Tire compositions and components containing free-flowing filler compositions

ES 2 373 344 T3

DESCRIPTION

Tire compositions and components containing free-flowing filler compositions

The present application relates to an invention that was developed in accordance with the joint research agreement within the meaning of 35 USC§103 (c). The joint research agreement dated May 7, 2001 was amended, between Continental AG and General Electric Company, on behalf of GE Advanced Materials, Silicones Division, now Momentive Performance Materials Inc.

CROSS REFERENCE TO RELATED REQUESTS

This application claims the priority of US Application No. 11 / 617,678, filed December 28, 2006.

This application refers to the following applications, filed on December 28, 2006:

Application No. 11 / 617,663, filed on Components Containing Polysulfides

<td> 28</td><td>of</td><td>December of</td><td> 2006,</td><td>titled</td>

<td>with</td><td colspan="2">Silated nuclei.</td><td></td><td></td>

<td> 28</td><td>of</td><td>December of</td><td> 2006,</td><td>titled</td>

Application n ° 11 / 617,649, filed on

Components Containing Free Flowing Charging Compositions.

Application No. 11 / 617,683, filed on Components Containing Polysulfides of December 2006, titled December 2006, titled Silated Cyclic Nuclei.

<td>Compositions</td><td>of</td><td>tires</td>

<td>Compositions</td><td>of</td><td>tires</td>

<td>Compositions</td><td>of</td><td>tires</td>

<td>Compositions</td><td>of</td><td>tires</td>

^Y^Y^Y^Y with

Application n ° 11 / 617.659, filed on

Components Containing Blocked Mercaptosillanic Coupling Agent.

Application No. 11 / 648,460, filed on December 28, 2006, entitled Freely Composition and Rubber Composition Containing It.

Flowing Load

Application No. 11 / 647,903, filed on December 28, Freely and Composition of Rubber that Contains it.

2006, entitled Composition of

Flowing Load

Application No. 11 / 647,780, filed on December 28, 2006, titled Blocked Mercaptosillanic Coupling Agents, Procedure to Obtain Them, and Uses in Rubber.

Application No. 11 / 648,287, filed on December 28, 2006, entitled Silated Core Polysulfides, their Preparation and their Use in Filled Elastomeric Compositions.

Application No. 11 / 647,901, filed on December 28, 2006, entitled Polysulfides with Silated Cyclic Nuclei, their Preparation and Use in Filled Elastomeric Compositions.

1. Field of the invention

The present invention relates generally to filler compositions, more particularly to free-flowing filler compositions containing, or derived from, polysulfides with silated cyclic nuclei, and to tire compositions and tire components containing the filler composition.

2. Background of the invention

Fuel savings and the need to protect the environment are economic and societal priorities. As a result, it has become desirable to produce elastomers with good mechanical properties so that they can be used in the form of usable rubber compositions for the construction of tires with improved properties, having in particular a reduced rolling resistance.

To this end, numerous solutions have been proposed, such as, for example, the use of coupling agents, star-forming or functionalizers with reinforcing filler, to modify elastomers in order to obtain a good interaction between the modified elastomer and the filler. reinforcing. In order to obtain the optimal reinforcing properties imparted by a filler, the filler is preferably present in the elastomeric matrix in a final form which is both as finely divided as possible and as homogeneously distributed as possible.

Without being bound by theory, the filler particles tend to attract each other and agglomerate in the elastomeric matrix. As such, there is a reduction in the number of filler-elastomer bonds created during the mixing process. As a result of these interactions, the consistency of the rubber composition increases and makes processing more difficult.

Rubber compositions reinforced with fillers, such as aluminas or aluminum (oxide) hydroxides, of

ES 2 373 344 T3 high dispersibility, and sulfur vulcanizable diene rubber composition, reinforced with a special precipitated silica of the highly dispersible type, are known in the art. The use of these fillers makes it possible to obtain tires or tire treads with improved rolling resistance, without adversely affecting the other properties, in particular those of grip, durability and wear resistance. Although the use of these specific, highly reinforcing siliceous or aluminous fillers has reduced the difficulties of processing rubber compositions containing them, such rubber compositions are nevertheless more difficult to process than conventionally black filled rubber compositions. smoke.

In particular, it is necessary to use a coupling agent, also known as a binding agent, whose function is to provide the connection between the surface of the filler particles and the elastomer, while facilitating the dispersion of this filler in the matrix. elastomer.

Sulfur-containing coupling agents, used for mineral charged elastomers, involve silanes in which two alkoxysilylalkyl groups are attached, each at one end of a chain of sulfur atoms. The two alkoxysilyl groups are linked to the chain of sulfur atoms by two similar hydrocarbon fragments, and in most cases identical. The general silanic structures just described, hereinafter referred to as "simple bispolysulfurosilanes", usually contain a chain of three methylene groups as the two mediating hydrocarbon units. In some cases, the methylene chain is shorter, containing only one or two methylenes per chain. The use of these compounds is mainly as coupling agents for elastomers with mineral fillers. These coupling agents work by chemically bonding silica or other mineral fillers to polymer when used in rubber applications. Without being bound by theory, it is believed that coupling is achieved by chemical bond formation between the silane sulfur and the polymer, and by hydrolysis of the alkoxysilyl groups and subsequent condensation with silica hydroxyl groups. Furthermore, the reaction of silane sulfur with the polymer is believed to occur when the SS bonds are broken and the resulting fragment is added to the polymer. It is further believed that a unique polymer bonding occurs for each silyl group bonded to the silica. This bond contains a single, relatively weak CS and / or SS bond or bonds, which form the weak bond between the polymer and the silica. Under great stress, these single CS and / or SS bonds can break and thus can contribute to the durability of the filled elastomer.

The use of polysulfurosilane coupling agents in the preparation of rubber is well known. These silanes contain two silicon atoms, each of which is attached to a disubstituted hydrocarbon group, and to three other groups, of which at least one is removable from silicon by hydrolysis. Two such hydrocarbon groups, each with its silyl group attached, are further attached to each end of a chain of at least two sulfur atoms. These structures thus contain two silicon atoms and a single continuous chain of sulfur atoms of varying length.

Polysulfurosilanes with hydrocarbon nuclei having a central molecular nucleus isolated from silicon in the molecule by sulfur-sulfur bonds are known in the art. Polysulfurosilanes which contain a nucleus which is an aminoalkyl group separated from the silicon atom by a single sulfur and a polysulfide group, and in which the polysulfide group is bonded to the nucleus at a secondary carbon atom, are also known in the art. Likewise also core fragments in which only two polysulfide groups are attached to the core.

However, polysulfide groups that are directly attached to an aromatic nucleus have reduced reactivity with the polymer (rubber). The aromatic nucleus is sterically bulky, which inhibits the reaction. Compositions in which polysulfides are directly attached to cyclic aliphatic fragments derived by vinylcyclohexene contain more than one silated nucleus and form large rings. The cyclohexyl nucleus is sterically more hindered than the aromatic nucleus, and it is less reactive. Although these compositions can form more than one sulfur bond to the polymeric rubber for each bonding of the coupling agent to silica through the silyl group, their effectiveness is low probably due to low reactivity.

Without being bound by theory, the low reactivity is due to the binding of the polysulfide to the secondary carbon of the cyclic nucleus structure. The placement of the polysulfide group is not optimal for the reaction with the accelerators and the reaction with the polymer.

The present invention overcomes the shortcomings of the above-mentioned compositions involving silane coupling agents in a number of ways. The silanes of the present invention described herein are not limited to two silyl groups, nor to one chain of sulfur atoms. In fact, the molecular architecture of the present invention includes multiple polysulfide chains that are oriented in a non-collinear (i.e. branched) configuration in the sense that the branch points occur on the main carbon chain that interconnects the chains. polysulfide) and provides a new configuration.

The fillers of the present invention have advantages over those of the prior art by providing multiple points of sulfur-to-polymer attachment per silicon-to-filler attachment point. The silanes of the charges

ES 2 373 344 T3 described herein may be asymmetric with respect to the groups at the two ends of the sulfur chains. Silyl groups, rather than appearing at the ends of the molecule, tend to appear more centrally, and are chemically linked to the nucleus through carbon-carbon or carbon-silicon bonds. The thioether bond also provides a convenient synthetic route to obtain the silanes of the present invention. The cyclic nucleus also contains multiple polysulfide groups that are attached to a carbon atom by a divalent straight chain alkylene group. Attachment of the polysulfide group to the primary carbon atom of the alkylene group significantly decreases the steric hindrance of the core, and increases the reactivity of the polysulfides with the polymer. Furthermore, the cyclic nucleus orients these alkylene chains containing the polysulfide groups away from each other to further reduce steric hindrance near the polysulfide groups. This distinction is what allows silane silicon to bind and remain bound (through the intermediation of a sequence of covalent chemical bonds) to the polymer at multiple points using the silanes of the present invention.

Also, without being bound by theory, the silanes with silated nuclei of the present invention include a Y-core structure. This Y-core structure is believed to allow for the bonding of the polymer to two different points or crosslinking to two chains. different polymeric compounds, and also allows attachment, such as by bonding, to a filler.

SUMMARY OF THE INVENTION

In a first embodiment of the present invention, a preformed free-flowing filler composition is provided, such as for use in tire compositions, comprising:

a) a charge;

b) a first silane which is a silated cyclic nucleus polysulfide of the general formula

[Y¹R¹Sx-] m [G¹(MR²SiX¹X²X³) a] n [G²] or [R³Y²] p (Formula 1) in which:

each case of G¹ is independently selected from a polyvalent cyclic cyclic or polyvalent cyclic heterocarbon species having 1 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH2) b-] cR⁴[- (CH2) dSx-] e; (Formula 2) each case of G² is independently selected from a polyvalent cyclic hydrocarbon or polyvalent cyclic heterocarbon species of 1 to about 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH2) b-] cR⁵[- (CH2) dSx-] e; (Formula 3) each case of R¹ and R³ is independently selected from a divalent hydrocarbon moiety having 1 to 20 carbon atoms;

each occurrence of Y and Y is independently selected from silyl (-SiX XX), hydrogen, alkoxy (-OR), carboxylic acid, ester (-C (= O) OR⁶), in which R⁶ it is a monovalent hydrocarbon group having 1 to 20 carbon atoms;

each case of R² is independently selected from a divalent hydrocarbon fragment having 1 to 20 carbon atoms including branched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups;

each case of R⁴ is independently selected from a polyvalent cyclic hydrocarbon fragment of 1 to about 28 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e, and includes alkyl, alkenyl, alkynyl, aryl and aralkyl groups cyclic and polycyclic in which + c + e - 1 hydrogens have been substituted, or a polyvalent cyclic heterocarbon fragment of 1 to 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e;

each case of R⁵ is independently selected from a polyvalent cyclic hydrocarbon fragment of 1 to about 28 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c + e, and includes cyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groups and polycyclics in which c + e - 1 hydrogens have been substituted, or a polyvalent cyclic heterocarbon fragment of 1 to 27 carbon atoms that was obtained by substitution of hydrogen atoms

ES 2 373 344 T3 equal to the sum of c + e;

each case of X¹ is independently selected from -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶it is a monovalent hydrocarbon group having 1 to 20 carbon atoms;

each case of X² and X³ is independently selected from hydrogen R⁶, in which R⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, X¹, in which X¹ is independently selected from the group consisting of -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶ it is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and -OSi-containing groups resulting from the condensation of silanols; and each case of the subscripts a, b, c, d, e, m, n, o, p, and x, is independently given by a, c and e are 1 to 3; b is 1 to 5; d is 1 to 5; m and p are 1 to 100; n is 1 to 15; o is 0 to 10; and x is 1 to 10; and optionally

c) a second silane having the general formula

[X¹X²X³Sir¹SxR³SiX¹X²X³] (Formula 4) in which:

each case of R¹ and R³ is independently chosen from a divalent hydrocarbon fragment having 1 to 20 carbon atoms that includes branched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups, in which one hydrogen atom was replaced by a silyl group (- SiX¹X²X³), in which X¹ is independently selected from -Cl, -Br, -OH, -OR⁶, and R ° C (= O) O-, where R⁶ is any monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes branched or straight chain alkyl, alkenyl, aryl or aralkyl groups, and X² and X³ are independently selected from the group consisting of hydrogen, R⁶, X¹, and -OSi-containing groups that result from the condensation of silanols.

In a second embodiment of the present invention, rubber compositions are provided, such as for use in a tire composition, comprising at least one rubber, at least one free-flowing filler composition of the present invention, a curing agent and, optionally, at least one other additive selected from the group consisting of sulfur compounds, activators, retardants, accelerators, processing additives, oils, plasticizers, tackifying resins, silicas, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents, reinforcing materials, and mixtures thereof.

The present invention also relates to tire compositions for forming a tire component, the compositions being formed by combining at least one preformed free-flowing filler composition and at least one vulcanizable rubber selected from natural rubbers, synthetic polyisoprene rubbers, polyisobutylene rubbers. random, polybutadiene rubbers, and styrene-butadiene rubbers (SBR);

the preformed free-flowing filler composition being formed by combining at least one active filler and a first silane;

the active filler including at least one active filler selected from carbon blacks, silicas, silicon-based fillers, and metal oxides present in a combined amount of at least 35 parts by weight per 100 parts by weight of total vulcanizable rubber, of which at least 10 parts by weight is carbon black, silica, or a combination thereof; and the first silane comprising at least one silated cyclic nucleus polysulfide having the general formula

[Y¹R¹Sx-] m [G¹(SR2SiX¹X²X³)_to]ⁿ[G²] or [R³Y²] p where:

each case of G¹ is independently selected from a polyvalent cyclic cyclic or polyvalent cyclic heterocarbon species having 1 to 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH2) b-] cR⁴[- (CH2) dSx-] e;

each case of G² is independently selected from a polyvalent cyclic hydrocarbon or polyvalent cyclic heterocarbon species of 1 to 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH2) b-] cR⁵[- (CH2) dSx-] e;

each case of R¹ and R³ is independently selected from a divalent hydrocarbon fragment that 5

ES 2 373 344 T3 has 1 to 20 carbon atoms;

each occurrence of Y and Y is independently selected from silyl (-SiX XX), hydrogen, alkoxy (-OR), carboxylic acid, ester (-C (= O) OR⁶), in which R⁶ it is a monovalent hydrocarbon group having 1 to 20 carbon atoms;

each case of R² is independently selected from a divalent hydrocarbon fragment having 1 to 20 carbon atoms including branched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups;

each case of R⁴ is independently selected from a polyvalent cyclic hydrocarbon fragment of 1 to about 28 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e, and includes alkyl, alkenyl, alkynyl, aryl and aralkyl groups cyclic and polycyclic in which + c + e - 1 hydrogens have been substituted, or a polyvalent cyclic heterocarbon fragment of 1 to 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e;

each case of R⁵ is independently selected from a polyvalent cyclic hydrocarbon fragment of 1 to about 28 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c + e, and includes cyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groups and polycyclic in which c + e - 1 hydrogens have been substituted, or a polyvalent cyclic heterocarbon fragment of 1 to 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c + e;

each case of X¹ is independently selected from -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶it is a monovalent hydrocarbon group having 1 to 20 carbon atoms;

each case of X² and X³ is independently selected from hydrogen R⁶, in which R⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, X¹, in which X¹ is independently selected from -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶ it is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and -OSi-containing groups resulting from the condensation of silanols; and each case of the subscripts a, b, c, d, e, m, n, o, p, and x, is independently given by a, c and e are 1 to 3; b is 1 to 5; d is 1 to 5; m and p are 1 to 100; n is 1 to 15; o is 0 to 10; and x is 1 to 10; and, wherein the tire composition is formulated to be vulcanizable to form a tire component compound having a Shore A hardness of not less than 40 and not greater than 95, and a glass transition temperature Tg (E "max). not less than -80 ° C and not more than 0 ° C.

The present invention also relates to tires, at least one component of which comprises cured tire compositions obtained from rubber compositions according to the present invention.

The present invention also relates to cured and uncured tire components, including, but not limited to, tire treads, including any tire component produced from any composition that includes at least one silated core polysulfide.

The examples presented here demonstrate that the fillers of the present invention provide a desirable balance of physical properties (performance to elastomeric compositions with mineral fillers) and improved wear characteristics to articles made from these elastomers, including tires and tire components. Improvements in rolling resistance are also apparent for elastomers used in tire applications.

The compositions of the present invention show excellent filler dispersion, and can achieve excellent machinability, and improved productivity in vulcanization.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is further described in the detailed description that follows by way of non-limiting examples of exemplary embodiments of the present invention, in which:

Fig. 1 shows HPLC analysis of the product from Example 1.

DEFINITIONS

In describing and claiming the present invention, the following terminology will be used.

ES 2 373 344 T3

The term "coupling agent" as used herein includes an agent capable of establishing a sufficient chemical and / or physical connection between the filler and the elastomer. Such coupling agents have functional groups capable of physically and / or chemically bonding to the charge, for example between a silicon atom of the coupling agent and the hydroxyl (OH) surface groups of the charge (for example, silanols of the charge). surface, in the case of silica); and, for example, sulfur atoms that are capable of physically and / or chemically bonding with the elastomer.

The term "filler" as used herein includes a substance that is added to the elastomer to extend the elastomer or to reinforce the elastomeric network. Reinforcing fillers are materials whose moduli are greater than the organic polymer of the elastomeric composition, and are capable of absorbing stress from the organic polymer when the elastomer is stressed. Fillers include fibers, particles, sheet-like structures, and can be composed of inorganic materials, organosilicon compounds, such as, by way of non-limiting example, silanes, silicones, and polysiloxanes, and intermediates comprising reactive monomers and additives. that have a silicon atom, and any other molecule, oligomer, polymer, or interpolymer that contains a silicon atom and a carbon atom, silicates, silica, clays, ceramic materials, carbon, organic polymers, diatomaceous earth. The filler of the present invention may be essentially inert to the silane with which it is mixed, or it may be reactive with it.

The term "particulate filler" or "particulate composition", as used herein, includes a particle or grouping of particles to form aggregates or agglomerates, including filler or reinforcing particles, including without limitation those that contain or are made of molecules. organic, oligomers, and / or polymers, for example poly (arylene ether) resins, or functionalized filler or reinforcing particle. The term "functionalized" is intended to include any particles treated with an organic molecule, polymer, oligomer, or otherwise (collectively, treating agent or agents), thereby chemically binding the treating agent or agents to the particle. The particulate filler of the present invention may be essentially inert to the silane with which it is mixed, or it may be reactive with it.

The term "support" as used herein includes a porous or high surface area filler that has high adsorption or absorption capacity and is capable of supporting up to 75 percent liquid silane while maintaining its free-flowing properties and dryness. The carrier filler of the present invention is essentially inert to silane, and is capable of releasing or desorbing liquid silane when added to the elastomeric composition.

The term " preformed" as used herein is to be understood to include a filler composition that is prepared prior to its addition to a rubber or rubber blend.

The term "rubber" includes natural or synthetic elastomers, including polyisoprene rubbers, polyisobutylene rubbers, polybutadiene rubbers, and styrene-butadiene rubbers.

The term "tire compositions" includes those compositions useful for the manufacture of tires or tire components, and includes rubber compositions that include at least one rubber, a silane, or a free-flowing filler composition that contains, or is derived from, silated core polysulfide, and at least one active filler such as, by way of non-limiting example, carbon blacks, silicas, silicon-based fillers, and metal oxides present either alone or in combination. For example, an active filler can be selected from the group described above (e.g., carbon blacks, silicas, silicon-based fillers, and metal oxides), and may be present, but need not be, in a combined amount of at least less 35 parts by weight per 100 parts by weight of total vulcanizable rubber, of which at least 10 parts may be carbon black, silica, or some combination thereof, and wherein said compositions can be formulated such that they are vulcanizable to form a tire component compound. The tire component compounds may have a Shore A hardness of not less than 40 and not greater than 95, and a glass transition temperature Tg (E "max) of not less than -80 ° C and not greater than 0 ° C. Shore A hardness is measured according to DIN 53505. The glass transition temperature Tg (E "max) is measured according to DIN 53513, with a specific temperature sweep of -80 ° C to + 80 ° C and a specific compression of 10 ± 0.2% at 10 Hz.

DETAILED DESCRIPTIONS OF THE PRESENT INVENTION

The free-flowing filler composition of the present invention is a preformed free-flowing filler composition for use in a tire composition, comprising:

a) a charge;

b) a first silane which is a silated cyclic nucleus polysulfide of the general formula

[Y¹R¹Sx-] m [G¹(MR²SiX¹X²X³) a] n [G²] or [R³Y²] p (1) in which each case of G¹ is independently selected from a cyclic hydrocarbon species

ES 2 373 344 T3 polyvalent or polyvalent cyclic heterocarbon having from 1 to about 30 carbon atoms and containing a polysulfide group represented by Formula (2)

[(CH2) b-] cR⁴[- (CH2) dSx-] e; (2) each case of G² is independently selected from a polyvalent cyclic cyclic or a polyvalent cyclic heterocarbon species of 1 to about 30 carbon atoms and containing a polysulfide group represented by Formula (3)

[(CH2) b-] cR⁵[- (CH2) dSx-] e; (3) each case of R¹ and R³ is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms including straight and branched chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups, in which one hydrogen atom was replaced by a Y group¹ or Y²;

each case of Y¹ and Y² is selected independently of, but not limited to, silyl (-SiX¹X²X³), alkoxy (OR⁶), hydrogen, carboxylic acid (-C (= O) OH), ester (-C (= O) OR⁶), in which R⁶ is any monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes branched or straight chain alkyl, alkenyl, aryl or aralkyl groups, and the like;

each case of R² is independently selected from a divalent hydrocarbon moiety having from 1 to about 20 carbon atoms including branched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups;

each case of R⁴ is independently selected from a polyvalent cyclic hydrocarbon fragment of 1 to about 28 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e, and includes alkyl, alkenyl, alkynyl, aryl and aralkyl groups cyclic and polycyclic in which + c + e - 1 hydrogens have been substituted, or a polyvalent cyclic heterocarbon fragment of 1 to 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e;

each case of R⁵ is independently selected from a polyvalent cyclic hydrocarbon fragment of 1 to about 28 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c + e, and includes alkyl, alkenyl, alkynyl, alkynyl, aryl, and aralkyl groups cyclic and polycyclic in which c + e - 1 hydrogens have been substituted, or a polyvalent cyclic heterocarbon fragment of 1 to 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c + e;

each case of X¹ is independently selected from -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶ is any monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes branched or straight chain alkyl, alkenyl, aryl or aralkyl groups;

each case of X² and X³ is independently selected from hydrogen, the members listed above for R⁶, the members listed above for X¹, and -OSi-containing groups that result from the condensation of silanols;

each case of the subscripts a, b, c, d, e, m, n, o, p, and x, is independently given by a is 1 to about 3; b is 1 to about 5; c is 1 to about 3; d is 1 to about 5; e is 1 to about 3; m is 1 to about 100, n is 1 to about 15; o is 0 to about 10; p is 1 to about 100, and x is 1 to about 10;

c) a second silane having the general formula

[X¹X²X³Sir¹SxR³SiX¹X²X³] (4) in which:

each case of R¹ and R³ is independently chosen from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms that includes straight chain branched alkyl, alkenyl, alkynyl, aryl or aralkyl groups in which one hydrogen atom was replaced by a silyl group ( SiX¹X²X³), where X¹ is independently selected from -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶ is any monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes branched or straight chain alkyl, alkenyl, aryl or aralkyl groups, and X² and X³ are independently selected from the group consisting of hydrogen, R⁶, X¹, and -OSi-containing groups that result from the condensation of silanols.

The term "heterocarbon", as used herein, refers to any hydrocarbon structure in which the carbon-carbon linking backbone is interrupted by bonding to hetero atoms, such as nitrogen, sulfur, phosphorous and / or oxygen atoms, or in which the carbon-carbon backbone is

ES 2 373 344 T3 interrupted by bonding to groups of atoms containing sulfur, nitrogen and / or oxygen, such as cyanurate (C3N3). Heterocarbon fragments also refer to any hydrocarbon in which one hydrogen or two or more carbon-bonded hydrogens are replaced by a sulfur, oxygen, or nitrogen atom, such as primary amine (-NH2), and oxo (= O), and the like.

Thus, R⁴ and R⁵ include, but are not limited to, cyclic, and / or polycyclic, polyvalent aliphatic hydrocarbons, which may be substituted with alkyl, alkenyl, alkynyl, aryl and / or aralkyl groups; Polyvalent cyclic, and / or polycyclic, heterocarbons optionally containing ether functionality via oxygen atoms, each of which is attached to two separate carbon atoms, polysulfide functionality, in which the polysulfide group (Sx-) is linked to two carbon atoms separated in G¹ or G² to form a ring, tertiary amine functionality via nitrogen atoms, each of which is attached to three separate carbon atoms, cyano (CN) groups, and / or cyanurate (C3N3) groups; aromatic hydrocarbons; and arenes derived by substitution of the aforementioned aromatics with straight or branched chain alkyl, alkenyl, alkynyl, aryl and / or aralkyl groups.

As used herein, "alkyl" includes linear, branched, and cyclic alkyl groups; "Alkenyl" includes any alkenyl group, linear, branched, or cyclic, containing one or more carbon-carbon double bonds, wherein the point of substitution may be on a carbon-carbon double bond or elsewhere in the group. ; and "alkynyl" includes any linear, branched, or cyclic alkynyl group, containing one or more carbon-carbon triple bonds, and also optionally also one or more carbon-carbon double bonds, wherein the point of substitution may be on a triple bond. carbon-carbon, a carbon-carbon double bond, or anywhere else in the group. Examples of alkyls include, but are not limited to, methyl, ethyl, propyl, isobutyl. Examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane, ethylidenenorbornyl, ethylidenyl norbornene, and ethylidene norbornenyl. Some examples of alkynyls include, but are not limited to, acetylenyl, propargyl, and methylacetylenyl.

As used herein, "aryl" includes any aromatic hydrocarbon from which a carbon atom has been removed; "Aralkyl" includes any of the aforementioned alkyl groups in which one or more hydrogen atoms have been substituted by the same number of the same and / or different aryl substituents (as defined herein); and "arenyl" includes any of the aforementioned aryl groups in which one or more hydrogen atoms has been substituted by the same number of the same and / or different alkyl substituents (as defined herein). Some examples of aryl include, but are not limited to, phenyl and naphthalenyl. Examples of aralkyls include, but are not limited to, benzyl and phenethyl, and some examples of arenyl include, but are not limited to, tolyl and xylyl.

As used herein, "cyclic alkyl", "cyclic alkenyl", and "cyclic alkynyl" also include bicyclic, tricyclic, and higher cyclic structures, as well as the aforementioned cyclic structures further substituted with alkyl, alkenyl, and / or alkynyl groups. . Representative examples include, but are not limited to, norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecatrienyl, and the like.

Representative examples of X¹ include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chlorine, and acetoxy. Representative examples of X² and X³ include the representative examples listed above for X¹as well as hydrogen, methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl, cyclohexyl, and straight chain higher alkyl, such as butyl, hexyl, octyl, lauryl, and octadecyl, and the like.

Representative examples of R¹, R² and R³ include straight chain terminal alkyls, additionally terminal substituted at the other end, such as -CH2-, -CH2CH2-, -CH2CH2CH2-, and CH2CH2CH2CH2CH2CH2CH2CH2-, and their beta-substituted analogs, such as -CH2 (CH2) uCH (CH3) -, where u is zero to 17; the structure derivable from methallyl chloride, -CH2CH (CH3) CH2-; any of the structures derivable from divinylbenzene, such as -CH2CH2 (CgH4) CH2CH2- and -CH2CH2 (CgH4) CH (CH3) -, in which the notation C6H4 represents a disubstituted benzene ring; any of the structures derivable from diallyl ether, such as -CH2CH2CH2OCH2CH2CH2- and -CH2CH2CH2OCH2CH (CH3) -; any of the structures derivable from butadiene, such as -CH2CH2CH2CH2-, -CH2CH2CH (CH3) -, and -CH2CH (CH2CH3) -; any of the structures derivable from piperylene, such as -CH2CH2CH2CH (CH3) -, -CH2CH2CH (CH2CH3) -, and -CH2CH (CH2CH2CH3) -; any of the structures derivable from isoprene, such as -CH2CH (CH3) CH2CH2-, -CH2CH (CH3) CH (CH3) -, CH2C (CH3) (CH2CH3) -, -CH2CH2CH (CH3) CH2-, -CH2CH2C (CH3 ) 2- and -CH2CH [CH (CH3) 2] -; any of the isomers of -CH2CH2-norbornyl-, -CH2CH2-cyclohexyl-; any of the diradicals obtainable from norbornane, cyclohexane, cyclopentane, tetrahydrodicyclopentadiene, or cyclododecene, by loss of two hydrogen atoms; the structures derivable from limonene, -CH2CH (4-methyl-1-CeHg-) CH3, in which the notation C6H9 represents isomers of the trisubstituted cyclohexane ring lacking substitution at position 2; any of the monovinyl-containing structures derivable from trivinylcyclohexane, such as -CH2CH2 (vinylC6Hg) CH2CH2- and CH2CH2 (vinylC6Hg) CH (CH3) -, in which the notation CgHg represents any isomer of the trisubstituted cyclohexane ring; any of the monounsaturated structures derivable from myrcene containing a trisubstituted C = C, such as -CH2CH [CH2CH2CH = C (CH3) 2] CH2CH2-, -CH2CH [CH2CH2CH = C (CH3) 2] CH (CH3) -, 9

ES 2 373 344 T3

CH2C [CH2CH2CH = C (CH3) 2] (CH2CH3) -, -CH2CH2CH [CH2CH2CH = C (CH3)] CH2-, -CH2CH2 (C) (CH3) [CH2CH2CH = C (CH3) 2], and -CH2CH [ CH (CH3) [CH2CH2CH = C (CH3) 2]] -; and any of the monounsaturated structures derivable from myrcene lacking a trisubstituted C = C, such as CH2CH (CH = CH2) CH2CH2CH2C (CH3) 2-, -CH2CH (CH = CH2) CH2CH2CH [CH (CH3) 2] -, -CH2C (= CHCH3) CH2CH2CH2C (CH3) 2-, -CH2C (= CH-CH3) CH2CH2CH [CH (CH3) 2] -, -CH2CH2C (= CH2) CH2CH2CH2C (CH3) 2-, CH2CH2C (= CH2) CH2CH2CH [CH (CH3) 2] -, -CH2CH = C (CH3) 2CH2CH2CH2C (CH3) 2-, and CH2CH = C (CH3) 2CH2CH2CH [CH (CH3) 2].

Representative examples of G¹ include, but are not limited to, structures derivable from divinylbenzene, such as -CH2CH2 (C6H4) CH (CH2 -) -, -CH2CH2 (C6Hs-) CH2CH2-, and -CH2 (CH -) (C6H4) CH (CH2- ) -, in which the notation C6H4 represents a disubstituted benzene ring and C6H3- represents a trisubstituted ring; any structures derivable from trivinylcyclohexane, such as -CH2 (CH -) (vinylC6Hg) CH2CH2-; (-CH2CH2) 3C6Hg, and (CH2CH2) 2C6H₉CH (CH3) -, -CH2 (CH -) (vinylC6Hg) (CH-) CH2-, -CH2CH2C6H₉[(CH-) CH2-] 2, -CH (CH3) C6Hg [(CH-) CH2-] 2, and C6Hg [(CH-) CH2-] 3, -CH2 (CH-) C6Hg [CH2CH2-] 2 , and -CH2 (CH-) C6Hg [CH (CH3) -] [CH2CH2 -], in which the notation C6H9 represents any isomer of the trisubstituted cyclohexane ring.

Representative examples of G² include, but are not limited to, structures derivable from divinylbenzene, such as - CH2CH2 (C6H4) CH2CH2-, -CH2CH2 (C6H4) CH (CH2 -) -, - CH2CH2 (C6H3-) CH2CH2-, -CH2 (CH-) (C6H4) CH (CH2 -) -, in which the notation C6H4 represents a disubstituted benzene ring and C6H3- represents a trisubstituted ring; any of the structures derivable from trivinylcyclohexane such as -CH2CH2 (vinylC6H9) CH2CH2-, (CH2CH2) C6H9CH2CH3, -CH2 (CH -) (vinylC6H9) CH2CH2-, (-CH2CH2) 3C6H9, (-CH2CH2) 2C6H9 , -CH2 (CH) (vinylC6H9) (CH-) CH2-, -CH2CH2C6H9 [(CH-) CH2-] 2, -CH (CH3) C6H9 [(CH-) CH2-] 2, C6H9 [(CH-) CH2-] 3, -CH2 (CH) C6H9 [CH2CH2-] 2, and -CH2 (CH-) C6H9 [CH (CH3) -] [CH2CH2-], in which the notation C6H9 represents any isomer of the trisubstituted cyclohexane ring .

Representative examples of silated cyclic core polysulfurosilanes of the present invention include, but are not limited to, any of the isomers of 4- (6-triethoxysilyl-3-thiahexyl) -1,2-bis- (9-triethoxysilyl-3 , 4,5,6-tetrathianonyl) cyclohexane; 1- (6-triethoxysilyl-3-thiahexyl) -2,4-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 2- (6-triethoxysilyl-3-thiahexyl) -1,4-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 4- (1-methyl-5-triethoxysilyl-2-thiapentyl) -1,2-bis (1-methyl-8-triethoxysilyl-2,3,4,5-tetrathiaoctyl) cyclohexane; 4- (5-triethoxysilyl-3-thiapentyl) -1,2-bis- (8-triethoxysilyl-3,4,5,6-tetrathiaoctyl) cyclohexane; 4- (6-triethoxysilyl-3-thiahexyl) -1,2-bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane; 4- (6-triethoxysilyl-3-thiahexyl) -1,2-bis- (8-triethoxysilyl-3,4,5-trithiaoctyl) cyclohexane; 4- (6-triethoxysilyl-3-thiahexyl) -1,2-bis- (12-triethoxysilyl-3,4,5,6tetrathiadodecyl) cyclohexane; 1- (6-triethoxysilyl-3-thiahexyl) -2,4-bis- (11-triethoxysilyl-3,4,5,6-tetrathiaamericacyl) cyclohexane; 4- (3-triethoxysilyl-1-thiapropyl) -1,2-bis- (13-triethoxysilyl-3,4,5,6,7-pentathiatridecyl) cyclohexane; 4- (6-diethoxymethylsilyl-3-thiahexyl) -1,2bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 4- (4-triethoxysilyl-2-thiabutyl) -1,2-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 4- (7-triethoxysilyl-3-thiaheptyl) -1,2-bis- (9-triethoxysilyl-3,4,5-trithianonyl) cyclohexane; 4- (5-triethoxysilyl-

2-thiapentyl) -1,2-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) benzene; 4- (5-triethoxysilyl-2-thiapentyl) -1,2-bis- (9-triethoxysilyl-3,4,5-trithianonyl) benzene; 4- (5-triethoxysilyl-2-thiapentyl) -1,2-bis- (9-triethoxysilyl-3,4-dithianonyl) benzene; bis-2- [4- (3-triethoxysilyl-2-thiapropyl) -3- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexyl] ethyl tetrasulfide; bis-2- [4- (3-triethoxysilyl-1-thiapropyl) -3- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexyl] ethyl trisulfide; bis-2- [4- (3-triethoxysilyl-1-thiapropyl) -3- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexyl] ethyl disulfide; bis-2- [4- (6-triethoxysilyl-3-thiahexyl) -3- (9-triethoxysilyl-3,4,5-trithianonyl) phenyl] ethyl tetrasulfide; bis-2- [4- (6-triethoxysilyl-3-thiahexyl) -3- (9-triethoxysilyl-3,4,5-trithianonyl) natyl] ethyl tetrasulfide; Bis-2- [4- (4-diethoxymethylsilyl-2-thiabutyl) -3- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) phenyl] ethyl trisulfide; bis-2- [4- (1-methyl-5-triethoxysilyl-2-thiapentyl) -3- (7-triethoxysilyl-3,4-dithiaheptyl) cycloheptyl] ethyl disulfide; bis-2- [4- (4-triethoxysilyl-2-thiabutyl) -3- (7-triethoxysilyl-3,4-dithiaheptyl) cyclooctyl] ethyl disulfide; bis-2- [4- (4-triethoxysilyl-2-thiabutyl) -3- (7-triethoxysilyl-3,4-dithiaheptyl) cyclododecyl] ethyl disulfide, 4- (6-triethoxysilyl-3-thiahexyl) -1, 2-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 2- (6-triethoxysilyl-3-thiahexyl) -1,4-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 1- (6-triethoxysilyl-3-thiahexyl) -2,4-bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane; 4- (6-triethoxysilyl-3-thiahexyl) -1,2-bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane;

2- (6-triethoxysilyl-3-thiahexyl) -1,4-bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane; 1- (6-triethoxysilyl-3-thiahexyl) -2,4-bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane; and their mixtures.

In another embodiment of the present invention, formulas (1), (2) and (3) are described, in which each case of R¹ and R³is independently selected from a divalent hydrocarbon fragment having 1 to about 5 carbon atoms including straight and branched chain alkyl, alkenyl, alkynyl, aryl, or aralkyl groups in which one hydrogen atom is replaced by a Y group¹ or Y²; each case of Y¹ and Y² is chosen independently of silyl (-SiX¹, X², X³); each case of R² is a straight chain hydrocarbon group represented by - (CH2) f-, where f is an integer from about 0 to about 5; each case of R⁴ is independently chosen from a polyvalent cyclic hydrocarbon fragment of 5 to about 12 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a + c + e, and includes cyclic alkyl or aryl in which they have been substituted a + c + e - 1 hydrogens; each case of R⁵ is independently chosen from a polyvalent hydrocarbon fragment of 5 to about 12 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c + e, and includes straight chain alkyl, alkenyl, alkynyl, aryl and aralkyl groups and branched in which c + e-1 hydrogens have been substituted; each case of X¹ independently chosen from any of the f hydrolyzable groups selected from -OH and -OR⁶, in which R⁶ is any monovalent hydrocarbon group having 1 to 5 carbon atoms, and includes alkyl groups, 10

ES 2 373 344 T3 straight or branched chain alkenyl, aryl or aralkyl; each case of X² and X³ is chosen independently of R⁶as defined for this embodiment, and any of X¹ as defined for this embodiment, and -OSi-containing groups that result from the condensation of silanols; each case of the subscripts a, b, c, d, e, f, m, n, o, p, and x, is given independently by a is 1 to about 2; b is 1 to about 3; c is 1; d is 1 to about 3; e is 1; f is 0 to about 5; m is 1; n is 1 to about 10; o is 0 to about 1; p is 1, and x is 1 to about 6.

According to another embodiment of the present invention, 30 to 99 weight percent of the silated core polysulfide of the filler composition of the present invention is mixed with 70 to 1 weight percent of another silane, including silanes of the structure depicted in the Formula (4)

[X¹X²X³Sir¹SxR³SiX¹X²X³] (4) in which each case of R¹ and R³ is independently chosen from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms that includes straight and branched chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups, in which one hydrogen atom was replaced by a silyl group , (-SiX¹X²X³), where X¹ independently chosen from any of the hydrolyzable groups selected from -Cl, -Br, -OH, -OR⁶, and R⁶C (= O) O-, where R⁶ is any monovalent hydrocarbon group having 1 to 20 carbon atoms, and includes a straight or branched chain alkyl, alkenyl, aryl or aralkyl group, and X² and X³ are taken independently of hydrogen, R⁶ as defined for this embodiment, any of X¹ as defined above, and -OSi-containing groups resulting from the condensation of silanols. This mixture of the silated core polysulfide of Formula (1) and the other silanes of Formula (4) corresponds to a weight ratio of about 0.43 to 99. In another embodiment, the mixture of the silated core polysulfide of Formula ( 1) and the other silanes of Formula (4) is in a weight ratio of about 1 to 19.

Representative examples of this silane described by Formula 4 are set forth in US Pat. 3,842,111, which is incorporated herein by reference, and includes bis- (3-triethoxysilylpropyl) disulfide; bis- (3-triethoxysilylpropyl) trisulfide; bis- (3-triethoxysilylpropyl) tetrasulfide; bis- (3-triethoxysilylpropyl) pentasulfide; bis (3-diethoxymethylsilylpropyl) disulfide; bis-triethoxysilylmethyl disulfide; bis- (4-triethoxysilylbenzyl) disulfide; bis- (3-triethoxysilylphenyl) disulfide; and the like.

The bonding of sulfur to a methylene group in R⁴ and R⁵ it is desired because the methylene group mitigates excessive steric interactions between the silane and the filler and polymer. Two successive methylene groups further mitigate steric interactions, and also add flexibility to the silane's chemical structure, thus enhancing its ability to accommodate orientation and positional constraints imposed by both rubber and filler surface morphologies in the interface, at the molecular level. The flexibility of silane becomes increasingly important as the total number of silicon and sulfur atoms attached to G¹ and G² increases from 3 to 4 and beyond. Structures in which the polysulfide group is directly attached to secondary and tertiary carbon atom ring structures, especially aromatic structures, are rigid and sterically hindered. Accelerators and curing agents cannot easily target themselves with the polysulfide group to effect the reaction, and the silated core polysulfide cannot readily target itself to satisfy the available binding sites on the silica and polymer. This would tend to leave sulfur groups unbound to the polymer, thereby reducing the efficiency by which the principle of multiple silane-to-polymer bonding via multiple sulfur groups on the silane is carried out.

The use of a sulfide group to attach the silicic group to the nucleus, -SR²SiX¹X²X³, provides a convenient and cost effective way to link the silyl group to the core. The sulfide group is less reactive than the polysulfide groups of the present invention, and therefore less likely to break during curing than rubbers containing the polysulfides with silated cyclic nuclei. The bonding of the sulfide of the silyl group to the nucleus also makes it easier to synthesize molecules with different lengths of the R² relative to R¹and R³, and therefore optimize the chemical structure of polysulfides with silated cyclic nuclei to achieve a bond between the inorganic filler, such as silica, and the rubber.

The function of the other silanes in the filler is to occupy sites on the surface of the silica that help disperse the silica and dock with the polymer.

The fillers of the present invention can be used as supports for liquid silanes and reinforcing fillers for elastomers, in which the silated core polysulfide is capable of reacting or bonding with the surface of elastomers. Supported fillers should not be reactive with the silated core polysulfide. The non-reactive nature of the fillers is demonstrated by the ability of the silated core polysulfide to be extracted over 50 percent of the charged silane using an organic solvent. The extraction procedure is given in US Patent 6,005,027. Supports include, but are not limited to, porous organic polymers, carbon black, diatomaceous earth, and silicas that are characterized by a relatively low differential of less than 1.3 between infrared absorbance at 3502 cm.^-2 of silica when taken at 105 ° C and when taken at 500 ° C, as described in US patent 6,005,027. In one embodiment, the amount of core polysulfide

ES 2 373 344 T3 silated and optionally the other silanes of Formula (4) that can be loaded onto the support is between 0.1 and 70 percent by weight. In another embodiment, the silated core polysulfide and optionally the other silanes of Formula (4) can be loaded onto the support at concentrations between 10 and 50 percent by weight. In still another embodiment, the filler is a particulate filler.

Reinforcing fillers useful in the present invention include fillers in which the silanes are reactive with the surface of the filler. Representative examples of fillers include, but are not limited to, inorganic fillers, siliceous fillers, metal oxides such as silica (pyrogenic and / or precipitated), titanium, aluminosilicate and alumina, clays and talc, and the like. Precipitated, particulate silica is useful for this purpose, particularly when the silica has reactive surface silanols. In one embodiment of the present invention, a combination of 0.1 to 20 percent silated core polysulfide is used, and optionally the other silanes of Formula (4), and 80 to 99.9 percent silica or other fillers. reinforcers for reinforcing various rubber products, including tire treads. In another embodiment, a filler comprises from about 0.5 to about 10 percent silated core polysulfide of Formula (1), and optionally a second silane of Formula (4), and about 90 to about 99, 5 weight percent particulate filler. In another embodiment of the present invention, alumina may be used alone with the silated core polysulfide, or in combination with silica and the silated core polysulfide. The term alumina can be described herein as aluminum oxide, or Al2Ü3. In a further embodiment of the present invention, the fillers can be in hydrated form.

Mercury porosity surface area is the specific surface area determined by mercury porosimetry. Using this method, the mercury penetrates the pores of the sample after heat treatment to remove volatiles. The mounting conditions can be adequately described using a sample of about 100 mg; removing volatiles for about 2 hours at about 105 ° C and atmospheric pressure; and an ambient pressure measurement range up to about 2000 bar. Such an evaluation can be carried out according to the method described in Winslow, Shapiro in ASTM bulletin, p. 39 (1959), or according to DIN 66133. For such evaluation, a CARLO-ERBA Porosimeter 2000 can be used. The mean specific surface porosity with mercury for silica should be in the range of about 100 to about 300 µm.²/ g.

The pore size distribution for silica, alumina, and aluminosilicate based on such mercury porosity evaluation is here considered to be such that five percent or less of their pores have a diameter less than about 10 nm, about 60 to about 90 percent of its pores are about 10 to about 100 nm in diameter, about 10 to about 30 percent of its pores are about 100 to about 1,000 nm in diameter, and about 5 to about 20 percent of its pores are larger than about 1,000 nm in diameter.

Silica can be expected to have an ultimate average particle size, for example in the range of about 10 to about 50 nm, as determined by electron microscopy, although silica particles can be even smaller, or possibly larger. , in size. For use in this invention, various commercially available silicas may be considered, such as those from PPG Industries under the trademark HI-SIL under the designations HI-SIL 210, 243, etc .; silicas available from Rhone-Poulenc, under, for example, the designation ZEOSIL 1165MP; silicas available from Degussa under, for example, the designations vN2 and VN3, etc., and silicas commercially available from Huber, having, for example, a designation of HUBERSIL7 8745.

In one embodiment of the invention, filler compositions may utilize silated cyclic core polysulfide with fillers such as silica, alumina, and / or aluminosilicates in combination with carbon black reinforcing pigments. In another embodiment of the invention, the filler compositions may comprise a mixture of particulate fillers of about 15 to about 95 weight percent siliceous filler, and about 5 to about 85 weight percent black. of carbon, and 0.1 to about 19 weight percent silated cyclic core polysulfide, where the carbon black has a CTAB value in a range of about 80 to about 150. In still another embodiment of the invention, it is desirable to use a weight ratio of siliceous fillers to carbon black of at least about 3 to 1. In still another embodiment, a weight ratio of siliceous fillers to carbon black of at least about 10 to 1. In still another embodiment of the present invention, the weight ratio of siliceous fillers to carbon black may range from 3 to 1 to about 30 to 1.

In one embodiment of the invention, the filler may comprise from about 60 to about 95 weight percent silica, alumina, and / or aluminosilicate, and correspondingly from about 40 to about 5 weight percent silica black. smoke and about 0.1 to 20 weight percent silated cyclic core polysulfide of the present invention, and optionally a second silane, provided that the mixture of the components add up to 100 percent. The siliceous filler and carbon black can be premixed, or they can be mixed together in the manufacture of vulcanized rubber.

The filler can be essentially inert to the silane with which it is mixed, as is the case with carbon black or organic polymers, or it can be reactive with it, for example the case with supports that possess functionality.

ES 2 373 344 T3 metallic hydroxyl surface, for example silicas and other siliceous particles which possess silanol functionality on the surface.

According to yet another embodiment of the present invention, there is provided a rubber composition, such as for use in tires, comprising:

(a) a rubber component;

(b) a free-flowing filler composition with a silated cyclic core polysulfide of Formula (1);

(c) and optionally a second silane, such as the silanes according to Formula (4).

The silated cyclic core polysulfurosilane or polysulfurosilanes, and optionally other silane coupling agents, may be premixed or pre-reacted with the filler particles prior to addition to the rubber blend, or they may be added to a rubber blend. during rubber processing and loading, or mixing stages. If the silated cyclic core polysulfurosilanes and optionally other silanes and filler are added separately to the rubber mixture during rubber mixing and filler, or the processing step, the silated cyclic core polysulfurosilane or polysulfurosilanes are considered to be it then combines in an on-site manner with the load.

In accordance with yet another embodiment of the present invention, there is provided a cured or uncured rubber composition, such as for use in tires, comprising:

(a) a rubber component;

(b) a free-flowing filler composition with a silated cyclic core polysulfide of Formula (1);

(c) optionally silanes, such as silanes of Formula (4);

(d) curing agents; and (e) optionally, other additives.

Rubbers useful in the filler compositions of the present invention include sulfur vulcanizable rubbers, including homopolymers and copolymers of conjugated dienes, and copolymers of at least one conjugated diene and an aromatic vinyl compound. Organic polymers suitable for the preparation of rubber compositions are well known in the art, and are described in various textbooks, including The Vanderbilt Rubber Handbook, Ohm, RF, RT Vanderbilt Company, Inc., 1990, and in the Manual for the Rubber Industry, Kemperman, T and Koch, S. Jr., Bayer AG, LeverKusen, 1993.

In one embodiment of the present invention, the polymer for use herein is a solution prepared styrene-butadiene rubber (SSBR). In another embodiment of the invention, the SSBR prepared in solution typically has a bound styrene content in the range of 5 to about 50 percent, and in another embodiment of about 9 to about 36 percent. According to another embodiment of the present invention, the polymer can be selected from the group consisting of emulsion-prepared styrene-butadiene rubber (ESBR), natural rubber (NR), ethylene-propylene copolymers and terpolymers (EP, EPDM), rubber of acrylonitrilobutadiene (NBR), polybutadiene (BR), and the like, and mixtures thereof.

In one embodiment, the rubber composition comprises at least one diene-based rubber or elastomer. Suitable conjugated dienes include, but are not limited to, isoprene and 1,3-butadiene; and suitable vinyl aromatic compounds include, but are not limited to, styrene and alpha-methylstyrene. Polybutadiene can be characterized as existing primarily, typically about 90% by weight, in the form of cis-1,4-butadiene, but other compositions can also be used for the purposes described herein.

Thus, the rubber is a sulfur curable rubber. Such a diene-based elastomer, or rubber, may be selected, for example, from at least one of cis-1,4-polyisoprene rubber (natural and / or synthetic), styrene / butadiene copolymer rubber prepared by polymerization emulsion, styrene / butadiene rubber prepared by polymerization in organic solution, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis-1,4-polybutadiene, medium vinyl polybutadiene rubber (35-50 percent vinyl), high vinyl polybutadiene rubber (50-75 percent vinyl), styrene / isoprene copolymers, styrene / butadiene terpolymer rubber / acrylonitrile prepared by emulsion polymerization, and butadiene / acrylonitrile copolymer rubber. For some applications, an emulsion polymerization derived styrene / butadiene (ESBR) may be used that has a relatively conventional styrene content of about 20 to 28 percent bound styrene, or an ESBR that has a medium to relatively high content. styrene bound about 30 to 45 percent.

ES 2 373 344 T3

Styrene / butadiene / acrylonitrile terpolymer rubbers prepared by emulsion polymerization, containing 2 to 40 weight percent acrylonitrile bound in the terpolymer, are also contemplated as diene-based rubbers for use in this invention.

The vulcanized rubber composition should contain a sufficient amount of filler composition to contribute a reasonably high modulus and high tear resistance. In one embodiment of the present invention, the combined weight of the filler composition can be as low as about 5 to about 120 parts per hundred parts of rubber (phr), or about 5 to about 100 pphr. In another embodiment, the combined weight of the filler composition is from about 25 to about 85 phr, and in another embodiment at least one precipitated silica is used as the filler. Silica can be characterized as having a specific surface area of ​​BET, as measured using nitrogen gas, in the range of about 40 to about 600 µm.²/ g. In one embodiment of the invention, silica has a specific surface area for BET in a range of about 50 to about 300 µm.²/ g. The BET method for measuring specific surface area is described in the Journal of the American Chemical Society, Volume 60, page 304 (1930). Silica can also typically be characterized as having a dibutyl phthalate (DBP) absorption value in a range of about 100 to about 350, and more usually about 150 to about 300. Furthermore, silica, as well as the alumina and aluminosilicate mentioned above, is expected to have a CTAB surface area in a range of about 100 to about 220. The CTAB surface area is the outer surface area as measured by cetyltrimethylammonium bromide with a pH of about 9. The method is described in ASTM D 3849.

The rubber compositions of the present invention can be prepared by mixing one or more silated cyclic core polysulfurosilanes and optionally other silanes with the organic polymer before, during or after formation of the filler composition in the organic polymer. Silated cyclic core polysulfurosilanes, and optionally other silanes, can also be added before or during the formation of the filler composition in the organic polymer, because these silanes facilitate and improve the dispersion of the filler. In another embodiment, the total amount of silated cyclic nucleus polysulfurosilane present in the resulting blend should be from about 0.05 to about 25 parts by weight per hundred parts by weight of organic polymer (phr); and 1 to 10 phr in another embodiment. In still another embodiment, the fillers can be used in amounts ranging from about 5 to about 120 phr, about 5 to about 100 phr, or about 25 to about 80 phr, and in still another embodiment from about from 25 to around 110, or around 25 to around 105.

In practice, sulfur vulcanized rubber products are prepared by thermomechanically mixing rubber and various ingredients in a sequential stepwise manner, followed by shaping and curing the formed rubber to obtain a vulcanized product. First, for the aforementioned mixing of rubber and various ingredients, typically exclusive sulfur and vulcanization accelerators with sulfur (collectively, curing agents), the rubber or rubbers and various ingredients are mixed to compose the rubber into at least one , and often (in the case of silica-loaded low rolling resistance tires) two or more preparatory thermomechanical mixing stage or stages in suitable mixers. Such preparatory mixing is called non-productive mixing or non-productive mixing steps. Such preparatory mixing is usually carried out at temperatures of from about 140 ° C to about 200 ° C, and for some compositions at around 150 ° C to about 170 ° C. Subsequent to such preparatory mixing steps, in a final mixing step, sometimes referred to as the productive mixing step, curing agents, and possibly one or more additional ingredients, are mixed with the rubber compound or composition, at lower temperatures of typically around 50 ° C to around 130 ° C in order to avoid or delay premature curing of the sulfur curable rubber, sometimes referred to as charring. The rubber mixture, also referred to as a rubber compound or composition, is typically allowed to cool, sometimes after or during an intermediate mill mixing of the process, between the various mixing steps mentioned above, for example to a temperature of about 50 ° C or lower. When it is desired to mold and cure the rubber, the rubber is placed in the appropriate mold at a temperature of at least about 130 ° C and up to about 200 ° C, which will cause vulcanization of the rubber by the groups containing a bond. SS (ie disulfide, trisulfide, tetrasulfide, etc .; polysulfide) in the polysulfurosilanes with silated nuclei and any other free sulfur sources in the rubber mixture.

Thermomechanical mixing refers to the phenomenon whereby, under high shear conditions in a rubber mixer, the shear forces and associated friction that appear as a result of mixing the rubber compound, or some mixture of the rubber compound itself, and the ingredients that make up the rubber, in the high shear mixer, the temperature increases autogenously, that is, it is "heated". Various mechanical reactions can occur at various stages in the mixing and curing processes.

The first reaction is a relatively fast reaction, and is considered here to take place between the charge and the silicon alkoxide group of polysulfides with silated cyclic nuclei. Such a reaction can occur at a relatively low temperature, such as, for example, around 120 ° C. The second reaction is considered

ES 2 373 344 T3 herein which is the reaction that takes place between the sulfur-containing portion of the silated cyclic core polysulfurosilane and the sulfur vulcanizable rubber at a higher temperature, for example above about 140 ° C.

Another source of sulfur can be used, for example in the form of elemental sulfur, such as, but not limited to, S8. A sulfur donor is considered herein as a sulfur-containing compound that releases free or elemental sulfur, at a temperature in a range from about 140 ° C to about 190 ° C. Such sulfur donors can be, for example, but are not limited to, polysulfide vulcanization accelerators and organosillanic polysulfides with at least two connecting sulfur atoms in their polysulfide bridge. The amount of free sulfur source addition to the mixture can be controlled or manipulated as a matter of choice relatively independently of the addition of the aforementioned silated cyclic core polysulfurosilane. Thus, for example, the independent addition of a sulfur source can be manipulated by the amount of addition thereof and by the sequence of addition relative to the addition of other ingredients to the rubber mixture.

In one embodiment of the invention, the rubber composition may therefore comprise about 100 parts by weight (phr) of at least one sulfur vulcanizable rubber selected from homopolymers and copolymers of conjugated dienes, and copolymers of at least one conjugated diene. and vinyl aromatic compound, and about 5 to 100 phr, preferably about 25 to 80 phr of at least one filler, up to about 5 phr of a curing agent, and about 0.05 to about 25 phr of at least one silated cyclic core polysulfurosilane as described in the present invention.

In another embodiment, the filler composition comprises from about 1 to about 85 weight percent carbon black based on the total weight of the filler composition, and up to about 20 parts by weight of at least one polysulfurosilane with silated cyclic core of the present invention based on the total weight of the filler composition, including about 2 to about 20 parts by weight of at least one silated cyclic core polysulfurosilane of the present invention based on the total weight of the filler composition.

The rubber composition is prepared by first mixing rubber, filler and silated cyclic core polysulfurosilane, or rubber, filler pretreated with all or a portion of the silated cyclic core polysulfurosilane and any remaining silated cyclic core polysulfurosilane, in a first mixing step. thermomechanical at a temperature of around 140 ° C to around 200 ° C for around 2 to around 20 minutes. The fillers can be pretreated with all or a portion of the silated cyclic core polysulfurosilane and any remaining silated cyclic core polysulfurosilane, in a first thermomechanical mixing step at a temperature of about 140 ° C to about 200 ° C for about 4 to 15 minutes. Optionally, the curing agent is then added in another thermomechanical mixing step at a temperature of about 50 ° C, and mixed for about 1 to about 30 minutes. The temperature is then heated again to between about 139 ° C and about 200 ° C, and cure is achieved in about 5 to about 60 minutes.

In another embodiment of the present invention, the process may also comprise the additional steps of preparing an assembly of a sulfur vulcanizable rubber or tire with a tread made of the rubber composition prepared according to this invention, and vulcanizing the assembly to a temperature in a range of about 130 ° C to about 200 ° C.

Other optional ingredients may be added in the rubber compositions of the present invention, including curing aids, i.e., sulfur compounds, activators, retarders and accelerators, processing additives such as oils, plasticizers, tackifying resins, silicas, others. fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents, reinforcing materials such as, for example, carbon black, etc. Such additives are selected based on the intended use and the sulfur vulcanizable material selected for use, and such selection is within the knowledge of one of skill in the art, as are the required amounts of such additives known to one of ordinary skill in the art. skill in the art.

Vulcanization can be carried out in the presence of additional sulfur vulcanizing agents. Examples of suitable sulfur vulcanizing agents include, for example, elemental sulfur (free sulfur) or sulfur donating vulcanizing agents, for example an aminodisulfide, polymeric polysulfide or adducts of sulfur with olefins which are conventionally added in the mixing step. of the final productive rubber composition. Sulfur vulcanizing agents, which may be common in the art, are used or added in the productive mixing stage in an amount ranging from about 0.4 to about 3 phr, or even, in some circumstances, up to about 8 phr, with a range of about 1.5 to about 2.5 phr and all subranges in between in one embodiment from 2 to about 2.5 phr and all subranges in between in another embodiment.

Optionally, vulcanization accelerators, i.e. additional sulfur donors, can be used here. I know

ES 2 373 344 T3 appreciates that it may include the following examples, benzothiazole, alkylthiuram disulfide, guanidine derivatives and thiocarbamates. Representatives of such accelerators may be, but are not limited to, mercaptobenzothiazole (MBT), tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), benzothiazole disulfide (MBTS), diphenylguanidine (DPG), zinc dithiocarbamate (ZBEC ), alkylphenol disulfide, zinc isopropylxanthate (ZIX), N-dicyclohexyl-2-benzothiazolsulfenamide (DCBS), N-cyclohexyl-2-benzothiazolsulfenamide (CBS), N-tert-buyl-2benzothiazolsulfenamide (TBBS), N-tert-buyl-2-benzothiazolsulfenimide (TBSI), tetrabenzylthiuram disulfide (TBzTD), tetraethylthiuram disulfide (TETD), N-oxydyethylenebenzothiazole-2-sulfenamide, N, N-diphenylthiourea, dithio-benzyl-2-amylsulfide, dithiocarbamylsulfide -sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-beta-hydroxyethylpiperazine) and dithiobis (dibenzylamine). Other additional sulfur donors can be, for example, thiuram and morpholine derivatives. Representative of such donors are, for example, but not limited to, dimorpholine disulfide, dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiacyl-2, N-dithiomorpholide, thioplasts, dipentamethylenethiuram hexasulfide, and disulfurocaprolactam.

Accelerators are used to control the time and / or temperature required for vulcanization, and to improve the properties of the vulcanizate. In one embodiment, a single throttle system can be used, that is, a main throttle. Conventionally, a main accelerator or accelerators are used in total amounts ranging from about 0.5 to about 4 phr and all sub-ranges in between in one embodiment, and about 0.8 to about 1.5 phr and all the subintervals in between in another embodiment. Combinations of a primary and secondary accelerator can be used, with the secondary accelerator being used in smaller amounts (from about 0.05 to about 3 phr and all sub-ranges in between) in order to activate and improve the properties of the vulcanizate. Delayed action accelerators can be used. Vulcanization retarders can also be used. Suitable types of accelerators are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthates. In one embodiment, the primary accelerator is a sulfenamide. If a second accelerator is used, the second accelerator can be a guanidine, dithiocarbamate, and / or thiuram compounds. Preferably, tetrabenzylthiuram disulfide is used as secondary accelerator, in combination with N-tert-buil-2-benzothiazolsulfenamide with or without diphenylguanidine. Tetrabenzylthiuram disulfide is a preferred accelerator since it does not lead to the production of nitrosating agents, such as, for example, tetramethylthiuram disulfide.

Typical amounts of tackifying resins, if used, comprise about 0.5 to about 10 phr and all subranges in between, usually about 1 to about 5 phr and all subranges in between. Typical amounts of processing aids comprise about 1 to about 50 phr and all subranges in between. Such processing aids can include, for example, aromatic, naphthenic, and / or paraffinic processing oils. Typical amounts of antioxidants comprise about 1 to about 5 phr. Representative antioxidants can be, for example, diphenyl-pphenylenediamine and others, such as, for example, those described in the Vanderbilt Rubber Handbook (1978), pages 344-346. Typical amounts of antiozonants comprise about 1 to about 5 phr and all subranges in between. Typical amounts of fatty acids, if used, which may include stearic acid, comprise about 0.5 to about 3 phr and all sub-ranges in between. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr and all sub ranges in between. Microcrystalline waxes are often used. Typical amounts of peptizers comprise about 0.1 to about 1 phr and all subranges in between. Typical peptizers can be, for example, pentachlorothiophenol and dibenzamidophenyl disulfide.

The rubber compositions of this invention can be used for various purposes. For example, it can be used for various tire compounds, waterproofing weatherstripping, and shoe soles. In one embodiment of the present invention, the rubber compositions described herein are particularly useful in tire treads, but can also be used for all other parts of the tire as well. Tires can be built, molded, shaped and cured by various methods that are known and will be readily apparent to those skilled in the art.

Preferred compositions include those compositions useful for the manufacture of tires or tire components, including vehicle tires, and include rubber compositions that include at least one vulcanizable rubber and at least one preformed filler. The fillers included in the preformed fillers may include, by way of non-limiting example, carbon blacks, silicas, silicon-based fillers, and metal oxides present either alone or in combinations. For example, an active filler can be selected from the group described above (e.g., carbon blacks, silicas, silicon-based fillers, and metal oxides), and may be present, but need not be, in a combined amount of at least less 35 parts by weight per 100 parts by weight of total vulcanizable rubber, of which at least 10 parts may be carbon black, silica, or some combination thereof, and wherein said compositions can be formulated such that they are vulcanizable to form a tire component compound. The tire component compounds may have a Shore A hardness of not less than 40 and not greater than 95, and a glass transition temperature Tg (E "max) of not less than -80 ° C and not greater than 0 ° C. Shore A hardness is measured according to DIN 53505. The glass transition temperature Tg (E "max) is measured according to DIN 53513, with a specific temperature sweep of -80 ° C to + 80 ° C and a specific compression of 10 ± 0.2% at 10 Hz. Preferably, rubber comprises vulcanizable rubbers

ES 2 373 344 T3 selected from natural rubbers, synthetic polyisoprene rubbers, polyisobutylene rubbers, polybutadiene rubbers, styrene-butadiene rubbers (SBR) randomly, and mixtures thereof. In addition, an active load includes a load that is interactive with the rubber or tire composition and itself, and changes properties of the rubber or tire composition.

EXAMPLES

The examples presented below demonstrate significant advantages of the silated cyclic core polysulfides described herein relative to those of the art currently in practice, and their performance as coupling agents in silica loaded rubber.

Example 1

Preparation of mixture of (6-triethoxysilyl-3-thia-1-hexyl) -bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane, related oligomers and bis- (3-triethoxysilylpropyl) polysulfide.

This example illustrates the preparation of a silated cyclic nucleus disulfide from a nucleus containing three vinyl groups through the formation of an intermediate thioacetatosilane. Tris- (4-oxo-3-thiapentyl) cyclohexane was prepared by reacting thioacetic acid with trivinylcyclohexane. In a 5 L three necked round bottom flask, equipped with a magnetic stir bar, temperature probe / controller, heating mantle, addition funnel, condenser, and air inlet, 1 , 2,4-trivinylcyclohexane (779 grams, 4.8 moles) and t-butyl peroxide (8.0 grams, 0.055 moles). Freshly distilled thioacetic acid (1297 grams, 16.8 moles) was added via addition funnel, over a 30 minute period. The temperature rose from room temperature to 59 ° C. The reaction mixture was allowed to cool to room temperature, t-butyl peroxide (25.3 grams, 0.173 mole) was added in two increments, and the reaction mixture was heated overnight at 75 ° C. After cooling to 42 ° C, air was bubbled into the reaction mixture, and exotherm was observed. The mixture was stirred overnight at 75 ° C, and then cooled to room temperature. The reaction mixture was steam-stripped to remove any low-boiling species, under reduced pressure and a maximum temperature of 135 ° C, to give the final product (1866 grams, 4.77 moles). The yield was 99 percent.

1,2,4-tris- (2-mercaptoethyl) cyclohexane was prepared by removing the acyl group. In a 5 L three-necked round bottom flask equipped with a magnetic stir bar, temperature probe / controller, heating mantle, addition funnel, distillation head and condenser, and inlet of nitrogen, tris- (4-oxo-3-thiapentyl) cyclohexane (1866 grams, 4.77 moles), and absolute ethanol (1219 grams, 26.5 moles) were charged. Sodium ethoxide in ethanol (99 grams of 21% sodium ethoxide, purchased from Aldrich Chemical) was added in five increments. The reaction mixture was heated, and the ethanol and ethyl acetate were removed. Ethanol (785 grams) was added, and the ethyl acetate and ethanol were distilled from the mixture at atmospheric pressure. Ethanol (1022 grams) was added to the mixture, and the ethyl acetate, ethanol, and low-boiling components were distilled from the mixture under reduced pressure at 73 ° C. The mercaptan intermediate (1,161 grams, 4.5 moles) was used in the next step for the synthesis. The yield was 93 percent.

Bis- (2-mercaptoethyl) (6-triethylsilyl-3-thia-1-hexyl) cyclohexane was prepared by reacting the trimercaptan intermediate with 3-chloropropyltrietioxysilane. In a 3 L, three necked round bottom flask equipped with a magnetic stir bar, temperature probe / controller, heating mantle, addition funnel, condenser, air inlet and scrubber. Sodium hydroxide 1,2,4-tris- (2-mercaptoethyl) cyclohexane (450 grams, 1.7 moles) were charged. Sodium ethoxide in ethanol (421 grams of 21% sodium ethoxide, purchased from Aldrich Chemical) was added over two hours. 3-Chloropropyltriethoxysilane (410 grams, 1.7 moles) was added slowly over a period of 2 hours, and then refluxed for 14 hours. An additional aliquot of 3-chloropropyltriethoxysilane (42.5 grams, 0.18 mole) was added, heated for 2.5 hours at 79 ° C, cooled, and then filtered. The crude product was distilled off under reduced pressure. The fraction that boiled between 191 and 215 ° C was collected (343 grams, 0.73 mol) and used in the next step of the synthesis. The yield of the product was 43 percent.

The product, (6-triethoxysilyl-3-thia-1-hexyl) -bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane, was prepared by reacting the silated dimercaptan intermediate with sulfur and 3-chloropropyltriethoxysilane. In a 3 L three necked round bottom flask equipped with a magnetic stir bar, temperature probe / controller, heating mantle, addition funnel, distillation head and condenser, and inlet of nitrogen, bis- (2-mercaptoethyl) (6-triethylsilyl-3-thia-1-hexyl) cyclohexane (326 grams, 0.7 mole), sodium ethoxide in ethanol (451 grams of 21% sodium ethoxide, purchased from Aldrich Chemical), sulfur powder (45 grams, 1.4 moles) and absolute ethanol (352 grams), and refluxed for 3 hours. 3-Chloropropyltriethoxysilane (336 grams,

1.4 moles), refluxed for 72 hours, cooled and filtered using a fritted glass filter with a pore size of 25-50 microns. The solids were washed with toluene, the organic layers were combined and steam stripped to remove the light ones. The final product (635 grams, 0.7 mole) was analyzed by HPLC. The chromatogram, shown in Figure 1, indicated a mixture of monomeric and

ES 2 373 344 T3 oligomers.

An isomer of (6-triethoxysilyl-3-thia-1-hexyl) -bis- (7-triethoxysilyl-3,4-dithiaheptyl) cyclohexane has the following structure:

<img file="ES2373344T3_D0001.tif" />

Example 2

Preparation of mixture of (6-triethoxysilyl-3-thia-1-hexyl) -bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane, related oligomers and bis- (3-triethoxysilylpropyl) polysulfide.

The silane dimercaptan intermediate, (6-triethoxysilyl-3-thia-1-hexyl) -bis- (2-mercaptoethyl) cyclohexane, was prepared by the procedure described in Example 1.

The product, mixture of (6-triethoxysilyl-3-thia-1-hexyl) -bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane, related oligomers and bis- (3-triethoxysilylpropyl) polysulfide, It was prepared by reacting the dimercaptan silane with base, sulfur and 3-chloropropyltriethoxysilane. In a 2 L three-necked round bottom flask equipped with a magnetic stir bar, temperature probe / controller, heating mantle, addition funnel, distillation head and condenser, and inlet of nitrogen, bis- (2-mercaptoethyl) (6-triethylsilyl-3thia-1-hexyl) cyclohexane (249.7 grams, 0.53 moles), sodium ethoxide in ethanol (345.2 grams of sodium ethoxide at 21 %, purchased from Aldrich Chemical), sulfur powder (102.5 grams, 3.2 moles) and absolute ethanol (250 grams), and refluxed for 24 hours. 3-Chloropropyltriethoxysilane (256.5 grams, 1.07 mol) was added, refluxed for 72 hours, cooled and then filtered using a 3.5 micron asbestos filter. The final product (487.4 grams, 0.47 mole, 88 percent yield) was analyzed by HPLC. The chromatogram indicated a mixture of products.

An isomer of (6-triethoxysilyl-3-thia-1-hexyl) -bis- (9-triethoxysilyl-3,4,5,6-tetrathianonyl) cyclohexane has the following structure:

<img file="ES2373344T3_D0002.tif" />

Comparative Example AC, Examples 3-5

The use of silanes in a low rolling resistance tire tread formulation.

A model low rolling resistance passenger tire tread formulation as described in Table 1 and a mixing procedure were used to evaluate representative examples of the silanes of the present invention. The silane in Example 2 was mixed as follows in a BANBURY® "B" mixer (Farrell Corp.) with a chamber volume of 103 cubic inches (1,690 cc). The mixing of the rubber was carried out in two stages. The mixer was turned on with the mixer at 80 rpm and the cooling water at 71 ° C. The rubber polymers were added to the mixer and force mixed for 30 seconds. The silica and the other ingredients in the Master Mix from Table 1, except for the silane and the oils, were added to the mixer and force mixed for 60 seconds. The mixer speed was reduced to 35 rpm, and then the silane and oils from the Master Mix were added to the mixer and force mixed for 60 seconds. The throat of the mixer was filled with powder and the ingredients were force mixed until the temperature reached 149 ° C. The ingredients were then mixed for an additional 3 minutes and 30 seconds. The speed of the mixer was adjusted to maintain the temperature between 152 and 157 ° C. The rubber was emptied (removed from mixer), sheeted on a laminator set at about 85 ° C to 88 ° C, and then allowed to cool to room temperature.

In the second stage, the Master Mix was reloaded into the mixer. The mixer speed was 80 rpm, the cooling water was set at 71 ° C, and the batch pressure was set at 6 MPa. The masterbatch was force mixed for 30 seconds, and then the temperature of the masterbatch was brought to 149 ° C, and then the mixer speed was reduced to 32 rpm and the rubber was mixed for 3 minutes and 20 seconds. at temperatures between 152 ° C and 157 ° C. After mixing, the rubber was emptied (removed from the mixer), sheeted on a sheeter set at about 85 ° C to 88 ° C, and then allowed to cool to

ES 2 373 344 T3 room temperature.

The rubber masterbatch and curing agents were mixed in a 15cm x 33cm two roll mill, which was heated to between 48 ° C and 52 ° C. Sulfur and accelerators were added to the rubber (Masterbatch) and thoroughly mixed in the roller mill and allowed to form a sheet. The sheet was cooled to ambient conditions for 24 hours before curing. The cure condition was 160 ° C for 20 minutes. The polysulfides with silated cyclic nuclei of Examples 1 and 2 were formulated into the tire tread formulation according to the above procedure, and their behavior was compared with the behavior of the silanes that were in practice in the prior art, bis- (3-triethoxysilyl-1-propyl) (TESPD), bis- (3-triethoxysilyl-1-propyl) tetrasulfide (TESPT), and 1,2,4-tris- (7-triethoxysilyl-3,4- dithiaheptyl) cyclohexane (TESHC), Comparative Examples AC. The test procedures were described in the following ASTM methods:

<td>Mooney charring</td><td>ASTM D1646</td>

<td>Mooney viscosity</td><td>ASTM D1646</td>

<td>Oscillating Disc Rheometer (ODR)</td><td>ASTM D2084</td>

<td>Storage Module, Loss Module, Tensile and Elongation</td><td>ASTM D412 and D224</td>

<td>DIN abrasion</td><td>DIN 53516 procedure</td>

<td>Heat build-up</td><td>ASTM D623</td>

<td>Permanent Hardening in Percentage</td><td>ASTM D623</td>

<td>Shore A hardness</td><td>ASTM D2240</td>

The results of this procedure are tabulated below in Table 1.

TESPD = bis- (3-triethoxy-silylpropyl) disulfide

TESPT = bis- (3-triethoxy-silylpropyl) tetrasulfide,

TESHC = 1,2,4-tris- (6-triethoxysilyl-3,4-dithiaheptyl) cyclohexane

Table 1

<td colspan="2">Sample number</td><td>Comp. TO</td><td>Comp. B</td><td>Comp. C</td><td>Example 3</td><td>Example 4</td><td>Example 5</td>

<td>Ingredients</td><td>Units</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Master mix</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>SMR-10, natural rubber</td><td>phr</td><td> 10,00</td><td> 10,00</td><td> 10,00</td><td> 10,00</td><td> 10,00</td><td> 10,00</td>

<td>Budene 1207, polybutadiene</td><td>phr</td><td> 35,00</td><td> 35,00</td><td> 35,00</td><td> 35,00</td><td> 35,00</td><td> 35,00</td>

<td>Buna VSL 5025-1,</td><td>phr</td><td> 75,63</td><td> 75,63</td><td> 75,63</td><td> 75,63</td><td> 75,63</td><td> 75,63</td>

<td>sSBR ext. with oil</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>N339, carbon black</td><td>phr</td><td> 12,00</td><td> 12,00</td><td> 12,00</td><td> 12,00</td><td> 12,00</td><td> 12,00</td>

<td>Ultrasil VN3 GR, silica</td><td>phr</td><td> 85,00</td><td> 85,00</td><td> 85,00</td><td> 85,00</td><td> 85,00</td><td> 85,00</td>

<td>Sundex 8125TN, process oil</td><td>phr</td><td> 6,37</td><td> 6,37</td><td> 6,37</td><td> 6,37</td><td> 6,37</td><td> 6,37</td>

<td>Erucical H102, rapeseed oil</td><td>phr</td><td> 5,00</td><td> 5,00</td><td> 5,00</td><td> 5,00</td><td> 5,00</td><td> 5,00</td>

<td>Flexzone 7P, antiozonant</td><td>phr</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td>

ES 2 373 344 T3

<td>TMQ</td><td>phr</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td>

<td>Solar radiation proof enhanced wax</td><td>phr</td><td> 2,50</td><td> 2,50</td><td> 2,50</td><td> 2,50</td><td> 2,50</td><td> 2,50</td>

<td>Kadox 720C, zinc oxide</td><td>phr</td><td> 2,50</td><td> 2,50</td><td> 2,50</td><td> 2,50</td><td> 2,50</td><td> 2,50</td>

<td>Industrene R. stearic acid</td><td>phr</td><td> 1,00</td><td> 1,00</td><td> 1,00</td><td> 1,00</td><td> 1,00</td><td> 1,00</td>

<td>Aktiplast ST, dispersant</td><td>phr</td><td> 4,00</td><td> 4,00</td><td> 4,00</td><td> 4,00</td><td> 4,00</td><td> 4,00</td>

<td>Silane TESPD</td><td>phr</td><td> 6,00</td><td></td><td></td><td></td><td></td><td></td>

<td>Silane TESPT</td><td>phr</td><td></td><td> 6,80</td><td></td><td></td><td></td><td></td>

<td>Silane TESHC</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Silane, Example 1</td><td>phr</td><td></td><td></td><td></td><td> 7,90</td><td></td><td></td>

<td>Silane, Example 2</td><td>phr</td><td></td><td></td><td></td><td></td><td> 6</td><td> 9</td>

<td>Catalysts</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Naugex MBT</td><td>phr</td><td> 0,10</td><td></td><td></td><td></td><td></td><td></td>

<td>CBS</td><td>phr</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td>

<td>Diphenylguanidine</td><td>phr</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td><td> 2,00</td>

<td>Sulfur Rubbermakers 167</td><td>phr</td><td> 2,20</td><td> 2,20</td><td> 2,20</td><td> 2,20</td><td> 2,20</td><td> 2,20</td>

<td colspan="8"></td>

<td>Rubber properties</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Mooney Properties</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Vioscosity at 100 ° C, ML 1-4</td><td>mooney units</td><td> 70</td><td> 75</td><td> 67</td><td> 68</td><td> 68,2</td><td> 68,7</td>

<td>MV at 135 ° C MS1 +</td><td>mooney units</td><td> 32,4</td><td> 37</td><td> 30</td><td> 34,6</td><td> 33,2</td><td> 34,5</td>

<td>Carbonization at 135 ° C, MS1 + ta</td><td>min.</td><td> 14,2</td><td> 8,1</td><td> 13,2</td><td> 7,3</td><td> 8,1</td><td> 5</td>

<td>Cured at 135 ° C MS1 + t18</td><td>min.</td><td> 18,5</td><td> 13,3</td><td> 17,1</td><td> 11,3</td><td> 13,3</td><td> 9,5</td>

<td colspan="8"></td>

<td>Rheomtero properties at 149 ° C</td><td>(ODR), 1st arc</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Ml</td><td>dN-m</td><td> 8,9</td><td> 10,1</td><td> 8,4</td><td> 8,6</td><td> 8,6</td><td> 9,1</td>

<td>Mh</td><td>dN-m</td><td> 34,9</td><td> 38,9</td><td> 38,5</td><td> 35,9</td><td> 32,9</td><td> 37,9</td>

<td>t90</td><td>Min.</td><td> 18</td><td> 17,1</td><td> 14,5</td><td> 11,5</td><td> 17,4</td><td> 13,5</td>

<td colspan="2">Physical properties, cured at t90 at 149 ° C</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Shore "A" Durometer</td><td>shore A</td><td> 66</td><td> 69</td><td> 68</td><td> 66</td><td> 66</td><td> 69</td>

ES 2 373 344 T3

100% modulus

300% modulus

Reinforcement index

Traction

Elongation

Abrasion (DIN)

<td>MPa</td><td> 2,35</td><td> 2,8</td><td> 2,56</td><td> 2,72</td><td> 2,38</td>

<td>MPa</td><td> 8,54</td><td> 10,88</td><td> 9,06</td><td> 11,42</td><td> 9,79</td>

<td></td><td> 3,63</td><td> 3,88</td><td> 3,54</td><td> 4,2</td><td> 4,11</td>

<td>MPa</td><td> 18,95</td><td> 18,19</td><td> 16,97</td><td> 21,57</td><td> 22,36</td>

<td> %</td><td> 582</td><td> 448</td><td> 492</td><td> 505</td><td> 590</td>

<td>mm³</td><td> 144</td><td> 145</td><td> 158</td><td> 132</td><td> 138</td>

Dynamic properties in cured state, 60 ° C, single shear without linearity (0-10%)

<td>^G initial</td><td>MPa</td><td> 8,1</td><td> 7,7</td><td> 9</td><td> 4,7</td><td> 6,91</td>

<td>AG '</td><td>MPa</td><td> 5,8</td><td> 5,2</td><td> 6,5</td><td> 2,65</td><td> 4,65</td>

<td>^G max</td><td>MPa</td><td> 1</td><td> 0,91</td><td> 1,07</td><td> 0,53</td><td> 0,786</td>

<td>t^an8max</td><td></td><td> 0,243</td><td> 0,228</td><td> 0,243</td><td> 0,186</td><td> 0,206</td>

2,89

12,32

4,26

22,13

500

135

6,2

3,87

0,66

0,189

Table 1, listing Comparative Examples AC and Examples 3-5, presents the performance parameters of the silated cyclic core polysulfide of the present invention, bis- (3-triethoxysilylpropyl) disulfide, bis- (3- triethoxy-silylpropyl) and 1,2,4-tris- (6-triethoxysilyl-3,4-dithiaheptyl) cyclohexane. The physical properties of the silated ring-core polysulfide compound rubber from Examples 1 and 2 are consistently and substantially superior to the control silanes.

The silated cyclic core polysulfide of the present invention provides superior performance to silica filled elastomeric compositions, including better coupling of silica to rubber, as illustrated by the higher index of reinforcement. The better reinforcement index translates into performance improvements for elastomeric compositions and articles made from these elastomers.

Example 6

Zeosil 1165 MP silica, from Rhone-Poulenc of Lyon, France (50 grams) was poured, with the following properties:

<td>Characteristic</td><td>Value</td>

<td>BET specific surface</td><td>180 m²/ g</td>

<td>CTAB specific surface</td><td>160 m²/ g</td>

<td>DOP adsorption</td><td>270 ml / 100 grams</td>

<td>Water loss at 105 ° C</td><td> 6%</td>

<td>Loss on ignition at 1000 ° C</td><td> 10,5%</td>

<td>SiO2</td><td> 98,5%</td>

<td>Al2O3</td><td> 0,4%</td>

<td>pH</td><td> 6,5</td>

in a 1 liter wide mouth jar. The opened jar was placed in a ventilated oven at 105 ° C, and allowed to dry for 4 hours. The infrared absorption differential is 1.12. The silated cyclic core polysulfide of Example 2 (50 grams) was added to the hot silica in one portion and the jar was closed and shaken by hand for 30 seconds. The resulting compound is a dry, free-flowing solid that does not stick to the walls of the container.

The extraction test was carried out in a 100 ml Soxhlet extraction apparatus equipped with a 250 round bottom flask. The mixture of silated core polysulfide and silica (30 grams) was placed in a paper cartridge, and He placed dry analytical grade acetone in the flask. The extraction test was carried out within 2 hours from the start of reflux. The flask was heated with a heating mat to 88 ° C. The cartridge was dried in a

ES 2 373 344 T3 explosion proof oven, 110 ° to constant weight. Weight loss was calculated as a percentage of extractable silane.

The mixture of the silated cyclic core polysulfide from Example 2 and silica is an example of silica used as a support.

Example 7

Zeosil 1165 MP silica, from Rhone-Poulenc of Lyon, France (50 grams) was poured, with the following properties:

<td>Characteristic</td><td>Value</td>

<td>BET specific surface</td><td>180 m²/ g</td>

<td>CTAB specific surface</td><td>160 m²/ g</td>

<td>DOP adsorption</td><td>270 ml / 100 grams</td>

<td>Water loss at 105 ° C</td><td> 6%</td>

<td>Loss on ignition at 1000 ° C</td><td> 10,5%</td>

<td>SiO2</td><td> 98,5%</td>

<td>Al2O3</td><td> 0,4%</td>

<td>pH</td><td> 6,5</td>

<td colspan="2">in a 1 liter wide mouth jar. The silated cyclic core polysulfide from Example 2 (3.5 grams) was added to the silica in one portion, and the jar was closed and shaken by hand for 10 minutes. The jar was opened, and the silated cyclic core polysulfide and silica were heated to 140 ° C for 1 hour using a heating mantle, and vigorously stirred using a mechanical mixer and a metal stirrer shaft. Heating the silica is intended to cause the reaction of the silated cyclic core polysulfide with the silica, and remove the ethanol that forms. The resulting compound is a dry, free-flowing solid that does not stick to the walls of the container. It is an example of a mixture in which the silated cyclic core polysulfide and silica have reacted to form an article in which the two components are covalently bonded to each other.</td>

<td>Example 8</td><td></td>

<td colspan="2">SIPERNAT 22 silica, from DeGussa AG of Frankfurt, Germany (50 grams) was poured, with the following properties:</td>

<td>Characteristic</td><td>Value</td>

<td>BET specific surface</td><td>180 m²/ g</td>

<td>CTAB specific surface</td><td>160 m²/ g</td>

<td>DOP adsorption</td><td>300 ml / 100 grams</td>

<td>Water loss at 105 ° C</td><td> 6%</td>

<td>Loss on ignition at 1000 ° C</td><td> 11%</td>

<td>SiO2</td><td> 98%</td>

<td>Al2O3</td><td> 0%</td>

<td>pH</td><td> 6,0</td>

in a 1 liter wide mouth jar. The silated cyclic core polysulfide of Example 1 (5.3 grams) was added to the silica in one portion, and the jar was closed and shaken by hand for 10 minutes. The jar was opened, and the silated cyclic core polysulfide and silica were heated to 140 ° C for 1 hour using a heating mantle, and vigorously stirred using a mechanical mixer and a metal stirrer shaft. Heating the silica is intended to cause the reaction of the silated cyclic core polysulfide with the silica, and remove the ethanol.

ES 2 373 344 T3 that is formed.

The resulting compound is a dry, free-flowing solid that does not stick to the walls of the container. It is an example of a mixture in which the silated cyclic core polysulfide and silica have reacted to form an article in which the two components are covalently bonded to each other.

Example 9

Carbon black N330, from Columbian Chemical in Marietta, Georgia (100 grams), was poured with the following properties:

Characteristic

Value

<td>BET specific surface</td><td>83 m²/ g</td>

<td>CTAB specific surface</td><td>82 m²/ g</td>

<td>Iodine value</td><td>82 m²/ g</td>

in a 1 liter wide mouth jar. The open jar containing carbon black N330 was placed in a ventilated oven at 120 ° C, and allowed to dry for 2 hours. To the hot carbon black, the silated cyclic core polysulfide of Example 2 (50 grams) was added, in one portion, and the jar was closed and shaken by hand for 10 minutes. The resulting compound is a free flowing dry black powder.

The extraction test was carried out in a 100 ml Soxhlet extraction apparatus equipped with a 250 round bottom flask. The mixture of silated cyclic core polysulfide and carbon black (30 grams) was placed in a paper cartridge. , and dry analytical grade acetone was placed in the flask. The extraction test was carried out within 2 hours from the start of reflux. The flask was heated with a heating mat to 88 ° C. The cartridge was dried in an explosion proof oven, at 110 ° to constant weight. Weight loss was calculated as a percentage of extractable silane.

The mixture of the silated cyclic core polysulfide from Example 2 and carbon black is an example of a filler used as a support. N330 is a reinforcing filler for elastomeric compositions. After desorption of the liquid silane from the carbon black in the elastomeric composition, the carbon black functions as a reinforcing filler.

Example 10

The use of mixtures of polysulfides with silated cyclic cores and silicas in a low rolling resistance tire tread formulation.

A model low rolling resistance passenger tire tread formulation was used as described in Table 1 except that a 12 phr mixture of silated cyclic core polysulfide and silica from Example 6 replaces the silane from Example 2 , and the amount of Ultrasil VN3 GR silica was adjusted to 79 phr, to evaluate the behavior of the silated core polysulfide on a silica support. The rubber compound is prepared according to the mixing procedure described in Example 3. The example illustrates the utility of a silated cyclic core polysulfide on a silica support.

Example 11

The use of mixtures of polysulfides with silated cyclic cores and silicas in a low rolling resistance tire tread formulation.

A model low rolling resistance passenger tire tread formulation was used as described in Table 1 except that a 92 phr blend of silated cyclic core polysulfide and silica from Example 7 replaces the silane from Example 2 and Ultrasil VN3 GR silica, to evaluate the behavior of the silated core polysulfide on a silica support. The rubber compound is prepared according to the mixing procedure described in Example 3. The example illustrates the utility of a silated cyclic core polysulfide that is preformed and coupled to silica.

Example 12

The use of mixtures of polysulfides with silated cyclic cores and silicas in a low rolling resistance tire tread formulation.

A model formulation of a low rolling resistance passenger tire tread was used

ES 2 373 344 T3 as described in Table 1 except that a mixture of 94 phr of polysulfide with silated cyclic nucleus and silica from Example 8 replaces the silane of Example 2 and the silica Ultrasil VN3 GR, to evaluate the behavior of the polysulfide with silated core on a silica support. The rubber compound is prepared according to the mixing procedure described in Example 3. The example illustrates the utility of a silated cyclic core polysulfide that is preformed and coupled to the silica filler prior to addition to the rubber blend.

Example 13

The use of mixtures of polysulfides with silated cyclic nuclei and carbon black in a low rolling resistance tire tread formulation.

A model low rolling resistance passenger tire tread formulation was used as described in Table 1 except that an 18 phr blend of silated cyclic core polysulfide and carbon black from Example 9 replaces the silane in Example 2 and 12 phr of carbon black, to evaluate the behavior of the silated core polysulfide on a carbon black support. The rubber compound is prepared according to the mixing procedure described in Example 3. The example illustrates the utility of a silated cyclic core polysulfide on a carbon black support.

It is noted that the above examples have been provided purely for the purpose of explanation, and are not to be construed as limiting the present invention in any way. While the present invention has been described with reference to exemplary embodiments, it is understood that the words used herein are words of description and illustration, rather than words of limitation. Changes may be made, within the scope of the appended claims, as presently noted and as modified, without departing from the scope of the present invention in its aspects. Although the present invention has been described herein with reference to particular means, materials, and embodiments, the present invention is not intended to be limited to the particulars described herein; instead, the present invention extends to all functionally equivalent structures, methods, and uses, such as being within the scope of the appended claims.