阅读说明：本技术 硅烷官能化的聚(法呢烯)和包含其的橡胶混合物 (Silane-functionalized poly (farnesene) and rubber mixtures comprising the same ) 是由 史蒂文·K·亨宁 让-马克·蒙萨利耶 田楠 于 2018-05-22 设计创作，主要内容包括：根据本发明的一个方面,提供了可固化橡胶组合物,其包含高分子量二烯弹性体；任选的炭黑成分；二氧化硅成分；以及含有法呢烯单体的法呢烯聚合物。所述法呢烯聚合物经至少一个硅烷基团改性,具有1,000g/mol至100,000g/mol的数均分子量,并且具有等于或小于-40℃的玻璃化转变温度。根据本发明的另一个方面,提供了用于生产用于轮胎的橡胶组合物的方法。所述方法包括通过将经至少一个硅烷基团改性的法呢烯聚合物、二氧化硅成分、高分子量二烯弹性体和任选的炭黑成分混合来形成组合物,所述法呢烯聚合物包含法呢烯单体；以及使所述组合物固化。(According to one aspect of the present invention, there is provided a curable rubber composition comprising a high molecular weight diene elastomer; optionally a carbon black component; a silica component; and farnesene polymers containing farnesene monomers. The farnesene polymer is modified with at least one silane group, has a number average molecular weight of 1,000 to 100,000g/mol, and has a glass transition temperature equal to or less than-40 ℃. According to another aspect of the present invention, a method for producing a rubber composition for a tire is provided. The method comprises forming a composition by mixing a farnesene polymer modified with at least one silane group, a silica component, a high molecular weight diene elastomer, and an optional carbon black component, the farnesene polymer comprising a farnesene monomer; and curing the composition.)

1. A curable rubber composition comprising:

a high molecular weight diene elastomer;

a silica component;

optionally a carbon black component; and

a farnesene polymer comprising a farnesene monomer, at least one end of which is modified with at least one silane group, wherein the farnesene polymer has a number average molecular weight of from 1,000g/mol to 100,000g/mol and a glass transition temperature equal to or less than-40 ℃.

2. The curable rubber composition of claim 1, wherein the farnesene polymer further comprises at least one of a vinyl aromatic monomer or a diene monomer.

3. The curable rubber composition of claim 1 or 2, wherein the farnesene polymer has a number average molecular weight of from 2,000g/mol to 50,000 g/mol.

4. The curable rubber composition of claim 3, wherein the farnesene polymer has a number average molecular weight of 2,500 to 10,000 g/mol.

5. The curable rubber composition of any one of claims 1 to 4, wherein the silica component is obtained from precipitation of a soluble silicate.

6. The curable rubber composition of any one of claims 1 to 5, further comprising at least one silane coupling agent.

7. The curable rubber composition of any one of claims 1 to 6, wherein the silane group is represented by the formula: -Si (OR)₃Wherein each R is independently a C1-C6 alkyl or aryl group.

8. The curable rubber composition of any one of claims 1-7, wherein the farnesene polymer is produced by anionic polymerization.

9. The curable rubber composition of any one of claims 1-8, wherein the farnesene polymer has a silane functionality of 2 or less.

10. A tire comprising a rubber composition obtained by curing a curable rubber composition comprising:

a high molecular weight diene elastomer;

a silica component;

optionally a carbon black component; and

a farnesene polymer comprising a farnesene monomer, at least one end of which is modified with at least one silane group, wherein the farnesene polymer has a number average molecular weight of from 1,000g/mol to 100,000g/mol and a glass transition temperature equal to or less than-40 ℃.

11. The tire of claim 10, wherein the farnesene polymer further comprises at least one of a diene monomer and a vinyl aromatic monomer.

12. The tire of claim 10 or 11, wherein the farnesene polymer has a number average molecular weight of 2,000 to 50,000 g/mol.

13. The tire of claim 12, wherein the farnesene polymer has a number average molecular weight from 2,500g/mol to 10,000 g/mol.

14. The tire of any one of claims 10 to 13, wherein the curable rubber composition further comprises at least one silane coupling agent.

15. Tyre according to any one of claims 10 to 14, wherein said silica component is obtained from the precipitation of soluble silicates.

16. The tire of any one of claims 10 to 15, wherein the curable rubber composition has been cured using at least one sulfur vulcanizing agent.

17. A method for producing a rubber composition suitable for use in a tire, the method comprising:

forming a composition by mixing a farnesene polymer modified with at least one silane group, a silica component, a high molecular weight diene elastomer, and optionally a carbon black component, the farnesene polymer comprising a farnesene monomer; and

allowing the composition to cure.

18. The method of claim 17, wherein the farnesene polymer is prepared by a process comprising polymerizing at least one farnesene monomer.

19. The method of claim 17 or 18, wherein the farnesene polymer is polymerized by living anionic polymerization.

20. The method of any one of claims 17-19, wherein the farnesene polymer is prepared by a process comprising modifying at least one terminus of the farnesene polymer to have a silane group.

21. The method of claim 20, wherein the process for preparing the farnesene polymer further comprises modifying at least one terminus of a living farnesene polymer by reacting the farnesene polymer with an alkylene oxide, followed by a proton source to produce a hydroxyl terminated farnesene polymer.

22. The method of claim 20 or 21, wherein the process for preparing the farnesene polymer further comprises modifying at least one terminus of the farnesene polymer by converting a terminal hydroxyl group on the farnesene polymer into a silane group.

Technical Field

The present invention relates to rubber compositions comprising silane-functionalized farnesene polymers, and more particularly to rubber compositions used to form tires comprising the rubber compositions.

Background

When producing rubber compositions, it is common to use fillers by replacing the higher priced ingredients of the rubber composition with cheaper ingredients that can impart some additional functionality to the final rubber product for the purpose of reducing cost. To achieve these advantages, it is often necessary to use additives in combination with the filler. For example, German publication No. DE 3010113 to Chemische Werke HuelsAG discloses the use of poly (butadiene) as a coupling agent for mineral fillers in polymers. Another german patent DE 3129082 issued to the same company discloses silane-grafted poly (butadiene) s as coupling agents for inorganic fillers. Japanese patent JP 62265301 issued to Nippon Soda co describes the preparation of silane grafted poly (butadiene) for use as a surface treatment for mineral fillers.

Fillers that do not themselves improve the mechanical properties of the rubber composition may be combined with dispersants and coupling agents to improve such properties. Dispersants and coupling agents interact physically or chemically with the polymer matrix and filler at the boundary between the two phases and have the potential to impart improved physical properties to the rubber composition. For example, U.S. Pat. Nos. 4,381,377 and 4,396,751 disclose homopolymers or copolymers of 1, 3-dienes combined with reactive silyl groups to form crosslinked products having improved modulus and cure rate. Accordingly, some research has focused on the potential use of such dispersants and coupling agents.

The specific advantageous physical properties of tires made from such compositions are of particular interest to tire manufacturers through manipulation of rubber compositions. A reduction in fuel consumption can be obtained by developing tyres with very low rolling resistance combined with excellent grip characteristics and handling behaviour. This can result in significant cost and environmental benefits as the improved physical characteristics of the tire can reduce fuel consumption. Accordingly, there is a continuing need for improved dispersants and coupling agents that will reduce manufacturing costs and produce rubber compositions having advantageous physical properties, including wet traction, improved rolling resistance, and low temperature performance.

Disclosure of Invention

Aspects of the invention relate to rubber compositions comprising silane-functionalized farnesene polymers.

According to one aspect of the invention, a rubber composition is disclosed comprising a high molecular weight diene elastomer, from 5phr to 120phr of silica, from 0phr to 100phr of carbon black, and a silane-modified (preferably terminally silane-modified) polymer containing farnesene monomers and optionally other dienes and/or vinyl aromatic monomers in polymerized form, wherein the silane-modified polymer has a number average molecular weight of from 1,000g/mol to 100,000g/mol and a glass transition temperature of less than-40 ℃ or less than-50 ℃.

In accordance with another aspect of the invention, a method of making a rubber composition is disclosed, the method comprising compounding in situ a high molecular weight diene elastomer, from 5phr to 120phr of silica, from 0phr to 100phr of carbon black, and a silane modified polymer containing farnesene monomer and optionally other diene and/or vinyl aromatic monomers in polymerized form, wherein the silane modified polymer has a number average molecular weight of from 1,000g/mol to 100,000g/mol and a glass transition temperature of less than-40 ℃ or less than-50 ℃.

According to another aspect of the present invention, there is provided a curable rubber composition comprising, consisting essentially of, or consisting of: a high molecular weight diene elastomer; a silica component; optionally a carbon black component; and farnesene polymers containing farnesene monomers. The farnesene polymer is modified with (i.e., comprises at least one silane group) at least one silane group, has a number average molecular weight of 1,000 to 100,000g/mol, and has a glass transition temperature equal to or less than-40 ℃ or equal to or less than-50 ℃.

According to another aspect of the present invention, there is provided a tire having a rubber composition obtained by curing a curable rubber composition. The curable rubber composition comprises, consists essentially of, or consists of: a high molecular weight diene elastomer; a silica component; optionally a carbon black component; and farnesene polymers containing farnesene monomers. The farnesene polymer is modified with at least one silane group (i.e., comprises at least one silane group, preferably in a terminal position), has a number average molecular weight of 1,000 to 100,000g/mol, and has a glass transition temperature equal to or less than-40 ℃ or equal to or less than-50 ℃.

According to still another aspect of the present invention, there is provided a method for producing a rubber composition for a tire. The method comprises, consists essentially of, or consists of: forming a composition by mixing a high molecular weight diene elastomer, a farnesene polymer modified by at least one silane group, a silica component, and optionally a carbon black component, the farnesene polymer comprising a farnesene monomer; and curing the composition.

Drawings

The invention is best understood from the following detailed description when read with the accompanying drawing figures, wherein like elements are given like numerals. Included in the drawings are the following figures:

FIG. 1 is a flow diagram depicting one non-limiting embodiment of a process for producing a silane-functionalized polymer, which may be a component of a rubber composition for a tire according to aspects of the present invention; and

FIG. 2 is a graph comparing glass transition temperatures of farnesene polymer, poly (butadiene) and poly (isoprene) at different amounts of 1, 2-vinyl monomer and 3, 4-vinyl monomer.

Detailed Description

The inventors have found that aspects of the present invention can be used to produce improved rubber compositions. Applicants have found that improved silica dispersion and low temperature performance can be achieved by adding a terminal silane functional low molecular weight polymer such as poly (farnesene) to a rubber mixture comprising silica and a silane coupling agent as filler. For example, according to one aspect of the present invention, greatly improved silica dispersion and low temperature properties can be achieved using the silane-functional (preferably terminal silane-functional) low molecular weight polymers disclosed herein, which can be particularly useful in applications associated with tire production. Improving silica dispersion by using low molecular weight silane functional polymers results in improved viscoelastic properties, which can be associated with increased fuel economy and improved winter performance of tire tread compounds.

The inventors have found that by incorporating hydrophobic silane functional additives, as discussed herein, the surface of the silica can be modified such that the dispersion force during mixing is improved and well dispersed filler conditions are achieved. Accordingly, embodiments of the present invention provide improved solutions to the inefficiencies of conventional rubber compositions for tires. For example, the inventors have recognized that carbon black can be readily dispersed in hydrocarbon-based elastomeric compounds and form a bonded polymer layer through van der waals interactions, while silica is hydrophilic and does not readily interact withThe hydrocarbon elastomer is mixed. In the absence of a hydrophobizing surfactant, the silica will form a separate network within the elastomeric compound. This secondary network will break and reform during dynamic strain (the process of losing a large amount of energy in the form of heat). However, with the aspect of the present invention, it is possible to modify the surface of silica, so that the dispersing force during mixing is improved, and a filler condition with good dispersion is achieved. Thus, reduced fuel consumption can be obtained by developing tires having very low rolling resistance combined with excellent grip characteristics and handling behavior. This can result in significant cost and environmental benefits as the improved physical characteristics of the tire can reduce fuel consumption. As discussed in more detail below, in one embodiment, the use of silane-functional poly (farnesene), particularly terminal silane-functional poly (farnesene), in combination with the silica component and the silane coupling component can result in greatly improved silica dispersion and low temperatures. In one embodiment, the silane groups are represented by the formula: -Si (OR)₃Wherein each R is independently C1-C6 alkyl (e.g., methyl, ethyl) or aryl (e.g., phenyl).

According to another aspect of the present invention, there is provided a sulfur-vulcanizable silica-containing rubber composition having improved processability and dynamic characteristics, the rubber composition comprising at least a silane-modified polymer comprising farnesene monomer and, optionally, other diene and/or vinyl aromatic monomers in polymerized form. The rubber composition may comprise 1 to 150 parts of a farnesene polymer, 5 to 120 parts of silica, 0 to 100 parts of carbon black, and 0 to 100phr of one or more high molecular weight diene elastomers. The rubber composition can comprise 1 to 140 parts of a farnesene polymer, for example, 2 to 110 parts of a farnesene polymer, 3 to 100 parts of a farnesene polymer, 5 to 90 parts of a farnesene polymer, 7 to 80 parts of a farnesene polymer, 9 to 70 parts of a farnesene polymer, 11 to 60 parts of a farnesene polymer, 13 to 50 parts of a farnesene polymer, 15 to 45 parts of a farnesene polymer, 17 to 40 parts of a farnesene polymer, or 19 to 30 parts of a farnesene polymer. In other non-limiting embodiments, the amount of farnesene polymer in the rubber composition is from 1 part to 50 parts farnesene polymer, from 50 parts to 100 parts farnesene polymer, or from 100 parts to 150 parts farnesene polymer. The amount of silica in the rubber composition can be, for example, 6 to 90 parts silica, 7 to 60 parts silica, or 8 to 40 parts silica. The high molecular weight diene elastomer used in the rubber composition may include, but is not limited to, styrene butadiene rubber, polyisoprene rubber or natural rubber, or blends of these rubber elastomers. The amount of high molecular weight diene elastomer in the rubber composition may be from 0phr to 100phr, from 5phr to 90phr, from 10phr to 80phr, from 15phr to 70phr, or from 20phr to 60phr of the high molecular weight diene elastomer. The number average molecular weight Mn of the high molecular weight diene elastomer may be 100,000Da or more, 200,000Da or more, 300,000Da or more, and the like.

The silane-modified polymer is preferably a silane-modified low molecular weight poly (farnesene) that can be used as a reactive plasticizer, more preferably having a number average molecular weight of 2,000 to 50,000, and most preferably having a number average molecular weight of 2,500 to 10,000. According to various embodiments, the silane-modified polymer (e.g., silane-modified low molecular weight poly (farnesene)) has a glass transition temperature (Tg) equal to or less than-40 ℃, -45 ℃, -50 ℃, -55 ℃, -60 ℃, or-65 ℃.

The present inventors have discovered that embodiments of the present invention provide advantages over rubber compositions that use non-functionalized liquid poly (butadiene). Non-functionalized liquid poly (butadiene) s have been used in tire compounding. Due to the wide range of glass transition temperatures (Tg) of low molecular weight diene elastomers, low molecular weight diene elastomers are used as plasticizers to improve the grip characteristics or low temperature performance of tires. However, these low molecular weight non-functionalized polymers have the disadvantage of producing tires with poor rolling resistance properties. However, according to one aspect of the invention, the rubber composition comprises a farnesene polymer having one or more silane groups (preferably at one or more terminal positions), which enables the rubber composition to have sufficient grip characteristics and low temperature performance in the absence of a low molecular weight diene. According to one aspect of the invention, a method is provided for producing a farnesene polymer comprising silane groups. Preferably, the method comprises functionalizing one or more chain ends of the farnesene polymer instead of the polymer backbone. In general, the method may comprise the steps of: forming a polymer having two active chain ends; and capping the active chain ends with a reactive compound containing a silane functional group or a reactive compound that produces a reactive group that can be further derivatized to a silane functional group.

In step 110, a polymer having two active chain ends is formed. In one embodiment, the polymer is formed using an anionic difunctional initiator. The polymerization is preferably carried out under conditions effective to provide living anionic polymerization. The present inventors have recognized that, according to conventional wisdom, the use of soluble difunctional anionic initiators is believed to require large amounts of polar solvents in their preparation and that when these polar solvents are transferred into the polymerization step they affect the resulting microstructure of the polymer, thereby facilitating 1, 2-vinyl incorporation relative to 1, 4-cis/trans incorporation of diene monomers. More specifically, since many bifunctional initiators are typically based on carbanions stabilized by lithium anions, such dilithium initiators can be very polar and exhibit limited or no solubility in standard hydrocarbon solvents. Polar solvents (usually ethers) can be used in the production and storage of dilithium initiators and can also be used as reaction medium for the resulting polymerization. The addition of lewis bases or lithium alkoxides can improve the system, but like ethers, at the expense of microstructure control. The lack of solubility of dilithium initiators in hydrocarbon media may limit their use in the production of certain polymers. Soluble dilithium initiators have been reported, but are butyl lithium adducts based on aromatic precursors and have drawbacks. Although soluble, the initiator species highly aggregate in solution and initiate slowly, which results in broad or multimodal molecular weight distributions, side reactions, and the potential for less than quantitative functionality.

Bifunctional initiators are generally prepared by reaction of lithium with butadiene, isoprene, dimethylbutadiene, styrene or alpha-methylstyrene (Houben-Weyl method der organischen Chemie, e.m ü ler ed.band 13/I, Georg Thieme 1970; h.l.hsieh, r.p.quirk, ionic polymerization-principles and comparative applications, Marcel Dekker 1996) Ziegler may first describe this reaction (k.ziegler, l.jakob, ann.511,45(1934)) a number of modifications to this reaction have been published (e.g., U.S. patent No. 3157604, the disclosure of which is incorporated herein by reference for all purposes) despite the fact that the high vinyl-functional monomer content in subsequent polymerizations leads to a highly solvated ether, such as tetrahydrofuran, which may lead to polymerization of polymers in which the high Tg-ionic backbone(s) and thus to a highly solvated backbone(s) which, despite the high vinyl-functional vinyl-polymer-Tg-polymer-production, which may result in a highly solvated backbone (high Tg-ionic backbone-polymer) and/or low Tg-ionic backbone-crosslinking polymer (which may lead to a high Tg-diene-polymer-Tg-polymer-which may be produced by incorporation under the same high-Tg-polymer-under the high-Tg-polymer-to-polymer-to-polymer-to-polymer-to-polymer-to-polymer-to-polymer-to-polymer-to-polymer-to-.

In step 112, the living chain ends of the farnesene polymer are blocked with at least one of a reactive compound containing a silane functional group or a reactive compound that provides a reactive group (e.g., a hydroxyl group) that can be further derivatized to a silane functional group (e.g., by reaction with an isocyanate-functional silane). The inventors have found that improved silica dispersion, processing, rolling resistance and winter performance behavior are achieved by at least partially replacing the non-functionalized polymer with a silane-functionalized polymer in a rubber mixture containing silica. For relatively low molar mass polymers, the terminal silane functionality also effectively "ties" the chain ends to the filler surface, or through intermolecular condensation reactions, reduces the additional contribution to energy loss through chain end motion upon dynamic strain. Thus, the inventors have found that functionalizing the end groups as disclosed herein results in a more effective reduction in heat build-up in the tire compound as compared to functionalizing by grafting to the backbone, which leaves the chain ends unaffected.

The method 100 advantageously enables the silica ingredients to be added/mixed into the silane-functional polymer in situ during compounding, rather than pre-blending or pre-reacting the silane coupling agent with the silica filler, which provides additional advantages by reducing the number of steps involved in the compounding process.

As another advantage, a variety of methods can be employed to produce the silane-modified polymers of the present invention. The first method involves producing poly (farnesene) by anionic polymerization and capping the living end of poly (farnesene) with a silane ester (e.g., tetraethoxysilane) instead of a proton. The second method is to react the living anionic poly (farnesene) chain ends with alkylene oxides (e.g., ethylene oxide, propylene oxide) followed by a proton source to produce hydroxyl-terminated poly (farnesene). The hydroxyl-terminated poly (farnesene) can then be reacted with an isocyanatosilane (e.g., 3- (triethoxysilyl) propyl isocyanate) to form a silane-terminated poly (farnesene). In a third approach, the terminal hydroxyl groups of the poly (farnesene) can be reacted with a diisocyanate, which can be further reacted with an aminosilane to produce the desired result.

Farnesene exists in isomeric forms, such as α -farnesene ((3E,7E) -3,7, 11-trimethyl-1, 3,6, 10-dodecatetraene) and β -farnesene (7, 11-dimethyl-3-methylene-1, 6, 10-dodecatriene). In one embodiment, the farnesene monomer is (E) - β -farnesene having the following structure:

and (E) - β -farnesene in which one or more hydrogen atoms have been replaced (e.g., substituted) by another atom or group of atoms.

Farnesene monomers used to produce various embodiments of the resins according to the invention can be prepared from petroleum resources by chemical synthesis, can be extracted from insects such as the aphididae family and/or plants such as apples. Thus, one advantage of the present invention is that poly (farnesene) can be derived from monomers obtained from renewable resources. It is preferably prepared by culturing the microorganism using a carbon source derived from a sugar. The poly (farnesene) used in the present invention can be efficiently prepared from farnesene monomers obtained from these sources.

The sugar used may be any one of monosaccharide, disaccharide and polysaccharide, or may be a combination thereof. Examples of monosaccharides include glucose, galactose, mannose, fructose and ribose. Examples of disaccharides include sucrose, lactose, maltose, trehalose, and cellobiose. Examples of polysaccharides include starch, glycogen, cellulose and chitin.

The cultured carbon source-consuming microorganism may be any microorganism capable of producing farnesene by culture. Examples thereof include eukaryotes, bacteria, and archaea. Examples of eukaryotes include yeast and plants. The microorganism may be a transformant obtained by introducing a foreign gene into a host microorganism. The foreign gene is not particularly limited, and it is preferably a foreign gene involved in farnesene production, because it can improve the efficiency of producing farnesene. In the case of recovering farnesene from the cultured microorganism, the microorganism may be collected by centrifugation and disrupted, and then farnesene may be extracted from the disrupted solution with a solvent. Such solvent extraction may be suitably combined with any known purification method, such as distillation.

The farnesene polymer may be a farnesene homopolymer, but in certain embodiments may be a copolymer of farnesene and one or more comonomers (in particular, one or more copolymers selected from vinyl aromatic monomers such as styrene and diene monomers such as butadiene). For example, such copolymers can have a comonomer content of 0.5 to 50 weight percent comonomer, with the balance being farnesene monomer.

One or more diene elastomers are used in the composition of the invention. Suitable diene elastomers for this purpose generally have a high molecular weight (for example a number average molecular weight Mn higher than 80,000Da) and contain residual unsaturated sites which are capable of curing (crosslinking) when the composition is heated to a sufficiently high temperature. In the context of the present invention, "diene elastomer" is understood to mean an elastomer (rubber) resulting at least in part from the polymerization of one or more diene monomers (monomers having two carbon-carbon double bonds, whether conjugated or not). Suitable diene elastomers include both homopolymers and copolymers. The diene elastomer may be functionalized.

The diene elastomer suitable for use in the curable rubber composition according to the invention may be "highly unsaturated", such as a polymer obtained from conjugated diene monomers having a molar content of polymerized units of conjugated diene monomers greater than 50%.

According to one embodiment of the present invention, the curable rubber composition may comprise one or more diene elastomers having a Tg of from-110 ℃ to-40 ℃. Mixtures of diene elastomers having different glass transition temperatures may also be employed. For example, the curable rubber composition may comprise a first diene elastomer having a Tg of from-110 ℃ to-75 ℃ and a second diene elastomer having a Tg different from the Tg of the first diene elastomer and in the range of from-75 ℃ to-40 ℃.

According to various aspects, highly unsaturated diene elastomers are used, in particular homopolymers obtained by homopolymerization of conjugated diene monomers having from 4 to 12 carbon atoms and/or copolymers obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms.

Suitable conjugated dienes are in particular 1, 3-butadiene; 2-methyl-1, 3-butadiene; 2, 3-di (C1-C5 alkyl) -1, 3-butadiene, e.g., 2, 3-dimethyl-1, 3-butadiene, 2, 3-diethyl-1, 3-butadiene; 2-methyl-3-ethyl-1, 3-butadiene; 2-methyl-3-isopropyl-1, 3-butadiene; aryl-1, 3-butadiene; 1, 3-pentadiene and 2, 4-hexadiene. Suitable vinylaromatic compounds are, for example, styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene, the commercially available mixture "vinyltoluene", p-tert-butylstyrene, methoxystyrene, chlorostyrene, vinylmesitylene, divinylbenzene and vinylnaphthalene and combinations thereof.

The copolymer may, for example, comprise from 99 to 20% by weight of diene units (in incorporated/polymerized form) and from 1 to 80% by weight of vinylaromatic units (in incorporated/polymerized form). The elastomer may have any microstructure depending on the polymerization conditions used, in particular on the presence or absence of the modifying and/or randomizing agent and on the amount of modifying and/or randomizing agent used. The elastomer may be, for example, a block elastomer, a statistical (random) elastomer, a sequential elastomer or a microsequential elastomer, and may be prepared in dispersion or in solution; they may be coupled and/or starred or alternatively functionalized with coupling and/or starring agents or functionalizing agents.

Particular embodiments of the present invention use polybutadienes comprising polybutadiene having a content of 1, 2-units of from 4% to 80%, or polybutadiene having a content of cis-1, 4 linkages greater than 80%; a polyisoprene; butadiene-styrene copolymers comprising a butadiene-styrene copolymer having a styrene content of from 5% to 50% by weight, and more particularly from 20% to 40%, a content of 1, 2-bonds of the butadiene moiety of from 4% to 65%, and a content of trans-1, 4 bonds of from 20% to 80%; butadiene-isoprene copolymers including butadiene-isoprene copolymers having an isoprene content of 5 to 90 wt% and a glass transition temperature of-40 to-80 ℃; isoprene-styrene copolymers, in particular those having a styrene content of from 5% to 50% by weight and a Tg of from-25 ℃ to-50 ℃. In the case of butadiene-styrene-isoprene copolymers, suitable butadiene-styrene-isoprene copolymers include, but are not limited to, butadiene-styrene-isoprene copolymers having a styrene content of from 5% to 50% by weight, and more particularly from 10% to 40%, an isoprene content of from 15% to 60% by weight, and more particularly from 20% to 50%, a butadiene content of from 5% to 50% by weight, and more particularly from 20% to 40%, a content of 1, 2-units of the butadiene portion of from 4% to 85%, a content of trans-1, 4 units of the butadiene portion of from 6% to 80%, a content of 1, 2-units plus 3, 4-units of the isoprene portion of from 5% to 70%, a content of trans-1, 4 units of the isoprene portion of from 10% to 50%, and more typically any butadiene-styrene-isoprene copolymer having a Tg of-20 ℃ to-70 ℃.

The diene elastomer of the composition according to a particular embodiment of the invention may be selected from the group of highly unsaturated diene elastomers comprising polybutadienes (BR), synthetic polyisoprenes (IR), Natural Rubber (NR), butadiene copolymers, isoprene copolymers and mixtures thereof.

In other embodiments, such copolymers may be selected from the group comprising butadiene-styrene copolymers (SBR), butadiene-isoprene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-butadiene-styrene copolymers (SBIR) and mixtures thereof.

The curable rubber compositions for the preparation of tires and other products according to the invention can comprise a single diene elastomer or a mixture of several diene elastomers, which can be used in combination with any type of synthetic elastomer other than diene elastomers, or even with polymers other than elastomers, such as thermoplastic polymers.

The high molecular weight diene elastomer may be selected from the group consisting of polybutadiene, polyisoprene, copolymers of butadiene and vinyl aromatic monomers, copolymers of isoprene and vinyl aromatic monomers, and combinations of two or more such diene elastomers. For example, elastomers that may be used in the present invention include styrene-isoprene-butadiene rubber (SIBR), styrene-isoprene rubber (SIR), and isoprene-butadiene rubber (IBR). In addition to synthetic rubbers, which may include neoprene (polychloroprene), polybutadiene (including cis-1, 4-polybutadiene), polyisoprene (including cis-1, 4-polyisoprene), butyl rubber, halogenated butyl rubber such as chlorinated butyl rubber or brominated butyl rubber, acrylonitrile and methyl methacrylate rubber, and ethylene/propylene terpolymers, also known as ethylene/propylene/diene monomer (EPDM), particularly ethylene/propylene/dicyclopentadiene terpolymers, natural rubber may also be used. Further examples of rubbers that may be used include carboxyl rubbers, and silicon-coupled and tin-coupled star-branched polymers. Generally, the high molecular weight diene elastomers useful in the present invention have a weight average molecular weight of at least 100,000g/mol (e.g., at least 150,000g/mol or at least 200,000 g/mol).

In one embodiment, the curable rubber composition comprises at least one polybutadiene having a relatively high 1, 4-cis content, for example, a 1, 4-cis content of at least 80%, at least 85%, or at least 90%. In another embodiment, the curable rubber composition comprises at least one styrene/butadiene rubber, particularly a solution polymerized styrene/butadiene rubber. Such copolymers may have a bound styrene content of, for example, 15 to 30 wt.%. The curable rubber composition may comprise two types of diene elastomers, for example, at least one high 1, 4-cis content polybutadiene and at least one solution polymerized styrene/butadiene rubber. The high 1, 4-cis butadiene rubber content may be, for example, 15phr to 35phr, and the solution polymerized styrene/butadiene rubber content may be, for example, 65phr to 85 phr.

Examples of reinforcing fillers that may be included in rubber compositions according to certain embodiments of the present invention include fumed silica fillers and finely divided precipitated silicas commonly used in rubber compounding. However, silica fillingThe material is preferably of the type obtained by precipitation from a soluble silicate, such as sodium silicate. For example, silica fillers may be produced according to the method described in U.S. patent No. 2,940,830, which is incorporated herein in its entirety for all purposes. SiO of precipitated hydrated silica pigments₂The content may be at least 50% by weight, and typically greater than 80% by weight on an anhydrous basis. The final particle size of the silica filler may be in the range of about 50 angstroms to 10,000 angstroms, preferably 50 angstroms to 400 angstroms, more preferably 100 angstroms to 300 angstroms. The average final particle size of the silica, as determined by electron microscopy, may be in the range of about 0.01 microns to 0.05 microns, although the size of the silica particles may be even smaller. The Brucella-Hermite-Teller ("BET") surface area of the filler, as measured using nitrogen, is preferably in the range of 40 square meters per gram to 600 square meters per gram, more preferably in the range of 50 square meters per gram to 300 square meters per gram. The BET method for measuring surface area is described in Journal of the American Chemical Society, volume 60, page 304 (1930), of the American Chemical Society. The silica may also have a dibutyl ("DBP") absorption value in the range of about 200 to about 400, with a range of about 220 to 300 being preferred.

In various embodiments of the present invention, various commercially available silicas and carbon blacks may be used as reinforcing fillers. Suitable types of carbon blacks include, but are not limited to, super abrasion furnace blacks (super abrasion furnace blacks), medium SAFs, high abrasion furnace blacks, easy mix channel blacks, fast extrusion furnace blacks (fast extrusion furnace blacks), high modulus furnace blacks, semi-reinforcing furnace blacks, thermal cracking blacks, and/or medium thermal cracking blacks. For example, silicas commercially available from PPG Industries under the Hi-Sil trademark may be used, such as those sold under the designations 210, 243, etc.; silica available from Rhone-Poulenc under the designations Z1165MP and Z165 GR; and silica available from Degussa AG under the designations VN2 and VN 3; and so on. Rhone-Poulenc Z1165MP silica is a preferred silica that is reported to be characterized as having a BET surface area of about 160 to 170, a DBP value of about 250 to 290, and a substantially spherical shape. Suitable examples of carbon blacks include, but are not limited to, N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991.

Representative reinforcing fillers may be included in rubber compositions according to various embodiments of the present invention in amounts ranging from about 5 parts by weight reinforcing filler to 100 parts by weight reinforcing filler per 100 parts by weight total rubber composition (phr). Preferably, about 10 to 50 parts by weight of reinforcing filler is used per 100 parts of rubber.

In compounding a rubber composition containing a filler, a coupling agent is generally used. Silane coupling agents are particularly preferred. Such coupling agents may be, for example, premixed or pre-reacted with the filler, or may be added to the rubber mix during the rubber/filler processing or mixing stage. The coupling agent is considered to be combined with the filler in situ if the coupling agent and filler are added separately to the rubber mixture during the rubber/filler mixing or processing stage. Any coupling agent known to those skilled in the art may be employed in the compositions of the present invention. The coupling agent is generally composed of a coupling agent having a constituent silane component (i.e., moiety) capable of reacting with the silica surface and also having a constituent component capable of reacting with the rubber. Preferably, the coupling agent is capable of reacting with a sulfur vulcanizable rubber containing carbon-to-carbon double or unsaturated bonds. In this way, the coupling agent (coupling agent) can act as a connecting bridge between the silica and the rubber, increasing the rubber reinforcing aspect of the silica.

The silane of the coupling agent may form a bond with the silica surface by hydrolysis, and the rubber reactive component of the coupling agent bonds to the rubber itself. Generally, the rubber reactive component of the coupling agent is temperature sensitive and tends to bond with the rubber during the final and higher temperature sulfur vulcanization stage. However, during the initial rubber/silica/coupling agent mixing stage prior to the subsequent vulcanization stage, some degree of bonding or bonding may occur between the rubber reactive component of the coupling agent and the rubber.

In addition to the reinforcing filler, the rubber composition may contain conventional additives including other fillers, peptizers, pigments, stearic acid, accelerators, sulfur vulcanizing agents, antiozonants, antioxidants, processing oils, activators, initiators, plasticizers, waxes, prevulcanization inhibitors, extender oils, and the like.

Examples of sulfur vulcanizing agents include, but are not limited to, elemental sulfur (free sulfur) or sulfur donating vulcanizing agents, such as amine disulfides, polymeric polysulfides, or sulfur olefin adducts. The amount of sulfur vulcanizing agent varies depending on the type of rubber and the particular type of sulfur vulcanizing agent, but is generally in the range of about 0.1phr to about 5phr, with a range of about 0.5phr to about 2phr being preferred.

Examples of antidegradants that may be in the rubber compositions according to various embodiments of the present invention include, but are not limited to, monophenols, bisphenols, thiobisphenols, polyphenols, hydroquinone derivatives, phosphites, phosphate blends, thioesters, naphthylamines, diphenolamines, and other diarylamine derivatives, p-phenylenediamine, quinolines, and blended amines. Antidegradants are generally used in amounts ranging from about 0.1phr to about 10phr, with a range of about 2phr to 6phr being preferred.

Examples of peptizers include, but are not limited to, pentachlorophenol, which may be used in amounts ranging from about 0.1phr to 0.4phr, with a range of about 0.2phr to 0.3phr being preferred.

Examples of processing oils include, but are not limited to, aliphatic-naphthenic aromatic resins, polyethylene glycols, petroleum, ester plasticizers, sulfurized vegetable oils, pine tar, phenolic resins, petroleum resins, polymeric esters, and rosins. Processing oils may be used in amounts ranging from about 0phr to about 50phr, with a range of about 5phr to 35phr being preferred.

Examples of initiators include, but are not limited to, stearic acid. The initiator may be used in an amount ranging from about 1phr to 4phr, with a range of about 2phr to 3phr being preferred.

Examples of accelerators include, but are not limited to, amines, guanidines, thioureas, mercaptans, thiurams, disulfides, thiazoles, sulfenamides, dithiocarbamates, and xanthates. In the case where only primary accelerator is used, the amount used may range from about 0.5phr to 2.5 phr. In the case of using a combination of two or more accelerators, the primary accelerator may be used in an amount ranging from 0.5phr to 2.0phr, and the secondary accelerator may be used in an amount ranging from about 0.1phr to 0.5 phr. Combinations of accelerators are known to produce a synergistic effect. Preferably, the primary accelerator is a sulfenamide. If a secondary accelerator is used, it is preferably a guanidine, dithiocarbamate and/or thiuram compound.

The rubber compositions according to embodiments of the present invention may be compounded by conventional means known to those skilled in the art, including mixers or blenders (e.g., a mixer)

Mixers), mills, extruders, and the like. The tire may be manufactured, shaped, molded and cured by various methods that will also be apparent to those skilled in the art.

For curing the curable rubber composition of the present invention, any conventional vulcanization or curing method known in the art may be used, for example, heating with superheated steam or hot air in a press or mold. Thus, the curable rubber composition can be cured by a process that includes heating the curable rubber composition at a temperature and for a time effective to cure the diene elastomer, which can be molded into a desired form.

Particular embodiments of the invention include tires, particularly tire treads, intended for passenger or light truck tires, but the invention is not limited to such tires. It should be noted that the tires of particular embodiments of the present invention are intended to be fitted on motor vehicles (including passenger vehicles) or non-motor vehicles, such as bicycles, motorcycles, racing vehicles, industrial vehicles such as vans, heavy vehicles such as buses and vans, off-highway vehicles such as agricultural, mining and construction machinery, aircraft, or other transport or handling vehicles.

The curable rubber compositions disclosed herein can be used in a variety of rubber products, such as tires, particularly tread compounds, and in tires, industrial rubber products, seals, synchronous belts, power transmission belt devices, and other components for other rubber articles. Accordingly, the present invention includes products made from the curable rubber compositions disclosed herein.

Within this specification, embodiments have been described in a manner that enables a clear and concise specification to be written, but for purposes of this specification and it will be appreciated that various combinations and subcombinations of the embodiments may be made without departing from the invention. For example, it is to be understood that all of the preferred features described herein apply to all of the aspects of the invention described herein.

In some embodiments, the invention herein may be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the composition or method. In addition, in some embodiments, the invention may be construed as not including any elements or process steps not specified herein.

Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the invention.