RU2285021C9 - Transparent and colorable elastomer composition and method for production thereof - Google Patents

Abstract

FIELD: polymers, in particular transparent and colorable elastomer compositions.

SUBSTANCE: claimed composition being base of master batch contains at least one elastomer with units derived from C₄-C₇-isoolefin and p-methylstyrene; at least one non-carbon black filler; and polybutene softener with number average molecular mass (M_n) from 400-10000. Method for production of said composition includes combining of components thereof.

EFFECT: elastomer composition with improved adhesion ability and attrition strength without losses of transparency and colorability.

22 cl, 16 tbl, 12 ex

Description

FIELD OF THE INVENTION

The present invention relates to transparent and dyeable elastomeric compositions, and more particularly, to transparent and dyeable elastomeric compositions of an isoolefin copolymer comprising a halomethyl styrene derivatized unit with a polybutene softener that can be used for reinforcement and which have high abrasion resistance and adhesion strength.

BACKGROUND OF THE INVENTION

Rubber compositions are used for a wide variety of purposes, including the manufacture of tire components such as treads and sidewalls, hoses, belts, shoe components, vibration isolation devices and diaphragms. Although the physical properties of the particular rubber compounds used for each application for them vary widely, one sign remains the same - color. Most rubber compounds are painted black. Moreover, most rubber compounds over time under the influence of heat, light, ozone, etc. initial color is lost. This is especially true for rubbers used as stress-sensitive parts such as tire sidewalls.

As the primary reason that most rubbers are black, practice in the art usually indicates the presence of carbon black as a reinforcing filler. Although it is, carbon black is not the only factor. In fact, the dark color, the creation of which is essentially impossible for the pigment, can be due to the wide variety of other fillers, curing agents, antioxidants, oils and rubbers themselves. So, in particular, naphthenic, aromatic and paraffin oils and resins can often cause discoloration, so they are undesirable. This is obvious in the case of compositions in which the carbon black is replaced by a silicon dioxide filler, and the color of the rubber, however, is changed. For example, EP-B1 0682071 describes a tire tread reinforced with silicon dioxide, which, due to the presence of aromatic petroleum oil as a softener, a binder, antioxidants and a sulfur vulcanizing group, is usually dark in color. In reality, it is not known how many of the components that make up the rubber composition should be changed so that a tintable composition is formed.

To improve the processability of elastomeric mixtures, resins and oils (or “substances to improve technological properties”) such as naphthenic, paraffin and aliphatic resins can be used. However, an increase in processability in the presence of oils and resins is achieved at the cost of loss of air tightness and increased unwanted color, not counting other undesirable effects on various other properties.

Polybutene oils and paraffin type emollients are already described in US Pat. No. 4,279,284 to Spadone, US Pat. No. 5,964,969 to Sandstrom et al. And European Application 0314416, filed by Mohammed. A paraffin type softener is described in US Pat. No. 5,631,316 to Costemalle et al. In addition, WO 94/01295, filed by Gursky et al., Describes the use of petroleum paraffins and naphthenic oils and resins in a rubber composition for tire sidewalls, and in US Patent Application Serial Number 09/691764, filed Oct. 18, 2000 (the assignee of which is the holder of the rights to the present invention) Waddell et al., Paintable rubber compositions are described. Other publications describing softeners or resins of elastomeric or adhesive compositions include US 5005625, 5013793, 5162409, 5178702, 5234987, 5234987, 5242727, 5397832, 5733621, 5755899, EP 0682071 A1, EP 0376558 B1, WO 92/16587, JP 110058, JP 110058 JP 05179068A and J03028244. None of these descriptions offers a way to solve the problem of improving the processability of elastomeric compositions that can be used to manufacture tire treads, pneumatic diaphragms, etc., while maintaining or improving the airtightness of these compositions. Further, these materials may be unacceptable for applications that require high abrasion resistance while maintaining the ability of the composition to stain, in particular in the case of, for example, the manufacture of tire sidewalls and soles.

The white sidewalls of tires are a type of tintable rubber. White coloring is achieved by using fillers instead of carbon black such as silicon dioxide, clay, talc and carbonates with the addition of titanium dioxide as a white pigment. However, giving a white color affects the price. Such fillers are more fragile than carbon black, which weakens the rubber composition, which does not strengthen the tire.

When used for purposes such as making soles for shoes and tire treads where a large amount of filler such as silicon dioxide is used, certain physical properties, such as rubber processability, vulcanization speed and final vulcanizate characteristics, such as traction and abrasion resistance. So, in particular, abrasion resistance is required for the rubber compositions capable of dyeing when used, for example, for the manufacture of tire sidewalls, when there is a need for abrasion resistance on the curb. In addition, in the manufacture of soles and application in the form of other elements of shoes, it is necessary that the elastomeric composition has long-term wear resistance. The object of the present invention is to provide a stainable elastomeric composition that has improved abrasion resistance and other improved physical characteristics while maintaining the ability to stain and transparency of the composition.

Summary of the invention

The present invention provides improved transparent and dyeable elastomeric compositions, which are the basis of the masterbatch. These transparent elastomeric compositions include isoolefin copolymers containing halomethylstyrene derivatized units mixed with a polybutene emollient. The isoolefin copolymer can be present in the composition on its own or can be vulcanized with rubbers such as polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, rubber with a high content of cis-polybutene or natural rubber. Such tintable rubber compositions have sufficient properties to function as a reinforcing element in a car tire, or have sufficient adhesion and abrasion resistance to function as soles. In a preferred embodiment, the stainable elastomeric compositions of the invention include at least one C ₄ -C ₇ isoolefin-p-methylstyrene copolymer, at least one non-particulate filler, such as silica, at least one binder and a polybutene softener.

DETAILED DESCRIPTION OF THE INVENTION

The abbreviation "part./100" refers to the number of parts per hundred parts of rubber, it is a measure generally accepted in the art in which the content of the components of the composition is expressed relative to the main, elastomeric component, i.e. in terms of 100 wt. frequent elastomer or elastomers.

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).

As used herein, the term “elastomer” refers to any polymer or polymer composition meeting the definition of ASTM D1566. The terms "elastomer" and "rubber", which are used in the present description, can be used interchangeably.

In one embodiment of the present invention, an elastomeric composition is obtained that exhibits transparency properties. The term "transparent", in the sense in which it is used in the present description, is defined as transmitting light without significant scattering, as a result of which it is possible to visually identify objects behind such an elastomeric composition. The degree of transparency can range from transparency in direct contact to full transparency. However, other embodiments of the invention are not limited to transparent compositions, in particular such as mixtures prepared for tire treads.

Elastomer

The compositions of the present invention include at least one halogenated elastomer. In one embodiment, the halogenated elastomer is a random copolymer comprising at least units derived from a C ₄ -C ₇ isoolefin, such as units derived from isobutylene, and units derived from halomethyl styrene. The halomethylstyrene unit may be an ortho-, meta- or para-alkyl-substituted styrene unit. In one embodiment, the halomethyl styrene derivatized unit is p-halomethyl styrene containing at least 80%, more preferably at least 90% by weight of the para-isomer. As a “halogen group”, any halogen atom may be present, preferably a chlorine or bromine atom. The halogenated elastomer may also include functionalized copolymers in which at least some of the alkyl substituent groups on the styrene monomer units contain a benzyl halogen atom or some other functional group, further described below. These copolymers in the present description are called "isoolefin copolymers comprising a unit derived from halomethylstyrene" or simply "isoolefin copolymers".

The isoolefin copolymer may also include units derived from other monomers, in particular units derived from C ₄ -C ₇ isoolefin and p-methylstyrene. The isoolefin of the copolymer may be a C ₄ to C ₁₂ compound, non-limiting examples of which are compounds such as isobutylene, 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. Such a copolymer may also further include units derived from a multiolefin. A multiolefin is a C ₄ to C ₁₄ polyunsaturated olefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene, as well as other monomers such as described in EP 0279456 and US 5506316 and 5162425. Suitable units derived from styrene monomers that may be present in the copolymer include styrene, methyl styrene, chlorostyrene, methoxystyrene, indene, indene derivatives and combinations thereof.

In another embodiment, the copolymers are random elastomeric copolymers of a unit derived from ethylene or a unit derived from a C ₃ to C ₆ α-olefin and a unit derived from halomethyl styrene, preferably p-halomethyl styrene, containing at least 80 %, more preferably at least 90% by weight of the para-isomer, and also include functionalized copolymers in which at least some alkyl substituent groups are in the styrene monomer unit yah contain benzylic halogen or some other functional group.

Preferred isoolefin copolymers can be characterized as copolymers comprising monomer units, statistically placed along the polymer chain, of the following formulas:

in which each of R and R ¹ independently represents a hydrogen atom, lower alkyl, preferably C ₁ to C ₇ alkyl or a primary or secondary alkyl halide, and X represents a functional group, such as a halogen atom. Suitable halogen atoms are chlorine, bromine or a combination thereof. In a preferred embodiment, each of R and R ¹ represents a hydrogen atom. The —CRR ₁ H and —CRR ₁ X groups may be substituents on the styrene ring in either the ortho, or meta, or para position, preferably in the para position. Up to 60 mol% of p-substituted styrene units included in the copolymer structure may have the above functionalized structure (2) in one embodiment and from 0.1 to 5 mol% in another embodiment. Nevertheless, in yet another embodiment, the content of the functionalized structure (2) is from 0.4 to 1 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 carboxylic acid residues, carboxylic acid salts, carboxylic acid esters, amides and imides, 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 described in US 5162445.

The most widely used of these functionalized materials are elastomeric random copolymers of isobutylene and p-methylstyrene, including from 0.5 to 20 mol% of p-methylstyrene units, in which up to 60 mol% of methyl substituent groups in the benzyl ring contain a bromine atom or chlorine, preferably a bromine atom (p-bromomethylstyrene), as well as their variants functionalized by acid or ester residues, in which the halogen atom is replaced by a residue of maleic anhydride or acrylic or methacrylic acid. These copolymers are called “halogenated isobutylene / p-methyl styrene copolymers” or “brominated isobutylene / p-methyl styrene copolymers”, which are technically available under the name EXXPRO ™ Elastomers (ExxonMobil Chemical Company, Houston, TX). It is obvious that the use of the terms “halogenated” or “armored” is not limited to the method of halogenation of a copolymer, they simply serve to describe a copolymer that includes units derived from isobutylene, units derived from p-methylstyrene, and units derived from p-halomethylstyrene .

In a preferred embodiment, these functionalized polymers have a substantially homogeneous compositional distribution, whereby the content of p-alkylstyrene units in at least 95% by weight of the polymer is in the 10% range relative to the average content of p-alkylstyrene units in the polymer. More preferred polymers are also characterized by a narrow molecular weight distribution (Mw / Mn) of less than 5, more preferably less than 2.5, a preferred average viscosity molecular weight in the range of 200,000 to 2,000,000, and a preferred number average molecular weight in the range of 25,000 to 750,000, as this is determined by gel permeation chromatography.

Such copolymers can be prepared by suspension polymerization of a monomer mixture using a Lewis acid as a catalyst, followed by halogenation, preferably bromination, in solution in the presence of halogen and a free radical polymerization initiator, such as heat and / or light, and / or a chemical initiator, and optional subsequent electrophilic substitution of the bromine atom with another functional derivatized unit.

Preferred halogenated isobutylene / p-methyl styrene copolymers are brominated polymers, which usually contain from 0.1 to 5 wt.% Bromomethyl groups. And, however, in yet another embodiment, the number of bromomethyl groups is from 0.2 to 2.5 wt. .%. To put it differently, preferred copolymers contain from 0.05 to 2.5 mol% of bromine atoms based on the weight of the polymer, more preferably from 0.1 to 1.25 mol% of bromine atoms and are practically free of ring halogen atoms or atoms halogen in the main polymer chain. In one embodiment, the copolymer is a copolymer of units derived from C ₄ to C ₇ isomonoolefin, units derived from p-methyl styrene, and units derived from p-halomethyl styrene, wherein the p-halomethyl styrene units are in an amount from 0.4 to 1 molar%, calculated on the copolymer. In another embodiment, this p-halomethylstyrene is p-bromomethylstyrene. Mooney viscosity (1 + 8, 125 ° C, ASTM D1646 standard, modified method) is from 30 to 60 units.

Filler

The elastomeric composition also contains a filler, preferably a non-particulate filler. These include, although not limited to, silicon dioxide, clay, talc, calcium carbonate, alumina, titanium oxide and zinc oxide. Furthermore, preferred transparent elastomeric compositions of the present invention do not contain carbon black. The transparency properties of the composition are partly achieved by the use of fillers ranging from 10 to 100 parts per hundred parts of rubber (part / 100) of the composition, particles of which are less than the wavelength of visible light. Silicon dioxide is preferred as the filler, but other fillers such as clays, talc and other mineral fillers can be used. Carbon black can also be used to the extent that the composition is no longer transparent or tintable.

The fillers of the present invention can be characterized by any particle size, which is usually in the range, in particular in the tire industry, 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 treatment by solution, pyrogen or similar methods, and these particles are characterized by specific surface area, including untreated precipitated silicon dioxide, crystalline silicon dioxide, colloidal silicon dioxide, aluminum and calcium silicates, colloidal silicon dioxide, and the like.

The tintable compositions of the present invention are prepared by replacing carbon black as a filler with a non-staining mineral filler, such as, although not limited to colloidal or precipitated silicas, clays, talc, calcium carbonates, aluminum oxides, titanium oxides and zinc oxides. A preferred filler is silica contained in the composition in an amount of from 10 to 100 ppm. Preferably, the silica used in the transparent elastomeric compositions of the present invention is a mixture of colloidal and precipitated silica. In addition, in a preferred embodiment, the precipitated silica is from 30 to 80 frequent. transparent elastomeric composition. In a more preferred embodiment, it is from 40 to 70 frequent. Other suitable non-black fillers and processing aids (e.g. binders) for these fillers are described in Blue Book 275-302, 405-410 (Lippincott & Peto Publications, Rubber World 2001). A preferred binder used in the transparent elastomeric compositions of the present invention is an organosilane crosslinking agent. In a preferred embodiment, the organosilane binder is from 2 to 15 wt.% (In terms of the mass of silicon dioxide) of the transparent elastomeric composition. In a more preferred embodiment, it comprises from 4 to 12 wt.% The composition.

In a preferred embodiment, one or more crosslinking agents are used in the elastomeric compositions of the present invention. In a more preferred embodiment, the binder is a bifunctional organosilane crosslinking agent. The term "organosilane crosslinking agent" means any silane-bound filler and / or crosslinking activator and / or silane enhancing agent known to those skilled in the art, including, although not limited to, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, methacryloylpropyltrimethoxysilane, gamma-aminopropyltriethoxysilane (marketed as Witco product A1100), gamma-mercaptopropyltrimethoxysilane (Witco product A189), and the like. and mixtures thereof. In a preferred embodiment, bis (3- (triethoxysilyl) propyl) tetrasulfan is used (marketed as a Si69 from Degussa).

Polybutene Softener

The composition of the invention contains a polybutene emollient. It is advisable to use polybutene, whose viscosity at 100 ° C exceeds 10 cSt and more preferably with a viscosity at 100 ° C from 10 to 6000 cSt. In one embodiment, the polybutene emollient 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 in one embodiment, preferably from 4 to 6 carbon atoms in another embodiment. And yet, 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 357-392 (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999) (later in this description of "polybutene emollient" or "polybutene").

In one embodiment, the polybutene emollient is a copolymer of at least isobutylene derivatized units, 1-butene derivatized units, and 2-butene derivatized units. In one embodiment, the 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 ones 2-butene 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 98 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 1-butene derivatized units comprise from 2 to 40 wt.% Of the copolymer, and units derived from 2-butene 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 emollients that 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 yet less than 6,000 in another embodiment. In one embodiment, the polybutene oil has a number average molecular weight of more than 400 and more than 700 in another embodiment, and yet in another embodiment more than 900. A combination of any lower limit with any higher limit described herein may be the preferred embodiment. 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 and from 700 to 8,000 in another embodiment. Values of acceptable viscosity of a polybutene softener at 100 ° C are in the range from 10 to 6000 cSt (centistokes) in one embodiment, from 35 to 5000 cSt at 100 ° C in another embodiment and, nevertheless, in another embodiment exceed 35 cSt at 100 ° C and exceed 100 cSt at 100 ° C in another embodiment.

The technical options for such a softener are PARAPOL ™ series softeners (ExxonMobil Chemical Company, Houston, TX), such as PARAPOL ™ 450, 700, 950, 1300, 2400 and 2500 products. The technically available PARAPOL ™ series polybutene softeners are synthetic liquid polybutenes, each individual composition having a specific molecular weight and all of their compositions can be used in the composition of the invention. The molecular weights (Mn) of PARAPOL ™ oils range from 420 (PARAPOL ™ 450 product) to 2700 (Mn) (PARAPOL ™ 2500 product), as determined by gel permeation chromatography. The MMP values (Mw / Mn) of PARAPOL ™ oils are in the range of 1.8 to 3 in one embodiment and from 2 to 2.8 in another embodiment.

Table 1 below shows some properties of PARAPOL ™ oils that can be used in embodiments of the present invention, the viscosity being determined according to ASTM D445-97 and the molecular weight by gel permeation chromatography.

Table 1
Properties of PARAPOL ™ 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 ™ softeners have the following other properties: the density (g / ml) of PARAPOL ™ softeners ranges from about 0.85 (PARAPOL ™ 450 product) to 0.91 (PARAPOL ™ 2500 product); the bromine number (g / g) for PARAPOL ™ oils is in the range of 40 for a softener with Mn 450 to 8 for a softener with Mn 2700.

The elastomeric composition according to the invention may include one or more types of polybutenes in the form of a mixture either between each other before addition to the elastomer or with an elastomer. In this way, the quantity and distinguishing properties (e.g. viscosity, Mn, etc.) of a mixture of polybutene emollients can be varied. For example, the PARAPOL ™ 450 product can be used when a lower viscosity is required for the composition of the invention, 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 composition can be adjusted. More specifically, the term “polybutene emollient” 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 herein.

The polybutene emollient or emollients are contained in the elastomeric composition 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 another embodiment and, however, from 5 to 30 ppm / 100 in another embodiment. In a preferred embodiment, the polybutene emollient does not contain aromatic groups or unsaturated bonds.

Additional rubber component

An additional rubber component may also be contained in the elastomeric composition of the invention. Such rubber may be contained in the composition in an amount of from 0 to 90 ppm / 100 and from 20 to 80 ppm / 100 in another embodiment. The transparent elastomeric compositions of the present invention are halogenated isoolefin / para-alkylstyrene triple copolymers that can be vulcanized with polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene-polybutadiene-polybutadiene rubber or natural rubber. Some examples of industrial rubbers are NATSYN ™ products (Goodyear Chemical Company), natural rubber products (SMR 20), and BUDENE ™ 1207 or BR 1207 (Goodyear Chemical Company). A preferred Sovulcanizate is high cis-linked polybutadiene (CD). 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%. An example of high cis units polybutadiene industrial products used in a vulcanized composition is BR 1207.

In one embodiment, the transparent elastomeric compositions of the present invention comprise from 10 to 100 ppm of the isoolefin-alkyl styrene copolymer (C ₄ -C ₇ isoolefin-alkyl styrene copolymer); from 10 to 100 ppm 100 silica; from 0 to 20 wt.% in terms of the mass of silicon dioxide of the binder and from 2 to 30 parts / 100 of the substance to improve technological properties (discussed further below). In one embodiment, dyeable or transparent elastomeric compositions typically also include from 10 to 90 ppm of polybutadiene, polyisoprene, styrene butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, high cis unit polybutadiene, or combinations thereof . In a more preferred embodiment, the transparent elastomeric compositions typically include from 20 to 80 ppm of polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, high cis unit polybutadiene, or combinations thereof.

Vulcanizing agents and accelerators

Compositions that are prepared in accordance with the present invention typically contain other components and additives that are commonly used in rubber compounds, such as pigments, accelerators, crosslinking and vulcanizing materials, antioxidants, antiozonants and fillers. In one embodiment, substances for improving technological properties (resins), such as naphthenic, aromatic or paraffin oils for filling rubber in the latex stage, may be contained in an amount of from 1 to 30 ppm. In another embodiment, naphthenic, aliphatic, paraffinic and other aromatic resins and oils in the composition are essentially absent. The term "essentially absent" means that naphthenic, aliphatic, paraffinic and other aromatic resins are contained in the composition, if any, in an amount of not more than 2 ppm.

Polymer compositions, for example those used in the manufacture of tires, are usually structured. It is known that the physical properties, performance, and wear resistance of vulcanized rubber compounds are directly related to the number (density) of cross-links and the type of cross-links formed during the vulcanization reaction [see, for example, Helt et al. In The Post Vulcanization Stabilization for NR , Rubber World, 18-23 (1991)]. Crosslinking and curing agents include sulfur, zinc oxide and fatty acids. Peroxide curing groups may also be used. Typically, polymer compositions can be crosslinked by the addition of vulcanizing agents, for example sulfur, metal oxides (i.e. zinc oxide), organometallic compounds, free radical initiators, etc., followed by heating. Thus, in particular, conventional vulcanizing groups that are typically used in the practice of the present invention include the following substances: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ and NiO. These metal oxides can be used in combination with the corresponding complex of metal stearate [for example, Zn (stearate) ₂ , Ca (stearate) ₂ , Mg (stearate) ₂ and Al (stearate) ₃ ] or with stearic acid and either a sulfur compound or an alkyl peroxide connection [see also, Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber World 25-30 (1993)]. The process carried out by this method can be accelerated, and during vulcanization of elastomeric mixtures, acceleration is often used.

Accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like. Acceleration of the vulcanization process can be achieved by adding a certain amount of accelerator to the composition. 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) 2,2'-benzothiazyl disulfide (MBTS), hexamethylene 1,6-bistiosulfate disodium dihydrate, 2- (morpholintio) benzothiazole (MBZ or MOP), a mixture of 90% MOP and 10% MBTS (product MOP 90), N-tert -butyl-2-benzothiazole sulfenamide (TBBS) and N-oxide-diethylenethiocarbamyl-N-oxide-diethylene sulfonamide (GR ) 2-ethylhexanoate, zinc (EGTS), N, N'-diethylthiourea (thiourea) (sold commercially as Thiate U by R.T.Vanderbilt).

In one embodiment, the at least one vulcanizing agent is contained in an amount of from 0.2 to 15 ppm / 100 and from 0.5 to 10 ppm / 100 in another embodiment. Vulcanizing substances include those components described above that promote or influence the cure of elastomers, such as metals, accelerators, sulfur, peroxides and other substances that are common in the art.

Processing

The materials are mixed using conventional means known to those skilled in the art in one stage or in several stages. In one embodiment, carbon black is added at a stage other than the stage of adding zinc oxide and other vulcanization activators and accelerators. In another embodiment, antioxidants, antiozonants, and recycling materials are added in the step after carbon black is added to the elastomer composition, and zinc oxide is added in the final step to maximize the modulus of the rubber composition. Thus, a sequence comprising two to three (or more) processing steps is preferred. Additional steps may include adding incremental amounts of filler and polybutenes.

The present invention provides improved elastomeric compositions comprising a copolymer of C ₄ -C ₇ isoolefin and p-methylstyrene, silicon dioxide, polybutene and optionally one or more binders. In order to improve some physical properties of the composition, other rubber may also be added. These compositions exhibit improved properties, including improved abrasion resistance, reduced cut growth, improved adhesion, reduced heat generation and mechanical properties during exposure to harsh heat generation conditions, in particular the conditions that are created when driving on flat tires and affect engine mounts trucks. A key element in the sense that it causes self-limiting heat generation is essentially an elastomer with an isoolefin (isobutylene) backbone. At low temperatures, such elastomers exhibit good damping characteristics, due to which mechanical energy is dissipated in the form of heat. However, as the elastomer warms up, the damping characteristics deteriorate, the properties of the elastomer become more elastic, and the ability to dissipate energy decreases.

Such materials are mixed using conventional means known to those skilled in the art in one stage or in several stages. So, for example, the elastomers of the present invention can be processed in one stage. In a preferred embodiment, silicon dioxide and silane are added at a stage other than the stage of adding zinc oxide and other vulcanization activators and accelerators. In a more preferred embodiment, antioxidants, antiozonants, and processing aid materials are added in the step after the silica and silane are introduced into the rubber processing, and zinc oxide is added in the final step to maximize the compound modulus. Thus, a sequence comprising two to three (or more) processing steps is preferred. Additional steps may include the addition of increasing amounts of filler and substances to improve technological properties.

The elastomeric compositions of the present invention can be used in a wide variety of applications, in particular for the manufacture of components of pneumatic tires, mainly tire sidewalls, as well as hoses, belts, solid tires, shoe parts, printing rollers, vibration isolation devices, pharmaceutical products, adhesives sealants in the application of protective coatings and in the manufacture of flexible cylinders for storing fluids and diaphragms for vulcanization purposes. More detailed descriptions of tire components can be found in Pneumatic Tire Compounding, WHWaddell, RSBhakuni, WWBarbin and PH Sandstrom in The Vanderbilt Rubber Handbook, 596-611 (RTVanderbilt Company, Inc. 1990), and a description of hose components and shoe parts in The Vanderbilt Rubber Handbook, 612-727.

One embodiment of the present invention is an elastomeric composition comprising a copolymer of C ₄ -C ₇ isoolefin and p-methylstyrene, a non-black filler and polybutene. This composition may also include an auxiliary rubber selected from polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, high cis units polybutadiene and combinations thereof. Another embodiment of the present invention includes compositions of isoolefin copolymers containing halomethyl styrene derivatives, such as an isobutylene-p-methyl styrene copolymer and a halogenated isobutylene-p-methyl styrene copolymer, with a non-particulate filler such as silicon dioxide or clay, and a polybutene softener.

The dyeable elastomeric compositions of the present invention have sufficient properties to function as soles and other details of a shoe and reinforcing element in a car tire, as well as for other applications for which it is advisable to use a dyeable transparent material. These dyeable elastomeric compositions of the present invention can be used to make dyed elastomeric products that can meet current performance requirements. Such tintable rubber compounds are prepared by replacing the carbon black filler with a non-tinting mineral filler, such as, although not limited to colloidal and precipitated silicas, clays, talc, calcium carbonates, aluminum oxides, titanium oxides and zinc oxides. The mineral filler should strengthen the polymer system and not interfere with effective staining. In addition, the remaining components of the tintable rubber composition are selected based on the fact that they do not impair the tintability of the elastomer. Moreover, the vulcanized paintable rubber compounds of the present invention have the same dynamic and physical properties as those that satisfy the performance requirements of modern black tire treads.

All components of transparent and tintable elastomeric compositions must be carefully selected so that they do not impair the transparency and / or tintability of the composition. So, for example, elastomers, fillers, substances to improve technological properties, antioxidants and vulcanizing groups should not change the initial color of the elastomeric mixture during the formation of this composition. Moreover, these components should not discolor the elastomeric composition as a result of exposure to radiation (including UV rays), heat, oxygen, ozone and deformation.

The elastomeric compositions of the present invention are not only capable of being transparent or acceptable for coloring, but can be vulcanized with other rubbers. Transparency usually depends on the amount of filler used. The result is an elastomer that can be used for a wide variety of purposes that go beyond the scope of known elastomers. The elastomeric compositions of the present invention can be used in a wide variety of applications, in particular for the manufacture of components for pneumatic tires, hoses, belts, solid tires, shoe parts, printing rollers, vibration dampers, pharmaceuticals, adhesives, sealants, and protective coatings and the manufacture of flexible cylinders for storing fluids and diaphragms for vulcanization purposes. In particular, the elastomeric compositions of the present invention can be used in soles and tires.

The stainable elastomeric compositions of the present invention exhibit improved hysteretic properties, adhesion, thermal aging resistance and preservation of aging properties in comparison with the known stainable elastomers. The result of this is a tintable rubber compound that has sufficient properties to function as a reinforcing element in a car tire. Paintable rubber gives the manufacturer the opportunity to manufacture a tire as an article with an improved appearance.

In one embodiment of the invention, the tire sidewall can be made by combining at least one copolymer of units derived from C ₄ -C ₇ isoolefin and p-methyl styrene, at least one filler, at least one polybutene softener having a number average molecular weight of at least at least 400, and at least one vulcanizing agent and vulcanization of these combined components.

Test methods

Vulcanization properties were determined using an MDR 2000 at the indicated temperature and arc of 0.5 °. Test samples were vulcanized at the indicated temperature, usually from 150 to 160 ° C, for a time that corresponded to T90 + the corresponding form heating time. Whenever possible, ASTM tests were performed to determine the physical properties of the vulcanized rubber compound. The stress / strain characteristics (tensile strength, elongation at break, modulus, fracture energy) were determined at room temperature using an Instron 4202 tensile testing machine. Shore hardness A was determined at room temperature using a Zwick Duromatic instrument. Abrasion loss was determined at room temperature by the mass difference using an ARN-40 abrasion test machine with a rotating sample holder (counterweight 5 N) and a rotating drum. The weight loss was brought into line with the weight loss of the rubber compound according to the DIN standard, with lower losses indicating a higher rate of abrasion resistance. The error (2σ) in determining the stress at 100% elongation was ± 0.11 MPa; the error (2σ) in determining the elongation was ± 13%. The error (2σ) in determining the tensile strength was ± 0.47 MPa.

The values “MH” and “ML” used in this case and throughout the present description refer to “maximum torque” and “minimum torque”, respectively. The value of "PE" is the Mooney plasticity value, the value of "ML (1 + 4)" indicates the value of the Mooney viscosity. The error (2σ) in this last determination is ± 0.65 units of viscosity using a Mooney viscometer. The value "T" indicates the time of vulcanization in minutes, and the value "Ts" indicates the time of vulcanization.

Dynamic properties (values of G *, G ', G' 'and tangent delta) were determined using a MTS 831 mechanical spectrometer, applied to samples for simple shear (shear configuration with double overlap) at temperatures of -20, 0 and 60 ° С using a frequency of 1 Hz with deformation values of 0.1, 2 and 10%. The temperature-dependent (-80 to 60 ° C) dynamic properties were determined using a Rheometrics ARES instrument at Sid Richardson Carbon Company, Fort Worth, TX and ExxonMobil Chemical, Beighton, TX. A sample of a rectangular configuration for twisting was tested at a frequency of 1 Hz and the corresponding deformation. The values of G "and tangent delta, set at 0 ° C during dynamic laboratory tests, can be used as predictive parameters of road adhesion of tires made from carbon black-filled rubber compounds based on BK / rBSK (styrene-butadiene rubber). Definition temperature-dependent (-90 to 60 ° C) high-frequency acoustic parameters were carried out by Sid Richardson Carbon Company using a frequency of 1 MHz and ethanol as a fluid.

The molecular weight of the PARAPOL ™ polybutene softener was determined by gel permeation chromatography, and the error in the values of the number average molecular weight (Mn) was ± 20%. The methodology for determining molecular weight (Mn and Mw) and molecular weight distribution (MMP) is generally presented in US Pat. No. 4,540,753 (issued to Cozewith et al.), In the references cited therein and in Verstrate et al., 21 Macromolecules 3360 (1988). During typical determinations, a set of 3 columns operates at 30 ° C. For elution, stabilized tetrahydrofuran (THF) or 1,2,4-trichlorobenzene (TCB) can be used as a solvent. These columns are calibrated using polystyrene standards of well-known molecular weights. Using the correlation between the established retention volume of polystyrene from the standards and the retention volume of the analyzed polymer, the molecular weight of this polymer is determined. The viscosity of the PARAPOL ™ polybutene emollient (Table 1) was determined in accordance with ASTM D445-97. Other test methods are listed in table 7.

EXAMPLES

Example 1

Conducted experiments with obtaining transparent elastomers. Masterbatches of EXXPRO ™ elastomers were prepared (copolymer or “triple copolymer”) from units derived from isobutylene, p-methyl styrene and p-bromomethyl styrene, technically available from ExxonMobil Chemical Company) with varying levels of bromination, comonomer units and molecular weight. These copolymers had the properties shown in table 2.

table 2
Elastomer Properties Property Triple copolymer EXXPRO ™ 97-2 EXXPRO ™ 89-1 EXXPRO ™ 90-10 p-methylstyrene units (wt.%) 10 5,0 7.5 p-bromomethylstyrene units (mol%) 0.98 0.75 1.20 Mooney viscosity [ML (1 + 8), 125 ° C] 45 ± 5 38 ± 5 45 ± 5

The test compositions were prepared to achieve the contents of the components of the masterbatch and vulcanizing additives listed in table 4. Product FLEXON ™ 785 is a naphthenic oil. DIAK # 1 is hexamethylenediamine carbonate available at Du Pont / Dow Elastomer Units. DFG is diphenylguanidine.

Test compositions (A to E) were tested for curing characteristics, hardness and tensile strength. The values "MH" and "ML" used throughout the present description relate to the "maximum torque" and "minimum torque", respectively. The value of "PE" is the Mooney plasticity value, the value of "ML (1 + 4)" indicates the value of the Mooney viscosity. The values of "T" indicate the time of vulcanization in minutes, and the values of "Ts" indicate the time of vulcanization. The results are presented in table 5. The tested compositions from A to E showed transparency in direct contact.

Example 2

ChromaMeter Minolta CR-100 was used to quantify lightness (L *), red-green (a *), and yellow-blue (b *) coatings of vulcanized rubber compounds in order to maximize light transmission (transparency measure) and minimize or control coloring. . As an indicator of a subjective assessment of the transparency of the components of the composition in direct contact, we also used the ability to read printed text through these vulcanized rubber compounds. Statistically designed experiments with component variation and statistical analysis of variation (ANOVA) of the effects on the vulcanization of the rubber compound, physical properties and color were performed.

In a simple rubber mixture prepared only with precipitated silica and a curing group with zinc oxide / zinc stearate, eight compositions (G to O) based on EXXPRO ™ elastomers with statistically varying contents of p-methyl styrene and p-bromomethyl styrene units were evaluated. It was found that a low content of either bromine and / or p-methylstyrene units caused maximum L * values with low, but not negative, a * and b * values (see table 6). The presence of the EXXPRO ™ MDX 89-1 product (5 wt.% P-MS units, 0.75 mol% Br-p-MS units) determined the maximum L * value and the lowest a * and b * values.

Example 3

Ten systems of a vulcanizing group / accelerator were tested, which were considered effective for co-vulcanization with other sulfur vulcanized rubber compounds for tires. Suitable vulcanizing groups were prepared using zinc oxide / stearic acid; zinc oxide / zinc stearate; hexamethylene di-1,6-bis (thiosulfate) disodium salt dihydrate (marketed as Duralink HTS ™ by Flexsys) / zinc stearate; Duralink HTS ™ product / zinc oxide and 1,3-bis (citraconimidomethyl) benzene (marketed as the Perkalink ™ 900 product by Flexsys) / zinc stearate, since their use led to the formation of transparent rubber compounds from almost colorless to yellow or beige. The zinc butylcimate / stearate system led to the formation of a clear, light brown colored rubber compound. The use of CBS (N-cyclohexyl-2-benzothiazole sulfenamide) provided the formation of a beige rubber compound, an amylphenyl disulfide polymer (from 18.5 to 21% sulfur) (marketed as Vultac 5 by Elf Atochem North America) and caused the formation of a gray rubber compound, and Product A1100 caused the formation of a brown rubber compound; none of these materials was visually transparent, based on the ability to read printed text. Other organic peroxides may also be used if they are not on a mineral filler such as clay.

Example 4

Using various accelerators, the vulcanization of the elastomeric composition was studied when the EXXPRO ™ elastomer was contained in the absence of other rubbers. Accelerators were evaluated at a fixed content of zinc oxide, stearic acid and zinc stearate (ZnSt ₂ ). Accelerators included the following products (trademarks in brackets): amino alcohol (Triethanolamine), zinc dithiocarbamate (Methyl Zimate), thiuram (Methyl Tuads), thiosulfate (Duralink HTS), thiourea (Thiate U), sulfenamide (CBS), thiazole (MTBS ), zincthiazole (ZMBT), amine (Hexamethylenetetramine) and amine (Diak # 3). When using the Thiate U product in this system at 160 ° C, a significant reduction in vulcanization time was achieved, as shown in Table 7. All of the tested compositions of Table 7 contained the following components in the following amounts: EXXPRO ™ 90-10, 100 ppm / 100; silica (Zeosil 1165MP), 50 ppm / 100; a substance for improving technological properties (Sundex 8125), 20 ppm / 100; stearic acid (HSt), 1.8 ppm / 100; zinc oxide (ZnO), 3 ppm / 100; zinc stearate (ZnSt ₂ ), 0.6 ppm / 100 and accelerators at a concentration of 0.6 ppm / 100. The use of zinc oxide, zinc stearate and the Thiate U vulcanizing agent / accelerator system provided the shortest vulcanization time while maintaining good mechanical properties. These accelerators were also tested at 180 ° C to obtain similar results (not shown).

Example 5

Precipitated silicas obtained by the aqueous acidification process were tested as a filler for a composition in which EXXPRO ™ MDX 89-1 was contained as an elastomer and the DURALINK HTS ™ / zinc stearate system was a curing group. It was noted that in the case of precipitated silica having approximately the same specific surface area according to CTAB (for adsorption of cetylammonium bromide) (approximately 170 m ² / g), the use of precipitated silica having a higher salt content (Zeosil 1165MP product of Rhone-Poulenc ) caused the formation of brown colored transparent rubber compounds, in contrast to precipitated silica with a lower salt content, due to which transparent rubber compounds formed, shennye yellow. The use of precipitated silica obtained using CO ₂ / hydrogen chloride as an acid (PPG Hi-Sil 243LD product) is more appropriate than the use of sulfuric acid product (JMHuber Zeopol 8745), since the former led to the formation of a clear rubber compound with a weaker yellow color. The use of precipitated silica with a larger specific surface area and low salt content (PPG Hi-Sil 195G product) is more appropriate since it appears to provide a more transparent rubber composition upon direct contact and to achieve improved physical properties of the vulcanized rubber composition. Taking into account the optical properties, it is advisable to use colloidal silicon dioxide with a high specific surface area obtained by the gas-phase condensation method, which results in the formation of silicon dioxide essentially free of salt (Cabot O-Sil M5 from Cabot).

Example 6

In this example, the elastomeric composition is a mixture of EXXPRO ™ elastomers and a polybutene substance to improve process properties, such as the PARAPOL ™ product. Varying the PARAPOL ™ product content from 10 to 20 ppm / 100 when Thiate U is used as an accelerator shows that increasing the PARAPOL ™ 950 product content increases transparency (higher L value from ChromaMeter) and reduces yellowness (lower b value * for the ChromaMeter device), as shown in Table 8 for the tested compositions from P to F. These data indicate that the abrasion resistance according to DIN is relatively low, but the presence of PARAPOL ™ improves the optical properties if be absent from the optical properties of only EXXPRO ™ elastomers, as shown in table 8. The b * values for samples from P to F are low when compared with the data in table 8, while the L values for samples from P to F are increased regarding the data in table 8, which is an advantage.

Example 7

Test compositions X to W in this example are mixtures of EXXPRO ™ elastomers and NATSYN ™ 2200 rubber in the absence of a PARAPOL ™ product. EXXPRO ™ transparent vulcanized rubber compounds were prepared using precipitated and colloidal silicon dioxide and sulfur vulcanizing group as fillers. All vulcanized rubber compounds were transparent in direct contact, but had a yellow to brown color depending on the specific components, and were rubber compounds with physical properties that were suitable for use with a wide variety of purposes for which rubber is used. Test compositions X to W are shown in Table 9. In the absence of high cis-linked polybutadiene, DIN abrasion was relatively low, although higher than the same values in Table 8, when EXXPRO ™ elastomers were the only elastomer component /rubber. Further, in the absence of the PARAPOL ™ product, the optical properties worsened, as evidenced by lower L values and higher b * values relative to those values shown, for example, in table 8, for compositions P to F.

Example 8

A composition for a tintable tire tread was prepared as shown in Table 10. This composition differs from the standard rubber composition for a tire tread in several respects. For example, to improve the dynamic and physical properties of a vulcanized rubber compound, instead of the same mass amount obtained by polymerization in a solution of styrene-butadiene rubber (rBSK), EXXPRO ™ elastomeric polymers are used. In addition, instead of the more conventional X50S product (which is 50 wt% Si69 product supported on N330 carbon black), a S169 product is used as a silane binder. In addition, an antiozonant is not used since it can also stain or discolor the tread composition. The ability of the rubber compound to stain can be further improved by the use of titanium dioxide as a non-reinforcing but bleaching pigment. Variants of this composition are presented in example 9.

Example 9

In this example, the tested compositions A1 to Z1 are variants of the composition shown in Table 10, which use the EXXPRO ™ elastomer and rBSK, including varying amounts of units of either styrene comonomer or vinyl comonomer. The viscoelastic nature of EXXPRO ™ elastomers increases the loss modulus (G '') or the tangent delta of the vulcanized rubber composition determined at 0 ° C (table 11). This dynamic value is determined during a laboratory test, the results of which can be used to predict wet grip of rubber compounds for tire treads. Higher value required. When EXXPRO ™ elastomers are used, the delta tangent determined at 60 ° C in laboratory equipment is reduced, indicating a lower heat generation value. This allows you to predict the rolling resistance of the tire. A lower value is required. The value of the complex module (G *), set at 60 ° C, is used as a laboratory tool for predicting such characteristics of the rubber composition for tire treads as dry conditions or cornering. When a racing class tire is required (i.e. classes H, V, Z), a higher value is required. The absolute significance of these beneficial effects when using EXXPRO ™ elastomers also depends on the particular polymers used in the composite system. When rBSK is used in place of cis-polybutadiene, DIN abrasion resistance is low.

Example 10

Using the EXXPRO ™ elastomer and a mixture of other rubbers, the effect of using the Varox 231XL alkyl peroxide curing group (R.T. Vanderbilt) instead of the traditional sulfur curing group was studied. Varox 231 XL is 1,1-bis (tert-butyl peroxyl) -3,3,5-trimethylcyclohexane in the form of a product with 40% active ingredient on an inert carrier of calcium carbonate (32%) and silicon dioxide (28% ) The test results presented in Table 12 for compositions I1 (sulfur vulcanization) and K1 (alkyl peroxide vulcanization) show that the use of a peroxide vulcanizing group increases transparency (a higher L value for ChromaMeter) and a lower yellow color (lower b * ChromaMeter), as opposed to what happens when using a sulfur vulcanizing group during vulcanization of a rubber compound prepared using FLEXON ™ 766 as a substance to improve technological properties. In general, comparing compositions I1 (sulfur vulcanization) and K1 (alkyl peroxide vulcanization), the use of the alkyl peroxide vulcanizing group improved the optical properties of the system, but due to the presence of NATSYN ™ 2200, the abrasion index values were relatively low according to the DIN standard.

Example 11

The results of tests of compositions L1 and M1 with the product Thiate U presented in Table 13 demonstrate the effects of using an alkyl peroxide vulcanizing group using a substance to improve the technological properties of PARAPOL ™. From a comparison of the data of table 12 and table 13, it is obvious that, in comparison with compositions I1 and K1, the tested compositions L1 and M1 have improved optical properties. When the product PARAPOL ™ 950 is used instead of the usual substance in the vulcanized peroxide composition instead of the usual substance to improve the technological properties, the data of Table 13 show that, due to the reduced yellowness (b *), the optical properties are improved and the transparency is increased (L) .

Example 12

The presented series of test compositions H1 to P1 demonstrates the improved properties of the elastomeric composition when EXXPRO ™ and BR 1207 elastomers are used as the main components to improve the technological properties of PARAPOL ™, alkyl peroxide (not bound to the carrier) is used as a curing agent, and the product Thiate U is used as an accelerator. The compositions of Example 12 are preferred embodiments of the present invention (Table 14).

Using binary compositions of the EXXPRO ™ MDX 90-10 product with high cis-linked polybutadiene rubber (BR 1207, BUDENE ™ 1207), brominated isobutylene-p-methyl styrene copolymer compositions were created for tire treads and rubber compounds not for the manufacture of shoe soles . The EXXPRO ™ elastomer is mainly used to increase adhesion, while polybutadiene is used to increase abrasion resistance. For the manufacture of soles, polymers were filled with precipitated and colloidal silicon dioxide to strengthen the polymers, but also in order to maintain good stainability for appearance. In order to further increase the abrasion resistance of the polybutadiene compositions, a silane binder is used in this example, but it shows little effect in EXXPRO ™ elastomers. Thus, process improvers, such as PARAPOL ™ 950 and PARAPOL ™ 2500, were added as part of the compositions. Table 14 lists the components of the test compositions H1 to P1 that were tested. Trigonox 29 is an alkyl peroxide manufactured by Akzo Nobel Chemicals, which is 1,1-ditret-butylperoxy-3,3,5-trimethylcyclohexane. Trigonox 29, unlike some alkyl peroxides available on the market, is not supported.

For these test rubber compounds, technological, vulcanizing, mechanical and optical properties were determined, the results obtained are presented in table 15A. These values were obtained using the methods described in the previous examples. The "T" values indicate the cure time in minutes. The values of "MOD" are the values of the module, and the values for the ChromaMeter instrument are presented above. With an increase in the amount of polybutadiene with a high content of cis units (BR 1207), the laboratory-determined abrasion resistance (wear resistance), tensile strength and elongation at break increase. However, the use of BC in increased quantities causes a decrease in the adhesion force of the rubber compound. Since bonding strength is increased when using increased amounts of EXXPRO ™ elastomers, a balance of properties can be achieved depending on the specific purpose of the application of the elastomeric composition.

It was unexpected that the use of the relatively high molecular weight product PARAPOL ™ 2500 instead of PARAPOL ™ 950 causes a slight yellowing, as indicated by the b * values of the ChromaMeter, and increased values of hardness, tensile strength and elongation at break. In addition, when comparing the test composition H1 (PARAPOL ™ 950 product is contained in an amount of 10 ppm / 100) with the test composition P1 (PARAPOL ™ 2500 product is contained in an amount of 10 ppm / 100), it was found that with an increase in the molecular weight of the substance for improving technological properties, the viscosity [VM (Mooney viscosity): ML (1 + 4)] increases. In general, compared to the test compositions C to W in Table 9, when the rubber component NATSYN ™ is used in place of the BR 1207 product, the use of the BR 1207 product improves DIN abrasion resistance. Moreover, in comparison with the tested compositions C to W in table 9, due to the presence of a substance for improving the technological properties of PARAPOL ™ instead of FLEXON ™ oil, the optical properties of compositions H1 to P1 are improved.

As described above, the viscoelastic nature or “dynamic properties” of the samples from H1 to P1 was determined; the results are presented in table 15B. The loss modulus (G``) or the tangent delta of the vulcanized rubber compounds was determined at -60, -30, 0, 30 and 60 ° C. The dynamic values set at 0 ° are the results of laboratory tests that can be used to predict wet grip of rubber compounds for tire treads and shoe soles. Higher value is required. Dynamic values at -30 ° C are predictive parameters of adhesion to a snowy road, while values at 30 ° C are predictive parameters of adhesion to a dry road surface. Dynamic values at 60 ° C serve as an indicator of rolling resistance. When EXXPRO ™ elastomers are used, the delta value set at 60 ° C in laboratory equipment is reduced, indicating a lower heat generation value. This allows predicting tire rolling resistance. Lower value required. The value of the complex module (G *), set at 60 ° C, is used as a laboratory tool for predicting behavior in dry conditions or cornering, characteristics of the rubber compound for the tire tread. When a racing class tire is required (i.e. classes H, V, Z), a higher value is required.

Although some typical variations and details are given to illustrate the invention, it will be apparent to those of ordinary skill in the art that a variety of changes can be made to the method and products presented herein without departing from the scope of the invention as defined by the appended claims.

All priority documents mentioned in the present description are included in it in full in accordance with all jurisdictions that allow such inclusion. Moreover, in accordance with all jurisdictions that allow such inclusion, all documents referred to in this description are fully included in the present description, as well as test methods.

Table 4
Preparation of Test Compositions A to E Recipes BUT B AT R D E Uterine mixture (frequent / 100) EXXPRO ™ 89-1 one hundred one hundred one hundred - - - EXXPRO ™ 97-2 - - - one hundred one hundred one hundred HiSil 233 45 45 45 45 45 45 FLEXON ™ 785 fourteen fourteen fourteen fourteen fourteen fourteen DIAK # 1 3 four four 3 four four DFG 3 2 3 3 2 3

Table 5
Properties of the tested compositions from A to E The properties BUT B AT R D E PE at 135 ° C Growth 5 pt., Min - - 4.14 2.17 0.42 1,67 Growth 10 pt., Min - - 4.33 2,57 1.75 1.89 ML (1 + 4) at 100 ° C - 108 125 127 - 128 MDR device at 155 ° С and 1/2 ° arc ML, DN • m 5.88 5.76 4.67 3.23 2.67 5.67 MN, dN • m 12.5 17.0 15,5 15.3 15.0 15.1 Ts2 min 1.7 1,2 0.9 - - 1,1 T25 min 1,2 1.7 1,2 - - 1.3 T90 min 35.3 31.3 27.8 25.9 - 28.9 Physical properties, vulcanized for 6.5 minutes at 155 ° C Shore A 60 60 60 64 58 61 Elongation stress by 100%, MPa 1,5 2.6 2.6 2.6 2.2 2.0 Elongation stress by 300%, MPa 4.6 5.8 6.2 6.1 8.2 4.8 Tensile Strength, MPa 6.0 7.6 9.1 8.8 8.7 7.1 Elongation at break,% 380 380 390 420 320 390 DIN abrasion resistance 71 - 66 69 69 68

Table 6
Optical Properties of EXXPRO ™ Rubber Compounds Test Composition p-methylstyrene units (wt.%) p-bromomethylstyrene units (wt.%) L * but* b * F 5 0.75 70.7 0.5 18.1 3 7.5 0.75 65.1 2,3 26.8 AND 7.5 1.7 58.8 5,4 38.9 TO 9.6 1.25 56.7 5.9 39.0 L 10 0.5 69.0 1.9 21.0 M 10 0.75 67.3 2,5 27.9 N 10 0.95 55.2 5.1 36.3 ABOUT 12.5 0.75 58.6 7.8 31.7

Table 8
The compositions and properties of the tested compositions from P to F of example 6 Component (frequent / 100) P R FROM T At F EXXPRO ™ 89-4 100.0 100.0 100.0 0,0 0,0 0,0 EXXPRO ™ 96-4 0,0 0,0 0,0 100.0 100.0 100.0 Silica Rhodia Zeosil 45 30,0 35.0 25.0 25.0 35.0 30,0 PARAPOL ™ 950 15.0 10.0 10.0 20,0 20,0 15.0 Zinc stearate 3,5 2.0 5,0 2.0 5,0 3,5 Thiate u 1,5 3.0 3.0 3.0 3.0 1,5 Vulcanization and physical properties Minimum torque, dN • m 3,1 4,5 2.9 2.1 3,1 3.3 Maximum torque, dN • m 7.9 9.0 6.0 5,0 6.0 7.7 Ts2 (min) 0.9 2,3 1,5 4.0 1,5 1.4 T50 (min) 1,2 2.7 1,1 2.2 1,0 1,6 T90 (min) 6.3 12.7 3,5 11.2 3.0 7.9 Hardness 46.7 51.5 45.7 43.1 42.9 47.1 Elongation at break 170.0 226.0 215.0 208.0 177.0 229.0 Tensile Strength (MPa) 5,4 8.1 5.2 4.1 4.0 5,4 Elongation stress by 20% (MPa) 0.8 0.9 0.6 0.4 0.8 0.7 Elongation stress 100% (MPa) 3.0 3.4 2.1 1,5 2.6 2,3 Elongation stress by 300% (MPa) 1,1 7.2 3.6 3,7 1,1 4.7 The energy of destruction (J) 1.4 3,1 2.0 1.3 1.4 2.1 DIN abrasion resistance 50,0 67.0 53.0 30,0 39.0 48.0 Optical properties ChromaMeter L value 83.0 81.9 80.6 83.1 84.9 84.9 A * value from ChromaMeter -0.2 -0.1 -0.1 -0.2 -0.5 -0.5 B * value from ChromaMeter 6.6 7.5 6.6 7.2 6.2 6.4

Table 9
The compositions and properties of the transparent rubber compounds of example 7 Component (frequent / 100) X Ts H W EXXPRO ™ MDX 96-4 fifty fifty fifty fifty NATSYN ™ 2200 fifty fifty fifty fifty HiSil 243LD Silicon Dioxide 45 0 0 35 HiSil 195T Silicon Dioxide 0 45 0 0 Zeosil 1115MP Silica 0 0 45 0 Silicon Dioxide Cab-O-sil M5 0 0 0 10 Si69 3.6 3.6 3.6 3.6 FLEXON ™ 766 6 6 6 6 Paraffin wax four four four four PEG 3350 four four four four Zinc oxide one one one one Stearic acid one one one one Sulfur 0.8 0.8 0.8 0.8 MBTS 0.6 0.6 0.6 0.6 TBBS 1,2 1,2 1,2 1,2 DFG 0.8 0.8 0.8 0.8 Vulcanization properties Minimum torque, dN • m 1.97 2,8 1.41 2.18 Maximum torque, dN • m 8.47 10.3 7.04 8.95 Difference between torques 6.5 7.49 5.63 6.78 Podvulcanization Ts2, min 1.26 1.29 1.33 1.29 The vulcanization time T50, min 1.49 1,57 1.51 1,54 The vulcanization time T90, min 2,5 2.29 2,52 2.41 Physical properties Hardness 49.9 53.5 47.1 51.1 Tear strain (%) 582.42 479.04 576.32 611.96 Destructive stress (MPa) 8.44 8.91 11.11 10.11 Elongation stress by 20% (MPa) 0.64 0.79 0.52 0.65 Elongation stress 100% (MPa) 1.43 1.84 1.25 1.45 Elongation stress by 300% (MPa) 4.23 5.49 4,57 4.32 The energy of destruction (J) 9.04 6.72 10.8 10 Scattering 6.1 5.1 8 5.5 DIN abrasion resistance 90 99 105 95 Mooney Viscometer Viscosity
(1 + 4) at 100 ° C 50.8 59.8 46.2 54,4 Optical properties ChromaMeter L value 69.7 74.5 77.1 76,2 A * value from ChromaMeter 3,5 1,2 1.7 0.4 B * value from ChromaMeter 44.6 40,2 37,2 38,2

Table 10
Preparation of a Paintable Rubber Compound of Example 8 Component frequent / 100 Brominated isobutylene-p-methylstyrene copolymer (EXXPRO ™), variable bromine content, p-methylstyrene units twenty Styrene-butadiene rubber (rBSK), variable content of styrene and vinyl units 55 Polybutadiene, 98% cis units 25 Precipitated Silica 75 Titanium dioxide twenty Silane Binder (10% Silicon Dioxide), Si-69 7.5 Aromatic oil Sundex 8125 24 Zinc oxide 2 Stearic acid one Antioxidant Mixed Diaryl-p-Phenylenediamine 0.75 Sulfur 1,2 Sulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide (CBS) 1.75 Diphenylguanidine 1,2

Table 14
The compositions of the tested compositions from H1 to P1 of example 12 Component Part / 100 H1 O1 P1 P1 EXXPRO ™ 89-1 thirty 40 fifty thirty BR 1207 70 60 fifty 70 Silicon Dioxide PPG HiSil 195G 35 35 35 35 Silane Binder Si69 2,52 2.16 1.8 2,52 Silicon Dioxide Aerosil 200 10 10 10 10 PARAPOL ™ 950 10 10 10 10 PARAPOL ™ 2500 0 0 0 10 Zinc stearate 5 5 5 5 Trigonox ™ 29 one 0.9 0.8 one Thiate u 0.8 0.9 one 0.8

Claims (22)

1. A transparent and dyeable elastomeric composition, which is the basis of the masterbatch, comprising at least one elastomer from units derived from C ₄ -C ₇ isoolefin and p-methylstyrene, at least one non-sitting filler and a polybutene emollient having a number average molecular weight (Mn) 400 to 10,000. 2. The composition according to claim 1, characterized in that the viscosity of the polybutene softener at 100 ° C exceeds 10 cSt. 3. The composition according to claim 2, characterized in that the polybutene softener at 100 ° C has a viscosity of from 10 to 6000 cSt. 4. The composition according to claim 1, characterized in that the non-particulate filler is selected from silicon dioxide, clay, talc, calcium carbonates, aluminum oxide, titanium oxide, zinc oxide and mixtures thereof. 5. The composition according to claim 1, characterized in that it further comprises a rubber selected from polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, polybutadiene with a high content of cis units and combinations thereof . 6. The composition according to claim 5, characterized in that the rubber is a polybutadiene with a high content of cis units. 7. The composition according to claim 1, characterized in that the elastomer is a triple copolymer of units derived from isobutylene, p-methylstyrene and p-bromomethylstyrene. 8. The composition according to claim 1, characterized in that it further includes a vulcanization accelerator selected from stearic acid, tetramethylthiuramdisulfide, 4,4'-dithiodimorpholine, tetrabutylthiuramdisulfide, benzothiazyl disulfide, hexamethylene sulphate dihydrate (1,6-2-bisti morpholintio) benzothiazole, N-oxide-diethylene thiocarbamyl-N-oxide-diethylene sulfonamide, zinc 2-ethylhexanoate and N, N'-diethylthiourea. 9. The composition of claim 8, wherein the vulcanization accelerator is N, N'-diethylthiourea. 10. The composition according to claim 1, characterized in that it further includes a vulcanizing group. 11. The composition of claim 10, wherein the curing group is selected from ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ , NiO, Zn (stearate) ₂ , Ca (stearate) ₂ Mg (stearate) ₂ and Al (stearate) ₃ . 12. The composition according to claim 10 or 11, characterized in that the curing group further includes an alkyl peroxide. 13. The composition according to claim 5, characterized in that the elastomer is contained in an amount of from 20 to 50 hours / 100 parts by weight 14. The composition according to claim 1, characterized in that the non-particulate filler is contained in an amount of from 30 to 80 hours / 100 wt. including elastomer. 15. The composition according to claim 1, characterized in that the polybutene softener is contained in an amount of from 2 to 30 hours / 100 wt. including elastomer. 16. The composition according to claim 4, characterized in that the non-particulate filler is silicon dioxide. 17. The composition according to claim 1, characterized in that the elastomer is halogenated. 18. The composition according to claim 1, characterized in that the polybutene emollient is a copolymer of units derived from isobutylene and units derived from 1-butene. 19. A method of obtaining a transparent and dyeable elastomeric composition, which is the basis of the masterbatch, comprising combining at least one elastomer from units derived from C ₄ -C ₇ isoolefin and p-methylstyrene, at least one non-seated filler and a polybutene softener having number average molecular weight (Mn) from 400 to 10,000. 20. The method according to claim 19, characterized in that it further comprises adding a curing agent and curing the mixture. 21. The method according to claim 19 or 20, characterized in that it further includes the addition of a vulcanization accelerator. 22. The method according to claim 19 or 20, characterized in that it further includes the addition of an additional rubber component.