MXPA99009978A - Preparation of reinforced elastomers, composed of these elastomers and wheels that have components of the mis - Google Patents

Abstract

Preparation of an elastomer, which contains a dispersion of a filler reinforcement, by the formation of this filler reinforcement in situ within the elastomer host, the resulting elastomer / filler composite and the rim having the component, which contains such a reinforcing elastomer. The invention includes a rubber composition of at least two elastomers, in which one of the elastomers is a preformed elastomer composite and the filler reinforcement formed in situ. A rim having a component of such a rubber composition, particularly a tread of the rim, is specifically considered.

Description

PREPARATION OF REINFORCED ELASTÓM EROS. COMPOUNDS OF THESE ELASTÓM EROS AND WHEELS THAT THEY HAVE COMPONENTS OF THEMSELVES This specification relates to two other specifications in a series of three specifications, which are DN1998-208, DN1998-209 and DN1998-210, all filed in the United States Patent and Trademark Office on the same date.

Field This invention relates to the preparation of an elastomer, which contains a filler reinforcement dispersion, by the formation of a filler reinforcement in situ within the elastomer host, to the resulting elastomer / filler composite and to tires having components which contain such reinforced elastomer. This invention further relates to a rubber composition of at least two elastomers, wherein one of these elastomers is a preformed composite of the elastomer and a filler reinforcement formed in situ. The invention also relates to a rim having a component of such a rubber composition. Particularly it refers to a tire with a tread of such a composition.

BACKGROUND Elastomers are conventionally reinforced with particulate reinforcing fillers such as, for example, carbon black and, sometimes, precipitated silica. Occasionally it is difficult to obtain a suitable homogeneous dispersion of the reinforcing filler, particularly silica, in the rubber composition, by conventionally mixing the rubber and the filler under high cut conditions. However, a suitable, homogeneous dispersion of the reinforcing filler particles within the rubber composition is sometimes convenient. In one aspect, it has hitherto been proposed to create a dispersion of the silica in elastomer (s) of polysiloxane polymers, such as poly (dimethylsiloxane), or (PDMS), by the in situ formation of the silica from a conversion of sol-gel, catalyzed with a base, of tetraethoxysilane (TEOS). For example, see "Precipitation of Silica-Titanium Mixed Oxide Fillers in Poly (Dimethylsiloxane) Networks, by Wen and J. Mark; Rubber Chem and Tech, (1994) r volume 67, No. 5, (pages 806- 819.) A process for preparing rubber products, by mixing TEOS with an unvulcanized rubber solution, in an organic solvent and subjecting it to a sol-gel condensation reaction to supply a silica in powder form has been suggested. For example, see Japanese Patent Application Publication 93/02152, In addition, a composition comprising a base rubber and globular silica, obtained by the sol-gel method, and having an average diameter of particles of 10 to 30 microns and a specific surface area of 400 to 700 square meters per gram The composition is suggested to be used in a tire flap For example, see Japanese Patent Application Publication 6145429. proposed a compos rubber composition of the tread as a composition of a basic rubber and spherical silica, prepared by the transformation of sol-gel. For example, see Japanese Patent Application Publication 6116440 and corresponding Japanese Patent Publication 2591569. In addition, an in situ formation of the silica from a TEOS sol-gel reaction, in an organic styrene rubber solution. butadiene, on which a tetrasulfide of bis (3-triethoxysilylpropyl) has previously been grafted to form triethoxysilyl groups, has been reported. ("The Effect of Bis (3-triethoxysilylpropyl) Tetrasulfide on Silica Reinforcement of Styrene-Butadiene Rubber", by Hasim, et al., In Rubber Chem &Tech, 1998, Volume 71, pages 289-299) . In the description of this invention, the term "per", as used herein and in accordance with conventional practice, refers to "parts by weight of a respective material per 100 parts by weight of rubber or elastomer". In the description of this invention, the terms "rubber" and "elastomer", when used herein, may be used interchangeably, unless otherwise indicated. The terms "rubber composition", "composite rubber" and "rubber compound" are used interchangeably to refer to "rubber that has been combined or mixed with various ingredients and materials" and such terms are well known to the experts in the techniques of mixtures of rubber or rubber compositions.

SUMMARY AND PRACTICE OF THE INVENTION In accordance with this invention, a method is provided for preparing an elastomer / filler composite, such as a dispersion of a filler formed in situ within an elastomer host, which comprises: A) mixing a precursor of filling, a condensation promoter and an elastomer host, selected from the host (A) of elastomer and the host (B) of elastomer, in a medium of (1) an organic solvent solution of the elastomer host or (2) an aqueous latex of the elastomer host, preferably in a solution of an organic solvent, to initiate a condensation reaction of the filler precursor and, for the elastomer host (A), and, optionally, for the host (B) ) of elastomer, subsequently adding and reacting an organosilane material with the filler / filler precursor, before completing the condensation reaction; followed by recovering the resulting elastomer / filler composite; or B) mixing, in an internal rubber mixer, a filler precursor, a condensation reaction promoter and an elastomer host, selected from the elastomer host (A) and the elastomer host (B), to initiate a condensation reaction of the filler precursor and, for the elastomer host (A), and, optionally, for the elastomer host (B), subsequently adding and reacting, in an internal rubber blender, an organosilane material with the filler / filling precursor, before completing the condensation reaction; followed by recovering the resulting elastomer / filler composite; or C) immersing an elastomer host, selected from the elastomer host (A) and the elastomer host (B), in a liquid fill precursor, and allowing the fill precursor to be embedded in the elastomer host to cause it swells, apply a reaction promoter to the swollen elastomer guest to initiate the condensation reaction of the filler precursor and, for the elastomer host (A), and, optionally, for the elastomer host (B), subsequently adding and reacting an organosilane material with the filler / filler precursor, before completing the condensation reaction; followed by recovering the resulting elastomer / filler composite; wherein the elastomer host (A) is selected from at least one of the homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with an aromatic vinyl compound, preferably selected from styrene and alpha-methylstyrene and, more preferably, styrene; wherein the elastomer host (B) is selected from at least one diene-based elastomer, functionalized at the end with alkoxy metal, having, for example, a general formula (I): (I) X-elastomer (OR) ) n wherein X is selected from silicon, titanium, aluminum and boron, preferably silicon, R is selected from alkyl radicals having from 1 to 4 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl radicals and isobutyl, more preferably ethyl radicals, and n is 3 for silicon and titanium and is 2 for aluminum and boron, and wherein the elastomer is selected from at least one of the homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with an aromatic vinyl compound, preferably selected from styrene and alpha-methylstyrene and, more preferably, styrene; and wherein the precursor of the filling is at least one material selected from the formulas (HA), (IIB) and (IIC): (HA) M (OR) x (R ') and (HB) (ROJx R'Jy -O-M1 (R ') z (R0) w (IIC) (R0) x (R ') and M- (CH2) r-M' (R ') z (R0) w where M and M' are the same or different and are selected from silicon, titanium, zirconium, boron and aluminum, preferably silicon, where R and R 'are selected, individually, from alkyl radicals having from 1 to 4 carbon atoms, preferably from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl radicals, wherein R is preferably an ethyl radical and R 'is preferably a methyl radical, and where the sum of each of the integers x + yy w + z is equal to 3 or 4, depending on the valence of the associated M or M1, depending on the case may be and, therefore, is 4 except when its associated M or M 'is boron or aluminum, for which it is 3, and in which r is from 1 to 15, preferably from 1 to 6; wherein the organosilane is at least one material selected from the formula (III), (IV) and (V), that is: an organosilane polysulfide of the formula (III) as: (III) Z - R * - Sm - R4"- Z in that it is a number in the range of 2 to about 8, and the average for m is in the range of (a) about 2 to 2.6, or (b) about 3.5 to 4.5; in which Z is represented by the following formulas, of which it is preferably (Z3): R2 R2 3 (Zl) Si - R2, (Z2) Si - R3 (Z3) Si - R3 R3 R3 R3 wherein R2, which are the same or different radicals, are selected, individually, from alkyl radicals having from 1 to 4 carbon atoms, and the phenyl radical, preferably from methyl and ethyl radicals; R3 are alike or different alkoxy groups, in which the alkyl radicals of these alkoxy groups are selected, individually, from alkyl radicals having from 1 to 4 carbon atoms, ie, methyl, ethyl, n-propyl radicals, isopropyl, n-butyl and isobutyl, and preferably an ethyl radical, whereby (Z) is preferably (Z3) co or a triethoxysilane radical; and R1 is a radical selected from the group consisting of alkyl radicals, substituted or unsubstituted, having a total of 1 to 18 carbon atoms, and an aryl radical, substituted or unsubstituted, having a total of 6 to 12 carbon atoms , wherein i is selected preferably from the ethyl, propyl and butyl radicals; An alkyl-alkoxy silane of the formula (IV), as: (IV) (OR4) 3-Si-R5 wherein the R can be the same or different alkyl radicals, having from 1 to 3 carbon atoms, selected from the methyl, ethyl, n-propyl and isopropyl radicals, and R5 is selected from alkyl radicals having from 1 to 18, preferably from 8 to 18, carbon atoms, and aryl radial or aryl radicals substituted by alkyl, having from 6 to 12 carbon atoms, wherein R 5 is preferably an alkyl radical; and a functional organosilane of the formula (V), such as: (V) (OR >? °) 3 - Si - (CH2) and - Y wherein the R6 are the same or different alkyl radicals, having from 1 to 3, preferably 1 or 2, carbon atoms, selected from methyl, ethyl, n-propyl and isopropyl radicals, preferably an ethyl radical, and _ is an integer from 1 to 12, alternatively from 2 to 4, and Y is selected from primary amino, mercapto, epoxide, thiocyanate, vinyl, methacrylate, ureido, isocyanate and ethylene diamine radicals. Also, according to this invention, a rubber composition prepared according to one or more methods of the invention is supplied. In addition, according to this invention, an article is provided having at least one component comprised of the rubber composition. Also, according to this invention, the article is selected from industrial bands and hoses. Further, according to this invention, a rim is provided having at least one component that includes the rubber composition. Also, according to this invention, a rim is provided having a tread comprised of the rubber composition. It is important to appreciate that the creation of an elastomer / filler composite is achieved by first initiating a condensation reaction of the filler precursor within a diene-based elastomer host and, before completing the reaction, reacting an organosilane with the filler material that It is formed in situ. In this manner, an almost sol-gel reaction is used, as regards the initial portion of the condensation reaction, for the in situ formation of the filler dispersion within the host elastomer. It is here considered that a significant departure from the prior art is the reaction of one or more indicated organosilane materials with the condensation product formed in situ, all within the host of the elastomer, to form an elastomer reinforcing dispersion of the filling material resulting, in a non-vulcanized elastomer. In this way, then, a product produced by the condensation reaction (e.g., the condensation reaction of TEOS) and the organosilane co-reactant, of the formulas (III), (IV), or (V), is obtained to form a dispersion of filler in situ? and within the elastomer host, which has a capacity to react further with the host elastomer itself. A further significant departure from past practice is the in situ creation of a prescribed filler material, within an elastomer host end functionalized with an alkoxy metal, which is a part (eg, a part of trialkoxysilyl or trialkoxytitanyl) ) to be coupled to the elastomer with the polar fillers synthesized in situ and which may, therefore, reduce the need to subsequently add an additional difunctional coupling agent - for example an organosilane polysulfide - to aid in the binding to the in situ synthesized filler to the elastomer. As a consequence, it is considered that, for some circumstances, only a minimum, if any, of such additional difunctional coupling agent can then be convenient. Various reinforcing fillers may also be subsequently mixed with the elastomer and reinforcing filler composite, formed in situ. For example, such additional fillers may be carbon black, precipitated silica and other fillers containing hydroxyl groups on their surfaces, such as, for example, the silica precipitated with aluminum impurities and the modified carbon blacks, which would have hydroxyl hydroxide. aluminum and / or silicon hydroxide on their respective surfaces. Exemplary of such silicas precipitated with aluminum impurities are, for example, aluminosilicates formed by a co-precipitation of a silicate and an aluminate. An example of the modified carbon black is, for example, a carbon black having silicon hydroxide on its external surface, by treating this carbon black with an organosilane, at an elevated temperature or by co-smoking a organosilane and an oil at elevated temperature. According to this invention, a composition of elastomer mixtures is provided, which is comprised of at least two diene-based elastomers, of which one elastomer is a previously formed elastomer / filler dispersion, such as the elastomer compound and the dispersion of the in situ formed filler of this invention, comprised of, based on 100 per elastomers, (A) from about 10 to 90 per at least one diene-based elastomer, selected from at least one homopolymer and isoprene copolymer and 1,3-butadiene and a copolymer of at least one diene, selected from isoprene and 1,3-butadiene, with an aromatic vinyl compound, selected from at least one styrene and alpha-methylstyrene, preferably styrene, and ( B) approximately 90 to 10 per of at least one of the previously formed elastomer / filler compounds, (C) at least one additional reinforcing filler, however, with the proviso that the tot that of the fill formed in situ and the additional reinforcement fill are present in an amount of about 30 to 120 per and where this additional reinforcement filler can be selected, for example, from at least one of the precipitated silica, aluminosilicate, black carbon and black of modified carbon, having hydroxyl groups, for example hydroxyl and / or silicon hydroxide groups, on its surface, and (D) optionally, a coupling agent, having a reactive part with one or more fillers and another interactive part with one or more elastomers. In addition, according to this invention, an article is provided having at least one component comprised of the mixed rubber composition. Also, according to this invention, a selected article of industrial hoses and bands is provided, having at least one component that includes the mixed rubber composition. As well, according to this invention, a rim is provided having at least one component comprised of the mixed rubber composition. In addition, according to this invention, a rim is provided having a tread comprised of the mixed rubber composition. Representative examples of the filler precursor material of the formula (HA) are, for example, ortho-silicate tetraethoxy, titanium ethoxide, titanium n-propoxide, tri-secondary aluminum butoxide, zirconium t-butoxide, n -zirconium butoxide, tetra-n-propoxy-zirconium, boron ethoxide, methyl triethoxy-silicate and dimethyl diethoxy-silicate. Representative examples of the filler precursor material of formula (IIB) are, for example, di-s-butoxyaluminoxy triethoxysilane and hexaetoxydisiloxane. Representative examples of the filler precursor material of the formula (IIC) are, for example, bis (triethoxysilyl) -methane and bis (triethoxysilyl) -ethane. Representative examples of the organosilane polysulfide of the formula (III) are, for example: (A) organosilane disulfide materials, containing from 2 to 4 sulfur atoms, with an average of 2 to 2.6, in their polysulfide bridges , and (B) organosilane polysulfide materials, containing from 2 to 8 sulfur atoms, with an average of 3.5 to 4.5, in their polysulphide bridges; wherein, the alkyl radical for the alkoxy component of the disulfide and polysulfide materials are selected from methyl, ethyl and propyl radicals, preferably an ethyl radical, and the alkyl radical for the silyl component is selected from ethyl radicals, propyl, particularly n-propyl, and butyl, preferably an n-propyl radical.

It will be appreciated that the activity of the sulfur bridge of the organosilane disulfide material (A) and the organosilane polysulfide material (B) is very different. In particular, the sulfur atoms of the organosilane disulfide material (A), which is primarily a disulfide, have much stronger bonds with each other than the sulfur atoms in the bridge of the organosilane polysulfide material (B). Thus, this material (B) of organosilane polysulfide can be some sulfur donor (a supplier of free sulfur) in a rubber composition at elevated temperatures, while the sulfur atoms of the organosilane disulfide material (A) are not consider here as such sulfur donors. This phenomenon can have a substantial effect on a formulation of a rubber composition that can be cured with sulfur. While a bis (3-alkoxysilyl alkyl) polysulfide material, such as, for example, bis- (3-triethoxysilylpropyl) disulfide, may be a preferable organosilane disulfide (A), representative examples of such a disulfide (A) of organosilane are: 2,2'-bis (trimethoxysilylethyl) disulfide; 3,3'-bis (trimethoxysilylpropyl) disulfide; 3, 3 * -bis (triethoxysilylpropyl) disulfide; 2, 2'-bis (triethoxysilylethyl) disulfide; 2,2'-bis disulfide (tripropoxysilylethyl); 2,2'-bis (tri-sec. -butoxysilylethyl) disulfide; 3,3'-bis (tri-t-butoxyethyl) disulfide; 3,3'-bis (triethoxysilylethyl-tolylene) disulfide; 3,3'-bis (trimethoxysilylethyl-tolylene) disulfide; 3,3'-bis (triisopropoxypropyl) disulfide; 3,3'-bis (trioctoxypropyl) disulfide; 2,2'-bis (2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis (dimethoxy-ethoxysilylethyl) disulfide; 3,3'-bis (methoxyethoxypropoxysilylpropyl) disulfide; 3,3'-bis (methoxy-dimethylsilylpropyl) disulfide; 3,3 * -bis (cyclohexoxy-dimethylsilylpropyl) disulfide; 4,4'-bis (trimethoxysilylbutyl) disulfide; 3,3'-bis (trimethoxysilyl-3-methylpropyl) disulfide; 3,3 * -bis disulfide (tripropoxysilyl-3-methylproyl); 3,3'-bis (dimethoxy-methylsilyl-3-ethylpropyl) disulfide; 3,3'-bis (trimethoxysilyl-2-methylpropyl) disulfide; 3,3 * -bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,3 * -bis (trimethoxysilylcyclohexyl) disulfide; 12, 12"-bis (trimethoxysilyldodecyl) disulfide, 12,12 • bis (triethoxysilyldodecyl) disulfide, 18,18'-bis (trimethoxysilyloctadecyl) disulfide, 18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2'-bis) trimethoxysilyl-2-methylethyl); 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2 '-bis disulfide (tripropoxysilyl-2-methylethyl); and 2,2'-bis (trioctoxysilyl-2-methylethyl) disulfide. Preferred such organosilane disulfides are: 3,3'-bis (trimethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (methoxy-dimethylsilylpropyl) disulfide and 3,3'-bis (cyclohexoxy-dimethylsilylpropyl) disulfide. While a bis (3-alkoxysilylalkyl) polysulfide material, such as, for example, a bis- (3-triethoxysilylpropyl) tetrasulfide or trisulfide, may be a preferred organosilane polysulfide (B), representative examples of such organosilane polysulfides ( B) are: bis- (3-trimethoxysilylpropyl) trisulfide, bis- (3-trimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylethyltolylene) trisulfide and bis (3-triethoxysilylethyltolylene) tetrasulfide. For the alkyl alkoxysilane of the Formula (IV), the aryl or substituted aryl radicals may be, for example, benzyl, phenyl, tolyl, methyl-tolyl and alpha-methyl-tolyl radicals.

One purpose of the alkyl alkoxysilane is, for example, to design the morphology and adhesion of the synthesized filler, in situ, specific to the matrix of the elastomer host. Representative examples of alkyl alkoxysilanes are, for example, but are not intended to be limited to propyltriethoxysilane, methyltriethoxysilane, hexadecyltri ethoxysilane and octadecyltriethoxysilane. Representative examples of primary amino functional organosilanes of the formula (V) are, for example, 3-amino-propyl-triethoxysilane, 2-aminoethyl-trietoxysilane and 4-aminobutyltriethoxysilane. Representatives of mercapto functional organosilanes are, for example, 3-mercapto-propyl-triethoxysilane, 2-mercaptoethyl-triethoxysilane and 4-mercaptobutyl-triethoxysilane. Representative of epoxy functional organosilanes is, for example, (3-glycidoxypropyl) -triethoxysilane. Representative of thiocyanate functional organosilanes is, for example, 3-thiocyanato-propyl-triethoxysilane. Representative of the functional vinyl organosilanes is, for example, vinyl triethoxysilane. Representative of the ureido radicals is ureidopropyl triethoxysilane. Representative of the isocyanate functional organosilanes is, for example, 3-isocyanatopropyltriethoxysilane. Representative of ethylene diamine is N (3-triethoxysilyl) -propyl-ethylenediamine. One purpose of the functional organosilane of the formula (V) is, for example, to aid in the adhesion of the filler to the host matrix of the elastomer. In practice, the diene-based elastomers for the elastomer (A) and the elastomer component of the elastomer (B) are considered to be selected from, for example, homopolymers and copolymers of monomers selected from isoprene and 1,3-butadiene and the copolymers of monomers selected from at least one of the isoprene and 1,3-butadiene with an aromatic vinyl compound, selected from styrene and alpha-methylstyrene, preferably styrene, and mixtures thereof. Representative of such elastomers, particularly for elastomer (A), are, for example, cis-1, 4-polyisoprene, cis-1,4-polybutadiene, isoprene / butadiene copolymers, premiere / butadiene copolymers including copolymers prepared by the emulsion polymerization and the copolymers prepared by solution polymerization of organic solvent, styrene / isoprene copolymers, 3,4-polyisoprene, trans-1,4-polybutadiene, styrene / isoprene / butadiene terpolymer, high polybutadiene vinyl, which has approximately 35 to 90 percent vinyl groups, and their mixtures.

Representatives of elastomer components, for the elastomer (B), are, for example, cis-1,4-polyisoprene, cis-1,4-polybutadiene prepared by organic solution polymerization, isoprene / butadiene polymers, styrene / butadiene copolymers, styrene / isoprene copolymers, 3,4-polyisoprene, trans-1,4-polybutadiene and styrene / isoprene / butadiene terpolymers, and mixtures thereof. In the practice of this invention, the diene-based elastomers (A) can be used as a tin-coupled or tin-capped elastomer. Such modified diene-based elastomers can be, for example, prepared by the polymerization or copolymerization, in an organic solution, monomers selected from one or more diene monomers, selected from 1,3-butadiene and isoprene, or styrene monomers together with 1,3-butadiene and / or isoprene and modifying the active polymer, before finishing the polymerization, with tin. Such tin-bonded elastomers may be, for example, cis-1,4-polyisoprene, cis-1, 4-polybutadiene, styrene / butadiene copolymers, styrene / isoprene / butadiene terpolymers, isoprene / butadiene copolymers and styrene / isoprene copolymers. An important and usual characterization of such elastomers is that a major portion, preferably at least 50 percent and more generally in a range of approximately 60 to 85 percent of the Sn bonds in the elastomer, are attached to units of diene of the copolymer, which can be referred to herein as "Sn-dienyl bonds", such as, for example, butadienyl bonds, in the case of butadiene-terminated polymers. Modification of the elastomer, such as tin coupling or tin finishing, can be accomplished by relatively conventional means and is believed to be well known to those skilled in the art. For example, a copolymer elastomer can be prepared by the copolymerization of the premiere with 1,3-butadiene and / or isoprene in an organic solution with an alkyl lithium catalyst. A co-catalyst or catalyst modifier can also be used. Such polymerization methods are well known to those skilled in the art. After the formation of the copolymer elastomer, but before the catalyst is still active and, therefore, while the copolymer is still considered an active copolymer, capable of further polymerization, the polymerization can be terminated with the reaction of the active copolymer with a tin compound. Various tin compounds can be used and tin tetrachloride is usually preferred. Thus, taking into account that the valency of the tin is four, typically the modified copolymer is considered as being coupled, with a accompanying molecular weight jump, or increase, with the modified copolymer being in what is sometimes referred to as a configuration of star, or coupled elastomer, configured, On the other hand, if a trialkyl tin compound is used, then only a single halogen is available and the modified copolymer is a topped copolymer. Such preparation of the coupled and capped copolymers, prepared by organic lithium catalysis, is believed to be known to those skilled in the art. It will be appreciated that the modified copolymer can be a mixture of coupled and topped copolymers. Examples of styrene / butadiene modified with tin, or coupled, can be found in, for example, U.S. Patent No. 5,064,910. The tin-coupled polymer or copolymer elastomer can also be coupled with tin with an organic tin compound, such as, for example, alkyl tin trichloride, dialkyl tin dichloride, and trialkyl tin monochloride, which provide variants of a copolymer coupled with tin, and trialkyl tin monochloride simply supplies a tin-finished copolymer. Therefore, a tin coupled elastomer can be the product of the reaction of at least one conjugated diene by premiere reaction together with at least one conjugated diene; wherein the diene is selected from 1,3-butadiene and isoprene, in a solution of an organic solvent and in the presence of a catalyst based on organic lithium, followed by the reaction of the active polymer with at least one compound having the formula : R74_vSnXn, in which n is an integer from 1 to 4 inclusive, X is a halogen selected from chlorine, iodine and bromine, preferably chlorine; and R7 is an alkyl radical selected from methyl, ethyl, propyl and butyl radicals. In another aspect of the invention, as discussed above, the diene-based elastomer may be end functionalized, as exemplified by formula (I), with, for example, an alkoxysilane unit. Such end functionalization can be achieved, for example, by cooling an anionic polymerization of the monomers in an organic solvent solution, during a diene-based elastomer formation, using, for example, chlorotriethoxysilane or sodium disulfide. 3,3'-bis (trietoxipropyl). For such end functionalization of the elastomers, the elastomers are preferably prepared by the polymerization of organic solvents and selected from at least one copolymer of styrene / butadiene, isoprene / butadiene copolymer, cis-1,4-polybutadiene, cis-1, 4-polyisoprene, styrene / isoprene copolymers, high vinyl polybutadiene, having a content in the range of about 35 to 90, and styrene / isoprene / butadiene terpolymer elastomers. For the carbon black reinforcement, which has silicon hydroxide on its surface, this modified carbon black can be prepared, for example, by the treatment of a carbon black reinforcement with an organic silane, at an elevated temperature or by the co-smoking of an organic silane and an oil, as discussed earlier. In the practice of this invention, as discussed above, the fill reinforcement formed in situ can be formed in an elastomer host, which is contained in an organic solvent solution or in a latex, preferably in a solvent solution. organic. For example, the elastomer may be provided in an organic solvent solution, for example, by (A) dissolving the elastomer in a suitable organic solvent, such as, for example, toluene, hexane, cyclohexane or THF (tetrahydrofuran), or (B) supplying the elastomer as a cement, or polymerizing, i.e. in the solution resulting from a solution polymerization of an organic solvent of appropriate monomers, to provide the elastomer in solution. Such solution polymerization of the organic solvent of the monomers, to obtain the elastomers, is well known to those skilled in the art. The elastomer can be supplied as a latex by the polymerization of the appropriate monomers in an aqueous soap solution, to form the latex based on the elastomer. Such preparation of the latexes is well known to those skilled in the art. Also, in the practice of this invention, the reinforcement filler formed in situ can also be formed by mixing the elastomer and one or more filler precursors and facilitating the condensation reaction of the filler precursor in an internal rubber mixing apparatus. , such as, for example, a Banbury type mixer or in an extruder. These internal mixers of rubbers and polymers are well known. Thus, the internal mixer can be, for example, at least one internal mixer in batches (for example a Banbury-type rubber mixer) in which the ingredients are introduced, introduced in sequence when appropriate in one or more mixing steps. internal in sequence and removed from the mixer after the mixture / reaction has reached a desired degree of completion. Continuous reaction mixing techniques can also be used. For example, a continuous extruder mixer can be used. Extruder mixers are usually presented as twin screw extruders, in which the screws can rotate in a co-rotation mode or a counter-rotation mode and the raised portions of their respective shafts can be engaged. It is preferred that the profile of the screw has a ratio of L / D (length to diameter) in the range of 5 to 70, depending on the desired mixing efficiency and the degree of dispersion of the ingredients within the elastomer mixture. Such a reactive extruder mixture of the various elastomers with the various ingredients is well known to those skilled in the art. For example, see U.S. Patent No. 5,711,904. For example, it is considered that the extruder can be a twin screw, where the elastomer host, filling precursor and condensation promoter are initially introduced into the extruder mixer and the optional organosilane is subsequently added to the reaction mixture within the extruder. , after about 50 to 70 percent of the total, general reaction time, and a corresponding separation length of the extruder from the initial introduction of the elastomer and precursor. For the preparation of the elastomer / filler composition by immersion of the elastomer host in a liquid filling precursor, the elastomer is allowed to simply swell in the presence of and consequently absorb the liquid precursor. Therefore, the liquid precursor is simply embedded in the elastomer host. Usually, the amount of the liquid precursor is adjusted so that little, if any, liquid precursor remains unabsorbed. Otherwise, either the swollen elastomer is simply removed from the vessel in which it has been immersed in the liquid precursor or, in an alternative, the liquid precursor is simply drained from such a vessel. In any case, the promoter of the condensation reaction is applied, usually directly, to the swollen elastomer, usually to its external surface and allowed to disperse via the absorbed precursor within the swollen elastomer and thus promote the condensation reaction of the precursor of filling from within the elastomer host and causing the creation in situ, or formation, of the dispersion of the filling. The optional organosilane is subsequently added to the swollen elastomer, before completing the condensation reaction. It can be considered, for example, that the elastomer host can be cut into individual segments, the segments submerged and mixed, for example by agitation, in a suitable container with a liquid filling precursor and a resulting swollen elastomer removed from any precursor of Remaining liquid filling. The condensation promoter can then be applied to the swollen elastomer guest fragments. The optional organosilane is subsequently added to the swollen elastomer before completing the condensation reaction. In the practice of this invention, various acid or basic condensation promoters may be used and, in general, it is understood that it will be well known to those of ordinary skill in the art. For example, representative of basic promoters are, for example, ammonia, ammonium hydroxide, N-butylamine, tertiary butyl amine, tetrahydrofuran (THF), sodium fluoride, several linear polyamines of proteins, such as, for example, hexamine of pentaethylene, diaminopropane, diethylenetriamine, triethylenetetraamine and polyallylamines, such as, for example, poly (allylamine hydrochloride), poly (L-lysine hydrobromide), poly (L-arginine hydrochloride) and poly (L-hydrochloride) histidine). For example, representative of acidic promoters are phosphoric acid, acetic acid, hydrofluoric acid and sulfuric acid. Metal salts and metal oxides can also be used as promoters or inhibitors of silane condensation reactions (ie, reactions of Lewis acids or bases). Examples of metal salts are, for example, zinc or aluminate sulphate, zinc stearate and aluminum stearate. Examples of metal oxides are, for example, zinc oxide and aluminum oxide.

Typical catalysts for curing the condensation reaction of silicon rubber can also be used. Examples are bis (2-ethylhexanoate) -tin and bis (neodecanoate) -tin. The actual selection of the condensation promoter will depend somewhat on whether the elastomer can be supplied in an organic solvent solution or as a latex and can be readily determined by one skilled in the art. Thus, the condensation reaction can be controlled by an acid or base promoter, depending somewhat on the kinetics of the required filler formation and the desired in situ filler structure. For example, while the individual circumstances may vary, a promoter of the acid or basic condensation reaction, or any other suitable condensation reaction promoter, may be applied in sequence to promote, first, the hydrolysis of the alkoxysilane (acid promoter). ) and then, secondly, the silane condensation reaction (basic promoter) that leads to the formation of the actual in situ filler. A particular advantage in using the above-mentioned formed elastomer, which contains the filler formed in situ in an elastomer composition, is the reduction of the mixing energy required for an elastomer-filler composite with a homogeneous, optimum filler dispersion, is say a more homogeneous dispersion within the elastomer with less agglomeration of the individual filler particles together to form larger aggregates. This is convenient because they can both improve the process of the elastomer composition during the mixing of the elastomer with other ingredients that make up the rubber and also several of the physical properties of the resulting rubber composition, as well as various performance properties. of the rim. Such improvements can be evidenced, for example, in a reduction of a hysteresis of the rubber composition and an improvement in a resistance of the rubber composition to abrasion, apparently as a result of the formation of a more homogeneous dispersion of the filling formed in in situ and improvement in an efficiency of the interaction of the filling with the elastomer host which can be particularly significant for a rubber composition of the tread of the rim. It is considered that the rubber compound, previously formed, of this invention, makes possible a more efficient integral dispersion of the reinforcing filler and particularly the hydrophilic filler particles (eg, silica, aluminosilicate and titanium dioxide) in a rubber composition. .

It is considered that the practice of this invention promotes a better handling of the desired fillers, limits the partial re-agglomeration of the particles formed in situ and thus enables a better homogeneous dispersion in the elastomer host and in a resulting rubber composition. . In the practice of this invention, it is considered that the integral, previously formed compound of the diene-based elastomer reinforcing filler, as a filler synthesized in situ, will reduce the agglomeration effect of the filler particles, and thus promote a dispersion more homogeneous hydrophilic filler (for example silica) in the rubber composition. In one aspect of the invention, it is desirable that the rubber composition of the elastomeric compound, previously formed, and one or more additional elastomers, be worked by (a) thermomechanically mixing the compound, in at least two mixing steps in sequence, with the conventional ingredients of the composition, all in the absence of curing agents, (i) at a maximum temperature in a range of about 160 to 180 ° C and for a duration of time, until reaching the maximum temperature, in the interval of about 1 to 10 minutes, at a temperature within about 5 to 10 seconds of the maximum temperature or (ii) at a maximum temperature in the approximate range of 155 to 1652C and for a time duration in reaching the maximum temperature, in the approximate interval of four to twenty minutes, at a temperature within about 5 to 10ac of the maximum temperature, followed by (b), a final thermomechanical mixing step in which the sulfur curing agents and the accelerators of The curing is combined with the mixture for about one to four minutes at a temperature of about 90 to 120 ° C, while the rubber mixture is cooled to a temperature below about 40 ° C, between each aforementioned mixing step. Depending on the speed of the mixer rotor, the fill factor and the rubber composition itself, the time to reach the maximum temperature may vary from about 2 to 5 minutes. The term "fill factor" is believed to be well known to those skilled in the art, as the volume portion of the internal mixer occupied by the rubber composition itself. Other parameters are the same, a rubber composition having a higher oil content will usually take longer to reach the maximum temperature. In practice, an internal rubber mixer is preferred for the individual mixing steps. In the stated mixing process, the term "curing agents" is intended to refer to curing agents of rubber vulcanization in a conventional sense, which means that the sulfur together with the resultant sulfur vulcanization accelerators or perhaps, although not preferred, the peroxide curing agents can be used. Classic carbon reinforcing blacks, considered for use in this invention, include carbon blacks used for the preparation of the carbon black compound, are, for example, carbon blacks having an Iodine Adsorption Number (ASTM test D1510) in a range of approximately 30 to 180 and sometimes even up to approximately 250 g / kg and a DBP (dibutylphthalate) Adsorption Number (ASTM test D2414) in the approximate range of 20 to 150 cm3 / 100 g Representative examples of such carbon blacks and references to the associated ASTM test methods can be found, for example, in the edition of The Vanderbilt Rubbber Handbook, 1990 on pages 416 to 418. The resulting physical properties, obtained by The rubber compositions cited will depend somewhat on the carbon black compound used, the coupler used and the rubber composition itself. This rubber composition itself can also be provided as a sulfur cured composition, through the vulcanization of the uncured elastomer composition. Sulfur cure is achieved in a conventional manner, that is, by curing under conditions of elevated temperatures and pressures for an adequate period of time. The curing agents for sulfur curing the rubber composition are those conventionally used for sulfur curable elastomers, which typically include sulfur and one or more appropriate healing accelerators and sometimes also a retarding agent. Such curing agents and their use for elastomeric compositions that can be cured with sulfur are well known to those skilled in the art. The sequencing processes for preparing the sulfur-curable rubber compositions, in which the elastomers and associated ingredients, excluding the curing agents, are first mixed in one or more steps in sequence, usually named " step (s) of non-productive mixing ", followed by a final mixing step of adding the curing agents, usually referred to as a" productive mixing step ", are also known to those skilled in the art. In the practice of this invention, additional diene-based elastomers can be mixed with the aforementioned elastomer composition, such as the homopolymers and copolymers of conjugated dienes and copolymers of one or more conjugated dienes and the aromatic vinyl compound. Such dienes can, for example, being selected from isoprene and 1,3-butadiene and such vinyl aromatics can be selected from styrene and alpha-methylstyrene. These elastomers, or rubbers, can be selected, for example, from at least one rubber of cis-1,4-polyisoprene (natural and / or synthetic rubbers, preferably natural rubber), 3,4-polyisoprene rubber, copolymer rubbers of styrene / butadiene, rubbers of isoprene / butadiene copolymers, styrene / isoprene copolymer rubbers, rubbers of styrene / isoprene / butadiene terpolymers, cis-1,4-polybutadiene rubber, trans-l rubber, 4-polybutadiene (70-956 percent trans), low vinyl polybutadiene rubber (10-30 percent vinyl), high vinyl polybutadiene rubber, which has approximately 35 to 90 percent 1,2 vinyl content, and butadiene / acrylonitrile copolymers prepared by the emulsion polymerization. It will be appreciated that additional silica, particularly precipitated silica, and / or carbon black, may also be mixed with the previously formed reinforced elastomer compound, and one or more additional elastomers. It is intended for the practice of this invention that the term "precipitated silica", when used herein, also includes the precipitated aluminosilicates as a form of the precipitated silica. These precipitated silicas are, for example, those obtained by the acidification of a soluble silicate, for example sodium silicate, generally excluding silica gels. Such silicas can be characterized, for example, by having a BET surface area, as measured using nitrogen gas, preferably in the approximate range of 40 to 600 and, more usually, in the approximate range of 50 to 300 square meters per gram. (m27g). The BET method for measuring surface area is described by Brunauer, Emmett and Te11er: in the Journal of the American Chemical Society (1938), page 309. A further reference may be Method DIN 66131. Silica can also typically be characterized by have a DBP Absorption Number (dibutylphthalate) in a range of approximately 100 to 400, and, more usually, around 150 to 300 cc / 100 g.

Various precipitated silicas, commercially available, may be considered for use in this invention, such as, by way of example only, and without limitation, the silicas commercially available from PPG Industries, under the trademark of Hi-Sil, with the designations 210, 243, etc .; available silicas of Rhone-Poulenc with, for example, the designations of Zeosil 1165MP, and silicas available from Degussa AG with, for example, the designations VN2 and VN3, BV3380GR, etc., and Huber, such as Zeopol 8745. They can be used several couplers and many are well known to those skilled in the art. For example, bis (trialkoxy-silylalkyl) polysulfides, containing from two to about eight sulfur atoms in their polysulfide bridge, can be used, with an average of about 2 to 5 sulfur atoms. For example, the polysulfide bridge can contain an average of about 2 to 3 or 3.5 to 5 sulfur atoms. The alkyl groups can be selected, for example, from methyl, ethyl and propyl groups. Therefore, a representative coupler can be, for example, a bis (triethoxysilylpropyl) polysulfide containing from 2 to 8, with an average of about 2 to 5, sulfur atoms in its polysulfide bridge. It will be appreciated that the coupler, if in liquid form, can be used in conjunction with a carbon black carrier, i.e., pre-mixed with a carbon black, before addition to the rubber composition, and such black of carbon will usually be included in the amount of total carbon black for the formulation of the rubber composition. It will be readily understood by those skilled in the art that the rubber composition will be made by methods generally known in the rubber composition art, such as the mixture of the various constituent rubbers that can be vulcanized with the sulfur, with various additive materials. commonly used, such as, for example, curing aids, such as sulfur, activators, retarding agents and accelerators, process additives, such as oils, resins that include tackifying resins, silicas and plasticizers, fillers, pigments , fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents and reinforcing materials, such as, for example, carbon black. As those skilled in the art know, depending on the intended use of the vulcanizable material with sulfur and vulcanized with sulfur (rubbers), the aforementioned additives are commonly selected and used in conventional amounts. In the preparation of the rubber composition, typical amounts of tackifying resins, if used, comprise about 0.5 to 10 per, usually about 1 to 5 per. Typical amounts of process aids comprise approximately 1 to 50 per. Such processing aids may include, for example, aromatic, naphthenic and / or paraffinic process oils. Typical amounts of antioxidants comprise approximately 1 to 5 per. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in The Vanderbilt Rubber Handbook (1978), pages 344-346. Typical amounts of antiozonant agents comprise about 1 to 5 per. Typical amounts of fatty acids, if used, which may include stearic acid, palmitic acid, linoleic acid or mixtures of one or more fatty acids, may comprise about 0.5 to 5 per. Stearic acid is often used in a relatively impure state, and is commonly named in the practice of rubber compositions, as "stearic acid" and will be so named in the description and practice of this invention. Typical amounts of zinc oxide comprise about 1 to 5 per. Typical amounts of waxes comprise about 1 to 5 per. Often, microcrystalline waxes are used. Typical amounts of peptization agents, if used, they comprise about 0.1 to 1 per. Typical peptizing agents can be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide. The vulcanization is conducted in the presence of a sulfur vulcanizing agent. Examples of suitable sulfur vulcanizing agents include elemental sulfur (free sulfur) or sulfur donating vulcanizing agents, for example, an amine disulfide, polymeric polysulfide or sulfur olefin adducts. Preferably, the sulfur vulcanizing agent is elemental sulfur. As is known to those skilled in the art, sulfur vulcanizing agents are used in an amount ranging from about 0.5 to 4 per or, in some circumstances, even up to about 8 per, with an approximate range of from 1 to 2.5, some times around 1 to 2, being preferred. Accelerators are used to control the time and / or temperature required for vulcanization and to improve the vulcanization properties. In one embodiment, a simple accelerator system, that is, a primary accelerator, can be used. Conventionally and preferably, one or more primary accelerators can be used in total amounts ranging from about 0.5 to 4, preferably about 0.8 to 2 per. In another embodiment, combinations of a primary and secondary accelerator can be used, with the secondary accelerator being used in amounts of approximately 0.05 to 3 per, in order to activate and improve the vulcanization properties. Combinations of these accelerators can be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by the use of any single accelerator. In addition, delayed action accelerators may be used that do not affect normal process temperatures, but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarding agents can also be used. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a second accelerator is used, this secondary accelerator is preferably a compound of a guanidine, dithiocarbamate or thiuram. The presence and relative amounts of the above ingredients, in addition to the carbon black and the coupler, are not considered as matter of this invention, which is directed more primarily to the preparation and use of the elastomer compounds formed previously, mentioned entities, with the dispersion of the integral silica. The ingredients are typically mixed in at least two stages, that is, at least one non-productive stage followed by a productive mixing step. The final curing agents are typically mixed in the final stage, which is conventionally referred to as the "productive" mixing step wherein the mixture typically occurs at a temperature, or final temperature, lower than the temperature (s) of mix, that the stage (s) of the previous nonproductive mixture (s). The rubber, carbon black and coupling agent, if used, are mixed in one or more non-productive mixing stages. The terms of "non-productive" and "productive" mixing stages are well known to those skilled in the rubber mixing art. In at least one of the non-productive mixing (NP) stages, the materials are mixed thermomechanically and the mixing temperature is allowed to reach a temperature of, for example, between 140 and 190 ° C. The rubber composition of this invention can be used for various purposes. For example, it can be used for various rim compounds. These tires can be constructed, shaped, molded and cured by various methods that are known and will be readily apparent to those skilled in the art. The invention can be better understood with reference to the following examples, in which the parts and percentages are by weight, unless indicated otherwise.

EXAMPLE I In this Example, a preformed elastomer / filler compound was prepared by dissolving a butadiene / styrene copolymer elastomer in a hydrocarbon solvent, then adding a liquid filler precursor to the solution and synthesizing a filler dispersion. in situ within the elastomer host via a condensation reaction. It will be appreciated that this Example attempts to be representative of an elastomer cement, obtained by copolymerizing styrene and 1,3-butadiene in an organic solvent since, in practice, it will usually be more preferable to use an elastomer cement rather than redissolve. an elastomer in an organic solvent. For an experimental portion of this Example, an organosilane was added to the mixture before completing the condensation reaction. By this method, the resulting filler formed in situ is in the form of an integral dispersion within the host elastomer. Samples of the elastomer / filler compounds are identified as samples A (mentioned as a Control for the purposes of this Example), B and C. For this Example, the elastomer used for Samples A and B were prepared by copolymerizing the styrene. with 1,3-butadiene in an organic solvent solution, in the presence of a lithium-based catalyst and recovering the elastomer. This elastomer may be mentioned in this Example as an "S-SBR", which has a bound styrene content of about 18 percent.

For this Example, the elastomer used for Sample C is similar to the elastomer used for Samples A and B, except that the copolymerization of 1,3-butadienop and styrene was quenched with bis (triethoxy-silylpropyl) disulfide (which it contains an average of about 2.2 sulfur atoms in its polysulfide bridge) leading to an end-terminated styrene / butadiene copolymer copolymer of tritoxysilylpropyl-mono-sulfane, which has a bound styrene content of about 18 percent. Such an elastomer can be referred to in this example as an "ST-SBR". The experiment was conducted first by dissolving the S-SBR or the ST-SBR, as the case may be, in a hexane solvent. Liquid tetraethoxysilane (TEOS), as a filler precursor, is then added to the elastomer solution, in a weight ratio of about% TEOS to elastomer and then water is added (weight ratio of water to TEOS of about 2/1), together with a promoter of the condensation reaction of 1,3-diaminopropane (promoter of about 2 weight percent of the total mixture including water). The condensation reaction was allowed to proceed apiroximately at room temperature, or about 25 ° C, while stirring the mixture.

For Samples B and C, before completing the TEOS condensation reaction, a bis (3-triethoxysilylpropyl) disulfide (containing an average of about 2.2 sulfur atoms in its polysulfide bridge) was added to the reaction system. The reaction was allowed to proceed for about one hour at about 25ac, while stirring the mixture. The resulting samples A, B and C were recovered by drying at about 80ac for about three hours in an open-air oven. The content of the silica filler dispersion, formed in situ, of the elastomer / filler compound, can be determined by thermogravimetric analysis. The silica particles formed in situ are considered as being substantially spherical in configuration, with a diameter ranging from about 5 to 300 nm, with some expansion of dendrites, as can be determined by electron transmission microscopy. A summary of Samples A (Control), B and C is shown in the following Table 1: Table 1 While the physical properties of the rubber composition, such as modulus and elongation, are usually measured for a rubber composition cured with sulfur, it was decided to measure such values for Unvulcanized Samples A, B and C, particularly since the Filling dispersion formed in situ with the elastomer hosts appeared to form an elastomer / filler composite with sufficient dimensional stability for such properties, which are to be determined as depicted in the following Table 1A: Table lA It is important to appreciate that the modulus and elongation values, measured for Sample A, demonstrate a potential for actual reinforcement, or effect, of the synthesized filler, in situ, within the elastomer host, because without the in situ synthesized filler a A person skilled in the art would expect the value of the module to be much smaller and the value of the elongation would be much greater for the elastomer. The major modulus and minor elongation properties reported for Sample B in Table 1A indicate that a greater host booster of the elastomer is obtained in the formation of the elastomer / filler composite by combining the use of the TEOS filler precursor with the Subsequent addition of the organosilane disulfide material, before completing the condensation reaction, instead of using the TEOS alone as in Sample A. The properties of the even greater modulus and lower elongation reported for Sample C in Table 1A, indicate that an even greater reinforcement of the elastomer is obtained in the formation of the elastomer / filler composite by combining the use of a functionalized elastomer at the alkoxy metal end together with the TEOS filler precursor and the subsequent addition of the organosilane disulfide material, before completing the condensation reaction, compared to using TEOS alone with an elastomer guest more conventional, as in Sample A, and compared with the use of TEOS together with the addition of the organosilane disulfide with a conventional elastomer host, as in Sample B. The greater reinforcement indicated for Samples B and C, is also considered here as particularly advantageous for the preparation of a elastomer / filler compound, previously formed, which can then be mixed with other elastomer and, optionally, additional reinforcing fillers, for the preparation of an elastomer composition for use in the preparation of various products, including, for example, tire components.

EXAMPLE II In this considered illustrative example, an elastomer / filler composite was prepared by dry blending a butadiene / styrene copolymer elastomer with a liguid filler precursor, ie tetraethoxysilane, or TEOS, and the synthesis of a In situ fill dispersion within the elastomer host by means of a condensation reaction. For the fine of this Example, the elastomer and liquid filling precursor were mixed and this filling precursor was allowed to proceed with the condensation reaction, in a double shaft extruder. In this manner, an elastomer / filler composite was prepared with the filler formed in situ being in the form of an integral dispersion within the host elastomer. Samples of the elastomer / filler compounds are identified herein as Samples D (a Control for the purposes of this Example), E and F. The elastomer used for Samples D (Control) and E was prepared by copolymerizing the styrene and the 1,3-butadiene in an organic solvent solution, in the presence of a lithium-based catalyst and recovery of the elastomer. The elastomer can be named in this Example as an "S-SBR", which has a bound styrene content of about 18 percent. The elastomer used for Sample F is similar to the elastomer used for Samples D and E, except that the copolymerization of 1,3-butadiene and styrene was quenched with bis (triethoxysilylpropyl) disulfide (containing an average of about 2.2. sulfur atoms in its polysulfide bridge), which leads to a styrene / butadiene elastomer terminated at one end of triethoxysilylpropyl monosulfan, which has a bound styrene content of about 18 percent. Such elastomer may be referred to in this Example as an "ST-SBR". For this Example, the elastomer / filler compound was prepared by first introducing the S-SBR or the ST-SBR, as the case may be, in the extruder, followed by adding the TEOS, in a weight ratio of about% of the TEOS to the elastomer, together with a promoter of the condensation reaction of the pentaethylenehexamine (promoter up to 3.5 percent in weight of the total mixture The double-shaft extruder was operated at a temperature of about 170ac with a general residence mixing time for the ingredients within the extruder of about 10 minutes.The non-productive rubber ingredients, including the elastomer , were added to the extruder cylinder and the fill precursor and the condensation reaction promoter were added to the extruder at a location equivalent to about 25 percent of the overall residence time For Samples E and F, before completion the condensation reaction of TEOS, an organosilane in the form of a bis (3-triethoxysilylpropyl) disulfide material (containing an average of about 2.2 sulfur atoms in its polysulfide bridge), was added to the extruder at a location equivalent to about 50 percent of the overall residence time. The silica particles, formed in situ, are considered to be substantially spherical in configuration, with diameters ranging from about 5 to 300 nm, with some dendritic expansion, as can be determined by electron transmission microscopy. A considered summary and the contents of the silica filler formed in situ proposed, Samples D (Control), E and F, are shown in the following Table 2: Table 2 EXAMPLE III In this considered illustrative example, an elastomer / filler compound was prepared by dry blending a butadiene / styrene copolymer elastomer with a liguid filler precursor, ie tetraethoxysilane, or TEOS, and the synthesis of a In situ fill dispersion within the elastomer host by means of a condensation reaction. For the fine of this Example, the elastomer and liquid filling precursor were mixed in a rubber mixer, of the Banbury type. In this manner, an elastomer / filler composite was prepared with the filler formed in situ as an integral dispersion within the host elastomer.

Samples of the elastomer / filler compounds are identified herein as Samples G (a Control for the purposes of this Example), H and I. The elastomer used for Samples G (Control) and H was prepared by copolymerizing the styrene and the 1,3-butadiene in an organic solvent solution, in the presence of a lithium-based catalyst and recovery of the elastomer. The elastomer can be named in this Example as an "S-SBR", which has a bound styrene content of about 18 percent. The elastomer used for Sample I is similar to the elastomer used for Samples G and H, except that the copolymerization of 1,3-butadiene and styrene was quenched with bis (triethoxysilylpropyl) disulfide (containing an average of approximately 2.2. sulfur atoms in its polysulfide bridge), which leads to a styrene / butadiene elastomer terminated at one end of triethoxysilylpropyl monosulfan, which has a bound styrene content of about 18 percent. Such elastomer may be referred to in this Example as an "ST-SBR". For this Example, the elastomer / filler compound was prepared by first introducing the S-SBR or the ST-SBR, as the case may be, into the internal rubber mixer, followed by adding the TEOS, in a weight ratio of about 1/2 of the TEOS to the elastomer, together with a promoter of the condensation reaction of the pentaethylenehexamine (promoter up to 3.5 weight percent of the total mixture.) The mixture was mixed in a rubber mixer for about 8 minutes, to a temperature of about 170 ° C. For Samples H and I, before completing the condensation reaction of the TEOS, an organosilane in the form of a bis (3-triethoxysilylpropyl) disulfide material (containing an average of about 2.2 atoms) of sulfur in its polysulphide bridge), was added to the Banbury-type blender after about 6 minutes of the aforementioned 8 minute mixing time The silica particles, formed in situ, are considered as essentially spherical in configuration, with diameters ranging from about 5 to 300 nm, with some dendritic expansion, as can be determined by electron transmission microscopy. A summary of the Samples G (the Control), H and I, is shown in the following Table 3: Table 3 While the physical properties of the rubber composition, such as modulus and elongation, are usually measured for a sulfur-cured rubber composition, it was decided to measure such values for the unvulcanized samples G, H and I, particularly since the Filling dispersion formed in situ with the elastomer hosts appeared to form an elastomer / filler composite with sufficient dimensional stability for such properties, which are to be determined as shown in the following Table 3A: Table 3A It is important to appreciate that the modulus and elongation values, measured for Sample G, demonstrate a potential of actual reinforcement, or effect, of the synthesized filler, in situ, within the elastomer host, because without the in situ synthesized filler a A person skilled in the art would expect the value of the module to be much smaller and the value of the elongation would be much greater for the elastomer. The properties of greater modulus and smaller elongation, reported for Sample H in Table 3A, indicate that a greater host booster of the elastomer is obtained in the formation of the elastomer / filler composite by combining the use of the TEOS filler precursor with the subsequent addition of the organosilane disulfide material. , before completing the condensation reaction, instead of using the TEOS alone as in Sample G. The properties of the even greater modulus and lower elongation reported for Sample I in Table 3A, indicate that an even greater reinforcement of the elastomer is obtains in the formation of the elastomer / filler composite by combining the use of a functionalized elastomer at the alkoxy metal end together with the TEOS filler precursor and the subsequent addition of the organosilane disulfide material, before completing the condensation reaction, compared to using TEOS alone with a more conventional elastomeric host, as in Sample G, and compared to n the use of the TEOS together with the addition of organosilane disulfide with a conventional elastomer host, as in Sample H. The higher reinforcement indicated for Samples H and I, is also considered to be particularly advantageous for the preparation of a compound elastomer / filler, preformed, which can then be blended with other elastomer and, optionally, additional reinforcing fillers, for the preparation of an elastomer composition for use in the preparation of various products, including, for example, the tire components.

EXAMPLE IV In this considered illustrative example, an elastomer / filler composite was prepared by dipping a butadiene / styrene copolymer elastomer into a liquid filler precursor, ie tetraethoxysilane, or TEOS, allowing the liquid precursor to be imbibed in the elastomer itself and synthesizing an in-situ filler dispersion within the elastomer host by means of a condensation reaction.

In this way, a filling formed in situ was obtained as an integral dispersion within the host elastomer. Samples of the elastomer / filler compounds are identified here as Samples J (a Control for the purposes of this Example), K and L. The elastomer used for Samples J (Control) and K was prepared by copolymerizing styrene and 1,3-butadiene in an organic solvent solution, in the presence of a lithium-based catalyst and recovery of the elastomer. The elastomer can be named in this Example as an "S-SBR", which has a bound styrene content of about 18 percent. The elastomer used for Sample L is similar to the elastomer used for Samples J and K, except that the copolymerization of 1,3-butadiene and styrene was quenched with bis (triethoxysilylpropyl) disulfide (containing an average of about 2.2. sulfur atoms in its polysulfide bridge), which leads to a styrene / butadiene elastomer terminated at one end of triethoxysilylpropyl monosulfan, which has a bound styrene content of about 18 percent. Such elastomer may be referred to in this Example as an "ST-SBR". For this Example, the elastomer / filler compound was prepared by first immersing in a suitable container, the S-SBR or the ST-SBR, as the case may be, in a liquid filling precursor (the TEOS) at a temperature of about 25 c for about an hour, to allow the TEOS to soak, or imbibe, the elastomer, thus forming a swollen elastomer. A promoter of the condensation reaction of n-butylamine was applied to the swollen elastomer. This promoter of the condensation reaction was used in an amount of about 3 weight percent of the elastomer and the TEOS in the swollen elastomer. For Samples J and K, before completing the condensation reaction of the TEOS, an organosilane in the form of a bis (3-triethoxysilylpropyl) disulfide material (containing an average of about 2.2 sulfur atoms in its bridge). polysulfidic), was applied to the swollen elastomer containing the TEOS: The silica particles, formed in situ, are considered as substantially spherical in configuration, with diameters ranging from about 5 to 300 nm, with some dendritic expansion, as can be determine by electron transmission microscopy. A considered summary and the content of the proposed silica of Samples J (Control), K and L, are shown in the following Table 4: Table 4 EXAMPLE V In this Example, illustrative samples of the elastomer compositions are considered as being prepared using the elastomer / filler compounds, previously formed, of Examples I, II, III and IV. Prepared samples are reported here as Samples 1-16, with Samples 1, 2, 5, 6, 9, 10, 13 and 14, being of the nature of Control Samples for the purposes of this Example. Control Samples 1, 5, 9 and 13 were prepared by mixing, in a first mixing step, in an internal rubber mixer, precipitated silica and a bis (3-triethoxysilylpropyl) disulfide compound, as a coupling agent, which has an average of about 2.2 sulfur atoms in its polysulphide bridge, with a rubber composition of a styrene / butadiene rubber and other rubber composition ingredient, excluding free sulfur, in at least one mixing stage (non-productive) ), high school. In a subsequent mixing stage, the free sulfur and one or more accelerators were mixed with the rubber composition. Control Samples 2, 6 and 10 were prepared similiarly as a second Control, except that the elastomeric compounds previously formed of Examples I-IV were added to the aforementioned preliminary nonproductive mixing step. Samples 3, 4, 7, 8, 11, 12, 15 and 16 were similarly prepared as Sample 1, except that the elastomer / filler compounds, previously formed, in addition to the previously formed control compounds, of Examples I -IV, they were mixed with the rubber composition in one or more (non-productive) preparatory mixing stages. Therefore, the amount of the precipitated silica was adjusted, according to the addition of the organosilane disulfide. In particular, the rubber compositions, which contain the materials mentioned in Tables 1 to 4, were prepared in a BR Banbury mixer, using three separate stages of addition (mixing), that is, two preparatory mixing steps and one step of final mix, at temperatures of 170, 160 and 120SC and for times of approximately 8 minutes, two minutes and two minutes, respectively, for the three general mixing stages. After each mixing step, the rubber mixture was separated into batches in a two-roll mill, mixed and ground for a short period of time, and sheets, or sheets, of the rubber, were removed from the mill and allowed to cool to a a temperature of about 30ac or less. The amounts of the elastomer / filler compound formed previously, S-SBR, ST-SBR, precipitated silica and organosilane disulfide, are listed as "variables" in the following Table 5.

Table 5 Parts Non-Productive Mixing Stages Composite1 elastomer / filler, formed Variable previously Styrene / butadiene rubber Variable Cis-1, 4-polybutadiene -'3 30 Oil 25 Fatty Acid5 Silica6 Variable Organosilane Disulfide7 Variable Table 5 (Continued) i) Preformed elastomer / filler compounds, prepared, in varying form, in Examples I, II, III and IV 2) Styrene / butadiene copolymer rubber, prepared by the solution polymerization, obtained from The Goodyear Tire & Rubber Company, which contains approximately 18 percent styrene and which has a glass transition temperature) Tg) of about -70 ° C. 3) Elastomer of cis-1, 4-polybutadiene, obtained as BUDENE® 1207 from The Goodyear Tire & Rubber Company.

) Oil.

) Fatty acid, primarily stearic acid. 6) Zeosil 1165 MP, from Rhone Poulenc. 7) A compound commercially available from Degussa GmbH, such as X266S, in the form of a 50/50 mixture, or a compound of S266 (trademark of Degussa) and carbon black. The S266 is a compound (I) of bis (3-triethoxysilylpropyl) disulfide it is understood to have an average of about 2.2 sulfur atoms in its polysulfide bridge. Thus, the compound contains 50 percent of the organosilane disulfide compound. 8) It can be obtained as S8 elemental sulfur from the company Kali Chemie, from Germany. 9) A type of phenylene diamine.

) A compound commercially available from Degussa GmbH as X50S, in the form of a 50/50 mixture of Si69, a trademark of Degussa GmbH, or which may be named as a compound (II) of bis- (3-) tetrasulfide. triethoxysilylpropyl), which has an average of about 3.8 sulfur atoms in its polysulphide bridge, with carbon black and, thus, the organosilane tetrasulfide is considered to be 50% of the compound and, therefore, 50% active.

The Samples are molded into a suitable mold and cured, or vulcanized, for about 16 minutes at a temperature of about 160ac. A summary of the variable additions of the materials for Samples 1 to 4 is shown in the following Table 6.

Table 6 A summary of the variable additions of the materials in Samples 5-8 is shown in the following Table 7.

Table 7 A summary of the variable additions of materials for Samples 9-12 is shown in Table 8 below. Table 8 A summary of the variable additions of the materials for Samples 13-16 is shown in the following Table 9.

Table 9 For the rubber compositions illustrated in Tables 6-9, it is important to appreciate that Samples 1, 5, 9 and 14 utilized a precipitated silica backing without a previously formed elastomer / filler compound of this invention. Therefore, 12 parts of the organosilane disulfide were added to the elastomer mixture to accommodate the aggregated precipitated silica as a coupling agent (as indicated above in this Example, the organosilane disulfide material was used as a compound of 50 / 50 of liquid disulfide and carbon black as a carrier and, thus, the actual amount of organosilane disulfide is 6 per). It is also important to appreciate that for Samples 2, 6, 10 and 14, where the previously formed elastomer / filler compound, prepared with the TEOS filler precursor is used, but without any addition of the organosilane material to the condensation reaction for the preparation of the elastomer / filler compound formed previously, a reduced amount of the precipitated silica is used, but the same amount of the organosilane disulfide assistant as for Samples 1, 5, 9 and 14. In this way, then, a The most efficient method of introducing a reinforcement in particles, dispersed homogeneously, in the rubber compound is considered here as being provided. It will be further appreciated that, for Samples 3, 7, 11 and 15, where a previously formed elastomer / filler composite of this invention, prepared with the TEOS filling precursor, along with the addition of the organosilane material to the damnation reaction is used, a reduced amount of precipitated silica is added, but the same amount of the assistant organosilane disulfide is added to the elastomer mixture . In this way, then, another more efficient method of introducing a reinforcement into particles dispersed homogeneously in a rubber compound is considered here as being provided. It will be further appreciated that, for Samples 4, 8, 12 and 16, where the previously formed elastomer / filler compound of this invention, prepared with an alkoxy metal end functionalized elastomer, the TEOS filling precursor together with the addition From the organosilane material to the condensation reaction is used, a reduced amount of both the precipitated silica and the assistant organosilane disulfide are added to the elastomer mixture. Indeed, the reduced amount of the added organosilane disulfide is used primarily to accommodate the aggregate precipitated silica. In this way, then, another, more efficient, method of introducing a reinforcement into particles, dispersed homogeneously in a rubber compound is considered here as being provided. One meaning of the presentation of these Samples is to demonstrate the preparation of rubber compositions with the introduction, considerably more efficiently, of the reinforcing filler, as a homogeneous dispersion, to the rubber composition, by means of the use of an elastomer compound. filler, previously formed, prepared according to this invention.

EXAMPLE VI Tires of size 195 / 65R15 are considered to be prepared, which individually use the rubber compositions of Samples 1-16 for their treads. While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention.

Claims (41)

1. A method for preparing an elastomer / filler composite, such as a dispersion of a filler, formed in situ, within an elastomer host, characterized by: mixing, in an internal mixer, a filler precursor, a reaction promoter condensation and an elastomer host, selected from the host (A) of elastomer and the host (B) of elastomer, to initiate a condensation reaction of the filler precursor and, for the host (A) of elastomer and, optionally, for the elastomer host (B), subsequently adding and reacting, in an internal mixer, an organosilane material with the filler / filler precursor, before completing the condensation reaction; followed by recovering the elastomer / filler compound; wherein the elastomer host (A) is selected from at least one of the conjugated diene homopolymers, conjugated diene copolymers, copolymers of conjugated diene with an aromatic vinyl compound, preferably selected from styrene and alpha-methylstyrene; wherein the elastomer host (B) is selected from at least one diene-based elastomer, functionalized at the alkoxy metal end, wherein the metal is selected from silicon, titanium, aluminum and boron, and wherein the elastomer is selected from at least one of the homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with an aromatic vinyl compound, selected from styrene and alpha-methylstyrene; wherein the precursor of the filling is at least one material selected from the formulas (HA), (IIB) and (IIC): (HA) M (OR) x (R ') and (IIB) (RO) x (R ') and M-0-M' (R ') z (RO) w (IIC) (RO) x (R ') and M- (CH2) r-M' (R ') z (RO) w where M and M 'are the same or different and are selected from silicon, titanium, zirconium, boron and aluminum, preferably silicon, where R and R * are alkyl radicals, selected from methyl, ethyl, n-propyl, isopropyl radicals, n -butyl and isobutyl, and where the sum of each of the integers x + yy w + z is equal to 3 or 4, except when its associated M or M1 is boron or aluminum, for which it is 3; and wherein r is from 1 to 15, wherein the organosilane is at least one material selected from the formula (III), (IV) and (V), that is: an organosilane polysulfide of the formula (III) as: (III) Z - ív "™ * Sjfl - R ~ Z where ra is a number in the range of 2 to about 8, and the average for m is in the range of (a) about 2 to 2.6, or (b) ) approximately 3.5 a 4. 5; where Z is represented by the following formulas: R2 R2 R3 (Zl) Si - R2, (Z2) Si - R3 (Z3) Si - R3 R3 R3 R3 wherein R2, which are the same or different radicals, are selected, individually, from alkyl radicals having from 1 to 4 carbon atoms, and the phenyl radical, preferably from methyl and ethyl radicals; R3 are alike or different alkoxy groups, in which the alkyl radicals of these alkoxy groups are alkyl radicals selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl radicals; and R1 is a radical selected from the group consisting of alkyl radicals, substituted or unsubstituted, having a total of 1 to 18 carbon atoms, and an aryl radical, substituted or unsubstituted, having a total of 6 to 12 carbon atoms , an alkyl-alkoxy silane, of the formula (IV), as: (IV) (OR4) 3-Si-R5 where R can be the same or different alkyl radicals, selected from the methyl, ethyl, n-propyl and isopropyl radicals, and R5 is selected from alkyl radicals having from 1 to 18 carbon atoms, and aryl radicals or aryl radicals substituted by alkyl, having from 6 to 12 carbon atoms; and a functional organosilane of the formula (V), such as: (V) (OR6) 3 - yes - (CH2) and - Y wherein the R are the same or different alkyl radicals, selected from methyl, ethyl, n-propyl and isopropyl radicals, preferably an ethyl radical, and is an integer from 1 to 12 and Y is selected from primary amino radicals, mercapto, epoxide, thiocyanate, vinyl, methacrylate, ureido, isocyanate and ethylene diamine.

2. The method of claim 1, characterized in that the internal mixer is at least an internal mixer in batches.

3. The method of claim 1, characterized by the internal mixer is a continuous internal extruder mixer.

4. The method of any of the preceding claims, characterized in that the elastomer is at least one elastomer (A).

5. The method of any of the preceding claims 1 to 3, characterized in that the elastomer is at least one elastomer (B) and where this elastomer (B) has the general formula (I) of: (I) elastomer-X- (OR) n wherein X is selected from silicon, titanium, aluminum and boron, R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl radicals, and n is 3 for silicon and titanium and is 2 for aluminum and boron, and wherein the elastomer is selected from at least one of the homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of at least one conjugated diene with an aromatic vinyl compound, preferably selected from styrene and alpha-methylstyrene.

6. The method of claim 5, characterized in that for the elastomer (B), X is silicon, R is an ethyl radical, n is 3 and, for the elastomer (B), the aromatic vinyl compound is styrene.

7. The method of claim 4, characterized in that the elastomer (A) is selected from at least one of the homopolymers and copolymers of 1,3-butadiene and isoprene, styrene copolymers with at least one of 1,3-butadiene and isoprene with styrene, tin coupled polymers and copolymers of 1,3-butadiene and isoprene, and styrene-coupled copolymers of styrene with at least one of 1,3-butadiene and isoprene, and mixtures thereof.

8. The method of any of the preceding claims 5 and 6, characterized in that the elastomer (B) is selected from at least one of the homopolymers and copolymers of 1,3-butadiene and isoprene and copolymers of 1,3-butadiene and / or isoprene with styrene and wherein the end functionalization is an alkoxysilane, wherein the alkyl radicals of the alkoxysilane are selected from at least one of the ethyl, methyl, n-propyl and isopropyl radicals, and mixtures thereof.

9. The method of any of the preceding claims, characterized in that the precursor of the filler is the precursor (HA).

10. The method of claim 9, characterized in that for the filling precursor (HA), M and M1 are silicon, R is an ethyl radical, R 'is a methyl radical and the sum of (x + y) is 4.

11. The method of claim 9, characterized in that the filler precursor is selected from at least one of the tetraethoxy ortho-silicate, titanium ethoxide, titanium n-propoxide, aluminum secondary tri-butoxide, zirconium t-butoxide, n zirconium butoxide, tetra-n-propoxy zirconium and boron ethoxide, methyl triethoxy silicate and dimethyl diethoxy silicate.

12. The method of any of the preceding claims 1 to 8, characterized in that the precursor of the filler is the precursor (HB).

13. The method of claim 12, characterized in that, for the filling precursor (IIB), M and M 'are silicon, R is an ethyl radical, R' is a methyl radical and the sum of each of x + y as well as of w + z is 4.

14. The method of claim 12, characterized in that the precursor (HB) is selected from at least one of the di-s-butoxyaluminoxy triethoxysilane and hexaetoxydisiloxane.

15. The method of any of the preceding claims 1 to 8, characterized in that the filling precursor is the precursor (TIC).

16. The method of claim 15, characterized in that, for the filling precursor (HC), M and M 'are silicon, R is an ethyl radical, R' is a methyl radical and the sum of each of x + y as well as w + z is from 4.

17. The method of claim 15, characterized in that the precursor (IIC) is selected from at least one of the bi (triethoxysilyl) methane and bis (triethoxysilyl) ethane.

18. The method of any of the preceding claims, characterized in that the organosilane is an organic polysulfide (III) material and wherein Z is Z3 and the alkyl radicals of R3 are selected from the ethyl, methyl, n-propyl, isopropyl, n-radicals Butyl and isobutyl.

19. The method of claim 18, characterized in that, for the organosilane polysulfide (III) material, m is an average of about 2 to 2.6.

20. The method of claim 18, characterized in that, for the organosilane polysulfide (III) material, m is an average of about 3.5 to 4.5.

21. The method of claim 18, characterized in that the organosilane polysulfide (III) material is selected from at least one of: 2,2,2-bis (trimethoxysilylethyl) disulfide; 3, 3 * 'bis (trimethoxysilylpropyl) disulfide; 3, 3"-bis (triethoxysilylpropyl) disulfide; 2, 2'-bis (triethoxysilylethyl) disulfide; 2, 2 • '-bis disulfide (tripropoxysilylethyl); 2, 2 •• -bis (tri-sec. -butoxysilylethyl) disulfide; 3 r 3"-bis disulfide (tri-t-butoxyethyl); 3 r 3"-bis disulfide (triethoxysilylethyl-tolylene); disulfide of 3, r 3"-bis (trimethoxysilylethyl-tolylene); 3, 3"-bis disulfide (triisopropoxypropyl); disulfide of 3? 3 • '-bis (trioctoxypropyl); 2/2 • 'bis (2'-ethylhexoxysilylethyl) disulfide; 2, 2"-bis (dimethoxy-ethoxysilylethyl) disulfide; 3, 3 1'-bis (methoxyethoxypropoxysilylpropyl) disulfide; 3, 3 * '-bis (methoxy-dimethylsilylpropyl) disulfide; 3 * 3 1'-bis (cyclohexoxy-dimethylsilylpropyl) disulfide; disulfide of 4, 4 • * -bis (trimethoxysilylbutyl); 3, 3 1'-bis (trimethoxysilyl-3-methylpropyl) disulfide; 3,3'-bis disulfide (tripropoxysilyl-3-methylproyl); 3,3'-bis (dimethoxy-methylsilyl-3-ethylpropyl) disulfide; 3,3'-bis (trimethoxysilyl-2-methylpropyl) disulfide; 3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,3'-bis (triraethoxysilylcyclohexyl) disulfide; 12, 12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18, 18'-bis (trimethoxysilyloctadecyl) disulfide; 18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2'-bis) trimethoxysilyl-2-methylethyl disulfide); 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2 * -bis disulfide (tripropoxysilyl-2-methylethyl); and 2,2'-bis (trioctoxysilyl-2-methylethyl) disulfide.

22. The method of claim 18, characterized in that the organosilane polysulfide (III) material is a bis (3-triethoxysilylpropyl) disulfide.

23. The method of claim 18, characterized in that the organosilane polysulfide (III) material is selected from at least one of bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) trisulfide.

24. The method of any of the preceding claims, characterized in that the organosilane is an alkyl-alkoxy-silane (IV).

25. The method of any of the preceding claims 1 to 17, characterized in that the organosilane is the alkyl-alkoxy silane (IV) and in which, for the alkyl-alkoxy silane (IV) R5 is an alkyl radical having from 8 to 18 carbon atoms.

26. The method of claim 24, characterized in that the alkyl-alkoxy silane (IV) is selected from at least one of propyltriethoxysilane, methyltriethoxysilane, hexadecyltriethoxysilane and octadecyl-triethoxysilane.

27. The method of any of the preceding claims 1 to 17, characterized in that the organosilane is a functional organosilane (V).

28. The method of claim 27, characterized in that, for the functional organosilane (V), R6 is an ethyl radical, and y is an integer from 2 to 4.

29. The method of claim 27, characterized in that the functional organosilane is selected from at least one of 3-amino-propyl-triethoxysilane, 2-aminoethyl-triethoxysilane, 4-aminobutyltriethoxysilane, 3-ercapto-propyl-triethoxysilane, 2-mercaptoethyl-triethoxy -silane, 4-mercaptobutyl-triethoxysilane, (3-glycidoxypropyl) -triethoxysilane, 3-thiocyanato-propyl-triethoxysilane, vinyl-triethoxysilane, ureidopropyl-triethoxysilane, 3-isocyanato-propyl-triethoxysilane, and N (3-triethoxysilyl) - propyl-ethylenediamine.

30. The method of any of the preceding claims, characterized in that the elastomer (A) is selected from at least one of cis-1,4-polyisoprene, cis-1,4-polybutadiene, isoprene / butadiene copolymers, styrene / butadiene copolymers , which include copolymers prepared by emulsion polymerization and copolymers prepared by solution polymerization of an organic solvent, styrene / isoprene copolymers, 3,4-polyisoprene, trans-1,4-polybutadiene, styrene / isoprene / butadiene terpolymer , high vinyl polybutadiene, which has about 35 to 90 percent vinyl groups.

31. The method of any of the preceding claims 1 to 29, characterized in that the elastomer component of the elastomer (B) is an elastomer prepared by the polymerization of an organic solvent, selected from at least one of the cis-1,4-polyisoprene, cis -1,4-polybutadiene, isoprene / butadiene copolymers, premiere / butadiene copolymers, including copolymers prepared by emulsion polymerization and copolymers prepared by the solution polymerization of an organic solvent, styrene / isoprene copolymers, 3, 4-polyisoprene, trans-l, 4-polybutadiene and styrene / isoprene / butadiene terpolymers.

32. The method of any of the preceding claims 1 to 29, characterized in that the elastomer coupled to the tin is the product of the reaction of at least one conjugated diene or by the reaction of styrene together with at least one conjugated diene, in which this diene is selects 1,3-butadiene and isoprene, in an organic solvent solution and in the presence of a catalyst based on organic lithium, followed by the reaction of the active polymer with at least one compound having the formula: R74_vSnXn, where n is an integer from 1 to 4 inclusive, X is chlorine; and R is an alkyl radical, selected from the methyl, ethyl, propyl and butyl radicals.

33. The method of any of the preceding claims, characterized in that the filler precursor is at least one metal selected from the tetraethoxy orthosilicate, titanium ethoxide, titanium n-propoxide, aluminum secondary tri-butoxide, zirconium t-butoxide, n - zirconium butoxide, tetra-n-propoxy zirconium and boron ethoxide, triethoxy silicate and dimethyl-diethoxy silicate, di-s-butoxyaluminoxy triethoxysilane and hexaetoxy-disiloxane, bis (triethoxysilyl) methane and bis (triethoxysilyl) -ethane .

34. The method of claim 33, characterized in that at least one of the bis (3-trialkoxysilylalkyl) polysulfide is reacted with the filler / filler precursor, before completing the condensation reaction.

35. The method of any of the preceding claims, characterized in that the condensation promoter is selected from (a) basic promoters, (b) acid promoters, (c) promoters of metal oxides and metal salts, and (d) promoters of organic tin compounds.

36. The method of any of the preceding claims, characterized in that the condensation promoter is selected from at least one of ammonia, ammonium hydroxide, N-butylamine, tert-butylamine, tetrahydrofuran (THF), sodium fluoride, pentaethylene-hexamine, diaminopropane , diethylenetriamine, triethylene tetraamine, poly (allylamine hydrochloride), poly (L-lysine hydrobromide), poly (L-arginine hydrochloride), poly (L-lysine hydrochloride), phosphoric acid, acetic acid, hydrofluoric acid, sulfuric acid , zinc oxide, aluminum oxide, zinc sulfate, aluminum sulfate, zinc stearate, aluminum stearaate, bis (2-ethylhexanoate) -tin and bis (neodecanonate) -tin.

37. An elastomer / filler composite, characterized in that it is prepared according to any of the foregoing methods of claims 1 to 36.

38. An elastomer composition, characterized in that it comprises, based on 100 parts by weight of elastomers, (A) approximately 10 to 90 per at least one elastomer based on diene, (B) approximately 90 to 10 per of at least one elastomer / filler composite, prepared according to the method of the preceding claims 1 to 36, (C) at least one additional reinforcing filler, in which the total of the filler, formed in situ, and additional reinforcement filler, is present in an amount of about 5 to 120 per, and where the additional reinforcing filler is selected from at least one of the precipitated silica, aluminosilicate, as a co-precipitate of an aluminate and a silicate, carbon black, and modified carbon black, having hydroxyl groups on its surface, prepared by the treatment of carbon black reinforcement with an organosilane, at an elevated temperature or by co-smoking an organosilane and an oil, at elevated temperature and (D) optionally, an additive of a coupling agent, having one reactive part with an additional reinforcing filler and another interactive part with one or more elastomers.

39. An article of manufacture, characterized in having at least one component comprised of an elastomer composition of any of the preceding claims 37 and 38.

40. A rim having at least one component characterized in that it comprises an elastomer composition of any of the preceding claims 37 and 38.

41. A rim, having a tread characterized in that it comprises an elastomer composition of any of the preceding claims 37 and 38.