HK1110328A - Silane compositions, processes for their preparation and rubber compositions containing same - Google Patents

Description

Silane composition, method for producing the same, and rubber composition containing the same

Cross reference to related applications

This application is a continuation-in-part application of U.S. serial No. 10/903,960 filed on 30.7.2004.

Background

Technical Field

The present invention generally relates to silane compositions, methods of making the same, and rubber compositions containing the same.

Description of the Related Art

Tire treads for modern tires must meet performance standards that require a wide range of desirable properties. Generally, three types of performance criteria are important in tread compounds. Which includes good wear resistance, good traction and low rolling resistance. Major tire manufacturers have developed tread compounds that provide lower rolling resistance for improved fuel economy and better braking/traction for safer driving. Thus, a rubber composition suitable for, for example, a tire tread should not only cause the resulting tire to exhibit the desired strength and ductility, particularly at high temperatures, but also good chip resistance, good abrasion resistance, desired slip resistance, and a low tan δ value at low frequencies for desired rolling resistance. In addition, a high composite dynamic modulus is essential for maneuverability and steering control.

Currently, silica has been added to rubber compositions as a filler in place of some or substantially all of the carbon black filler to improve such properties as lower rolling resistance. Although more expensive than carbon black, the advantages of silica include, for example, improved wet traction, low rolling resistance, and the like, and reduced fuel consumption. However, in comparison to carbon black, there is often a lack of, or at least an insufficient degree of, physical and/or chemical bonding between the silica particles and the rubber to render the silica a rubber reinforcing filler, thereby providing less strength to the rubber. Thus, silica filler systems generally require the use of coupling agents.

Generally, coupling agents are used to improve the rubber reinforcing properties of silica. Such coupling agents may be premixed or pre-reacted with the silica particles, for example, or added to the rubber mixture during the rubber/silica processing or mixing stages. If the coupling agent and silica are added separately to the rubber mixture in the rubber/silica processing or mixing stage, it is believed that the coupling agent subsequently combines with the silica.

The coupling agent is generally a bifunctional molecule that reacts with silica at one end and crosslinks with rubber at the other end. In this way, the reinforcement and strength of the rubber, such as toughness, strength, modulus, tensile and abrasion resistance, are particularly improved. The coupling agent is believed to cover the surface of the silica particles, which then prevents the silica from coalescing with other silica particles. By disturbing the coalescence process, the dispersion and therefore also the wear and fuel consumption are improved. The present coupling agents have several problems associated with them, such as toxicity, compatibility with other ingredients used in the rubber composition.

Therefore, there is a need for improved coupling agents.

Brief description of the invention

According to one embodiment of the present invention, there is provided a silane composition comprising

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein R and R¹Independently a hydrocarbyl group of 1 to about 20 carbon atoms; r²Each independently hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms; r^aIs an alkylene group of 1 to 12 carbon atoms, M is a divalent hydrocarbon linking group of 1 to about 20 carbon atoms for linking the silicon atom to the L group; l is a covalently bonded hydrocarbon linker of 1 to about 20 carbon atoms, or is selected from-O-, -S-, -NR³A heteroatom linking group of (A) wherein R³Is a bond or a hydrocarbyl group of 1 to about 20 carbon atoms; ar is a substituted or unsubstituted aryl group; q is an integer of 1 to 4; t and c are each independently 0 or 1; x, y and z are each independently an integer from 1 to 3, provided that t is 1 when L is a heteroatom group.

According to a second embodiment of the present invention, there is provided a process for the preparation of a silane composition comprising reacting at least one compound of the general formula

(RO)_x(R¹)_(3-x)-Si-M-T

Wherein R, R¹M and x have the abovementioned meanings, T is selected from mercapto compounds, hydroxy compounds and compounds of the formula-NR⁴R⁵Wherein R is⁴、R⁵Independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms, and wherein R⁴And R⁵At least one of which is hydrogen,

a silane reactant represented by the general formula

X-(R^a)_cAr-(CR²＝CR² ₂)_y

Wherein Ar, R²Ra, c and y have the aforementioned meanings, X is an anion of an organic or inorganic acid,

the unsaturated reactants represented are reacted in the presence of an effective amount of at least one base.

According to a third embodiment of the present invention, there is provided a method of preparing a silane composition comprising reacting at least one compound of the formula R_bHSiZ_3-bTo representWherein each R is independently a hydrocarbyl group of 1 to 20 carbon atoms; z is a halogen atom, and b is 0 to 3,

and at least one compound of the formula

[R⁶R⁷C＝CR⁸M¹]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein Ar, R²，L，R^aC, q, y and z have the abovementioned meanings, R⁶，R⁷And R⁸Each independently hydrogen or a hydrocarbyl group of 1 to about 6 carbon atoms, M¹Is a bond or a divalent hydrocarbon linking group of 1 to about 18 carbon atoms, wherein R⁶、R⁷、R⁸And M¹The total number of carbon atoms incorporated does not exceed about 18,

the unsaturated reactants indicated are reacted in the presence of at least one hydrosilation catalyst.

According to a fourth embodiment of the present invention, there is provided a rubber compound comprising (a) a rubber component; (b) a filler; (c) at least one silane composition of the formula

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

R, R therein¹、R²、R^aM, L, Ar, x, t, c, q, y and z have the aforementioned meanings, with the proviso that t is 1 when L is a heteroatom group.

According to a fifth embodiment of the present invention, there is provided a method of preparing a rubber composition comprising adding to a reaction-forming mixture of a rubber composition an effective amount of at least one silane composition of the formula

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

R, R therein¹、R²、R^aM, L, Ar, x, t, c, q, y and z have the aforementioned meanings, with the proviso that t is 1 when L is a heteroatom group.

The term "phr" is used herein as its art-recognized meaning, i.e., referring to parts of each material per hundred parts by weight (100) of rubber.

Detailed Description

In one embodiment of the present invention, there is provided a silane composition of the general formula:

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

wherein R and R¹Hydrocarbyl groups independently of 1 to about 20 carbon atoms, examples of which include linear or branched aliphatic, cycloaliphatic, and aromatic groups, and cycloaliphatic and aromatic groups substituted with one or more linear or branched aliphatic, cycloaliphatic, and/or aromatic groups; in one embodiment R²Each independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms, or in the second embodiment 1 to 6 carbon atoms, examples of which include alkyl, substituted alkyl, cycloaliphatic or aromatic groups; m is in one embodiment a divalent hydrocarbon linker of 1 to about 20 carbon atoms, and in a second embodiment a divalent alkyl linker of 1 to 8 carbon atoms, for linking the silicon atom and the L group; l is a covalently bonded hydrocarbon linker of 1 to about 20 carbon atoms or is selected from the group consisting of-O-, -S-, -NR-³A heteroatom linking group of (A) wherein R³Is a bond or a hydrocarbyl group of 1 to about 20 carbon atoms; r^aIs alkylene of 1 to 12 carbon atoms; ar is a saturated or unsaturated aromatic group (e.g., benzene or benzyl) optionally substituted with one or more linear or branched aliphatic, cycloaliphatic, and/or aromatic groups of 1 to 12 carbon atoms; q is an integer from 1 to 4; t and c are each independently 0 or 1; x, y and z are each independently 1 to 3An integer provided that t is 1 when L is a heteroatom group. In one embodiment, L may be any polyfunctional aromatic group, or a cyclic or linear aliphatic hydrocarbon group of 1 to about 20 carbon atoms. In one embodiment, each R is independently an alkyl group of 1 to 8 carbon atoms. In a second embodiment, each R is independently an alkyl group of 1 to 3 carbon atoms. In a third embodiment, each R is independently an alkyl group of 2 carbon atoms. In one embodiment, R¹Each independently an alkyl group of 1 to 6 carbon atoms. In a second embodiment, R¹Each independently an alkyl group of 1 to 3 carbon atoms. In a third embodiment, R¹Each independently is an alkyl group of 1 carbon atom.

In general, the silane compositions of the invention can be prepared by combining at least one silane of the general formula

(RO)_x(R¹)_(3-x)-Si-M-T

R, R therein¹M and x have the aforementioned meanings, and T is one or more members selected from the group consisting of mercapto compounds, hydroxy compounds and compounds of the formula-NR⁴R⁵Wherein R is⁴And R⁵Independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms, and wherein R⁴And R⁵At least one of (a) is hydrogen,

a silane reactant represented by the general formula

X-(R^a)_cAr-(CR²＝CR² ₂)_y

Wherein Ar, R²、R^aC and y have the aforementioned meanings, x is an anion of an organic or inorganic acid,

the unsaturated reactant represented is obtained by reacting in the presence of at least one base in an effective amount. Useful organic or inorganic acid anions include, for example, halogen atoms (i.e., F, Cl, Br, or I), sulfonates, sulfinates, or carboxylates, and the like, and combinations thereof. From a synthetic chemical point of view, x is any group that can act as a leaving group during the nucleophilic substitution reaction. Suitable halides for use herein include, for example, chloro-, bromo-, fluoro-, and the like.

Examples of silane reactants include aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- (aminopropyl) ethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylphenyldimethoxysilane, 2-aminoethyltriethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutylmethyldimethoxysilane, 4- (trimethoxysilyl) -2-butylamine, 3- [ diethoxy (hexyloxy) silyl ] -1-propylamine, 3- [ tris (pentyloxy) silyl ] -1-propylamine, 3- [ tris (2, 2, 2-trifluoroethoxy) silyl ] -1-propylamine, 3- [ tris [2- (2-phenoxyethoxy) ethoxy ] silyl ] -1-propylamine, 3- [ tris [ (2-ethylhexyl) oxy ] silyl ] -1-propylamine, 3- [ tris (hexyloxy) silyl ] -1-propylamine, 3-triisopropoxysilylproparopylamine, 3- [ tris (3-methylbutyloxy) silyl ] -1-propylamine, 3- [ tris (2-ethoxyethoxy) silyl ] -1-propylamine, 3- [ bis (1, 1-dimethylethoxy) methoxysilyl ] -1-propylamine, 3- [ (1, 1-dimethylethoxy) diethoxysilyl ] -1-propylamine, 3- [ (1, 1-dimethylethoxy) dimethoxysilyl ] -1-propylamine, 3- (trimethoxysilyl) -1-pentylamine, 4-amino-3, 3-dimethylbutyltrimethoxysilane, 4-amino-3, 3-dimethylbutyltriethoxysilane, etc.; mercaptosilanes such as mercaptopropyltriethoxysilane, and the like. The silane reactant can be prepared by any commercially available method, for example, aminosilanes can be prepared by the method disclosed in U.S. patent No. 6,242,627. In one embodiment, the unsaturated reactant comprises vinylbenzyl chloride and/or divinylbenzene methyl chloride. In another embodiment, the unsaturated reactant is vinyl benzyl chloride.

The reaction of the at least one silane reactant with the at least one unsaturated reactant is advantageously carried out in the presence of an effective amount of at least one base. The base employed herein may be any strong base. Suitable strong bases include, but are not limited to, alkali metal alkoxides (alcoholates), alkaline earth metal alkoxides (alcoholates), and the like, and mixtures thereof. Examples of useful alkoxides include sodium methoxide, sodium ethoxide, calcium methoxide, calcium ethoxide, sodium propoxide, sodium tert-butoxide, potassium propoxide, potassium tert-butoxide, lithium methoxide, lithium ethoxide, lithium propoxide, lithium tert-butoxide, and the like, and combinations thereof. Alternatively, the base used herein can be an amine, an amide, and the like, and combinations thereof. Examples of such amines and amides include tertiary amines, heterocyclic organic tertiary amines and N, N-disubstituted amides, such as triphenylamine, tribenzylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, trioctylamine, pyridine, quinoline, N, N-dimethylaniline, N-methyl-2-pyrrolidone and polyvinylpyrrolidone and combinations thereof. In one embodiment, the amine catalyst used herein is a tertiary amine, such as trialkyl monoamines, e.g., triethylamine, tributylamine, diisopropylethylamine, and the like; trialkyl diamines such as diazabicyclooctane, diazabicycloundecane, tetramethylethylenediamine, and the like. In another embodiment, triethylamine and diisopropylethylamine are used as the amine catalyst.

As will be readily appreciated by those skilled in the art, the above-described reaction to form the silane compositions of the present invention may be carried out by first mixing at least one base with the silane reactant to form a mixture, and then combining the mixture with the unsaturated reactant. Alternatively, the reaction can be carried out by adding the base to the reaction medium of the silane and unsaturated reactant in a simple operating step or in multiple stages. In general, the effective amount of base used in the process of the present invention can generally range from about 1 molar equivalent to about 10 molar equivalents relative to the silane reactant, and all subranges therebetween. In another embodiment, the effective amount of base used in the process of the present invention can range from about 1.1 molar equivalents to about 2 molar equivalents relative to the silane reactant, and all subranges therebetween.

Advantageously, at least one silane reactant and at least one unsaturated reactant are reacted in a desired ratio to form the silane compositions of the present invention. The reaction may be carried out at a temperature ranging from about 0 ℃ to about 120 ℃ and all subranges therebetween. In another embodiment, the temperature of the reaction may range from about 25 ℃ to about 70 ℃ and all subranges therebetween. The time period for the reaction can range from about 1 hour to about 24 hours and all subranges therebetween. Generally, the molar ratio of silane reactant to unsaturated reactant ranges from about 1: 0.1 to about 1: 10 and all subranges therebetween. In another embodiment, the molar ratio of silane reactant to unsaturated reactant ranges from about 1: 0.5 to about 1: 2 and all subranges therebetween.

It will be appreciated by those skilled in the art that the above silane compositions may be the reaction product of a complex mixture comprising compounds, for example T at the silane reactant is of the formula-NH₂In the case of the amines of (1). The reaction product mixture thus obtained does not have to be separated in order to isolate one or more specific components. Therefore, the reaction product mixture can be used as it is for the rubber composition of the present invention. Thus, when the reaction is complete, the solution of the reaction product of the silane and unsaturated reactant, the base and any by-product alcohol, may be additionally filtered and/or stripped to remove any unwanted base, by-products or volatile heavies using any of the well-known techniques commercially available, such as vacuum or pressure filtration.

In another process of the present invention, the above silane composition may be prepared by reacting at least one hydrosilation compound with at least one compound of the formula

[R⁶R⁷C＝CR⁸M¹]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein Ar, R²，L，R^aC, q, y and z have the abovementioned meanings, R⁶，R⁷And R⁸Each independently hydrogen or a hydrocarbyl group of 1 to about 6 carbon atoms, e.g. alkyl of 1 to about 6 carbon atoms, cycloalkyl (e.g. cyclopentane, cyclohexane) and aryl (e.g. phenyl) groups of 4 to about 6 carbon atoms, M¹Is a bond or 1 to about 18 carbon atomsWherein R is⁶、R⁷、R⁸And M¹Having a total number of carbon atoms not exceeding about 18,

the unsaturated reactant represented by the formula (I) is obtained by reaction.

Suitable hydrosilation compounds useful in the process are of the formula R_bHSiZ_3-bDescribed wherein R is_bEach independently a hydrocarbyl group of 1 to about 20 carbon atoms including, for example, alkyl groups of 1 to about 20 carbon atoms, cycloalkyl groups of about 4 to about 12 carbon atoms, aryl groups; b is 0 to 3, and Z is a halogen atom (e.g., F, Cl, Br or I). Examples of hydrosilation compounds described by the above formula that may be useful in the present process include trimethylsilane, dimethylsilane, triethylsilane, dichlorosilane, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, cyclopentyldichlorosilane, methylphenylchlorosilane, (3, 3, 3-trifluoropropyl) dichlorosilane, and the like, and mixtures thereof. In one embodiment, the hydrosilation compound comprises at least one of dimethylchlorosilane, methyldichlorosilane, dichlorosilane, and trichlorosilane. In another embodiment of the present invention, the hydrosilane compound is trichlorosilane. Examples of suitable unsaturated reactants for use in the present process include diethylene benzene, diisopropenylbenzene, dibutylene benzene, 1, 4-bis (2-methylstyrene) -benzene and the like and mixtures thereof.

The hydrosilation compound and the unsaturated reactant are contacted, typically in the presence of a hydrosilation catalyst, to form a hydrosilation compound. Any hydrosilation catalyst may be used herein, such as a catalyst comprising at least one active hydrosilation metal in elemental or compound form. Useful active hydrosilation metal catalysts include, but are not limited to, ruthenium, rhodium, cobalt, palladium, iridium, platinum, chromium, and molybdenum metals in elemental or compound form. In one embodiment, the active hydrosilation metal is ruthenium or platinum in elemental or compound form.

An illustrative list of hydrosilation metal catalysts that may be used in this embodiment includes, for example, group VIII compounds,such as RhCl₃、Rh(PPh₃)₃Cl (wherein Ph is phenyl), H₂PtCl₆Soluble platinum catalysts, including Speier catalyst (H)₂PtCl₆In i-PrOH), Karstedt's catalyst (H as described in U.S. Pat. Nos. 3,715,334 and 3,775,452)₂PtCl₆And divinyltetramethyldisiloxane), Ashby catalyst (e.g., H as described in U.S. Pat. nos. 3,159,601 and 3,159,662)₂PtCl₆And tetravinyltetramethyldisiloxane) and Lamoreoux catalyst (e.g., H in n-octanol as described in U.S. Pat. No. 3,220,972)₂PtCl₆)。

In another embodiment, the hydrosilation catalyst may be one or more active free radical initiators. Any reactive free radical initiator can be used herein. Examples of such active free radical initiators include, but are not limited to, organic peroxide type initiators such as acetyl peroxide, t-butyl peroxide, benzoyl peroxide, and the like; azo type initiators, such as azobisisobutyronitrile, and the like, and mixtures thereof.

Any conventional reaction vessel in the art may be employed when siliconizing unsaturated reactants in the present invention. The reaction vessel may be charged with a system comprising at least one hydrosilation compound reactant, an unsaturated reactant, and a hydrosilation metal catalyst, the specific order of addition being not limited. To enhance the reaction, stirring may be employed, but is not required. In one embodiment, the hydrosilation reaction is carried out at room temperature to about 160 ℃ and all subranges therebetween. In a second embodiment, the hydrosilation reaction may be carried out at a temperature ranging from about 40 ℃ to about 100 ℃ and all subranges therebetween. In addition, the reaction may occur at atmospheric pressure; however, if desired, the pressure may be increased and a substantially inert organic solvent such as toluene may be used to enhance the reaction conditions.

The amounts of the hydrosilation compound reactant, unsaturated reactant and hydrosilation catalyst used in the process of the present invention are not limited. The only requirement is that the desired hydrosilation reaction take place. In one embodiment, the hydrosilylation catalyst may be advantageously used at a concentration of about 0.1ppm to about 1 part. In a second embodiment, the hydrosilation catalyst may be used at a concentration of about 10ppm to about 1000 ppm. The molar ratio of the hydrosilation reactant to the unsaturated reactant can vary widely, for example, from about 1: 100 to about 100: 1. In another embodiment, the molar ratio of the hydrosulfide to the unsaturated reactant can range from about 1: 10 to about 10: 1. In yet another embodiment, the molar ratio of the hydrosulfide to the unsaturated reactant can range from about 2: 1 to about 1: 2.

If necessary, the hydrosilylated composition can be further reacted, e.g., to provide alkoxy groups on the silicon atom, following the hydrosilylation reaction. For example, where a halogen atom is attached to silicon, such as when trichlorosilane is used as the hydrosulfide, the hydrosilylated compositions of the present invention can be prepared by reacting the above hydrosilylated composition with one or more ether forming agents in an effective amount under ether forming reaction conditions. Useful ether forming agents include, but are not limited to, alkyl orthoformates, dialkyl orthoformates, trialkyl orthoformates such as triethyl orthoformate, and the like, and mixtures thereof. In one embodiment, alkoxy groups may advantageously be bonded to the silicon atom at temperatures of from about 0 ℃ to about 100 ℃ and all subranges therebetween. In a second embodiment, alkoxy groups may advantageously be bonded to the silicon atom at temperatures of from about 25 ℃ to about 80 ℃ and all subranges therebetween. The reaction can be carried out in the absence of a catalyst or in the presence of a catalyst, for example, an acid-type mineral acid catalyst such as sulfonic acid, Lewis-type acid, and the like, and mixtures thereof. In one embodiment, the concentration of the ether forming agent relative to the remaining halogen atoms on the hydrosilylated compound generally ranges from about 0.5 molar equivalents to about 100 molar equivalents and all subranges therebetween. In the second embodiment, the concentration of the ether forming agent relative to the remaining halogen atoms on the hydrosilylated compound generally ranges from about 1 molar equivalent to about 10 molar equivalents and all subranges therebetween.

As one skilled in the art will readily recognize, depending on the particular reaction and reaction conditions, not all of the desired alkoxy groups may be formed, for example, in the case of further reaction of the reaction product obtained by reacting trichlorosilane with an unsaturated reactant, the alkoxylated hydrosilylated composition may not be sufficiently alkoxylated and may still have a chlorine group attached to the silicon atom. Thus, to provide a trialkoxysilane composition, it may be necessary to further react the alkoxylated hydrosilation intermediate to remove residual chlorine groups, for example, by further reacting the alkoxylated hydrosilation intermediate with a second ether forming agent under ether forming reaction conditions. In one embodiment, the reaction may be conducted at a temperature of from about 0 ℃ to about 80 ℃ and all subranges therebetween. In a second embodiment, the reaction may be conducted at a temperature of from about 20 ℃ to about 75 ℃ and all subranges therebetween. Useful ether forming agents include, but are not limited to, alcohols such as methanol, ethanol, and the like. The reaction can be carried out in the absence of a base, or in the presence of a base such as a trialkylamine, for example triethylamine. In one embodiment, the concentration of the second ether forming agent relative to the alkoxylated hydrosilation intermediate generally ranges from about 0.5 molar equivalents to about 100 molar equivalents and all subranges therebetween. In the second embodiment, the concentration of the second ether forming agent relative to the alkoxylated hydrosilation intermediate generally ranges from about 1 molar equivalent to about 20 molar equivalents and all subranges therebetween. Upon completion of the reaction, the solution may be further filtered and/or stripped to remove any unwanted catalyst, by-products or volatile heavies using any commercially available well-known technique, such as vacuum or pressure filtration.

The silane compositions of the present invention are useful as coupling agents. In one embodiment, the silane compositions of the present invention are particularly useful as coupling agents in rubber compositions. Generally, the rubber composition of the present invention comprises at least (a) a rubber component; (b) a filler; and (c) at least one of the silane compositions described above.

The rubber component used in the rubber composition of the present invention is based on an unsaturated rubber, such as a natural or synthetic rubber. Representative of highly unsaturated polymers useful in the practice of the present invention are diene rubbers. Such rubbers typically have iodine values of from about 20 to about 400 and all subranges therebetween, although highly unsaturated rubbers having higher or lower iodine values (e.g., having an iodine value of from about 50 to about 100 and all subranges therebetween) may also be employed. Illustrative of diene rubbers that may be used are polymers based on conjugated dienes, such as 1, 3-butadiene; 2-methyl-1, 3-butadiene; 1, 3-pentadiene; 2, 3-dimethyl-1, 3-butadiene; and the like, as well as copolymers of such conjugated dienes with monomers such as styrene, alpha-methylstyrene, acetylenes such as vinyl acetylene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, and the like. In one embodiment, highly unsaturated rubbers are employed, which include, but are not limited to, natural rubber, cis-polyisoprene, polybutadiene, poly (styrene-butadiene), styrene-isoprene copolymers, isoprene-butadiene copolymers, styrene-isoprene-butadiene trimers, polychloroprene, chloro-isobutylene-isoprene, nitrile-chloroprene, styrene-chloroprene, and poly (acrylonitrile-butadiene). Also, mixtures of two or more highly unsaturated rubbers with elastomers having a lower degree of unsaturation, such as EPDM, EPR, butyl or halogenated butyl rubbers, are also contemplated by the present invention.

Fillers useful in the rubber compositions of the present invention include, but are not limited to, metal oxides such as silica (e.g., fumed and precipitated), titanium dioxide, aluminosilicates and alumina, siliceous materials including clays and talc, carbon black and the like, and mixtures thereof. The term "alumina" may be described herein as alumina, or Al₂O₃. The filler may be hydrated or in anhydrous form.

The silica filler may be of any type well known in connection with the reinforcement of rubber compositions. Examples of suitable silica fillers include, but are not limited to, silica, precipitated silica, amorphous silica, vitreous silica, fumed silica, fused silica, synthetic silicates such as aluminum silicate, alkaline earth metal silicates such as magnesium silicate and calcium silicate, natural silicates such as kaolin and other silicatesNatural silica, and the like. Highly dispersed silicates are also useful, for example, in one embodiment with BET surfaces from about 5 to about 1000m²G and all subranges therebetween, from about 20 to about 400m in a second embodiment²G and all subranges therebetween, and the diameter of the primary particles is from about 5 to about 500nm and all subranges therebetween, and from about 10 to about 400nm and all subranges therebetween. These highly dispersed silicas can be prepared, for example, by precipitation of silicate solutions or by flame hydrolysis of silicon halides. The silica may also be present as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides, and the like. Commercially available silica fillers well known to those skilled in the art include, for example, Cabot Corporation under the trademark Cab-O ═ Sil^®(ii) a PPG Industries are available under the trademarks Hi-Sil and Ceptane; rhodia is under the trademark Zeosil and Degussa AG is under the trademark Ultrasil and Couppsil. Mixtures of two or more silica fillers may be used to prepare the rubber compositions of the present invention.

Silica fillers can be incorporated into rubber compositions in widely varying amounts. In one embodiment, the amount of silica filler may range from about 5 to about 100phr and all subranges therebetween. In a second embodiment, the amount of silica filler ranges from about 25 to about 85phr and all subranges therebetween.

Suitable carbon black fillers include any commercially available carbon black that is commercially manufactured and is well known to those skilled in the art, for example, in one embodiment, the carbon black may have a surface area (EMSA) of at least 20m²(ii) carbon black per gram, and in a second embodiment, the carbon black may be an EMSA of at least 35m²G up to 200m²Carbon black in a proportion of/g or more. The surface area values of the carbon blacks used in the present application are determined by ASTM test D-3765 using the cetyltrimethylammonium bromide (CTAB) technique. Among the useful carbon blacks are furnace blacks, channel blacks and lamp blacks. More specifically, examples of the carbon black include Super Abrasion Furnace (SAF) black, High Abrasion Furnace (HAF) black, Fast Extrusion Furnace (FEF) black, Fine Furnace (FF) black, Intermediate Super Abrasion Furnace (ISAF) black, semi-reinforcing furnace (SRF) blackMiscible (medium processing) channel blacks, hard processing channel blacks and conducting channel blacks. Other carbon blacks that may be utilized include acetylene blacks. Mixtures of two or more of the above blacks may be used to prepare the rubber compositions of the present invention. The surface area typical values for the usable carbon blacks are summarized in table 1 below.

TABLE 1 carbon blacks

ASTM surface area

Name (m)²/g)

(D-1765-82a) (D-3765)

N-110 126

N-234 120

N-220 111

N-339 95

N-330 83

N-550 42

N-660 35

The carbon black utilized in the invention may be in pellet form or a flocculated mass of non-pellets. In one embodiment, the use of pelletized carbon black facilitates handling. In one embodiment, the carbon black may be incorporated into the rubber composition in an amount ranging from about 0.5 to about 100phr and all subranges therebetween. In a second embodiment, carbon black may be incorporated into the rubber composition in an amount ranging from about 1 to about 85phr and all subranges therebetween.

The silane compositions of the present invention may be premixed or pre-reacted with filler particles or added to the rubber mixture during rubber and filler processing or mixing stages. If the silane composition and filler are added separately to the rubber mixture during the rubber and filler mixing or processing stage, the silane composition is considered to be combined with the filler in situ. In one embodiment, the silane composition is present in the rubber composition in an amount ranging from about 0.05 to about 25phr and all subranges therebetween. In a second embodiment, the silane composition is present in the rubber composition in an amount ranging from about 1 to about 10phr and all subranges therebetween. The rubber compositions of the present invention may be formulated in any conventional manner well known in the rubber compounding art using a variety of commonly used additive materials. Examples of such commonly used additive materials include curing aids such as sulfur; an activator; retarders, accelerators, processing additives such as oils; resins such as tackifying resins; a plasticizer; a pigment; a fatty acid; zinc oxide; a wax; an antioxidant; an antiozonant; a peptizing agent; reinforcing materials, and the like, and combinations thereof. The additives mentioned above are selected according to the intended use of the rubber composition and are used in conventional amounts.

Accelerators are typically used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system, i.e., a primary accelerator, may be used. In one embodiment, the primary accelerator may be used in a total amount ranging from about 0.5 to about 4phr and all subranges therebetween. In the second embodiment, the primary accelerator may be used in a total amount ranging from about 0.8 to about 1.5phr and all subranges therebetween. To activate and improve the properties of the vulcanizate, minor amounts (about 0.05 to about 3phr and all subranges therebetween) of secondary accelerators are also used, with a combination of primary and secondary accelerators. Delayed action accelerators may also be used. Vulcanization retarders may also be used. Suitable types of accelerators are, for example, amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. In one embodiment, the primary accelerator is a sulfenamide. If a secondary accelerator is used, the secondary accelerator may be a guanidine, dithiocarbamate, or thiuram compound.

In one embodiment, the tackifying resin may be used in an amount ranging from about 0.5 to about 10phr and all subranges therebetween. In a second embodiment, the amount of tackifying resin may range from about 1 to about 5phr and all subranges therebetween. The processing aid may be used in an amount of from about 1 to about 50phr and all subranges therebetween. Such processing aids include, for example, aromatic, naphthenic and/or paraffinic processing oils. Antioxidants can be used in amounts of from about 1 to about 5 phr. Such antioxidants include, for example, diamines such as diphenyl-p-phenylenediamine. The antiozonants can be used in amounts ranging from about 1 to about 5phr and all subranges therebetween. Fatty acids such as stearic acid may be used in amounts ranging from about 0.5 to about 3phr and all subranges therebetween. The amount of zinc oxide may range from about 2 to about 5phr and all subranges therebetween. The amount of wax used may range from about 1 to about 5 phr. The peptizing agent can be used in an amount of from about 0.1 to about 1phr and all subranges therebetween. Such peptizers include, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.

The rubber composition of the present invention can be used to manufacture products such as tires, motor devices, rubber bushings, power transmission belts, printing rollers, rubber shoe soles and soles, rubber floor tiles, casters, elastomeric seals and gaskets, conveyor belt covers, hard rubber battery cases, automobile floor mats, truck fenders, ball mill liners, windshield wiper blades, and the like. In one embodiment, the rubber composition is advantageously used in a tire as any or all of the thermoset rubber containing portions of the tire. Which includes a tread, tire sidewalls and frame portions for, but not exclusively used in, truck tires, passenger tires, off-the-road tires, vehicle tires, high speed tires, and motorcycle tires, also containing a number of different reinforcement layers therein. Such rubber or tread compositions may be used in the manufacture of tires or in the retreading of used tires. In one embodiment of the invention, the rubber composition has a reinforcement index (ratio of 300% to 100% modulus) of at least about 4. In another embodiment, the index is at least 4.5. In a third embodiment, the Δ G' value of the composition is less than 6.0. In yet another embodiment, the composition has a tan delta maximum of less than 0.250.

The following non-limiting examples are intended to further illustrate the invention and are not intended to limit the scope of the invention in any way.

EXAMPLE 1 preparation of a styrene thioether triethoxysilane reaction product of mercaptopropyltriethoxysilane and vinylbenzyl chloride

To a mixture of mercaptopropyltriethoxysilane (338.3g, 1.42 moles) and sodium ethoxide solution (21 wt% ethanol, 459.9g, 1.42 moles) was added 4-vinylbenzyl chloride (216.8g, 1.42 moles) over a period of 1.5 hours in a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, condenser, temperature sensor, and addition funnel. The mixture was stirred at room temperature for one hour, the ethanol was filtered and stripped with a short path distillation head at 70 ℃ under full vacuum. 479.2g of product were recovered in about 95% yield.

EXAMPLE 2 preparation of bis-styrylaminotriethoxysilane reaction product of aminopropyltriethoxysilane and vinylbenzyl chloride

To a mixture of aminopropyltriethoxysilane (165.7g, 0.74 moles) and triethylamine (137.0g, 1.3 moles) was added 4-vinylbenzyl chloride (201.4g, 1.3 moles) over a period of 16 hours at 70 ℃ in a 1 liter three-necked round bottom flask equipped with a mechanical stirrer, addition funnel and temperature sensor. The resulting solution was cooled to room temperature to 16 hours, filtered, and then stripped of triethylamine with a short path distillation head under sufficient vacuum at room temperature. 252.0g of product was recovered in about 100% yield.

Example 3 preparation of triethoxysilane from hydrosilylation of diisopropenylbenzene

And (1).To a mixture of diisopropenylbenzene (3762.0g, 23.77 moles), hexane (2500mL), platinum (O) -2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane complex (11.2g of a 0.104M solution) and Ionol antioxidant (butylated hydroxytoluene) (2.8g) was added trichlorosilane (2042.1g, 15.07 moles) over 6 hours at 55 ℃. The addition was performed in two batches, each time in a 5 liter 3-neck round bottom flask equipped with a magnetic stir bar, condenser, heating mantle and temperature sensor. Combining the two batches of the obtained material, and then fillingThe hexane was stripped under partial vacuum. The residue was distilled at 150 ℃ under full vacuum using a short path distillation head. 1616.2g of 1- (1-methyl-2-trichlorosilylethyl) -3-propenylbenzene are recovered. The yield was 55%.

And 2. step 2.To a mixture of triethyl orthoformate (2241.0g, 15.1 moles), Ionol antioxidant (3g) and hydrochloric acid (0.1g of a 37% aqueous solution) was added 1- (1-methyl-2-trichlorosilylethyl) -3-propenylbenzene (1616.2g, 5.5 moles) over a period of 4 hours at 50 ℃ in a 5 liter three necked round bottom flask equipped with a magnetic stir bar, heating mantle and temperature sensor. The reaction vessel was heated at 50 ℃ for 64 hours. After about 700 grams of low boilers had been distilled off, additional triethyl orthoformate (730g, 4.9 moles) was charged to the reaction vessel. The reaction vessel was heated at 50 ℃ for 8 hours before the product, i.e., the mixture of 1- (1-methyl-2-triethoxysilylethyl) -3-propenylbenzene and 1- (1-methyl-2-diethoxy chlorosilylethyl) -3-propenylbenzene, was distilled. The material was distilled using a kugelrohr apparatus at 120 ℃ under full vacuum. 1110.8 g of material were recovered. The yield was 68%.

Step 3To a mixture of 1- (1-methyl-2-triethoxysilylethyl) -3-propenylbenzene and 1- (1-methyl-2-diethoxysilylethyl) -3-propenylbenzene (992.5g), triethylamine (509.6g, 5.03 moles) and hexane (4000mL), ethanol (275.8g, 6.0 moles) was added over 2 hours at 5 ℃ in a 5 liter three-necked round bottom flask equipped with a mechanical stirrer, addition funnel and temperature sensor. The resulting mixture was filtered and the hexane, triethylamine and ethanol were stripped using a short path distillation head. 901.0g of 1- (1-methyl-2-triethoxysilylethyl) -3-propenylbenzene were recovered.

EXAMPLE 4 preparation of an isopropyl derivative of the bis-styrylaminotriethoxysilane reaction product of aminopropyltriethoxysilane and vinylbenzyl chloride.

To ammonia at room temperature in a 1 liter three necked round bottom flask equipped with a magnetic stirrer, addition funnel and temperature sensor and nitrogenTo a mixture of propyltriisopropoxysilane (373g, 1.42 mol) and triethylamine was added 4-vinylbenzyl chloride (216g, 1.42 mol) over 2 hours, and the temperature was raised to 80 ℃ by the exothermic heat of reaction. After cooling, gas chromatography of the reaction mixture showed unreacted starting aminosilane, the desired mono-adduct styrene silane, and the bis-adduct styrene silane, (i-PrO)₃Si-CH₂CH₂CH₂N(CH₂-C₆H₄-CH＝CH₂)₂。

Comparative example 1 an attempt was made to synthesize a mono-adduct of mercaptopropyltriethoxysilane with divinylbenzene

The synthesis of the mono-adduct of mercaptopropyltriethoxysilane with divinylbenzene in the absence of base results in a very slow reaction with by-products. However, before the experiment was terminated, a small amount of the desired styrene silane was formed and detected by gas chromatography. In the experiment, 400ml of hexane and 222.1 grams of divinylbenzene (1.705 moles) were added under nitrogen to a 2L round bottom flask equipped with an addition funnel, magnetic stirrer and condenser. 336g (1.53 moles) of gamma-mercaptopropyltriethoxysilane was charged to the addition funnel at first room temperature and then at 50 ℃ and added dropwise. No reaction occurred. The reaction mixture was heated to 80 ℃ for 9.5 days and traces of the mono-adduct styrene silane were observed by gas chromatography.

Example 5. use of the silanes of examples 1 to 3 in low rolling resistance tire tread formulations.

The general procedure for silane compounding and testing follows: (1) silica-filled synthetic rubber (procedure a); (2) silica-filled Natural Rubber (NR) (procedure B) and (3) carbon black-filled tread compound (procedure C). Procedures A-C are set forth below.

Procedure A

The silica-filled treads of the synthetic rubbers containing the silanes of examples 1 to 3 were evaluated according to the low rolling resistance passenger vehicle tire tread formulation described in Table A below and the present mixing procedure. The tread comprising the silane of example 1 was mixed in a "B" banbury (tm) (farrell corp) mixer having a chamber volume of 103 cubic inches (cu.in.) (1690cc) as follows. The rubber masterbatch was mixed in two steps. The mixer was started at 120rpm with sufficient cooling water. The rubbery polymer was added to the mixer and ram mixed for 30 seconds. Half of the silica and all of the silane were added and tamped mixed for 30 seconds, with about 35-40g of the silica in an Ethylene Vinyl Acetate (EVA) copolymer bag. The remaining silica and oil in the EVA bag were next added and ram mixed for 30 seconds. The mixer port (throat) was brushed three times and the mixture was tamped and mixed for 15 seconds each time. The temperature of the rubber masterbatch was increased to between 160 ℃ and 165 ℃ in about one minute as required and the stirring speed of the mixer was increased to 160 or 240 rpm. Dumping the masterbatch (removal from the mixer); the sheet is formed on a rolling mill set at 50 ℃ to 60 ℃ and then cooled to ambient temperature.

The rubber master batch was added to the mixer at 120rpm and the cooling water was fully turned on and ram mixed for 30 seconds. The remaining ingredients were added and mixed by tamping for 30 seconds. The mixer mouth was brushed and the mixer speed increased to 160 or 240rpm to bring the contents temperature to between 160 c and 165 c in about two minutes. The rubber master batch was mixed for eight minutes and the speed of the BANBURY mixer was adjusted to maintain the temperature between 160 ℃ and 165 ℃. Dumping the masterbatch (removal from the mixer); the sheet is formed on a rolling mill set at 50 ℃ to 60 ℃ and then cooled to ambient temperature.

The rubber masterbatch and curative were mixed on a 6 inch diameter 13 inch long (15cm x 33cm) twin roll mill heated to between 50 ℃ and 60 ℃. Sulfur and accelerators were added to the rubber masterbatch and mixed thoroughly in a roll mill to form a sheet. The sheet was cooled to ambient conditions for 24 hours before curing. Rheological properties were measured using a Monsanto R-100 Oscillating disk rheometer (oscillometric DiskRheometer) and a Monsanto M1400 Mooney Viscometer (Mooney Viscometer). Samples were cut from 6-mm plaques (plaques) cured at 160 ℃ for 35 minutes or 2-mm plaques cured at 160 ℃ for 25 minutes for measuring mechanical properties.

The silanes of examples 2 and 3 were also compounded into the tread formulation following procedure a above.

Procedure B

The typical low rolling resistance passenger vehicle tread formulation described in Table B, and the mixing procedure were used to prepare silica-filled treads of natural rubber containing the silanes of examples 1 to 3. The tread comprising the silane of example 1 was mixed in a "B" banbury (tm) (Farrell Corp.) mixer having a chamber volume of 103 cubic inches (1690cc) as follows. The mixing of the rubber master batch is completed according to two steps. The mixer was started, the whole mixer was at 77rpm and the cooling water was 140 ℉ (60 ℃). The rubbery polymer was added to the mixer and ram mixed for 30 seconds. Half of the silica and all of the silane were added and tamped mixed for 30 seconds, with about 35-40g of the portion of the silica in an Ethylene Vinyl Acetate (EVA) bag. The remaining silica and oil in the EVA bag were next added and ram mixed for 30 seconds. The mixer was brushed three times at the mouth with each mix tamping for 20 seconds. The temperature of the rubber masterbatch was raised to 300 ℉ (150 ℃), and the RPM was increased if necessary. The masterbatch was immediately dumped (removed from the mixer), formed into a sheet on a roll set at 170 and 180 ℉ (75-80 ℃) and then allowed to cool to ambient temperature.

The rubber masterbatch was added to a mixer at 77rpm with cooling water at 140 ℉ (60 ℃), and ram mixed for 30 seconds. The remaining ingredients were added, tamped and mixed for 60 seconds. Cleaning and brushing the mixer opening; the temperature is raised to 300 ℉ (150 ℃), and higher rpm is used if necessary. The compounds were mixed at 290 to 300 ℉ (145-150 ℃) for 3 minutes. The compound was dumped (removed from the mixer), formed into a sheet on a roll mill set at about 170 f 180 ℉ f (75-80 c), and then cooled to ambient temperature.

The rubber masterbatch and curative were mixed on a 6 inch diameter 13 inch long (15cm x 33cm) twin roll mill heated to between 50 ℃ and 60 ℃. Sulfur and accelerators were added to the rubber masterbatch and mixed thoroughly in a roll mill to form a sheet. The sheet is cooled to ambient temperature before curing. Rheological properties were measured using a Monsanto R-100 oscillatory Disk Rheometer (Oscillating Disk Rheometer) and a Monsanto M1400 Mooney Viscometer (Mooney Viscometer). Samples were cut from 6-mm plaques cured at 160 ℃ for 35 minutes or 2-mm plaques cured at 160 ℃ for 25 minutes for measuring mechanical properties.

The silanes of examples 2 and 3 were also compounded into tire tread formulations following procedure B above.

Procedure C

The typical low rolling resistance passenger tire tread formulation described in table C, and mixing procedure were used to prepare carbon black filled treads of natural rubber containing the silanes of examples 1 to 3. The tread comprising the silane of example 1 was mixed in a "B" banbury (tm) (Farrell Corp.) mixer having a chamber volume of 103 cubic inches (1690cc) as follows. The mixing of the rubber master batch is completed according to two steps. The mixer was started, the mixer was at 77rpm throughout, and the cooling water was at 140 ℉ (60 ℃ C.) throughout. The rubbery polymer was added to the mixer and ram mixed for 30 seconds. All carbon black and all oil were added and ram mixed for 60 seconds. The mixer mouth was brushed and the mixture was ram down mixed for 20 seconds. The mixer mouth was cleaned a second time to raise the temperature of the rubber masterbatch to 300 ℉ (150℃) and the rpm increased if necessary. The masterbatch was immediately dumped (removed from the mixer), formed into a sheet on a roll mill set at about 170 f 180 ℉ (75-80 c), and then cooled to ambient temperature.

The rubber masterbatch was added to the mixer at 77rpm with cooling water of 140 ℉ (60 ℃), and ram mixed for 30 seconds. The remaining ingredients were added, tamped and mixed for 60 seconds. Cleaning and brushing the mixer opening; the temperature is raised to 300 ℉ (150 ℃), and higher rpm is used if necessary. The compound was dumped (removed from the mixer), formed into a sheet on a roll mill set at about 170 f 180 ℉ f (75-80 c), and then cooled to ambient temperature.

The rubber masterbatch and curative were mixed on a 6 inch diameter 13 inch long (15cm x 33cm) twin roll mill heated to between 50 ℃ and 60 ℃. Sulfur and accelerators were added to the rubber masterbatch and mixed thoroughly in a roll mill to form a sheet. The sheet was cooled to ambient temperature for 24 hours before curing. Rheological properties were measured using a Monsanto R-100 Oscillating disk rheometer (oscillometric DiskRheometer) and a Monsanto M1400 Mooney Viscometer (Mooney Viscometer). Samples were cut from 6-mm plaques cured at 160 ℃ for 35 minutes or 2-mm plaques cured at 160 ℃ for 25 minutes for measuring mechanical properties.

The silanes of examples 2 and 3 were also compounded into tire tread formulations according to procedure C above.

The silanes of examples 1 to 3 were compounded into tire tread formulations of the following A, B or C formulations following the respective procedures A, B and C described above. Formulation a is based on passenger car tires SBR and formulation B is based on truck tires. The properties of the silanes prepared in examples 1 to 3 were compared with those of standard polysulfide silanes without silane coupling agent (silane α), and bis- (3-triethoxysilyl-1-propyl) tetrasulfide (TESPT, silane β), and bis- (triethoxysilylpropyl) disulfide (TESPD, silane γ) commonly used in the prior art. The results of these procedures and tests are listed in table 2 below.

TABLE A

Typical Low Rolling resistance Tread formulation A

PHR	Composition (I)
		75	sSBR (12% styrene, 46% vinyl, T)g：42℃)
25	BR(98％cis，Tg：104℃)
		80	Silica (150-190 m)2/gm，ZEOSIL1165MP，Rhone-Poulenc)
32.5	Aromatic process oils (high viscosity, Sundex 8125, Sun)
		2.5	Zinc oxide (KADOX 720C, Zinc Corp.)
1	Stearic acid (INDUSTRENE, Crompton)
		2	6PPD antiozonant (SANTOFLEX 6PPD, Flexsys)
1.5	Microcrystalline wax (M-4067, Schumann)
		3	N330 carbon black (Engineered Carbons)
1.4	Sulfur (#104, Sunbelt)
		1.7	CBS accelerator (SANTOCURE, Flexsys)
2	DPG accelerator (PERKACIT DPG-C, Flexsys)

TABLE B

Typical Low Rolling resistance Tread formulation B

PHR	Composition (I)
		100	SMR-L NR
3	N-110 carbon black
		50	Silica (150-190 m)2/gm，ZEOSIL1165MP，Rhone-Poulenc)
5	Aromatic process oils (high viscosity, Sundex 8125, Sun)
		4	Zinc oxide (KADOX 720C, Zinc Corp.)
2	Stearic acid (INDUSTRENE, Crompton Corp.)
		2	Naugard Q antioxidant (polymeric dihydrotrimethylquinoline, Crompton Corp.)
2.5	N-1, 3-dimethylbutyl-N' -phenyl-P-phenylenediamine (Flexzone 7P antiozonant, Crompton Corp.)
		1	Sunscreen modified wax (Crompton Corp.)

1.4	Rubbermakers sulfur 104(Sunbelt)
		1.6	TBBS promoter (Delac NS, Crompton Corp.)
2	DPG accelerator (PERKACIT DPG-C, Flexsys)

Watch C

Typical Low Rolling resistance Tread formulation C

PHR	Composition (I)
		100	SMR-L NR
50	N-110 carbon black
		5	Aromatic process oils (high viscosity, Sundex 8125, Sun)
4	Zinc oxide (KADOX 720C, Zinc Corp.)
		2	Stearic acid (INDUSTRENE, Crompton Corp.)
2	Naugard Q antioxidant (polymeric dihydrotrimethylquinoline, Crompton Corp.)
		2.5	N-1, 3-dimethylbutyl-N' -phenyl-P-phenylenediamine (Flexzone 7P antiozonant, Cormpton Corp.)
1	Sunscreen modified wax (Crompton Corp.)
		1.4	Rubbermakers sulfur 104(Sunbelt)
1.6	TBBS promoter (Delac NS, Crompton Corp.)

The following tests were carried out on treads prepared according to formulations A to C described above, in the following manner (in all the examples): mooney Scorch (Mooney Scorch) @135EC (ASTM procedure D1646); mooney viscosity @100 ℃ (ASTM procedure D1646); oscillatory Disk Rheometer (ODR) @149 deg.C; 1 ° (arc), (ASTM Procedure D2084); physical Properties, cure t90@149 deg.C (ASTM procedures D412 and D224) (G' and G ", dynes/cm)²) (ii) a DIN abrasion, mm³(DIN program 53516); heat generation (ASTM procedure D623). The results of these tests are shown in table 2 below.

TABLE 2

Performance of representative silanes in typical low rolling resistance tire formulations
											Silane	α	βTESPT	βTESPT	γTESPD	γTESPD	Example 1	Example 1	Example 2	Example 3*	Example 3
Amount (phr) procedure Mooney viscosity (ML1+4) 300% modulus (KPSI) ratio-300% to 100% modulus Δ G' tan. delta. maximum	0C6021005.26.10.272	7A7120406.60.850.155	4B4921104.72.650.18	6.22A6813655.61.50.203	3.54B5419454.43.10.2	9.42A6513205.31.190.18	5.29B5115554.62.70.208	6.27B4817804.71.90.2	2.76B5215504.83.410.180	5.3B43122352.50.182

^*The silane used was the intermediate formed in step 2 of example 3.

Although the invention has been described in its preferred embodiments with a certain degree of particularity, it is evident that many alternatives and modifications thereof are possible as will be apparent to those skilled in the art upon reading the foregoing description. It is therefore to be understood that the invention may be practiced otherwise than as specifically described herein without departing from its spirit and scope.

Claims (69)

1. A silane composition comprising

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein R and R¹Independently a hydrocarbyl group of 1 to about 20 carbon atoms; r²Each independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms; m is a divalent hydrocarbon linking group of 1 to about 20 carbon atoms for linking the silicon atom to the L group; l is a covalent bond of 1 to about 20 carbon atomsA hydrocarbon linking group or a group selected from-O-, -S-, -NR-³A heteroatom linking group of (A) wherein R³Is a bond or a hydrocarbyl group of 1 to about 20 carbon atoms; r^aIs alkylene of 1 to 12 carbon atoms; ar is a substituted or unsubstituted aryl group; q is an integer of 1 to 4; t and c are each independently 0 or 1; x, y and z are each independently an integer from 1 to 3, provided that t is 1 when L is a heteroatom group.

2. The silane composition of claim 1, wherein x is 1, R and R¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

3. The silane composition of claim 1, wherein x is 2, R and R¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

4. The silane composition of claim 3, wherein L is a heteroatom linking group.

5. The silane composition of claim 4, wherein the heteroatom linking group is-NR³-。

6. The silane composition of claim 1, wherein x is 3, R is independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

7. The silane composition of claim 6, wherein L is a heteroatom linking group.

8. The silane composition of claim 7, wherein the heteroatom linking group is-NR³-。

9. A process for preparing a silane composition comprising reacting at least one compound of the formula

(RO)_x(R¹)_(3-x)-Si-M-T

Wherein R and R¹Independently a hydrocarbyl group of 1 to about 20 carbon atoms; m is a divalent hydrocarbon linking group of 1 to about 20 carbon atoms for linking the silicon atom to the T group; t is selected from the group consisting of mercapto compounds, hydroxy compounds and compounds of the formula-NR⁴R⁵Wherein R is⁴And R⁵Independently is hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms, and wherein R is⁴And R⁵At least one is hydrogen, x is an integer from 1 to 3;

a silane reactant represented by the general formula

X-(R^a)_cAr-(CR²＝CR² ₂)_y

Wherein X is an anion of an organic or inorganic acid; r^aIs an alkyl group of 1 to 12 carbon atoms; ar is a substituted or unsubstituted aryl group; r²Each independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms; c is 0 or 1, y is an integer from 1 to 3;

the representative unsaturated reactant is reacted.

10. The method of claim 9, wherein the base is added to the silane reactant to form a mixture, and then the mixture of silane reactant and base is reacted with the unsaturated reactant.

11. The process of claim 9, wherein the base is an alkali or alkaline earth metal alkoxide.

12. The method of claim 11, wherein the alkoxide is selected from the group consisting of sodium methoxide, sodium ethoxide, calcium methoxide, calcium ethoxide, sodium propoxide, sodium tert-butoxide, potassium propoxide, potassium tert-butoxide, lithium methoxide, lithium ethoxide, lithium propoxide, lithium tert-butoxide, and combinations thereof.

13. The process of claim 9 wherein the base is a tertiary amine.

14. The method of claim 13, wherein the tertiary amine is a trialkylamine.

15. The process of claim 14 wherein the trialkylamine is triethylamine.

16. The method of claim 9, wherein when the silane reactant is reacted with the unsaturated reactant, the molar ratio of silane reactant to unsaturated reactant is from about 1: 0.1 to about 1: 10.

17. The method of claim 9, wherein when the silane reactant is reacted with the unsaturated reactant, the molar ratio of silane reactant to unsaturated reactant is from about 1: 0.5 to about 1: 2.

18. The method of claim 9, wherein the effective amount of base is about 1 to about 10 molar equivalents of base relative to the silane reactant.

19. The method of claim 9, wherein the effective amount of base is about 1.1 to about 2 molar equivalents of base relative to the silane reactant.

20. The method of claim 9, wherein x is 1, R and R¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

21. The method of claim 9, wherein x is 2, R and R¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

22. The method of claim 20 wherein the heteroatom linking group is of the formula-NR⁴R⁵The amine of (1).

23. The method of claim 21 wherein the heteroatom linking group is of the formula-NR⁴R⁵The amine of (1).

24. The process of claim 9 wherein x is 3, R is independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

25. The method of claim 24 wherein the heteroatom linking group is of the formula-NR⁴R⁵The amine of (1).

26. The method of claim 9, further comprising a solvent.

27. The method of claim 26, wherein the solvent is an alcohol.

28. The process of claim 9 wherein the silane reactant is selected from the group consisting of aminosilanes, mercaptosilanes, and mixtures thereof, and the unsaturated reactant is selected from the group consisting of vinylbenzyl chloride, divinylbenzyl chloride, and mixtures thereof.

29. The process of claim 9 wherein the silane reactant is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- (aminopropyl) ethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylphenyldimethoxysilane, 2-aminoethyltriethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutylmethyldimethoxysilane, 4- (trimethoxysilyl) -2-butylamine, 3- [ diethoxy (hexyloxy) silyl ] -1-propylamine, 3- [ tris (pentyloxy) silyl ] -1-propylamine, 3- [ tris (2, 2, 2-trifluoroethoxy) silyl ] -1-propylamine, 3- [ tris [2- (2-phenoxyethoxy) ethoxy ] silyl ] -1-propylamine, 3- [ tris (2-ethylhexyl) oxy ] silyl ] -1-propylamine, 3- [ tris (hexyloxy) silyl ] -1-propylamine, 3-triisopropoxysilylproparopylamine, 3- [ tris (3-methylbutyloxy) silyl ] -1-propylamine, 3- [ tris (2-ethoxyethoxy) silyl ] -1-propylamine, 3- [ bis (1, 1-dimethylethoxy) methoxysilyl ] -1-propylamine, 3- [ (1, 1-dimethylethoxy) diethoxysilyl ] -1-propylamine, 3- [ (1, 1-dimethylethoxy) dimethoxysilyl ] -1-propylamine, 3- (trimethoxysilyl) -1-pentylamine, 4-amino-3, 3-dimethylbutyltrimethoxysilane, 4-amino-3, 3-dimethylbutyltriethoxysilane, mercaptopropyltriethoxysilane and mixtures thereof, the unsaturated reactant being selected from the group consisting of vinylbenzyl chloride, divinylbenzyl chloride and mixtures thereof.

30. A process for preparing a silane composition comprising reacting at least one compound of the formula R in the presence of at least one hydrosilation catalyst_bHSiZ_3-b

Wherein each R is_bIndependently a hydrocarbyl group of 1 to about 20 carbon atoms; z is a halogen atom, b is from 0 to 3,

a silicon hydride compound represented by the general formula

[R⁶R⁷C＝CR⁸M¹]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein Ar is a substituted or unsubstituted aryl group; r²Each independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms; r⁶、R⁷And R⁸Each independently hydrogen or a hydrocarbyl group of 1 to about 6 carbon atoms, M¹Is a bond or a divalent hydrocarbon linking group of 1 to about 18 carbon atoms, wherein R⁶、R⁷、R⁸And M¹Not more than about 18 total carbon atoms; l is a covalently bonded hydrocarbon linker of 1 to about 20 carbon atoms or is selected from the group consisting of-O-, -S-, -NR-³Wherein R is³Is a bond or a hydrocarbyl group of 1 to about 20 carbon atoms; r^aAlkylene of 1 to 12 carbon atoms; c is 0 or 1; y and z are independently integers from 1 to 3; q is an integer of 1 to 4,

the representative unsaturated reactant is reacted.

31. The method of claim 30 wherein b is 0 and Z is chloro in the hydrosilane.

32. The method of claim 30 wherein b is 0, Z is chlorine, and s is 1 in the unsaturated reactant.

33. The method of claim 32, wherein Y is selected from the group consisting of-O-, -S-, -NR ™³A heteroatom of (A), wherein R³Is a bond, hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms.

34. The process of claim 30 wherein the hydrosilation catalyst is H₂PtCl₆，RhCl₃，Rh(PPh₃)₃Cl, Speier catalyst, Karstedt catalyst, Ashby catalyst or Lamoreoux catalyst.

35. The method of claim 30, wherein the hydrosilation catalyst is a free radical initiator.

36. The method of claim 30, further comprising reacting the product of the reaction of the hydrosilation reactant when b is 0, 1, or 2 with a first ether forming agent to provide an alkoxy group attached to the silicon atom.

37. The method of claim 30, further comprising reacting the product of the hydrosilation reactant where b is 0 and Z is chlorine with a first ether forming agent to provide an alkoxy group attached to the silicon atom.

38. The method of claim 37, wherein the first ether forming agent is a trialkyl orthoformate.

39. The process of claim 38 wherein the trialkyl orthoformate is triethyl orthoformate.

40. The process of claim 37, further comprising adding a second ether forming agent.

41. The process of claim 40 wherein the second ether forming agent is an alcohol.

42. The process of claim 30, wherein the concentration of the hydrosilation catalyst is from about 0.1ppm to about 1 part.

43. The method of claim 30, wherein the concentration of the hydrosilation catalyst is from about 10ppm to about 1000 ppm.

44. The process of claim 30 wherein when reacting the hydrosilane reactant with the unsaturated reactant, the molar ratio of the hydrosilane reactant to the unsaturated reactant is from about 1: 100 to about 100: 1.

45. The process of claim 30 wherein when reacting the hydrosilane reactant with the unsaturated reactant, the molar ratio of the hydrosilane reactant to the unsaturated reactant is from about 1: 10 to about 10: 1.

46. The method of claim 30 wherein when reacting the hydrosilane reactant with the unsaturated reactant, the molar ratio of the hydrosilane reactant to the unsaturated reactant is from about 2: 1 to about 1: 2.

47. A rubber composition comprising (a) a rubber component; (b) a filler; and (c) a silane composition comprising

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein R and R¹Independently isA hydrocarbyl group of 1 to about 20 carbon atoms; r²Each independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms; m is a divalent hydrocarbon linking group of 1 to about 20 carbon atoms for linking the silicon atom to the L group; l is a covalently bonded hydrocarbon linker of 1 to about 20 carbon atoms or is selected from the group consisting of-O-, -S-, -NR-³A heteroatom linking group of (A) wherein R³Is a bond or a hydrocarbyl group of 1 to about 20 carbon atoms; r^aAlkylene of 1 to 12 carbon atoms; ar is a substituted or unsubstituted aryl group; q is an integer of 1 to 4; t and c are each independently 0 or 1; x, y and z are each independently an integer from 1 to 3, provided that t is 1 when L is a heteroatom group.

48. The rubber composition of claim 47 wherein the composition has a reinforcement index of at least about 4.

49. The rubber composition of claim 47 wherein the composition has a Δ G' value of less than 6.

50. The rubber composition of claim 47, wherein the composition has a tan delta maximum of less than 0.250.

51. The rubber composition of claim 47 wherein the filler is one or more fillers selected from the group consisting of silica fillers, carbon black fillers and mixtures thereof.

52. The rubber composition of claim 47 wherein the filler is a silica filler selected from the group consisting of: silica, precipitated silica, amorphous silica, vitreous silica, fumed silica, fused silica, synthetic silicates, alkaline earth metal silicates, highly dispersed silicates and mixtures thereof.

53. The rubber composition of claim 47 wherein x is 1, R and R in the silane composition¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

54. The rubber composition of claim 47 wherein in the silane composition x is 2, R and R¹Is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, Ar is phenyl.

55. The rubber composition of claim 54, wherein L is a heteroatom linking group.

56. The rubber composition of claim 55, wherein the heteroatom linking group is-NR³-。

57. The rubber composition of claim 47 wherein in the silane composition x is 3, R is independently methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

58. The rubber composition of claim 57, wherein L is a heteroatom linking group.

59. The rubber composition of claim 58, wherein the heteroatom linking group is-NR³-。

60. The rubber composition of claim 47, wherein the silane composition is present in an amount of about 0.05 to about 25 phr.

61. The rubber composition of claim 60 wherein the silane composition is present in an amount of from about 1 to about 10 phr.

62. A tire tread comprising the rubber composition of claim 47.

63. A tire having the tread of claim 62 comprising a rubber composition.

64. A tire tread comprising the rubber composition of claim 47, wherein said silane composition is present in an amount sufficient to maximize the ratio of 300% modulus of elongation to 100% modulus of elongation.

65. A method of preparing a rubber composition comprising admixing an effective amount of at least one compound of the formula

[(RO)_x(R¹)_(3-x)-Si-M_t]_q-L-[(R^a)_cAr-(CR²＝CR² ₂)_y]_z

Wherein R and R¹Independently a hydrocarbyl group of 1 to about 20 carbon atoms; r²Each independently hydrogen or a hydrocarbyl group of 1 to about 20 carbon atoms; m is a divalent hydrocarbon linking group of 1 to about 20 carbon atoms for linking the silicon atom to the L group; l is a covalently bonded hydrocarbon linker of 1 to about 20 carbon atoms or is selected from the group consisting of-O-, -S-, -NR-³A heteroatom linking group of (A) wherein R³Is a bond or a hydrocarbyl group of 1 to about 20 carbon atoms; r^aAlkylene of 1 to 12 carbon atoms; ar is a substituted or unsubstituted aryl group; q is an integer of 1 to 4; t and c are each independently 0 or 1; x, y and z are each independently an integer of 1 to 3, with the proviso that t is 1 when L is a heteroatom group,

the silane composition of (a) is added to the rubber composition reaction forming mixture.

66. The method of claim 65, wherein x is 1, R and R¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

67. The method of claim 66, wherein x is 2, R and R¹Independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, dodecyl or phenyl, and Ar is phenyl.

68. The method of claim 67, wherein L is a heteroatom linking group.

69. The method of claim 68, wherein the heteroatom linking group is-NR³-。