this agent can be contained in an amount of from 0.1 to 40 ppm / 100 in one embodiment, however, from 0.2 to 20 ppm / 100 in another embodiment and from 0 , 3 to 10 ppm / 100 in another embodiment.

An exfoliating agent can be added to the mixture at any stage. So, for example, this additive can be introduced into the elastomer followed by the addition of a layered filler, or it can be introduced in a combination of at least one elastomer and at least one layered filler, or nevertheless, in yet another embodiment, the additive can first be mixed with a layered filler followed by the addition of elastomer.

Examples of some industrial products are products called Cloisites, which are manufactured by Southern Clay Products, Inc. in Gunsalas, Texas. Examples are Cloisite Na ⁺ , Cloisite 30B, Cloisite 10A, Cloisite 25A, Cloisite 93A, Cloisite 20A, Cloisite 15A and Cloisite 6A. They are also available under the names SOMASIF and LUCENTITE clays from CO-OP Chemical Co., LTD. in Tokyo, Japan. Examples include SOMASIF ™ MAE, SOMASIF ™ MEE, SOMASIF ™ MPE, SOMASIF ™ MTE, SOMASIF ™ ME-100, LUCENTITE ™ SPN and LUCENTITE (SWN).

The amount of clay or layered clay introduced into the nanocomposites in accordance with one embodiment of the invention is sufficient to provide improved mechanical properties or barrier properties of the nanocomposite, for example, tensile strength at break or permeability to oxygen. The amount of clay in the nanocomposite is usually in the range from 0.5 to 10 wt.% In one embodiment and from 1 to 5 wt.% In another embodiment, in terms of the polymer component of the nanocomposite. The content of clay or layered clay expressed in parts per hundred parts of rubber may be from 1 to 30 ppm in one embodiment and from 5 to 20 ppm in another embodiment.

Structuring agents, curing agents, curing groups and curing processes

In some embodiments, elastomeric mixtures and articles made from these mixtures may include or be made using at least one vulcanizing group, at least one vulcanizing agent, at least one structuring agent, and / or are processed during the vulcanization of the elastomeric mixture . Used in the present description, the term "at least one group of vulcanizing substances" refers to any material or method suitable for imparting rubber properties of vulcanized material, as is usually understood in this industry. At least one group of vulcanizing substances may include any and at least one of the following substances.

In a preferred embodiment, the elastomeric mixtures of the present invention use one or more structuring agents, preferably when silicon dioxide is the main filler or is contained in combination with another filler. Structuring and curing agents include sulfur, zinc oxide and fatty acids. In a more preferred embodiment, the binder may be a bifunctional organosilane structuring agent. The term "organosilane structuring agent" means any silane-linked filler and / or structurant activator and / or silane enhancing agent known to those skilled in the art, including, although not limited to, vinyltriethoxysilane, vinyl-tris- (beta- methoxyethoxy) silane, methacryloylpropyltrimethoxysilane, gamma-aminopropyltriethoxysilane (marketed as Witco product A1100), gamma-mercaptopropyltrimethoxysilane (Witco product A189), and the like. and mixtures thereof. In one embodiment, bis- (3- (triethoxysilylpropyl) tetrasulfide (marketed as a Si69 by Degussa) is used.

Peroxide curing groups or polymer curing groups may also be used.

Heat or radiation-induced polymer crosslinking can be used.

Polymer blends, such as those used in tire manufacturing, are usually cured, thereby improving the mechanical properties of the polymers. The physical properties, performance, and durability of vulcanized rubber compounds are known to be directly related to the number (density) of cross-links and the type of cross-links formed during the vulcanization reaction [see, for example, WFHelt et al. The Post Vulcanization Stabilization for NR , Rubber World, 18-23 (1991)].

Sulfur is the most common chemical curing agent for diene-containing elastomers. It exists in the form of a diamond-shaped 8-membered ring or in an amorphous polymer form. The sulfur vulcanizing group also consists of an accelerator for activating sulfur, an activator and a moderator to help control the rate of vulcanization. Accelerators are used to control the onset and rate of vulcanization, the number and type of sulfur cross-links that form. These factors play a significant role in determining the operational properties of the vulcanizate.

Activators are chemicals that increase the rate of vulcanization by first reacting with accelerators to produce rubber-soluble complexes, which then interact with sulfur to form sulfonating agents. General classes of accelerators include amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like.

Moderators can be used to delay the start of vulcanization in order to provide unvulcanized rubber with sufficient processing time.

By their reaction with metal oxides, halogen-containing elastomers such as halogenated star-shaped butyl rubber, brominated butyl rubber, chlorinated butyl rubber (star-brominated butyl rubber (isobutylene-isoprene copolymer), halogenated isobutylene-polyethylene chloropolyrene-polyethylene chloropolymer and polyethylene can be structured. The metal oxide is believed to interact with halogen groups in the polymer to form an active intermediate, which then further interacts with the formation of carbon-carbon bonds. Zinc halide, which serves as an autocatalyst for this reaction, is released as a by-product.

Typically, polymer mixtures can be structured by the addition of vulcanizing agents, for example sulfur, metal oxides, organometallic compounds, initiators of free radical polymerization, etc., followed by heating. Thus, in particular, the usual vulcanizing groups, which are typically used in the practice of the present invention, are the following metal oxides: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ and NiO. These metal oxides can be used alone or in combination with an appropriate metal fatty acid complex (e.g., zinc stearate, calcium stearate, etc.) or with organic and fatty acids added on their own, such as stearic acid, and optionally with other vulcanizing agents such as sulfur and a sulfur compound, an alkyl peroxide compound, diamines and their derivatives (for example, DIAK products marketed by DuPont) [see also, Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber World, c.25-30 (1993)]. The process of vulcanization of elastomers, carried out by this method, can be accelerated, and during the vulcanization of elastomeric mixtures, they often resort to acceleration.

Acceleration of the vulcanization process when carrying out the present invention is achieved by adding to the composition a certain amount of accelerator, often an organic compound. The mechanism of accelerated vulcanization of natural rubber involves complex interactions between a vulcanizing agent, a vulcanization accelerator, activators and polymers. Ideally, in the formation of effective cross-links that bind two polymer chains to each other and increase the overall strength of the polymer matrix, all available vulcanizing agent is consumed. A wide variety of accelerators are known in the art, which include, although not limited to, the following products: stearic acid, diphenylguanidine (DFG), tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBT) 2-mercaptobenzothiazyl disulfide (MBTC), hexamethylene-1,6-bistiosulfate disodium salt dihydrate (marketed as DURALINK ™ HTS by Flexsys), 2- (morpholintio) benzothiazole (MBZ or MOP), 90% MOP and 10% MBS (product MOP 90), N-tert-butyl-2-benzothiazolsulfenamide (TB BS) and N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOC), zinc 2-ethylhexanoate (EHC) and thiourea.

Other components

The mixtures prepared in accordance with the present invention, as a rule, contain other components and additives that are usually used in rubber compounds, in particular effective amounts of other uncolored and non-bleached substances to improve technological properties, pigments, antioxidants and / or antiozonants.

Processing

Mixtures of elastomers may be reactor mixtures and / or mixtures of melts. The components can be mixed by combining the polymer components, filler and intercalate clay in any suitable mixing device, such as open rollers, Brabender ™ closed rubber mixer, Banbury ™ closed rubber mixer with tangential rotors, Krupp closed rubber mixer with compatible rotor blocks or, preferably, a mixer / syringe machine according to a method known in the art. The mixing is carried out at temperatures in the range to the melting point of the elastomer and / or auxiliary rubber used in the mixture, in one embodiment, from 40 to 250 ° C in another embodiment, and nevertheless from 100 to 200 ° C in another embodiment, under conditions a shear action sufficient to allow the clay intercalate to delaminate and become uniformly dispersed within the polymer to form a nanocomposite.

As a rule, initially from 70 to 100% of the elastomer or elastomers are mixed for 20 to 90 seconds or until the temperature reaches a range of 40 to 75 ° C. Then, as a rule, 3/4 of the filler and the remaining amount of elastomer, if any, are added to the rubber mixer, and stirring is continued until the temperature reaches a range of 90 to 150 ° C. Then add the remaining filler, as well as a substance to improve the technological properties and stirring is continued until the temperature reaches a range from 140 to 190 ° C. Subsequently, the masterbatch mixture is subjected to finishing by leafing on open rollers and allowed to cool, for example, to a temperature of 60 to 100 ° C, after which vulcanizing agents are added.

In one embodiment, mixing with clays is carried out according to a method known to those skilled in the art in which clay is added to the polymer at the same time as carbon black. Substances for improving technological properties in the mixing cycle, as a rule, are added later, after carbon black and clay achieve adequate dispersion in the elastomeric matrix.

The vulcanized rubber compounds according to the invention may include various elastomers and fillers together with the substance to improve technological properties. The mixtures of the invention typically include isobutylene-based elastomers such as a halogenated isobutylene / p-methyl styrene copolymer, butyl rubber and a halogenated star-shaped butyl rubber (EOGB), either alone or in some combination with each other, and in one embodiment, the substance to improve technological properties contained in an amount of from 5 to 30 ppm./100.

In one embodiment, the mixture is a halogenated butyl rubber component in an amount of from 70 to 97 ppm / 100, which may include general purpose rubber in an amount of from 3 to 30 ppm / 100, and a substance for improving technological properties, contained in an amount of from 3 to 30 ppm / 100, a filler such as carbon black in an amount of from 20 to 100 ppm / 100, and exfoliating clay in an amount of from 0.5 to 20 ppm / 100 in one embodiment and from 2 to 15 ppm / 100 in another embodiment. Vulcanizing agents such as phenolic resins, sulfur, stearic acid and zinc oxide may be present in an amount of from 0.1 to 10 ppm.

In another embodiment, the mixture may be a halogenated butyl rubber component contained in an amount of from 75 to 97 ppm / 100 in one embodiment and from 80 to 97 ppm / 100 in another embodiment, and a substance for improving technological properties contained in an amount of from 3 up to 30 ppm / 100, a filler such as carbon black in an amount of from 20 to 100 ppm / 100 and exfoliating clay in an amount of from 0.5 to 20 ppm / 100 in one embodiment and from 2 to 15 ppm / 100 in another embodiment. Vulcanizing agents such as phenolic resins, sulfur, stearic acid and zinc oxide may be present in an amount of from 0.1 to 10 ppm.

However, in yet another embodiment, the mixture may be a halogenated butyl rubber component contained in an amount of from 85 to 97 ppm / 100 in one embodiment and from 90 to 97 ppm / 100 in another embodiment, and a substance for improving technological properties contained in an amount of from 3 to 30 ppm / 100, a filler such as carbon black in an amount of from 20 to 100 ppm / 100 and exfoliating clay in an amount of from 0.5 to 20 ppm / 100 in one embodiment and from 2 to 15 part./100 in another embodiment. Vulcanizing agents such as phenolic resins, sulfur, stearic acid and zinc oxide may be present in an amount of from 0.1 to 10 ppm.

An isobutylene-based elastomer that can be used in carrying out the invention can be mixed with various other rubbers or plastics, as described herein, in particular with thermoplastic resins such as nylons and polyolefins, such as polypropylene and propylene copolymers. These mixtures can be used as pneumatic diaphragms, such as diaphragms of vulcanizer-formators, tires, car tire chambers, inner shells of tires, pneumatic tubes (such as pneumatic shock absorbers), diaphragms, and also for other purposes where high air-holding capacity is required or oxygen. In one embodiment, the vulcanized mixture, when the product is molded from it, has an oxygen permeability of MOCON at 60 ° C. at about 40.0 cc · mm / m ² · day · mmHg, in another embodiment, about 45, 0 cc · mm / m ² · day · mm Hg, alternatively about 50.0 cc · mm / m ² · day · mm Hg or in another embodiment about 75.0 cc · mm / m ² · day · mmHg

In one embodiment, the pneumatic diaphragm can be manufactured by combining at least one random copolymer comprising a unit derived from an isomonoolefin with C ₄ no C ₇ , at least one filler and a functionalized polymeric substance to improve technological properties having a number average molecular weight greater than 400, and at least one vulcanizing agent and vulcanization of these combined components, as described above.

In some embodiments, elastomeric mixtures may optionally include:

a) at least one filler, for example calcium carbonate, clay, mica, silicon dioxide, silicates, talc, titanium dioxide, starch, wood flour, carbon black and mixtures thereof;

b) at least one clay, for example montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, coconite, magadite, kenyaite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite and mixtures thereof, optionally treated with modifying agents;

c) at least one oil for filling rubber in the latex stage, for example aromatic oil, naphthenic oil, paraffin oil, and mixtures thereof;

g) at least one substance for improving technological properties, for example plastomer, polybutene, poly-alpha olefin oils or mixtures thereof;

e) at least one vulcanizing group or vulcanizing substance, or at least one treatment to which the elastomeric mixture is subjected to obtain a vulcanized mixture;

e) any combination of components from a) to e).

Elastomeric mixtures, as presented above, can be used in the manufacture of pneumatic membranes, such as inner casings of tires and chambers used in the manufacture of tires. Methods and equipment used for the manufacture of inner shells of tires and the tires themselves are well known in the art (see, for example, US No. 6834695, 6832637, 6830722, 6822027, 6814116, 6805176, 6802922, 6802351, 6799618, 6796348, 6796347, 6617383, 6564625 and 6538066). By any particular method of manufacturing products, such as inner shells of tires and the tires themselves, the scope of the invention is not limited.

Industrial Applicability

The rubber compounds according to the invention can be extruded, subjected to direct compression, blow molding, injection molding and layering in the manufacture of products of various configurations, including fibers, films, layered materials, layers, industrial parts such as automobile parts, electrical appliance housings, consumer products , packaging, etc.

In particular, these rubber compounds can be used in materials of such products for various purposes, where tires are used, such as tires for trucks, tires for buses, tires for cars, tires for motorcycles, high cross-country tires, tires for aircraft, etc. Rubber compounds can serve as either the material from which the finished product is made, or a component of the finished product, such as the inner shell of the tire. The product can be selected from pneumatic diaphragms, pneumatic membranes, films, layers (microlayers and / or multilayers), inner shells of tires, tubes, sidewalls, treads, diaphragms of vulcanizer-formatters, tires, etc.

In another application, elastomeric mixtures can be used in airbags, air springs, bellows-type air cylinders, hoses, battery packs and belts such as conveyor belts and car belts.

They can be used in molded rubber parts and are widely used in automotive suspension vibration isolators, suspension brackets for automobile exhaust pipes and body mounts.

Moreover, these elastomeric mixtures can also be used as adhesives, sealing compounds, sealants and putties for glazing. They can also be used as plasticizers in rubber compounds from which stretch wrapping films are made, as dispersants in lubricants and in materials for compounding and filling electrical cables.

As for other applications, however, the elastomer (s) or elastomeric mixtures according to the invention are also effective in some applications, such as chewing gum, as well as for medical purposes, in particular in pharmaceutical sealing devices and locking elements, coatings for medical devices and technology for the manufacture of paint rollers.

All the priority documents, publications and patent applications mentioned in the present description, test methods (such as ASTM methods) are fully included as references to the extent that their contents are not consistent with the present invention, in accordance with all jurisdictions that allow such inclusion.

When numerical lower limits and numerical upper limits are indicated herein, ranges from any lower limit to any upper limit are contemplated.

Although the invention has been described and illustrated with reference to specific embodiments, various other modifications are obvious to those skilled in the art that can be easily implemented without departing from the spirit and scope of the invention. Therefore, there are no intentions to limit the scope of the attached claims to the examples and illustrations given in the present description previously, since the claims should be construed as encompassing all the features of the claimed novelty that are inherent in the present invention, including all the distinguishing features that are specialists in this field the technology to which the invention relates would be construed as their equivalents.

EXAMPLES

Physical Test Methods

Test methods are summarized in table 1.

Vulcanization properties were determined using an MDR 2000 device with an arc of 0.5 ° or ODR 2000 with an arc of 3 ° and the indicated temperature. Test samples were vulcanized at the indicated temperature, typically from 150 to 160 ° C for a time corresponding to t90 + appropriate heating of the mold. The values “MH” and “ML” used in this case and throughout the present description refer to “maximum torque” and “minimum torque”, respectively. The value "PM" is the value of the Mooney scorch, the value "ML (1 + 4)" indicates the value of the Mooney viscosity. The error (2σ) in this last definition is ± 0.65 units. Mooney viscosity. The value "t" indicates the time of vulcanization in minutes, and the value "ts" indicates the time of vulcanization.

When possible, ASTM tests were performed to determine the physical properties of the vulcanized mixture (see table 1). The stress / strain properties (tensile strength at break, elongation at break, modulus, fracture energy) were determined at room temperature using an Instron 4202 tensile testing machine or an Instron IX automated material testing system on March 6, 08, 2008. The tensile strength measurements were carried out at room temperature on samples (in the form of a dumbbell) of a width of 0.25 inches (0.62 cm) and a length of 1.0 inch (2.5 cm) (between two extended ends). The thickness of the samples was varied and measured manually using a Mitutoyo digital measuring instrument connected to a system computer. Samples were stretched at a slider speed of 20 inches / min (51 cm / min) and stress / strain data were recorded. The average stress / strain values of at least three samples were recorded. The error (2σ) in determining the tensile strength was ± 0.47 MPa. The error (2σ) for elongation of 100% was ± 0.11 MPa, the error (2σ) in determining the relative elongation at break was ± 13%. Shore A hardness was determined at room temperature using a Zwick Duromatic instrument.

Permeability to oxygen was determined using a MOCON OxTran model 2/61 instrument, operating on the principle of dynamic determination of oxygen penetration through a thin film according to the publication of Pasternak et al. In Journal of Polymer Science: Part A-2, Volume 8, p. 467 (1970) . The units of measure are cc · mm / m ² · day · mmHg In general, this method consists in the following: a flat film or rubber samples are clamped in diffusion cells, from which residual oxygen is removed by blowing using an oxygen-free carrier gas. This gaseous carrier is directed to the sensor until a stable zero value is established. Further, pure oxygen or air is introduced from the outside of the chamber with diffusion cells. Oxygen diffusing through the film into the chamber is directed to a sensor that detects the rate of oxygen diffusion.

Permeability tests were carried out according to the following method. Thin vulcanized test samples from reference mixtures were fixed in diffusion cells and conditioned in an oil bath at 65 ° C. To determine the permeability of this sample for air, the time required for the penetration of air through it was noted. Test samples were round plates with a diameter of 12.7 cm and a thickness of 0.38 mm. The error (2σ) in determining air permeability is ± 0.245 (× 10 ⁸ ) units.

In one embodiment, the mixture has a permeability of MOCON at 60 ° C. less than 56.0 × 10 ⁻⁸ cc · mm / m ² · day · mmHg

In another embodiment, the mixture has a permeability of MOCON at 60 ° C less than 50.0 × 10 ⁸ cc · mm / m ² · day · mm Hg

However, in yet another embodiment, the mixture has a MOCON permeability at 60 ° C. of less than 45.0 × 10 ⁻⁸ cc · mm / m ² · day · mmHg

Such a mixture can be used for the manufacture of any number of products. In one embodiment, the product is selected from apertures of a vulcanizer formator for tires, tires for vulcanization of tires, inner shells of tires, chambers for automobile tires and pneumatic nipples. Other useful items that can be made using the mixtures of the invention include hoses, seals, molded products, cable sheaths, and other products described in The Vanderbilt Rubber Handbook 637-772 (edited by RFOhm, ed., RTVanderbilt Co., Inc. 1990).

Table 1 Test methods Parameter Units Test Mooney viscosity (polymer) ML 1 + 8, 125 ° C, unit ASTM D 1646 Mooney viscosity (rubber compound) ML 1 + 4, 100 ° C, unit ASTM D1646 Durability to processing (tension at elongation by 100%) psi ASTM D 412 MOCON (at 60 ° C) cc · mm / m ² · day · mm Hg See text Breathability at 65 ° C cm ³ · cm / cm ² · s · at × 10 ⁸ See text Fragility ° C ASTM D 746 Mooney scorch time ts5, 125 ° C, min ASTMD 1646 Oscillating disk plastometer (ODP) value at 160 ° С, arc: ± 3 ° ASTM D 2084 Moving head plastometer (BCP) at 160 ° C, arc: ± 0.5 ° ML dn · m MN dn · m ts2 min t50 min t90 min Physical properties of the vulcanized in the press mixture Tc 90 + 2 min at 160 ° C ASTM D 2240 ASTMD 412 Head C Hardness And on Shore Tensile stress at 20, 100, 300% MPa Tensile strength MPa Elongation at break % Energy of destruction N / mm (J) After aging with hot air, 72 hours at 125 ° C Hardness And on Shore Tensile stress at 20, 100,300% MPa ASTM D 573 Tensile strength MPa Elongation at break % Energy of destruction N / mm (J) Flexometer de Mattia mm in kilocycles ASTM D 573 (modified method)

Functional Polymer Testing

By mixing in a closed Krupp rubber mixer equipped with compatible rotor blocks in a two-stage method, a functionalized polymer, polyisobutylene succinic anhydride (PIBYAA, exp. 3), was introduced into the bromobutyl rubber mixture for the inner shell of the tire together with other rubber components of the recipe (see table 2). A batch of 1200 grams was used at each mixing stage. In the first stage, mixing was carried out at a constant rotor speed of 60 rpm by loading all polymers and stirring for 30 s. Next, 75% carbon black was added and the mixture was continued to mix for another 30 s. Non-particulate fillers (clay, etc.) and substances for improving technological properties (emollient, NFP, functional polybutene of the present invention) were added and the mixture was continued to mix for another 30 s. The remaining carbon black and resins (Struktol 40MS, SP-1068) were added and the mixture was continued to mix until a total of 240 seconds passed or the temperature reached 300 ° F in the mixer, whichever was the first. The second stage was mixing (a 1200-gram batch) in a closed Krupp rubber mixer equipped with compatible rotor blocks at a rotor speed of 45 rpm. To control the temperature of the closed rubber mixer used maximum cooling. At this stage, one initial masterbatch and all vulcanization stabilizers (stearic acid, zinc oxide, sulfur, accelerator) were added and the mixture was continued to mix until a total of 150 s passed or until the temperature reached 220 ° F in the mixer, depending on of what turned out to be the first. After each mixing step in the Krupp mixer, open rollers were used to scroll through the rubber compounds. Mixtures with a naphthenic softener, control 1, and NFP with a polyisobutylene substance to improve technological properties, control 2, were prepared similarly to those described in comparative examples. The formulations are presented in table 3.

Table 3 Test bromobutyl rubber compounds for the inner shell of the tire Component Control 1 Control 2 Exp. 3 BIIR 2222 one hundred one hundred one hundred NR, SMR 20 Carbon black N660 60 60 60 SP-1068 four four four Struktol 40MS 7 7 7 Calsol 810 latex rubber filling oil 8 Polybutene, Parapol 950 8 Functionalized Polybutene, PIBSA C-9220 8 Stearic acid one one one Zinc Oxide, Kadox 911 one one one Sulfur 0.5 0.5 0.5 MBTS 1.25 1.25 1.25

The results of vulcanization and tests for the physical properties of the vulcanized material show that the use of the functionalized PIBYAA polymer (exp. 3) retains the reduced air permeability of the MOCON device, achieved when PIB NFP substance is used in the mixture for the inner shell of the tire to improve technological properties (control 2) instead of naphthenic oil for filling rubber in the latex stage (control 1). Material exp. 3 is characterized by a higher Mooney scorch value compared to that achieved using PIB NFP (control 2) and an increased vulcanization time ts2 compared to that achieved using naphthenic oil for filling rubber in the latex stage (control 1) and PIB NFP ( control 2), which allows to simplify the processing at subsequent stages of tire manufacturing. Material exp. 3 is characterized by a lower value of resistance to cut growth, determined on a de Mattia flexometer, in comparison with those achieved using naphthenic oil for filling rubber in the latex stage (control 1) or PIB NFP (control 2) (see table 4) . Other vulcanization properties and physical properties of the vulcanized material are preserved.

By mixing in a closed Krupp rubber mixer in a two-stage method, which is almost identical to the method for preparing control mixtures 1 and 2 and experimental mixture 3, a functionalized polymer, polyisobutylene succinic anhydride (PIBYAA, exp. 6) were introduced into the mixture of bromobutyl rubber for the inner shell of the tire together with other rubber components of the recipe (see table 2). Mixtures with naphthenic oil for filling rubber in the latex stage, control 4, and NFP polyisobutylene substance to improve technological properties, control 5, were prepared similarly to those described in comparative examples. The mixtures are presented in table 5.

Table 5 Test compounds of bromobutyl rubber for the inner shell of the tire Mixture Control 4 Control 5 Exp.6 MIC 2222 one hundred one hundred one hundred Carbon black N660 60 60 60 Clay, Cloisite 20A 0 5 5 Latex Stage Rubber Filling Oil, Calsol 810 8 PIB, TRS 5230 8 PIBSA 55 8 SP-1068 four four four Struktol 40MS 7 7 7 Stearic acid one one one Zinc Oxide, Kadox 911 one one one Sulfur 0.5 0.5 0.5 MBTS 1.25 1.25 1.25

The results of vulcanization and tests for the physical properties of the vulcanized material show that the use of the functionalized PIBYAA polymer (exp. 6) retains the reduced air permeability of the MOCON device, achieved when PIB NFP substance is used in the mixture for the inner shell of the tire to improve technological properties (control 5) instead of naphthenic oil for filling rubber in the latex stage (control 4). Material exp.6 has a higher Mooney vulcanization value when compared with the values in the case of naphthenic oil for filling rubber in the latex stage (control 4) and PIB NFP (control 5), which makes it possible to simplify the processing at subsequent stages of tire manufacturing. Other vulcanization properties and physical properties of the vulcanized material are preserved, as shown in table 6.

By mixing in a closed Krupp rubber mixer in a two-stage method, which is almost identical to the method for preparing control mixtures 1 and 2 and experimental mixture 3, a functionalized polymer, polyisobutylene succinic anhydride (PIBYAA, exp. 9) were introduced into the mixture of star-shaped bromobutyl rubber for the inner shell of the tire together with other rubber components prescription (see table 2). Mixtures with naphthenic oil for filling rubber in the latex stage, control 7, and NFP with a polyisobutylene substance to improve technological properties, control 8, were prepared in a similar manner as comparative examples. These mixtures are presented in table 7.

Table 7 Star bromobutyl rubber test mixtures for tire inner shell Mixture Control 7 Control 8 Exp. 9 SBB 6222 one hundred one hundred one hundred Carbon black N660 60 60 60 Clay, Cloisite 20A 0 5 5 Latex Stage Rubber Filling Oil, Calsol 810 8 PIB, TRS 5230 8 PIBSA 55 8 SP-1068 four four four Struktol 40MS 7 7 7 Stearic acid one one one Zinc Oxide, Kadox 911 one one one Sulfur 0.5 0.5 0.5 MBTS 1.25 1.25 1.25

The results of vulcanization and tests on the physical properties of the vulcanized material show that the use of PIBNA (exp. 9) retains the reduced air permeability of the MOCON device, achieved when PIB NFP substance is used in the mixture for the inner shell of the tire to improve technological properties (control 8) comparison with naphthenic oil for filling rubber in the latex stage (control 7). Material exp. 9 has a higher Mooney scorch value when compared with the values in the case of naphthenic oil for filling rubber in the latex stage (control 7) and PIB NFP (control 8), and an increased vulcanization time ts2 when compared with the vulcanization time in the case of naphthenic oil for filling rubber in the latex stage (control 7), which allows to simplify the processing at subsequent stages of tire manufacture. Other vulcanization properties and physical properties of the vulcanized material are preserved (see table 8).

Table 8 Properties of test mixtures of star-shaped bromobutyl rubber for the inner shell of the tire Properties Control 7 Control 8 Exp. 9 NDC at 160 ° C, arc: 0.5 ° ML, DN 1,2 1.3 1,2 MN, dNm 4.2 5.2 3.8 ts2 min 6.2 8.1 8.9 t50 min 4.9 7.8 6.3 t90 min 11.0 13.8 11.7 Mooney viscosity, ML (1 + 4) at 100 ° C 50.6 49.9 46.9 Mooney scorch at 135 ° C, t5 14.8 18.2 21.5 Shore A 44.5 50.7 45.5 Stress / strain 100% module, MPa 0.93 1.33 1,04 300% module, MPa 2.81 4.05 2.91 Tensile Strength, MPa 8.2 9,4 8.2 Elongation at break,% 824 759 852 The energy of destruction, MPa 10,2 11.5 10.8 MOCON air permeability cc · mm / m ² · day · mmHg 70.0 53.5 55.5 ARES at 60 ° C, 10 Hz, 2% strain G ', MPa 2.88 3.03 2.86 G ", MPa 0.46 0.57 0.60 G ^* , MPa 2.91 3.09 2.92 Tangent delta 0.15 0.188 0.211

By mixing in a closed Krupp rubber mixer in a two-stage method, which is almost identical to the method for preparing control mixtures 1 and 2 and experimental mixture 3, a functionalized polymer, polyisobutylene succinic anhydride (PIBYAA, exp. 13) was introduced into the formulation of brominated isobutylene / para-methyl styrene rubber for the inner shell of the tire together with other rubber components of the recipe (see table 2). Similarly, as comparative examples, mixtures were prepared with naphthenic oil for filling rubber in the latex stage, control 10 and 11, and NFP with a polyisobutylene substance to improve technological properties, control 12. The mixture is presented in table 9.

Table 9 Test mixtures of brominated isobutylene / para-methyl styrene rubber for tire inner shell Mixture Control 10 Control 11 Control 12 Exp. 13 Exxpro MDX 89-1 one hundred one hundred one hundred one hundred Carbon black N660 60 55 55 55 Clay, Cloisite 20A four four four Carbon black N660 fifteen fifteen fifteen fifteen SP-1068 four four four four Struktol 40MS 7 7 7 7 Stearic acid one one one one Latex Stage Rubber Filling Oil, Calsol810 8 8 PIB, TRS1300 8 Functionalized PIB, PIBSA C9220 8 Zinc Oxide, Kadox 911 one one one one Sulfur 0.5 0.5 0.5 0.5 MBTS 1.25 1.25 1.25 1.25

The results of vulcanization and tests on the physical properties of the vulcanized material show that the use of PIBAA (exp. 13) retains the reduced air permeability of the MOCON device, achieved when PIB NFP substance is used in the mixture for the inner shell of the tire to improve technological properties (control 12) comparison with naphthenic oil for filling rubber in the latex stage (control 10 and 11). Material exp. 13 has a higher vulcanization time ts2 when compared with the vulcanization time in the case of naphthenic oil for filling rubber in the latex stage (control 10 and 11) and PIB NFP (control 12). The material of the experiment is characterized by a lower value of Mooney viscosity, when compared with the values in the case of PIB NFP (control 12), which allows to simplify the processing at subsequent stages of tire manufacturing. Other vulcanization properties and physical properties of the vulcanized material are retained (see table 10).

By mixing in a closed Krupp rubber mixer in a two-stage method, which is almost identical to the method for preparing control mixtures 1 and 2 and experimental mixture 3, a functionalized polymer, polyisobutylene succinic anhydride (PIBYAA, exp. 16) were introduced into the compound of brominated isobutylene / para-methyl styrene rubber for the inner shell of the tire with other rubber components of the recipe (see table 2). Similarly, as comparative examples, mixtures were prepared with naphthenic oil for filling rubber in the latex stage, control 14, and NFP with a polyisobutylene substance to improve technological properties, control 15. The mixtures are presented in table 11.

Table 11 Test mixtures of brominated isobutylene / para-methyl styrene rubber for tire inner shell Mixture Control 14 Control 15 Exp.16 Exxpro MDX 01-5 one hundred one hundred one hundred Carbon black N660 60 60 60 Clay, Cloisite 20A 0 5 5 Latex Stage Rubber Filling Oil, Calsol 810 8 PIB, TRS 5230 8 PIBSA 55 8 SP-1068 four four four Struktol 40MS 7 7 7 Stearic acid one one one Zinc Oxide, Kadox 911 one one one Sulfur 0.5 0.5 0.5 MBTS 1.25 1.25 1.25

The results of vulcanization and tests on the physical properties of the vulcanized material show that the use of PIBAA (exp. 16) retains the reduced air permeability of the MOCON device, achieved when PIB NFP substance is used in the mixture for the inner shell of the tire to improve technological properties (control 15) comparison with naphthenic oil for filling rubber in the latex stage (control 14). Material exp.16 has a higher vulcanization time ts2, when compared with the vulcanization time in the case of naphthenic oil for filling rubber in the latex stage (control 14) and PIB NFP (control 15), which makes it possible to simplify the processing at subsequent stages of tire manufacture. Other vulcanization properties and physical properties of the vulcanized material are preserved (see table 12).

By mixing in a tangential mixer using a classic 2-stage mixing cycle, a functionalized polymer, polyisobutylene succinic anhydride (PIBYA, exp. 19) was introduced into the brominated isobutylene / para-methyl styrene rubber formulation for the inner shell of the tire together with other rubber components of the recipe (see table 2) . In the first mixing step, a GK 400 mixer was used (with a batch size of approximately 450 pounds) for a duration of 4 minutes. The appropriate batches of carbon black, TDAE oil, SP-1068 resins were automatically weighed out to increase the stickiness and stearic acid and loaded directly into the mixer in accordance with the appropriate time and / or temperature. In a second step, mixing was carried out in a closed GK 160 rubber mixer (with a batch size of about 150 pounds). Mixtures with TDAE oil to improve technological properties (control 17 and 18) were prepared in the same way as described in comparative examples for experimental mixture 19. The formulations are presented in table 13.

Table 13 Test mixtures of brominated isobutylene / para-methyl styrene rubber for tire inner shell Mixture Control 17 Control 18 Exp. 19 Exxpro MDX 01-5 one hundred one hundred one hundred Carbon black N660 60 60 60 Clay, Cloisite 20A 0 5 5 Latex Stage Rubber Filling Oil, Calsol 810 8 8 PIBYA 8 SP-1068 four four four Struktol 40MS 7 7 7 Stearic acid one one one Zinc Oxide, Kadox 911 one one one Sulfur 0.5 0.5 0.5 MBTS 1.25 1.25 1.25

The results of vulcanization and tests for the physical properties of the vulcanized material show that the use of PIBAA (experiment 19) reports reduced values of air permeability for the MOCON device and air permeability for the MOCON device after aging, when compared with those achieved when in the mixture for the inner shell of the tire use TDAE oil to fill the rubber in the latex stage (controls 17 and 18). Material exp. 19 has a higher vulcanization time ts2 when compared with the vulcanization time in the case of TDAE oil for filling rubber in the latex stage (control 17 and 18), which makes it easier to process at subsequent stages of manufacture. Material exp. 19 has a higher fatigue to fracture value when compared with the same value in the case of TDAE oil for filling rubber in the latex stage (control 17 and 18). Other vulcanization properties and physical properties of the vulcanized material (see table 14) are preserved.

Claims (12)

1. A method of preparing an elastomeric mixture, comprising contacting at least one elastomer derivatized from a C ₄ to C ₇ isomonoolefin with a process improvement material that comprises at least one functionalized polymer having at least one succinic anhydride group, where the functionalized polymer comprises C ₂ -C ₁₂ -α-olefin derivatized units or C ₄ -C ₁₀ isoolefin derivatized units, has a number average molecular weight M _n of 800 to 2500 and viscosity from 35 to 1000 cSt at 100 ° C. 2. The method according to claim 1, in which at least one anhydride group includes an anhydride functional group in an amount of from about 05 to about 2.0 mol%. 3. The method according to any one of claims 1 to 2, in which the functionalized polymer does not contain any aromatic groups or unsaturated bonds. 4. The method according to any one of claims 1 to 3, in which at least one elastomer comprises halogenated butyl rubber, star-shaped halogenated butyl rubber or a halogenated random copolymer of isobutylene and methyl styrene. 5. The method according to any one of claims 1 to 3, in which at least one elastomer is halogenated with chlorine or bromine. 6. The elastomeric mixture prepared according to the method according to any one of claims 1 to 3. 7. The elastomeric mixture according to claim 6, which is prepared with 30 parts / 100 or less of a substance to improve technological properties. 8. The elastomeric mixture according to claim 6, which is prepared with 20 part./100 or less substance to improve technological properties. 9. A product made of an elastomeric mixture according to claim 6. 10. The product according to claim 9, which has a permeability to air on the MOCON device (as defined in the present description) 56.0 cc · mm / m ² · day · mm Hg or less. 11. The product according to any one of claims 9 to 10, which has a Mooney scorch value of t5 at 135 ° C. for 12.5 minutes or longer. 12. The product according to any one of paragraphs.9-10, which is selected from the group including inner shells of tires, diaphragms of vulcanizer formators, pneumatic membranes, chambers, pneumatic diaphragms, films, layers (microlayers and / or multilayers), treads and sidewalls.