MXPA99009016A - Reinforced rubbish preparation and its use in plain - Google Patents

Abstract

The invention relates to the preparation of a rubber composition containing silica-based filler reinforcements by the use of an organosilane disulfide compound blended with a rubber composition in at least one non-productive mixing step of preparation followed by use of an organosilane polysulfide compound mixed with the rubber composition in a subsequent productive step of mixing. The invention also relates to the resulting rubber composition and to the use thereof in tire

Description

REINFORCED RUBBISH PREPARATION AND USE ON TIRE TREES FIELD OF THE INVENTION This invention relates to rubber compositions containing silica-based reinforcement and the use of an organosilane disulfide compound mixed with a rubber composition in at least one mixing stage. non-productive followed by the use of an organosilane polysulfide compound in a subsequent productive mixing step. The invention also relates to prepared rubber compositions of this type and particularly to tires having treads made from said compositions. BACKGROUND OF THE INVENTION For various applications, the use of rubber that requires high strength and resistance to abrasion, particularly applications such as tires and various industrial products, for example, employs a sulfur cured rubber containing substantial amounts of rubber fillers. reinforcement. Carbon black is usually used for this purpose and normally offers good physical properties or improves the physical properties of rubber cured with sulfur. Sometimes silica precipitated in particles is also used for this purpose, especially when the silica is used in combination with a coupling agent. In some cases, a combination of precipitated silica and carbon black is used for reinforcement fillers for various rubber products including tire treads. Coupling agents, such as, for example, an organosilane polysulphide having an average of 3.5 to 4 sulfur atoms in its polysulphide bridge, have been used for the coupling of silica precipitated with elastomers. Examples of an organosilane polysulfide of this type is bis-3 (triethoxysilylpropyl) polysulfide with an average of about 3.8 sulfur atoms in its polysulfide bridge. The possibility arises that a polysulfide of this type can be a sulfur donor, by means of the liberation of free sulfur, during a typical high-cut mixing of a rubber composition at an elevated temperature, for example, at temperatures of 100 ° C. and more, depending on the polysulfide used and the temperature and time of mixing. The small amount of sulfur released is then available to be combined with a diene-based elastomer and / or possibly partially vulcanize a diene-based elastomer. However, it is considered here that an organosilane polysulfide compound which is primarily a disulfide having an average of about 2.6 or fewer sulfur atoms in its polysulfide bridge, is not normally a good sulfur donor under these mixing conditions due to the relatively strong sulfur-sulfur bonds typical of an organosilane disulfide - as compared to an organosilane polysulfide with an average of at least 3.5 sulfur atoms in its polysulfide bridge. Accordingly, it is considered here that, for the organosilane (disulfide) polysulfide compound containing an average of less than 2.8 and particularly within a range of about 2 to about 2.6 sulfur atoms in its polysulfide bridge, the release of Free sulfur, if it exists, occurs at a relatively low speed during a high-cut rubber mixing stage, even at a mixing temperature within a range of about 150 ° C to about 185 ° C according to the global conditions of mixed, including the mixing time itself. It is also taught that bis- (3-triethoxysilylpropyl) disulfide, as a variety of organosilane disulfide, is useful in a sulfur-curable elastomer composition containing silica, even in a high purity form of said disulfide, for example, in U.S. Patent No. 4,046,550 and in German Patent Publication DT 2,360,471. However, it is considered here that said disulfide does not readily liberate free sulfur generally in said aforementioned rubber / silica / coupler mixing operation. As examples of organosilane polysulfides for use as silica couplers, see U.S. Patent Nos. 4,076,550; 4,704,414; and 3,873,489. For examples of organosilane disulfide added in a mixing step of non-productive rubber composition, of preparation, together with a small amount of free sulfur, see U.S. Patent Nos. 4,076,550; 5,580,919 and 5,674,932. In practice, elastomeric products vulcanized with sulfur are typically prepared by rubber thermomechanical mixing and various step-by-step ingredients followed sequentially by shaping and curing the rubber compound to form a vulcanized product. First, for the aforementioned mixing of the rubber and various ingredients, typically excluding free sulfur and vulcanization accelerators with sulfur, the elastomer or the elastomers and various rubber composition ingredients are mixed in at least one, and usually at least 2 stages(s) of preparation thermomechanical mixing, sequential in suitable mixers, usually internal rubber mixers. Said preparation mixing is often referred to as a "non-productive mixing" or "non-productive mixing steps or stages" said preparation mixing is usually carried out at temperatures within a range of about 140 ° C to 190 ° C and more often within a range of about 140 ° C or 150 ° C to about 185 ° C. After said sequential mixing step (s), free sulfur and vulcanization accelerators are mixed with sulfur, and possibly one or more additional ingredients with the rubber compound, or composition, in a productive mixing step. final, typically at a temperature comprised within a range of about 100 ° C to about 130 ° C, which is a temperature lower than the temperatures employed in the aforementioned preparation mixing stage (s) in order to avoid or delay the premature curing of the sulfur curable rubber, which is sometimes known as "burning" of the rubber composition. Said non-productive, sequential mixing steps and the subsequent productive mixing step are well known to those skilled in the rubber mixing art. By thermomechanical mixing we understand that the rubber compound, or rubber composition and rubber forming ingredients, are mixed in a rubber mixture under high cutting conditions where it is heated in an autogenous manner, with a concurrent rise in temperature, as result of mixing primarily due to cutting and associated friction within the rubber mixture in the rubber mixer. Said aspects of the procedure of thermomechanical mixing of rubber compound and associated cutting and raising of the concurrent temperature are well known to those skilled in the art of the preparation of rubber and its mixture. In practice, it is believed that the method prescribed by the inventors of (1) adding an organosilane disulfide in a non-productive mixing step of rubber composition followed by (2) the subsequent addition of an organosilane polysulfide with an average of 3.5 to 4.5 sulfur atoms in its polysulphide bridge together with a small amount of free sulfur in a productive stage of rubber composition for a rubber composition reinforced with silica-based element, particularly to control the associated sulfur / elastomer interaction as well as interaction with a silane / silica network, or product, created by the disulfide reaction in the mixing, preparation, step (s), step (s) is novel and inventive in relation to the prior practice. In one aspect, it is believed that the decoupling of an initial silane / silica reaction with a subsequent release of free sulfur, and an additional silane reaction, to interact with the elastomer (s) and the silane / silica network in a sequential rubber composition mixing process is achieved by the use of a separate and selective addition combination of a preliminary organosilane disulfide mixing step and the addition of an organosilane polysulfide followed by vulcanization of the rubber composition in accordance with the method of this invention is a significant difference in relation to the prior practice. The term "phr" as used herein, and in accordance with conventional practice, refers to "parts of a respective material per 100 parts by weight of rubber, or elastomer." In the description of this invention, the terms "rubber" and "elastomer",. If they are used here, they can be used interchangeably, unless otherwise indicated. Terms such as "rubber composition", "rubber compound" and "rubber compound", if used herein, are used interchangeably to refer to "rubber that has been mixed with various ingredients and materials" and "conformation of "rubber" or "shaping" can be used to refer to the "mixing of said materials". Such terms are well known to those skilled in the art of rubber blending or rubber forming technique. A reference to a "Tg", of elastomer, if used herein, refers to a "glass transition temperature" which can be determined by a differential scanning calorimeter at a heating rate of 10 ° C per minute. SUMMARY AND PRACTICE OF THE INVENTION In accordance with this invention, a process for preparing a rubber composition comprises the steps of: (A) mixing thermomechanically in at least one mixing step of sequential preparation and at a temperature within a range of about 150 ° C at about 185 ° C and in the absence of addition of free sulfur (1) 100 parts by weight of at least one diene-based elastomer selected from conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene and aromatic vinyl, (2) from about 30 to about 100, alternatively from about 30 to about 90 phr of a particulate reinforcing filler comprising from about 5 to about 85% by weight of carbon black and, accordingly, from about 15 to about 95% of at least one additional reinforcing filler selected from at least one of the group that consists of alumina and silica-based fillers, selected from at least one of precipitated silica, aluminosilicate and modified carbon black containing silicon hydroxide on its surface, and (3) from about 0.05 to about 20, alternatively from about 0.05 to about 10 parts by weight per part by weight of said alumina and silica-based filler of at least one organosilane disulfide compound of the formula (I): (I) Z-R1-Sn-R1-Z followed by: B) the mixed with free sulfur and at least one organosilane polysulfide of the formula (II) in a subsequent mixing step at a temperature within a range of about 100 ° C to about 130 ° C (II) Z-Rl-Sm-Rl -Z where n is a number from two to approximately 6 and where the average for n is within a range of approximately 2 to approximately 2.6; where m is a number from 2 to about 8 and the average for n is within a range of about 3.5 to about 4.5; where Z is selected within the group consisting of: R2 R2 R3 (Zl) Si-R2 (Z2) YES-R3 (Z3) YES-R3 R3 R3 and R3 where R2 can be the same radical or a different radical and is selected individually from the group consisting of alkyl radicals having from 1 to 4 carbon atoms and phenyl radical, preferably methyl and ethyl radicals; R3 can be the same radical or different radicals and is selected individually from the group consisting of alkyl radicals having 1 to 4 carbon atoms, phenyl radical, alkoxy groups having 1 to 8 carbon atoms and cycloalkoxy groups with 5 to 8 carbon atoms, preferably methyl and ethyl groups; and R 1 is a radical selected from the group consisting of a substituted or unsubstituted alkyl radical having a total of 1 to 18 carbon atoms and a substituted or unsubstituted aryl radical having a total of 6 to 12 carbon atoms where R 1 is preferably selected from ethyl, propyl and butyl radicals. In practice, it is preferred, for the aforementioned mixing step (B) that the total free sulfur and about 50% of the sulfur in the polysulfide bridge of said organosilane polysulfide of the formula (II) be within a range from about 0.93 to about 4, alternatively from about 0.93 to about 2.8 phr. In practice, between each mixing step, the rubber composition is allowed to cool to a temperature below about 40 ° C, for example, within a range of about 40 ° C to about 20 ° C. In practice, the total mixing time for such preparation (non-productive) mixing steps may be within a range of about 20, alternately from about 4 to about 15 minutes and from about 1 to about 3 minutes for said Subsequent step of mixing (productive). Preferably, said organosilane disulfide compound (I) and organopolysulfide compound (II) are bis- (3-trialkoxysilylalkyl) polysulfide; wherein the alkyl radicals of the alkoxy groups are selected from methyl and ethyl groups and the alkyl radical of the silylalkyl group is selected from ethyl, propyl and butyl radicals. For said formula (I), the organosilane disulfide compound is, primarily, an organosilane disulfide, and is usually a mixture of organosilane polysulfide, wherein at least 55%, usually, at least 65% of n is 2, and preferably from about 80 to about 100% of n is 2. In the case of organosilane polysulfide compound of the formula (II), generally at least 70%, and preferably from about 80 to about 100% n It is within a range of about 3.5 to about 4.5. In one aspect, the organosilane polysulfide of the formula (I) has the property of releasing at least a portion of its sulfur at a temperature within a range of about 150 ° C to about 185 ° C.

Particularly, it can be considered, according to the selection and amount of the organosilane polysulfide used, that the free sulfur released from said organosilane polysulfide (II) during the molding and curing of the rubber composition at an elevated temperature within a range of about 140. ° at about 185 ° C can, for example, be within a range of about 0.13 to about 1 phr whereas from about 40 to about 60% of the sulfur atoms in the polysulphide bridge of the polysulfide are released in the form of sulfur free. A global philosophy of this invention is here considered as a sense of first separately and selectively promoting a silane reaction with the reinforcement fillers without a premature release of free sulfur and then, subsequently, promoting both an additional silane reaction with the product of the first silane reaction previously promoted by the organosilane disulfide compound (I) as well as a release of free sulfur through the subsequent addition of the organosilane polysulfide (II). A particular benefit is seen in that the prevention of a premature release of free sulfur during the mixing step (s) of preparation elastomers allows a lower viscosity of the rubber composition during mixing and, therefore, promotes better processing of the rubber composition as it is being mixed. An additional benefit of the process of the present invention is the subsequent silane reaction with the product of the first silane reaction together with a subsequent generation of free sulfur. This is achieved by manipulating the first mixing of the organosilane disulfide compound (I) with the elastomer (s) and the reinforcing fillers followed by the subsequent and separate mixing of the organosilane (II) polysulfide compound with the rubber and silane-filler network product. It is considered that this process is novel and represents a significant change in relation to the previous practice. In practice, then, an accumulation of viscosity of the rubber composition during its mixing stage, non-productive (s), of preparation, due to a premature partial vulcanization placed by a liberation of free sulfur to Starting from an organosilane polysulfide compound (II) having an average of about 3.5 to about 4.5 atom atoms in its polysulfide bridge is avoided. However, the benefits of the reaction of the organosilane component of the organosilane disulfide compound (I) with the reinforcing fillers is still obtained. By the subsequent addition of the organosilane polysulfide compound (II) in the production stage under mixing conditions at lower temperature and allowing the added organosilane (II) polysulfide compound to help vulcanize the rubber composition both because it allows the The silane portion of the organosilane polysulfide compound (II) interacts with the previously created organosilane / silica compound, or network of said compounds, as well as releasing the free sulfur at the highest curing temperature. This aspect of the present invention, as understood, is achieved by employing in an (I) version of organosilane disulfide compound having an active silane portion but not releasing significant free sulfur in such a way that the free sulfur does not is released during the mixing, nonproductive (s), preliminary (s) step and such that the sulfur can then be added separately through the organosilane polysulfide compound (II) described above in the vulcanization of the rubber composition. In this way, the benefits of an initial and selective reaction of the silane portion of the organosilane disulfide compound with the silica-based filler is obtained but the release of free sulfur is retarded, and the interaction of additional silane until after the ( of the step (s) of preliminary nonproductive mixing (s) at the highest mixing temperature and the subsequent step of productive mixing at the lower mixing temperature and until the vulcanization of the rubber composition at the temperature Higher Therefore, while the mechanism may not be fully understood, it is believed that vulcanization of the rubber composition at the elevated temperature is enhanced by the presence of the silane component of the organosilane polysulfide and its resultant combination with an organosilane / silica compound. and / or network previously created by the interaction of silane of organosilane disulfide and alumina and / or based on silica. In one aspect of the present invention said process is provided where said preparation mixing is carried out in at least two sequential thermomechanical mixing steps wherein at least two of said mixing steps are carried out at a temperature within a range from about 140 to about 185 ° C, with intermediate cooling of the rubber composition between at least 2 of said mixing steps at a temperature of less than about 40 ° C. In accordance further with this invention, the rubber composition prepared according to the method of the present invention is provided., particularly in which said rubber composition is cured with sulfur at an elevated temperature in a range of about 140 ° C to about 184 ° C. In addition, in accordance with this invention, an article is provided with at least one component of said rubber composition.

In addition, in accordance with this invention, a rim is provided having at least one component of said rubber composition. Further, in accordance with this invention there is provided a rim having a tread of said rubber composition, particularly where said rim tread is designed to be in contact with the ground. In one aspect, the prepared rubber composition is vulcanized in a suitable mold at an elevated temperature within a range of about 140 ° C to about 190 ° C. Further, in accordance with the present invention, the process comprises the further steps of preparing an assembly of a vulcanized and sulfur rim or rubber with a tread band comprising the rubber composition prepared in accordance with the process of this invention and the vulcanization of the assembly at a temperature within a range of about 140 ° C to about 185 ° C or 190 ° C. Accordingly, the invention also contemplates a vulcanized rim separated by said process. In practice, the organosilane disulfide of the formula (I) and the organosilane polysulfide of the formula (II) are typically liquid and are preferably provided individually in the form of an organosilane disulfide compound of the formula (I) and carbon black and the organosilane polysulfide of the formula (I). the formula (I) and carbon black, to provide them in the form of a relatively dry or substantially dry powder wherein the carbon black acts as a vehicle. A contemplated benefit for adding the organosilane disulfide and polysulfide to a particle form of this type is to assist in its dispersion in the mixing steps associated with the rubber composition. In one aspect of the invention, optionally a total of about 0.05 to about 5 phr of at least one alkylalkoxysilane can be thermomechanically mixed in the preparation mixing step (s), particularly when said alkylsilane has the formula: R ' -Si- (OR) 3, where R is a methyl, ethyl, propyl or isopropyl radical and R'is a saturated alkyl radical having from 1 to 18 carbon atoms, or an aryl radical, or an aryl radical saturated substituted alkyl having from 6 to 12 carbon atoms. Said substituted aryl or aryl radicals may be, for example, benzyl, phenyl, tolyl, methyltholyl, and alphamethyltolyl radicals. One purpose of the alkylalkoxy silane is, for example, to improve the filler incorporation and the aging of the compound. Representative examples of alkylsilanes are, for example, without being limited thereto, propyltriethoxysilane, methyltriethoxysilane, hexadecyltriethoxysilane and octadecyltriethoxysilane. In practice, as discussed above, the organosilane polysulfide compound of the formula (II) is added in the lower temperature productive mixing step, which subsequently liberates free sulfur at the highest temperature experienced during molding and curing. the resulting rubber composition wherein it is contemplated that the silane component of the organosilane polysulfide compound of the formula (II) will react with the silane-filler network previously formed through the above reaction with the organosilane disulfide compound previously added to the formula (I). While a real calculation may have to be made on an individual basis, according to the actual number of sulfur atoms in the sulfur bridge as well as according to other factors, the amount of free sulfur to be added in the productive mixing stage plus the amount of sulfur Free released through the organosilane polysulfide compound of the formula (II), is within a range from about 0.93 to about 4, alternatively from about 0.93 to about 2.8 phr. This considers that from about 40 to about 60% of the sulfur of the organosilane polysulfide compound of the formula (II) is released in the form of free sulfur during the curing step. In practice, it is preferred that at least one phr of the free sulfur and at least one phr of the organosilane polysulfide compound of the formula (II) are added in the productive mixing step. In the stage of productive mixing, vulcanization accelerators are conventionally added. Some vulcanization accelerators are not conventionally considered as sulfur donors in the sense of free sulfur release, being appreciated that they may be, for example, of the benzothiazole type, alkylthiuram disulfide, guanidine derivatives and thiocarbamates. Representative of said accelerators are, for example, without limitation, mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butyl xanthate, N-dicyclohexyl-benzothiazole sulfenamide, N-cyclohexyl- 2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N, N-diphenylthiourea, dithiocarbamyl sulfenamide, N, N-diisopropylbenzothiazole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-beta-hydroxy-ethyl-piperazine) and dithiobis (dibenzylamine). Those skilled in the art of rubber composition are well aware of these materials as vulcanization accelerators with sulfur for elastomers vulcanizable with sulfur. If desired, even though it is not preferred in the practice of this invention, additional conventional sulfur donors can be added in the final, productive mixing step, to the extent that the total amount of free sulfur added in the step of Productive mixed and the free sulfur released in the curing step from the aforementioned organosilane polysulfide compound and the sulfur donor additive is within a range from about 0.93 to about 4 ph. Representative examples of such sulfur donors are, for example, derivatives of thiuram and morpholine. Representative examples of such materials are dimorpholine disulfide, dimethylthiuram tetrasulfide, benzothiazil-2, N-dithomorpholide, thioplast, dipentamethylenethiurahexasulfide, and disulfurocaprolactam, such materials being k to those skilled in the art of rubber composition as sulfur donors. In the average in which such sulfur donors are added in the productive mixing stage, the amount of free sulfur to be added is correspondingly reduced. For the filler reinforcement of this invention, silica-based pigments are contemplated that may be employed in combination with carbon black. In one aspect of the invention, it is preferred that the silica-based filler be precipitated silica. In another aspect of the invention it is preferred that the silica-based filler be carbon black having silicon hydroxide on its outer surface. In a further aspect of the invention, it is preferred that the silica-based filler be an aluminosilicate as a coprecipitated combination of silica and aluminum with an aluminum content in the range of about 0.05 to about 10% of said silica / aluminum filler compound. . The carbon black having silicon hydroxide on its surface can be prepared, for example, by co-extracting a silane organ and oil at an elevated temperature. In practice, the reinforcing filler may consist of from about 15 to about 95% by weight of precipitated silica, alumina, aluminosilicate and / or carbon black containing silicon hydroxide on its surface and, correspondingly, from about 5 to about 85% by weight of carbon black. When it is desired that the rubber composition containing both a silica based filler such as precipitated silica, alumina, aluminosilicate and / or carbon black having silicon hydroxide on its surface, as well as carbon black reinforcement fillers, it is often preferable that the weight ratio between such filler (s) based on silica and the carbon black is at least 1.1 / 1 and frequently at least 3/1, up to at least 10/1 and, therefore, within a range of about 1.1 / 1 to about 30/1. For the aforementioned organosilane disulfide of the formula (I), and the organosilane polysulfide of the formula (II), representative R 2 radicals are alkyl radicals and representative R 1 radicals are selected from alkaryl, phenyl and haloaryl radicals. Thus, in one aspect of the invention, the radicals R2 and Rl are mutually exclusive. Preferably said radicals are alkyl radicals. Representative examples of such alkyl radicals are methyl, ethyl, n-propyl and n-decyl radicals, with the n-propyl radical being preferred. Representative examples of aralkyl radicals are benzyl and alpha, alpha-dimethylbenzyl radicals, if said radicals are to be used. Representative examples of alkaryl radicals are o-tolyl and P-nonylphenol radicals, if such radicals are to be employed. A representative example of a haloaryl radical is a p-chlorophenol radical, if said radical is to be used.

Representative examples of organosilane polysulfides of the compound of the formula (II) are, for example, without limitation, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide. , bis (3-triethoxyylpropyl) tetrasulfide, bis (3-triethoxysilylethyltolylene) trisulphide and bis (3-triethoxysilylethyltolylene) tetrasulfide. Representative examples of organosilane disulfide compound of the formula (I) are, for example: 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'-bi (tri-sec, butoxysilylethyl) disulfide; 2,2'-bis (tri-t-butoxyethyl) disulfide; 2, 2'-bis (triethoxysilylethyl toluene) disulfide; 2,2'-bis (trimethoxysilylethyl toluene) 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-methylprolyl) disulfide; 3, 3'-bis disulfide (tripropoxysilyl-3-methylpropyl); 3, 3'-bis (dimethoxymethylsilyl-3-ethylpropyl) disulfide: 3,3'-bis (trimethoxysilyl-2-methylpropyl) disulfide of 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) disulfide; 2, 2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2, 2'-bis disulfide (tripropoxysilyl-2-methylethyl); and 2,2'-bis (trioxysilyl-2-methylethyl) disulfide. The preferred organosilane disulfide for compound (I) is 3,3'-bis- (triethoxysilylpropyl) disulfide, which is also represented by bis- (3-triethoxysilylpropyl) disulfide. In the practice of this invention, as indicated above, the rubber composition comprises at least one elastomer based on diene, or rubber. Suitable conjugated dienes are isoprene and 1,3-butadiene and suitable vinyl aromatic compounds are styrene and alpha-methyl styrene. Thus, it is considered that the elastomer is a sulfur-curable elastomer. Such a diene-based elastomer, or rubber, can be selected, for example, from at least one of 1,4-polyisoprene cis (natural and / or synthetic) rubber, and preferably natural rubber, a styrene copolymer rubber / butadiene prepared by emulsion polymerization, styrene / butadiene rubber prepared by polymerization in organic solution, 3, 4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubbers, 1,4-polybutadiene cis, medium vinyl polybutadiene rubber (from 35 to 50% vinyl), high vinyl polybutadiene rubber (from 50 to 75% vinyl), styrene / isoprene propolymers, styrene / butadiene / acrylonitrile terpolymer rubber prepared by emulsion and rubber polymerization of butadiene / acrylonitrile copolymer. By E-SBR prepared by emulsion polymerization, it is understood that styrene and 1,3-butadiene are copolymerized in an aqueous emulsion. This is well known to those skilled in the art. The bound styrene content may vary, for example, from about 5 to 50%. The SBR prepared by solution polymerization (S-SBR) typically has a styrene content bound within a range of about 5 to about 50, preferably about 9 to about 36%. The S-SBR can be prepared in a convenient way, for example, by organolithium catalysis in the presence of an organic hydrocarbon solvent. As mentioned above, the precipitated silicas used in this invention are precipitated silicas, such as, for example, the precipitated silicas obtained by the acidification of a soluble silicate, for example, sodium silicate. Such precipitated silicas are well known in the art. Likewise, as previously mentioned, a variation of the contemplated aluminosilicate is obtained by the coprecipitation of silica and aluminum. Such precipitated silicas can be characterized, for example, by having a BET surface area as measured using nitrogen gas, preferably within the range of about 40 to about 600 and more usually within a range of about 50 to about 300 meters. squares per gram. The BET method of surface area measurement is described in the Journal of the American Chemical Society, Volume 60, page 304 (1930). The silica can also be typically characterized in that it has a dibutyl phthalate (DBP) absorption value within a range of about 100 to about 350, and more usually within a range of about 150 to about 300 ml / 100 g. In addition, the silica, as well as the aforementioned alumina and the aluminosilicate, can have a surface area of CTAB within a range of about 100 to about 220. The CTAB surface area is the external surface area in accordance with that evaluated by bromide of cetyltrimethylammonium with a pH of 9. The method is described in ASTM D 3849 for adjustment and evaluation. The surface area of CTAB is a well known means to characterize silica. The surface area / mercury porosity is the specific surface area determined by mercury porosimetry. For this technique, mercury penetrates the pores of the sample after heat treatment to remove volatile substances. The adjustment of the conditions can be described adequately as using a sample of 100 mg; removing volatile substances for two hours at a temperature of 105 ° C and under ambient atmospheric pressure; a range of pressure measurement from ambient pressure to 2000 bar. Said evaluation can be carried out in accordance with the method described in Wislow, Shapiro in ASTM Bulletin, page 39 (1959) or according to DIN 66133. For an evaluation of this type, a 2000 PORLO-ERBA porosimeter can be used. The specific surface area according to the average mercury porosity for the precipitated silica should preferably be within a range of about 100 to 300 square meters / g. A suitable pore size distribution for silica, alumina and aluminosilicate in accordance with said mercury porosity evaluation is desirably considered here as 5% or less of its pores having a diameter of less than about 10 nm; 60 to 90% of its pores with a diameter of about 10 to about 100 nm; from 10 to 30% of its pores with a diameter of about 100 to about 1000 nm; and from 5 to 20% of its pores with a diameter greater than about 1000 nm. The silica may have an average ultimate particle size, for example, within the range of 0.1 to 0.5 microns as determined by the electron microscope, even though the silica particles may be even smaller, or possibly larger in size. Several commercially available silicas can be considered for use in this invention as for example, without limitation, silicas commercially available from PPG Industries under the trade name Hi-Sil with the designations Hi-Sil 210, 243, etc; silicas available from Rhone-Poulenc, for example with the designation Zeosil 1165MP, silicas available from Degussa GmbH, for example with the designations VN2 and VN3, etc., and silicas commercially available from Huber having, for example, a designation of Hubersil 8745 The alumina, for the purposes of this invention, is natural and synthetic aluminum oxide (AL203). In some cases, alumina has been used for such purposes, either alone or in combination with silica. The term "alumina" can be described herein as "aluminum oxide or A1203". The use of alumina in rubber compositions can be illustrated, for example, in U.S. Patent No. 5,116,886 and in European Patent Publication EPO 631,982 A2. It is recognized that alumina can have various forms namely acid, neutral and basic forms. In general, it is considered here that the neutral form may be preferred. Aluminosilicates, for the purpose of this invention, can be employed as natural or synthetically prepared materials, particularly co-precipitated silica and aluminum. For example, see U.S. Patent No. 5,723,529. In general, the term "aluminosilicate" can be described as natural or synthetic materials wherein the silicon atoms of a silicon dioxide are partially replaced, or substituted, either naturally or synthetically by aluminum atoms. For example, from about 5 to about 90, alternatively from about 10 to about 80% of silicon atoms of a silicon dioxide can be replaced or substituted, naturally or synthetically by aluminum atoms to provide an aluminum silicate. A suitable process for such preparation can be described, for example, as by coprecipitation by pH adjustment of a basic solution or mixture, of silicate and aluminate as well, for example, by a chemical reaction between SiO 2, or silanols in the surface of a silicon dioxide and NaA102. For example, in said coprecipitation process, the synthetic coprecipitated aluminosilicate can have from about 5 to about 95% surface composed of silica portion and, corresponding, from about 95 to about 5% of its surface composed of aluminum portions. Examples of natural aluminosilicates are, for example, muscovite, beryl, dichroite, sepiolite and kaolinite. Examples of synthetic aluminosilicates are, for example, zeolite and those which can be represented by formulas such as, for example, ((A1203) x. (Si02) and. (H20) z); ((Al203) x. (YES02) y.MO); where M is magnesium or calcium. The use of aluminosilicates in rubber compositions can be presented, for example, in U.S. Patent No. 5,116,886; European Patent Publication EPO 064,982 A2, Rubber Chem. Tech., volume 50 page 606 (1988) and volume 60, page 84 (1983). It will be readily understood by those skilled in the art that the rubber composition can be shaped by methods generally known in the rubber forming art, such as the mixing of several vulcanizable constituents with sulfur with various additive materials commonly employed. such as, for example, curing aids such as sulfur, activators, retardants and accelerators, processing additives, such as oils, resins including tackifying resins, silica and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes , antioxidants and antiozonants, peptizing agents as well as reinforcing materials such as, for example, carbon black. As those skilled in the art know, according to the intended use of the vulcanizable material with sulfur and vulcanized with sulfur (rubber), the additives mentioned above are selected and are usually employed in conventional amounts. Typical amounts of reinforcing type black (s) for this invention, if employed, are in accordance with the above. It will be noted that the silica coupler can be used in combination with a carbon black, ie, premixed with a carbon black prior to addition to the rubber composition, and said carbon black must be included in the aforementioned amount of black of smoke for the formulation of the rubber composition. Typical amounts of tackifying resins, if employed, comprise from about 0.5 to about 10 phr, usually from about 1 to about 5 phr. Typical amounts of processing aids comprise from about 1 to about 50 phr. Such processing aids may include, for example, aromatic, naphthenic, and / or paraffinic processing oils. Typical amounts of antioxidants comprise from about 1 to about 5 phr. Representative antioxidants may, for example, diphenyl-p-phenylenediamine and others, such as those presented in The Vandrbilt Rubber Hanbook (1978), pages 344-346. Typical amounts of antiozonants comprise from about 1 to about 5 phr. Typical amounts of fatty acids, if employed, which may include stearic acid comprise from about 0.5 to about 3 phr. Typical amounts of zinc oxide consist of about 2 to about 5 phr. Typical amounts of waxes consist of about 1 to about 5 phr. Frequently, microcrystalline waxes are used. Typical amounts of peptizers comprise from about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide. The vulcanization is carried out in the presence of a sulfur vulcanization agent. Examples of suitable sulfur vulcanization agents include, for example, elemental sulfur (free sulfur) or sulfur donor vulcanizing agents, including the aforementioned organosilane polysulfide (II). As discussed above, if desired, additional sulfur donor compound can be employed such as, for example, an amine disulfide, polymeric polysulfide or sulfur olefin adducts. Sulfur vulcanization agents are conventionally added in the final, productive, stage of mixing the rubber composition. Accelerators are used to control the time and temperature that are required to vulcanize and to improve the properties of the vulcanized product. In one embodiment, a single accelerator system, i.e., primary accelerator, may be employed. Conventionally, and preferably, primary accelerator (s) are employed in total amounts ranging from about 0.5 to about 4, preferably from about 0.8 to about 1.5 phr. In another embodiment, combinations of a primary accelerator and a secondary accelerator can be employed with the secondary accelerator being used in lower amounts (from about 0.05 to about 3 phr) in order to activate and improve the properties of the vulcanized product. Combinations of these accelerators can produce a synergistic effect on the final properties and are relatively better than what is produced by the use of any of the accelerators alone. In addition, delayed action accelerators which are not affected by normal processing temperatures can be employed but produce a satisfactory cure at usual vulcanization temperatures. Vulcanization retardants can also be used. Suitable types of accelerators that can be employed 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, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiura compound. The rubber composition of this invention can be used for various purposes. For example, it can be used for several rim compounds. Such rims can be constructed, shaped, molded and cured by various methods well known to those skilled in the art. The invention will be better understood with reference to the following examples wherein parts and percentages are by weight unless otherwise indicated. EXAMPLE I Vulcanizable rubber mixtures with sulfur containing silica reinforcement were prepared and said preparations were reported here as experiments (samples), Ex. 1, Ex. 2, and Ex. 3. Particularly, Ex. 1 is intended to be a first control in which a bis (triethoxysilylpropyl) tetrasulfide compound (formula I) having an average of about 3.8 sulfur atoms in its polysulfide bridge is mixed with the rubber composition in one step of nonproductive preparation mix in an internal rubber mixer. Particularly, Ex. 2 is intended to be a second control in which a bis (3-triethoxysilylpropyl) disulfide compound (formula I) having an average of about 2.2 sulfur atoms in its polysulfide bridge is mixed with the rubber composition in a stage of non-productive mixing, of preparation in an internal rubber mixer. Finally, and in accordance with this invention, a bis (3-triethoxysilylpropyl) disulfide compound (formula I) having an average of about 2.2 sulfur atoms in its polysulfide bridge is mixed with the rubber composition in a step of non-productive mixing, of preparation, in an internal rubber mixer, followed by a separate and subsequent addition of a bis (3-triethoxysilylpropyl) tetrasulfide compound (formula I), which has an average of about 3.8 sulfur atoms in its polysulfide bridge, to the rubber composition in the final mixing stage, productive in an internal rubber mixer. Particularly, for the sample Ex. 3, which is intended to be exemplary of this invention, 6.64 phr of the organosilane disulfide compound of the formula (I) is added in the non-productive mixing step, of preparation and a pH of the organosilane polysulfide compound of the formula (II), and 1.4 phr of sulfur are added in the productive mixing stage. Therefore, for the productive mixing stage, the aggregate calculated sulfur, based on 50% of the sulfur atoms in the polysulfide bridge of the organosilane (II) polysulfide compound, is 1.4 phr (free sulfur) + 0.3 of phr (from the organosilane polysulfide) which is equal to 1.53 phr. It will be noted that the actual sulfur may differ in some way from the calculated sulfur, depending on the amount of sulfur released from the organosilane polysulfide compound (II). After each mixing step, the rubber mixture was formed in batches in a two-roll mill, mixed in a mill for a short period of time and pieces, or sheets, of rubber were removed from the mill and left to cool at a temperature of about 30 ° C or less. Rubber compositions containing the materials mentioned in Table 1 were prepared in a BR Banbury mixer using 3 separate stages of addition (mixing) namely, two stages of preparation mixing and a final stage of mixing at temperatures of 170 ° C, 160 ° C and 120 ° C and times of approximately 8 minutes, 2 minutes, and 2 minutes, respectively, for the three stages of the overall mixing.

The amounts of organosilane disulfide and organosilane polysulphide are listed as "variables" in Table 1 and their addition is presented more specifically in Table 2. Table 1 (tread) Parts Non-productive mixing steps E -SBR1 25 Isoprene / butadiene2 rubber 45 1, 4-polybutadiene cis3 20 Natural rubber4 10 Processing aids5 25 Fatty acid 2 Silica7 83 Organosilane disulfide (A) 8 Variable Mixing stage Sulfur9 Variable Zinc oxide 2.5 Antioxidant (s) 10 3 Sulfenamide and 4 Guanidine Accelerators Organosilane Polysulfide (B) n Variable 1) Styrene / butadiene copolymer rubber prepared by emulsion polymerization, obtained from The Goodyear Tire & Rubber Company with a content of approximately 40% styrene and having a glass transition temperature of about -31 ° C. The E-SBR is reported in the table on a dry weight basis of elastomer, even though the E-SBR is extended with oil and composed of approximately 25 phr of SBR and approximately 15 phr of oil. Elastomers of isoprene / butadiene copolymer (50/50 isoprene / butadiene) with a glass transition temperature of about -44 ° C obtained from The Goodyear Tire & Rubber Company. ) Cis 1,4-polybutadiene elastomer obtained as BUDENE® 1207 from The Goodyear Tier & Rubber Company. ) 1, 4-natural cis polyisoprene. ) Oil. ) Stearic acid primarily. ) Zeosil 1165 MP from Rhone Poulenc. ) A compound commercially available from Degussa GmbH, X266S in the form of a 50/50 mixture or compound, of Si266 (trademark of Degussa) and carbon black. YES 266 is a bis- (3-triethoxysilylpropyl) disulfide compound (I) which is believed to have an average of about 2.2 sulfur atoms in its polysulphide bridge. Thus, the compound contains 50% of the organosilane disulfide compound corresponding to formula I. 9) Obtained as S8 elemental sulfur from the Kali Chemie Company of Germany. 10) A type of phenylene diamine. 11) 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 what may be known as a bis- (3-triethoxysilylpropyl) tetrasulfide compound (II) that have an average of approximately 3.8 sulfur atoms in their polysulphide bridge, with carbon black and, consequently, the organosilane tetrasulfide is considered as forming 50% of the compound and, therefore, 50% active, which corresponds to the compound of formula II. The samples of Ex. 1, Ex. 2 and Ex. 3, were molded into a suitable mold and cured, or vulcanized, for about 16 minutes at a temperature of about 160 ° C. Various physical properties of the rubber compositions appear in the following Table 2 where the addition of the organosilnane disulfide and the organosilane polysulfide as well as the addition of free sulfur are also presented. Table 2 Sample No. Ex. 1 Ex. 2 Ex. 3 Mixed non-productive Polysul- coupling agent 13.28 0 0 furo (B) Disulfide coupling agent 0 13.28 13.2! (A) Productive mixing Sulfur 1.4 2.1 1.4 Polysul- 0 0 2 coupling agent furo (B) Physical properties Mooney1 55 45 44 Rheometer (150 ° C) T90 (minutes) 7.72 8.02 7.27 Torque torque delta 36.5 35.5 34.2 T90, (minutes) 15.52 12.95 12.07 Effort-deformation Resistance to tension, Mpa 15.2 13.6 16.3 Elongation at break (%) 505 452 530 Module at 100%, Mpa 2.2 2.3 2.7 Module at 300%, MPa 9.1 9.3 9.0 Module at 300/100 4.13 4.04 4.3 Bounce at 100 ° C (%) 60.7 61.6 60.0 23 ° C, (%) 36.2 37.4 37.7 Shore Hardness A 69.7 67.3 67.3 Tan delta Dinalizer at 50 ° C 0.228 0.216 0.229 Abrasion DIN (CC) 110 11.65 98 1) Viscosity of Mooney (ML-4) at 100 ° C of the rubber mixture from the productive mixing stage. Particularly, Ex. 3 of this example shows that the addition of the organosilane disulfide compound (formula I) during the non-productive mixing step plus the subsequent controlled addition of the bis- (3-triethoxysilylpropyl) tetrasulfide compound (formula I) in the productive stage of mixing resulted in increased tensile strength, an increased elongation and an increased module-to-module ratio without significantly affecting the hot and cold bounce values compared to the first control and the second control (ie, Ex. 1 and Ex. 2). This is considered beneficial since it is considered here that it is indicative of a better performance in terms of wear without significantly affecting the attraction in wet condition and the rolling resistance in the case of a tire having a tread developed with said composition. rubber. In addition, the viscoelastic, dynamic physical properties illustrated in Table 2 for rubber compositions (Tan. Delta) show the same tendency as hot bounce. This is considered beneficial here since it indicates that said compounding approach illustrated in Ex. 3 did not adversely affect the hysteresis of the rubber composition and, therefore, did not adversely affect the rolling resistance of the tire overall in the case of a tire having a tread made with said rubber composition, in comparison with the controls Ex. 1 and Ex. 2. In addition, the abrasion value according to DIN of Ex. 3 is significantly less than the abrasion value of the two controls Ex. 1 and Ex. 2 and, therefore, may indicate less tread wear in the case of a tire tread band which is considered here as corresponding to the aforementioned observation of modules. In addition, the Mooney viscosity values shown by Ej.3 as well as by Ex. 2, as a measure of the viscosity of the rubber mixture, emphasize the advantage of adding the organosilane disulfide instead of the organosilane polysulfide in the non-productive mixing step of preparation in relation to the rubber composition processing. Particularly, the Mooney values illustrated in Table 2 are significantly lower for Ex. 3 and for Ex. 2 that the value of Mooney for Ex. 1. Accordingly, the use of organosilane disulfide (Formula I) in the nonproductive mixing step (s) of preparation, with subsequent and separate addition of the organosilane polysulfide (formula II) in the mixing step , productive, final, it was observed that it significantly improved several properties of the rubber composition of the cured rubber compositions, which is also accompanied by a beneficial processing of the rubber in the non-productive mixing stage (ie: a low viscosity of the rubber). Accordingly, it is here considered to have been shown of a mixing combination of a prescribed organosilane disulfide with elastomer (s) and silica in a non-productive mixing step (s), followed by the Subsequent addition of a subsequent prescribed organosilane polysulfide, productive mixing step at lower temperature, followed by vulcanization of the rubber composition at the elevated temperature increases the physical properties of the cured or vulcanized rubber composition. By its preparation of the rubber composition the silane interaction of an organosilane disulfide prescribed with a silica is separated from the release of free sulfur from a subsequently added organosilane polysulfide (II), under the prescribed temperature conditions which includes also a subsequent interaction of the silane component of the organosilane polysulfide compound (II) with the previously formed silane / filler compound, or network caused by the interaction of the organosilane disulfide compound (I) with the silica in the step of mixed nonproductive preparation. EXAMPLE I Tires of size 195/65 R15 were prepared which were used individually in the rubber compositions of samples 1, 2 and 3 of Example I for their treads and are correspondingly known as Examples. 1, 2, and 3 in this Example II. The following results were obtained as shown in table 3 with the values for the control Ej.l, normalizing to a value of 100 and the corresponding values for Ex. 2 and Ex. 3 being reported comparatively to Ex. 1 of control. For the normalized values reported in Table 3, a higher value for rolling resistance indicates lower rolling resistance so that a higher value is better; a higher value for tread wear means a lower tread wear in such a way that a higher value is better; and a higher value for patination in wet condition means greater traction and resistance to skating on a wet surface in such a way that a higher value is better. Table 3 Ex. 1 Ex .2 Ex .3 Resistance to rolling 100 101 101 Wear of tread 100 102 111 Patination in wet condition 100 102 103 This example demonstrates that a tire with a tread of the rubber composition separated from In accordance with this invention, namely, Ex. 3, it provides better tread wear (less wear) of rim than tires with tread of the rubber composition of Ejs. 1 and 2. This is considered here as helpful because the observed joint state skidding, the rolling resistance illustrated in Table 3 is not substantially or appreciably affected. Furthermore, the processing of the rubber composition is not substantially affected and is still improved compared to the example preparation, as shown in Table 2 for the Mooney viscosity (ML-4). Particularly, an improvement is evidenced by the practice of this invention as to the nature of a combination of (1) rubber composition processing, (2) physical properties and (3) rubber rim properties, particularly rubber tread. tire. While some representative embodiments and details were 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 (3)

CLAIMS. A process for the preparation of a rubber composition, characterized in that it comprises the steps of: (A) mixing thermomechanically in at least one sequential mixing (non-productive) mixing step and at a temperature within a range of about 150 ° C to about 185 ° C and in the absence of addition of free sulfur (1) 100 parts by weight of at least one diene-based elastomer selected from conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene and aromatic vinyl compound, ( 2) from about 30 to about 100 phr of a particulate reinforcing filler comprising (a) from about 5 to about 85% by weight of carbon black and, therefore, (b) from about 15 to about 95% by weight. at least one additional reinforcing filler selected from at least one of the members of the group consisting of alumina and silica-based fillers selected from among at least one of precipitated silica, aluminosilicate, and modified carbon black containing silicon hydroxide on its surface, and (3) from about 0.05 to about 20, alternatively from about 0.05 to about 10 parts by weight per part by weight of said alumina and said silica-based filler of at least one organosilane disulfide compound of the formula (I): (I) Z-R1-Sn-R1-Z followed by: B) the mixture of free sulfur and at least one compound of organosilane polysulfide of the formula (II) therewith in a subsequent (productive) mixing step at a temperature comprised within a range of about 100 ° C to about 130 ° C: (II) Z-Rl-Sm-Rl -Z where n is a number from 2 to approximately 6, and the average for n is within a range of approximately 2 to 2.6; where m is a number from 2 to about 8 and the average for m is within a range of about 3.5 to about 4.5; where Z is selected within the group consisting of R2 R2 R3
1. (Zl) YES-R2 (Z2) Si-R3 (Z3) YES-R3
2. R3 R3 and R3 where R2 can be the same radical or a different radical and is selected individually from the group consisting of alkyl radicals having from 1 to 4 carbon atoms and phenyl radical; R3 can be the same radical or a different radical and is selected individually from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, phenyl radical, alkoxy groups having from 1 to 8 carbon atoms and cycloalkoxy groups with 5 to 8 carbon atoms and R 1 is a radical selected from the group consisting of a substituted or unsubstituted alkyl radical having a total of 1 to 18 carbon atoms and substituted or unsubstituted aryl radicals having a total of 6 to 12 carbon atoms. The process of claim 1, characterized in that said preparation mixing is carried out in at least two internal mixing steps for a total internal mixing time for said preparation mixing steps. (non-productive) within a range of about 4 to about 15 minutes and the mixing time for said subsequent (productive) internal mixing step is within a range of about 1 to about 3 minutes, and where between each step of mixed, the rubber composition is mixed in an open roller mill for about 2 to about 6 minutes and then allowed to cool to a temperature below about 40 ° C; wherein said organosilane disulfide compound (I) and organosilane polysulfide compound (II) are bis- (3-alkoxysilylalkyl) polysulfides wherein the alkyl radicals of the alkoxy component are selected from methyl and ethyl radicals and the alkyl radical of the components of silylalkyl is selected from ethyl, propyl and butyl radicals, and where for the mixing step (B), the total addition of free sulfur and about 50% of the sulfur in the polysulfide bridge of said organosilane polysulfide compound ( II) is within a range of about 0.93 to about 4 phr. The process of any of the preceding claims, characterized in that said organosilane disulfide compound (I) and organosilane polysulfide compound (II) are bis- (3-alkoxysilylalkyl) polysulfides wherein the alkyl radicals of the alkoxy component are selected from methyl and ethyl radicals and the alkyl radical of the silylalkyl component is selected from ethyl, propyl and butyl radicals, and where for the mixing step (B), the total addition of free sulfur and about 50% of the sulfur in the polysulfide bridge of said polysulfide compound organosilane (II) is within a range of about 0.93 to about 4 phr. The process of any of the preceding claims, characterized in that an organosilane component of said organosilane disulfide compound (I) reacts during said preparation mixing step (s) with hydroxyl groups of at least one of said aluminosilicate, precipitated silica and modified carbon black to form a silane-based compound; wherein said subsequently added organosilane polysulfide (II) interacts with said previously formed silane-based compound and releases free sulfur during vulcanization of the rubber composition at a temperature within a range of about 140 ° C to about 190 ° C. The process of any of the preceding claims, characterized in that said organosilane disulfide compound (I) and said organosilane polysulfide compound (II) are each individually added in the form of a compound comprising from about 25 to about 75% in weight thereof and, accordingly, from about 75 to about 25% by weight of particulate carbon black. The process of any of the preceding claims, characterized in that said particulate reinforcement consists of (a) carbon black and (b) said at least one precipitated silica, aluminum silicate and modified carbon black; wherein said aluminosilicate is prepared by the coprecipitation of aluminum silicate and electrolytes to form a silica / aluminum compound containing from about 5 to about 95% by weight of aluminum, and wherein said modified carbon black is prepared by the reaction of a organosilane with carbon black at an elevated temperature or by co-mingling a silane organ and oil at an elevated temperature. The process of any of the preceding claims, characterized in that said organosilane disulfide compound (I) and organopolysulfide (II) compound are of a bis- (3-trialkoxysilylalkyl) polysulfide wherein (a) the alkyl radicals or the alkoxy groups are selected from methyl and ethyl groups and the alkylene radical of the silylalkyl group is selected from ethyl, propyl and butyl radicals, and where (b) for the organosilane disulfide (I) at least 55% of n is 2. 8. The process according to any of the preceding claims, characterized in that a total of about 0.05 to about 5 phr of at least one alkylalkoxysilane is added to said step (s) of thermomechanical mixing (s) of preparation; wherein said alkylsilane has the formula (III): (III) R'-Si- (0R ") 3 where R" is selected from at least one of the methyl, ethyl, propyl and isopropyl radicals and R 'is a saturated alkyl having from 1 to 18 carbon atoms either an aryl radical or a saturated substituted saturated alkyl aryl radical having from 6 to 12 carbon atoms. . The process of claim 8, characterized in that said alkylalkoxysilane is selected from at least one of the following: propyltriethoxysilane, methyltriethoxysilane, methyltriethoxysilane, hexadecyltriethoxysilane and octadecyltriethoxysilane. The process of any of the preceding claims, characterized in that, for said diene-based elastomer, said conjugated dienes are selected from isoprene and 1,3-butadiene and said aromatic vinyl compounds are selected from styrene and alpha-methylstyrene. The process of any of claims 1-9 characterized in that said diene-based elastomer is selected from at least one of synthetic and natural cis 1,4-polyisoprene rubber, styrene / butadiene copolymer rubber prepared by emulsion polymerization, styrene / butadiene copolymer rubber prepared by polymerization in organic solution, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis 1,4-polybutadiene rubber, vinyl polybutadiene rubber medium (from 35 to 50% vinyl), high vinyl polybutadiene (50% -90% vinyl) as well as styrene / acrylonitrile terpolymer rubber prepared by emulsion and rubber polymerization of butadiene / acrylonitrile copolymer. The process of any of the preceding claims, characterized in that said compound comprises at least one of the following: 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'-bi (tri-sec, butoxysilylethyl) disulfide; 2,2'-bis (tri-t-butoxyethyl) disulfide; 2, 2'-bis (triethoxysilylethyl toluene) disulfide; 2,2'-bis (trimethoxysilylethyl toluene) 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 (methoxyethoxypropylsilylpropyl) disulfide / 3,3'-bis (methoxy dimethylsilylpropyl) disulfide;
3. 3-, 3- 'bis (cyclohexoxy dimethylsilylpropyl) disulfide; 4,4'-bis (trimethoxysilylbutyl) disulfide; 3, 3'-bis (trimethoxysilyl-3-methylprolyl) disulfide; 3, 3'-bis disulfide (tripropoxysilyl-3-methylpropyl); 3, 3'-bis (dimethoxymethylsilyl-3-ethylpropyl) disulfide: 3,3'-bis (trimethoxysilyl-2-methylpropyl) disulfide of 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) disulfide; 2, 2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2, 2'-bis disulfide (tripropoxysilyl-2-methylethyl); and 2,2'-bis (trioxysilyl-2-methylethyl) disulfide. The process of any of claims 1-11, characterized in that the organosilane compound of the formula (I) is 3-, 3- 'bis (triethoxysilylpropyl) disulfide and wherein the organosilane polysulfide compound of the formula (II) is at least one of the following: bis- (3-trimethoxysilylpropyl) trisulfide, bis- (3-trimethoxysilylpropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) trisulfide, bis- (3-triethoxysilylpropyl) tetrasulfide, bis (trisulfide) (3- triethoxysilylethyltolylene) and bis- (3-triethoxysilylethyltolylene tetrasulfide), bis- (3-triethoxysilylethyltolylene) trisulphide and bis- (3-triethoxysilylethyl toluene tetrasulfide) 14. The process of any of claims 1-11 characterized in that the organosilane disulfide compound of the formula (I) is disulfide is 3,3'-bis (triethoxysilylpropyl) and wherein the organosilane polysulfide compound of the formula (II) is at least one of bis- (3-) trisulfide trimetoxisililp ripyl), bis- (3-trimethoxysilylpropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) trisulfide and bis- (3-triethoxysilylpropyl tetrasulfide). The process of any of the preceding claims, comprising an additional step of vulcanizing sulfur with the resulting mixed rubber compositions at a temperature within a range of about 140 ° to about 190 ° C. 6. The process of any of the claims 1-14, characterized in that it comprises an additional step of vulcanizing with sulfur the resulting mixed rubber composition at a temperature comprised within a range of about 140 ° C to about 190 ° C; where the total free sulfur and about 50% of the sulfur in the polysulfide bridge of said organosilane polysulfide (II) is within a range of about 0.93 to about 4. 17. The process of any of the preceding claims 1- 14, characterized in that it comprises an additional step of vulcanizing with sulfur the resulting mixed rubber composition at a temperature within a range of about 140 ° C to about 190 ° C; where the total free sulfur and about 50% sulfur in the polysulfide bridge of said organosilane polysulfide (II) is within a range of about 0.93 to about 2.8 18. A rubber composition prepared in accordance with the process of any of the preceding claims 15-17. The process of any of the preceding claims 1-13 characterized in that it comprises additional steps of shaping said rubber composition to form a rim tread, applying said rim tread on a rim tread housing for forming an assembly and molding and vulcanizing said assembly at a temperature comprised within a range of about 104 ° C to about 190 ° C to form a rim. The process of claim 19, characterized in that the total free sulfur and approximately 50% of sulfur in the polysulfide bridge of said organosilane polysulfide (II) is within a range of about 0.93 to about 4. A vulcanized rubber tire prepared in accordance with the process of any of the preceding claims 19 and 20. A rim having a component of the composition of claim 18. A tire having a tread of the composition of claim 18. A article of manufacture having at least one component of the rubber composition of claim 18. A industrial product selected from at least one band and hose having at least one components of the rubber composition of claim 18.