Rubber vulcanization process using eutectic mixtures

Abstract

A method for preparing a vulcanizable composition is provided, comprising combining a vulcanizable rubber, a curative, and a eutectic composition. A method for preparing a vulcanizable composition includes the steps of: (i) combining a vulcanizable rubber, a curative, a metal compound, and a eutectic composition, wherein the metal compound is zinc oxide; and the eutectic composition has the formula Cat. + X - zY(where Cat + is a cation and X - is a counter anion, Y is a hydrogen bond donor, a metal halide, or a metal halide hydrate, and z represents the number of Y molecules (e.g., Lewis acids or Bronsted acids) that combine with, react with, or interact with the counter anion.

Description

[Technical Field]

[0001] SUMMARY OF THE INVENTION An embodiment of the present invention relates to a process for sulfur curing a diene-based rubber composition in the presence of zinc oxide and a eutectic solvent. [Background technology]

[0002] Zinc oxide, typically in combination with stearic acid, is commonly used in the sulfur vulcanization of rubber. It is believed that the zinc species and / or zinc oxide function as sulfur crosslinking activators. It is also believed that the zinc oxide and stearic acid form zinc species in situ, and that the zinc species, combined with the zinc oxide, affect the speed and quality of the sulfur vulcanization process.

[0003] Zinc oxide, traditionally used in the sulfur vulcanization process, is 10m 2 / g, and such zinc oxide may be referred to as micro zinc oxide. Generally, rubber vulcanization, particularly in tire technology, requires at least about 2 pbw of zinc oxide per 100 parts by weight (pbw) of rubber to produce the desired cure. 2 Nano zinc oxide with a BET surface area of greater than 1 / g has also been proposed, and it has been suggested that the use of nano zinc oxide could ultimately provide improved processes requiring lower inputs of zinc oxide or other zinc species. However, the use of nano zinc oxide presents several difficulties, including manufacturing issues and particle agglomeration.

[0004] There remains a desire to reduce the concentration of zinc, particularly zinc oxide, used in the manufacture of tire components. Summary of the Invention

[0005] One or more embodiments of the present invention provide a process for preparing a rubber vulcanizate, the process comprising providing a vulcanizable composition comprising a sulfur-based curative, zinc oxide, and a eutectic composition, and heating the vulcanizable composition to achieve vulcanization.

[0006] Yet another embodiment of the present invention provides a rubber vulcanizate comprising a vulcanized rubber network comprising a metal compound dispersed throughout the rubber network, wherein the vulcanizate comprises less than 2 parts by weight of zinc oxide per 100 parts by weight of rubber.

[0007] Yet another embodiment of the present invention provides a rubber vulcanizate prepared by a process comprising the steps of preparing a rubber vulcanizate, the process comprising: providing a vulcanizable composition comprising a sulfur-based curative, zinc oxide, and a eutectic composition; and heating the vulcanizable composition to effect vulcanization.

[0008] Yet another embodiment of the present invention provides a method for preparing a vulcanizable composition, comprising combining a vulcanizable rubber, a curative, and a eutectic composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] Embodiments of the present invention are based, at least in part, on the discovery of a sulfur vulcanization process for rubber compositions, which involves curing the rubber in the presence of a metal compound (such as a zinc species) and a eutectic composition. Surprisingly, it has been found that by including the eutectic composition in the vulcanizable composition, the total metal compound dosage required to achieve a desired cure can be significantly reduced without adversely affecting the rubber cure rate and / or cure quality. In certain embodiments, the inclusion of the eutectic composition has also surprisingly resulted in other improvements in one or more vulcanizate properties, such as reduced wear and reduced rolling resistance. Accordingly, embodiments of the present invention provide cured tire components having relatively low concentrations of metals, such as zinc, and technologically useful cure levels. Vulcanizable composition

[0010] As described above, the eutectic composition is introduced into a vulcanizable composition to produce a sulfur-cured vulcanizate. In addition to the eutectic composition, one or more embodiments of the vulcanizable composition include a vulcanizable rubber, a filler, a sulfur-based vulcanizing agent, stearic acid, and a metal compound (e.g., zinc oxide or a zinc oxide derivative). Other optional additional ingredients may also be included, including, but not limited to, process oils and / or extender oils, resins, waxes, cure accelerators, anti-scorching agents, anti-aging agents, antioxidants, and other rubber compounding additives known in the art. eutectic mixture

[0011] In one or more embodiments, a eutectic composition includes a composition formed by combining two or more compounds to provide a product compound with a melting point lower than the melting point of each of the combined compounds. For purposes of this specification, a eutectic composition may be referred to as a eutectic mixture, a eutectic complex, or a eutectic pair. Each of the combined compounds may be referred to as a eutectic component, a eutectic constituent, a eutectic member, or a compound (e.g., a first compound and a second compound) to form the eutectic composition. Depending on the relative amounts of each eutectic component and the temperature at which the observation is made, the eutectic composition may be in the form of a liquid, which may be referred to as a eutectic liquid or a eutectic solvent. For a given composition, if the relative amounts of each component are at or near the lowest melting point of the eutectic mixture, the composition may be referred to as a deep eutectic solvent, which may also be referred to as a DES.

[0012] Without being bound by any particular theory, it is believed that the eutectic components combine or otherwise react or interact to form a complex. Thus, any reference to a eutectic mixture, or eutectic compound, eutectic pair, or eutectic complex includes compounds and reaction products, or complexes, in which the components combine to provide a lower melting point than the individual components. For example, in one or more embodiments, a useful eutectic composition can be defined by Formula I below: Cat + X - zY During the ceremony, Cat+ is a cation and X - is a counter anion (e.g., a Lewis base), and z refers to the number of Y molecules that interact with the counter anion (e.g., a Lewis acid or a Bronsted acid). + may contain an ammonium, phosphonium, or sulfonium cation. - may include, for example, a halide ion. Y may include, for example, a hydrogen bond donor, a metal halide, or a metal halide hydrate. In one or more embodiments, z is a number that achieves a deep eutectic solvent, while in other embodiments, z is a number that achieves a complex that, if not a deep eutectic solvent, has a lower melting point than each of the corresponding eutectic components.

[0013] In one or more embodiments, useful eutectic compositions include compounds of acids and bases, which may include Lewis acids and bases or Bronsted acids and bases. In one or more embodiments, useful eutectic compositions include compounds of quaternary ammonium salts and metal halides (referred to as Type I eutectic compositions), compounds of quaternary ammonium salts and metal halide hydrates (referred to as Type II eutectic compositions), compounds of quaternary ammonium salts and hydrogen bond donors (referred to as Type III eutectic compositions), or compounds of metal halide hydrates and hydrogen bond donors (referred to as Type IV eutectic compositions). Instead of ammonium compounds, analogous sulfonium or phosphonium compounds may be employed, which can be readily envisioned by those skilled in the art. Quaternary ammonium salts

[0014] In one or more embodiments, the quaternary ammonium salt is a solid at 20° C. In these or other embodiments, the metal halide and the hydrogen bond donor are solids at 20° C.

[0015] In one or more embodiments, useful quaternary ammonium salts (which may also be referred to as ammonium compounds) may be defined by the following Formula II: (R1)(R2)(R3)(R4)-N + -Φ - wherein each of R1, R2, R3, and R4 is independently hydrogen or a monovalent organic group, or alternatively, two of R1, R2, R3, and R4 combine to form a divalent organic group; and Φ - is a counter anion. In one or more embodiments, at least one of R, R, R, and R, in other embodiments at least two of them, and in still other embodiments at least three of them are not hydrogen.

[0016] In one or more embodiments, the counter anion (e.g., Φ - ) is a halide (X - ), nitrate (NO3 - ), tetrafluoroborate (BF4 - ), perchlorate (ClO4 - ), triflate (SO3CF3 - ), and trifluoroacetate (COOCF3 - In one or more embodiments, Φ - is a halide ion, and in certain embodiments, a chloride ion.

[0017] In one or more embodiments, the monovalent organic groups comprise hydrocarbyl groups, and the divalent organic groups comprise hydrocarbylene groups. In one or more embodiments, the monovalent and divalent organic groups comprise heteroatoms, such as, but not limited to, oxygen and nitrogen, and / or halogen atoms. Thus, the monovalent organic groups can include alkoxy, siloxy, ether, and ester groups, as well as carbonyl or acetyl substituents. In one or more embodiments, the hydrocarbyl and hydrocarbylene groups contain from 1 (or the appropriate minimum number) to about 18 carbon atoms, in other embodiments from 1 to about 12 carbon atoms, and in other embodiments from 1 to about 6 carbon atoms. The hydrocarbyl and hydrocarbylene groups can be branched, cyclic, or linear. Exemplary types of hydrocarbyl groups include alkyl groups, cycloalkyl groups, aryl groups, and alkylaryl groups. Exemplary types of hydrocarbylene groups include alkylene groups, cycloalkylene groups, arylene groups, and alkylarylene groups. In certain embodiments, the hydrocarbyl group is selected from the group consisting of methyl, ethyl, octadecyl, phenyl, and benzyl groups. In certain embodiments, the hydrocarbyl group is a methyl group and the hydrocarbylene group is an ethylene or propylene group.

[0018] Useful types of ammonium compounds include secondary ammonium compounds, tertiary ammonium compounds, and quaternary ammonium compounds. In these or other embodiments, the ammonium compound includes an ammonium halide, examples of which include, but are not limited to, ammonium chloride. In certain embodiments, the ammonium compound is a quaternary ammonium chloride. In certain embodiments, R1, R2, R3, and R4 are hydrogen, and the ammonium compound is ammonium chloride. In one or more embodiments, the ammonium compound is asymmetric.

[0019] In one or more embodiments, the ammonium compound includes an alkoxy group and may be defined by Formula III: (R1)(R2)(R3)-N + -(R4-OH)Φ - wherein each of R1, R2, and R3 is independently hydrogen or a monovalent organic group, or alternatively, two of R1, R2, and R3 combine to form a divalent organic group, and R4 is a divalent organic group; and Φ - is a counter anion. In one or more embodiments, at least one of R, R, and R, in other embodiments at least two of them, and in still other embodiments at least three of them are not hydrogen.

[0020] Examples of ammonium compounds defined by Formula III include, but are not limited to, N-ethyl-2-hydroxy-N,N-dimethylethanaminium chloride, 2-hydroxy-N,N,N-trimethylethanaminium chloride (also known as choline chloride), and N-benzyl-2-hydroxy-N,N-dimethylethanaminium chloride.

[0021] In one or more embodiments, the ammonium compound includes a halogen-containing substituent and may be defined by formula IV: Φ - -(R1)(R2)(R3)-N + -R4X wherein each of R1, R2, and R3 is independently hydrogen or a monovalent organic group, or alternatively, two of R1, R2, and R3 combine to form a divalent organic group, R4 is a divalent organic group, X is a halogen atom, and Φ - is a counter anion. In one or more embodiments, at least one of R, R, and R, in other embodiments at least two of them, and in still other embodiments at least three of them are not hydrogen. In one or more embodiments, X is chlorine.

[0022] Examples of ammonium compounds defined by Formula III include, but are not limited to, 2-chloro-N,N,N-trimethylethanaminium (also known as chlorocholine chloride) and 2-(chlorocarbonyloxy)-N,N,N-trimethylethanaminium chloride. Hydrogen bond donor compounds

[0023] In one or more embodiments, hydrogen bond donor compounds, which may also be referred to as HBD compounds, include, but are not limited to, amines, amides, carboxylic acids, and alcohols. In one or more embodiments, the hydrogen bond donor compound comprises a hydrocarbon chain moiety. The hydrocarbon chain moiety may have a carbon chain length of at least 2, in other embodiments at least 3, and in other embodiments at least 5 carbon atoms. In these or other embodiments, the hydrocarbon chain moiety has a carbon chain length of less than 30, in other embodiments less than 20, and in other embodiments less than 10 carbon atoms.

[0024] In one or more embodiments, useful amines include compounds defined by the following formula: R1-(CH2) x -R2 wherein R1 and R2 are -NH2, -NHR3, or -NR3R4, and x is an integer of at least 2. In one or more embodiments, x is from 2 to about 10, in other embodiments from about 2 to about 8, and in still other embodiments from about 2 to about 6.

[0025] Specific examples of useful amines include, but are not limited to, aliphatic amines, ethylenediamine, diethylenetriamine, aminoethylpiperazine, triethylenetetramine, tris(2-aminoethyl)amine, N,N'-bis(2aminoethyl)piperazine, piperazinoethylethylenediamine, tetraethyleneepithanamine, propyleneamine, aniline, and substituted anilines, and combinations thereof.

[0026] In one or more embodiments, useful amides include compounds defined by the following formula: R-CO-NH2 wherein R is H, NH2, CH3, or CF3.

[0027] Specific examples of useful amides include, but are not limited to, urea, 1-methylurea, 1,1-dimethylurea, 1,3-dimethylurea, thiourea, urea, benzamide, and acetamide, and combinations thereof.

[0028] In one or more embodiments, useful carboxylic acids include mono-, di-, and tri-functional organic acids, which may include alkyl acids, aryl acids, and mixed alkyl-aryl acids.

[0029] Specific examples of useful monofunctional carboxylic acids include, but are not limited to, aliphatic acids, phenylpropionic acid, phenylacetic acid, and benzoic acid, and combinations thereof. Specific examples of useful difunctional carboxylic acids include, but are not limited to, oxalic acid, malonic acid, adipic acid, and succinic acid, and combinations thereof. Specific examples of useful trifunctional carboxylic acids include citric acid and tricarballylic acid, and combinations thereof.

[0030] Types of alcohols include, but are not limited to, mono-ols, di-ols, and tri-ols. Specific examples of mono-ols include aliphatic alcohols, phenols, substituted phenols, and mixtures thereof. Specific examples of di-ols include ethylene glycol, propylene glycol, resorcinol, substituted resorcinols, and mixtures thereof. Specific examples of tri-ols include, but are not limited to, glycerol and benzenetriol, and mixtures thereof. Metal Halide

[0031] Types of metal halides include, but are not limited to, chlorides, bromides, iodides, and fluorides. In one or more embodiments, these metal halides include, but are not limited to, transition metal halides. Those skilled in the art can readily envision the corresponding metal halide hydrates.

[0032] Specific examples of useful metal halides include, but are not limited to, aluminum chloride, aluminum bromide, aluminum iodide, zinc chloride, zinc bromide, zinc iodide, tin chloride, tin bromide, tin iodide, iron chloride, iron bromide, and iron iodide, and combinations thereof. Those skilled in the art can easily imagine the corresponding metal halide hydrates. For example, aluminum chloride hexahydrate and copper chloride dihydrate correspond to the above halides. Eutectic complex formation

[0033] Those skilled in the art can select appropriate eutectic components in appropriate molar ratios to provide the desired eutectic composition. Those skilled in the art will understand that the molar ratio of the first compound (e.g., a Lewis base) to the second compound (e.g., a Lewis acid) in the pair will vary based on the compounds selected. As those skilled in the art will appreciate, the melting point depression of a eutectic solvent includes the eutectic point, which is the molar ratio of the first compound to the second compound that results in the minimum melting point depression (i.e., a deep eutectic solvent). However, the molar ratio of the first compound to the second compound can be varied and still result in a depression of the melting point of the eutectic solvent relative to the individual melting points of the first and second compounds, even if it is not the minimum melting point. Thus, the practice of one or more embodiments of the present invention includes forming eutectic solvents with molar ratios outside the eutectic point.

[0034] In one or more embodiments, each compound in the eutectic pair and the molar ratio of the first compound to the second compound in the pair are selected to produce a mixture having a melting point less than 130° C., and in other embodiments, less than 110° C., in other embodiments less than 100° C., in other embodiments less than 80° C., in other embodiments less than 60° C., in other embodiments less than 40° C., and in other embodiments less than 30° C. In these or other embodiments, each compound in the eutectic pair and the molar ratio of the compounds to each other are selected to produce a mixture having a melting point greater than 0° C., and in other embodiments, greater than 10° C., in other embodiments greater than 20° C., in other embodiments greater than 30° C., and in other embodiments greater than 40° C.

[0035] In one or more embodiments, each compound in the eutectic pair and the molar ratio of the first compound to the second compound in the pair are selected to produce a eutectic solvent with the ability or capacity (sometimes referred to as solubility or dissolving power) to dissolve a desired metal compound. As will be understood by those skilled in the art, this solubility can be quantified based on the weight of metal compound dissolved in a given weight of eutectic solvent at a specified temperature and pressure for a specified time when preparing a saturated solution. In one or more embodiments, the eutectic solvents of the present invention are selected to achieve a solubility of greater than 100 ppm, in other embodiments greater than 500 ppm, in other embodiments greater than 1000 ppm, in other embodiments greater than 1200 ppm, in other embodiments greater than 1400 ppm, and in other embodiments greater than 1600 ppm, when zinc oxide is dissolved at 50° C. and atmospheric pressure for 24 hours, where ppm is measured on a solute weight to solvent weight basis.

[0036] In one or more embodiments, a eutectic solvent is formed by combining a first compound with a second compound in an appropriate molar ratio to provide a solvent composition (i.e., a composition that is liquid at a desired temperature). The mixture can be mechanically agitated using a variety of techniques, including, but not limited to, solid-state mixing or blending techniques. Generally speaking, the mixture is mixed or otherwise agitated until a visually homogeneous liquid is formed. The mixture can also be formed at elevated temperatures. For example, a eutectic solvent can be formed by heating the mixture to a temperature above 50°C, in other embodiments above 70°C, and in other embodiments above 90°C. Mixing can be continued while the mixture is heated. Once the desired mixture is formed, the eutectic solvent can be cooled to room temperature. In one or more embodiments, the eutectic solvent can be cooled at a controlled rate of less than 1°C / min.

[0037] In one or more embodiments, useful eutectic compositions are commercially available. For example, deep eutectic solvents are commercially available from Scionix under the trade name Ionic Liquids. Useful eutectic compositions are also generally known, as described in U.S. Patent Application Publication Nos. 2004 / 0097755 (A1) and 2011 / 0207633 (A1), both of which are incorporated herein by reference. vulcanizable rubber

[0038] In one or more embodiments, vulcanizable rubber (sometimes simply referred to as rubber or vulcanizable elastomer) can include polymers that can be vulcanized to create compositions with rubbery or elastomeric properties. These elastomers can include natural rubber and synthetic rubber. Synthetic rubbers are typically derived from the polymerization of conjugated diene monomers, copolymerization of conjugated diene monomers with other monomers (e.g., vinyl-substituted aromatic monomers), or copolymerization of ethylene with one or more α-olefins and, optionally, one or more diene monomers.

[0039] Exemplary elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, and epichlorohydrin rubber, as well as mixtures thereof. These elastomers can have a myriad of macromolecular structures, including linear, branched, and star structures. These elastomers may also contain one or more functional units, which typically contain heteroatoms. Filler

[0040] As mentioned above, the vulcanizable compositions of the present invention may contain one or more fillers. These filler materials may include reinforcing and non-reinforcing fillers. Exemplary fillers include carbon black, silica, and various inorganic fillers.

[0041] Useful carbon blacks include furnace blacks, channel blacks, and lamp blacks. More specific examples of carbon blacks include super abrasion furnace blacks, medium super abrasion furnace blacks, high abrasion furnace blacks, high speed extrusion furnace blacks, fine furnace blacks, semi-reinforced furnace blacks, medium processed channel blacks, hard processed channel blacks, conductive channel blacks, and acetylene blacks.

[0042] In certain embodiments, the carbon black has a surface area (EMSA) of at least 20 m 2 / g, in other embodiments at least 35m 2 / g. Surface area values can be determined using the cetyltrimethylammonium bromide (CTAB) technique according to ASTM standard D-1765. The carbon black can be in pelletized or non-pelletized flocculent form. The preferred form of carbon black can depend on the type of mixing equipment used to mix the rubber compound.

[0043] Examples of suitable silica fillers include precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, calcium silicate, aluminum silicate, magnesium silicate, and the like.

[0044] In one or more embodiments, silica can be characterized by its surface area, which is a measure of its reinforcing properties. The BET (Brunauer, Emmet and Teller) method (described in J. Am. Chem. Soc., vol. 60, p. 309 et seq.) is a widely accepted method for determining surface area. The BET surface area of silica is approximately 450 m 2 / g. A useful range of surface area is from about 32 to about 400 m 2 / g, about 100~250m 2 / g, and about 150 to about 220 m 2 / g is an example.

[0045] When one or more silicas are used, the pH of the silicas is generally from about 5 to about 7, or slightly above 7, and in other embodiments from about 5.5 to about 6.8.

[0046] In one or more embodiments, when silica is used as a filler (alone or in combination with other fillers), a coupling agent and / or shielding agent may be added to the rubber composition during mixing to enhance interaction between the silica and the elastomer. Useful coupling and shielding agents are described in U.S. Patent Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, and 5,684,171. , 5,684,172, 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and 6,683,135, which are incorporated herein by reference. Examples of sulfur-containing silica coupling agents include bis(trialkoxysilylorgano) polysulfides or mercapto-organoalkoxysilanes. Types of bis(trialkoxysilylorgano) polysulfides include bis(trialkoxysilylorgano) disulfides and bis(trialkoxysilylorgano) tetrasulfides.

[0047] Other useful filler materials include various inorganic and organic fillers.An example of an organic filler is starch.An example of an inorganic filler is silica, aluminum hydroxide, magnesium hydroxide, titanium oxide, boron nitride, iron oxide, mica, talc (hydrated magnesium silicate), and clay (hydrated aluminum silicate). resin

[0048] As mentioned above, the vulcanizable compositions of the present invention may include one or more resins. These resins can include phenolic resins, as well as hydrocarbon resins such as, for example, cycloaliphatic resins, aliphatic resins, aromatic resins, and terpene resins, as well as combinations thereof. Useful resins are commercially available under various trade names from a variety of companies, including, for example, Chemfax, Dow Chemical Company, Eastman Chemical Company, Idemitsu, Neville Chemical Company, Nippon, Polysat Inc., Resinall Corp., Pinova Inc., Yasuhara Chemical Co., Ltd., Arizona Chemical, and SI Group Inc., and Zeon.

[0049] In one or more embodiments, useful hydrocarbon resins may be characterized by a glass transition temperature (Tg) of from about 30 to about 160° C., and in other embodiments, from about 35 to about 60° C., and in other embodiments, from about 70 to about 110° C. In one or more embodiments, useful hydrocarbon resins may also be characterized by a softening point greater than their glass transition temperature (Tg). In certain embodiments, useful hydrocarbon resins have a softening point of from about 70 to about 160° C., and in other embodiments, from about 75 to about 120° C., and in other embodiments, from about 120 to about 160° C.

[0050] In certain embodiments, one or more cycloaliphatic resins are used in combination with one or more of an aliphatic resin, an aromatic resin, and a terpene resin. In one or more embodiments, one or more cycloaliphatic resins are used as the major weight component (e.g., greater than 50% by weight) of the total resin. For example, the resin used may comprise at least 55% by weight of one or more cycloaliphatic resins, in other embodiments at least 80% by weight, and in other embodiments at least 99% by weight of one or more cycloaliphatic resins.

[0051] In one or more embodiments, cycloaliphatic resins include both cycloaliphatic homopolymer resins and cycloaliphatic copolymer resins, including those derived from cycloaliphatic monomers and those derived from cycloaliphatic monomers, optionally in combination with one or more other (non-cycloaliphatic) monomers, provided that, by weight, the majority of the total monomers are cycloaliphatic. Non-limiting examples of suitable and useful cycloaliphatic resins include cyclopentadiene ("CPD") homopolymer or copolymer resins, and dicyclopentadiene ("DCPD") homopolymer or copolymer resins, and combinations thereof. Non-limiting examples of cycloaliphatic copolymer resins include CPD / vinyl aromatic copolymer resins, DCPD / vinyl aromatic copolymer resins, CPD / terpene copolymer resins, DCPD / terpene copolymer resins, CPD / aliphatic copolymer resins (e.g., CPD / C5 fraction copolymer resins), DCPD / aliphatic copolymer resins (e.g., DCPD / C5 fraction copolymer resins), CPD / aromatic copolymer resins (e.g., CPD / C9 fraction copolymer resins), DCPD / aromatic copolymer resins (e.g., DCPD / C9 fraction copolymer resins), CPD / aromatic copolymer resins -aliphatic copolymer resins (e.g., CPD / C5 and C9 fraction copolymer resins), DCPD / aromatic-aliphatic copolymer resins (e.g., DCPD / C5 and C9 fraction copolymer resins), CPD / vinyl aromatic copolymer resins (e.g., CPD / styrene copolymer resins), DCPD / vinyl aromatic copolymer resins (e.g., DCPD / styrene copolymer resins), CPD / terpene copolymer resins (e.g., limonene / CPD copolymer resins), and DCPD / terpene copolymer resins (e.g., limonene / DCPD copolymer resins). In certain embodiments, the cycloaliphatic resin may include a hydrogenated form of one of the above cycloaliphatic resins (i.e., a hydrogenated cycloaliphatic resin). In other embodiments, the cycloaliphatic resin does not include any hydrogenated cycloaliphatic resins, or in other words, the cycloaliphatic resin is not hydrogenated.

[0052] In certain embodiments, one or more aromatic resins are used in combination with one or more of an aliphatic resin, a cycloaliphatic resin, and a terpene resin. In one or more embodiments, one or more aromatic resins are used as the major weight component (e.g., greater than 50% by weight) of the total amount of resin. For example, the resin used may comprise at least 55% by weight of one or more aromatic resins, in other embodiments at least 80% by weight, and in other embodiments at least 99% by weight of one or more aromatic resins.

[0053] In one or more embodiments, aromatic resins include both aromatic homopolymer resins and aromatic copolymer resins, including those derived from one or more aromatic monomers in combination with one or more other (non-aromatic) monomers, provided that the majority of any type of monomer is aromatic. Non-limiting examples of useful aromatic resins include coumarone-indene resins and alkyl-phenol resins, as well as vinyl aromatic homopolymer or copolymer resins, which may be derived, for example, from one or more of alpha-methylstyrene, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para-(tert-butyl)styrene, methoxystyrene, chlorostyrene, hydroxystyrene, vinylmesitylene, divinylbenzene, vinylnaphthalene, or vinyl aromatic monomers obtained from the C9 or C8-C10 fractions. Non-limiting examples of vinyl aromatic copolymer resins include vinyl aromatic / terpene copolymer resins (e.g., limonene / styrene copolymer resins), vinyl aromatic / C5 fraction resins (e.g., C5 fraction / styrene copolymer resins), and vinyl aromatic / aliphatic copolymer resins (e.g., CPD / styrene copolymer resins and DCPD / styrene copolymer resins). Non-limiting examples of alkyl-phenol resins include p-tert-butylphenol-acetylene resins and alkylphenol-formaldehyde resins (e.g., alkylphenol-acetylene resins, such as resins with a low degree of polymerization). In certain embodiments, the aromatic resin may include a hydrogenated form of one of the above aromatic resins (i.e., a hydrogenated aromatic resin). In other embodiments, the aromatic resin does not include any hydrogenated aromatic resins; in other words, the aromatic resin is not hydrogenated.

[0054] In certain embodiments, one or more aliphatic resins are used in combination with one or more of a cycloaliphatic resin, an aromatic resin, and a terpene resin. In one or more embodiments, one or more aliphatic resins are used as the major weight component (e.g., greater than 50% by weight) of the total amount of resin. For example, the resins used may comprise at least 55% by weight of one or more aliphatic resins, in other embodiments at least 80% by weight, and in other embodiments at least 99% by weight of one or more aliphatic resins.

[0055] In one or more embodiments, aliphatic resins include both aliphatic homopolymer resins and aliphatic copolymer resins, including those derived from one or more aliphatic monomers in combination with one or more other (non-aliphatic) monomers, provided that the majority of any type of monomer is aliphatic. Non-limiting examples of useful aliphatic resins include C5 homopolymer or copolymer resins, C5 / C9 copolymer resins, C5 / vinyl aromatic copolymer resins (e.g., C5 / styrene copolymer resins), C5 / alicyclic copolymer resins, and C5 / C9 / alicyclic copolymer resins, as well as combinations thereof. Non-limiting examples of alicyclic monomers include, but are not limited to, cyclopentadiene ("CPD") and dicyclopentadiene ("DCPD"). In certain embodiments, the aliphatic resin may comprise a hydrogenated form of one of the above aliphatic resins (i.e., a hydrogenated aliphatic resin). In other embodiments, the aliphatic resin does not include any hydrogenated aliphatic resin; in other words, in such embodiments, the aliphatic resin is not hydrogenated.

[0056] In one or more embodiments, terpene resins include both terpene homopolymer resins and terpene copolymer resins, including those derived from one or more terpene monomers in combination with one or more other (non-terpene) monomers, provided that the majority of any type of monomer is a terpene. Non-limiting examples of useful terpene resins include α-pinene resins, β-pinene resins, limonene resins (e.g., L-limonene, D-limonene, and dipentene, a racemic mixture of L- and D-isomers), β-phellandrene, δ-3-carene, δ-2-carene, pinene-limonene copolymer resins, terpene phenolic resins, and aromatically modified terpene resins, as well as combinations thereof. In certain embodiments, the terpene resin may comprise a hydrogenated form of one of the above terpene resins (i.e., a hydrogenated terpene resin). In other embodiments, the terpene resin does not include any hydrogenated terpene resin; in other words, in such embodiments, the terpene resin is not hydrogenated. hardener

[0057] Rubber curatives (also called vulcanizing agents) include sulfur-based curing systems. Curatives are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 20 (3rd ed., 1982), pp. 365-468, and particularly in "Vulcanization Agents and Auxiliary Materials," (pp. 390-402), and in the "Vulcanization" section of A.Y. Coran, Encyclopedia of Polymer Science and Engineering, (2nd ed., 1989), which are incorporated herein by reference. In one or more embodiments, the curative is sulfur. Examples of suitable sulfur vulcanizing agents include "rubbermaker's" soluble sulfur, sulfur-donating vulcanizing agents such as amine disulfide, polymeric polysulfides, or sulfur olefin adducts, and insoluble polymeric sulfur. Vulcanizing agents can be used alone or in combination. One skilled in the art can readily select the amount of vulcanizing agent to achieve the desired level of cure.

[0058] In one or more embodiments, the curing agent is used in combination with a cure accelerator. In one or more embodiments, the accelerator is used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized rubber. Examples of accelerators include thiazole vulcanization accelerators (e.g., 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazyl-sulfenamide (CBS)), and guanidine vulcanization accelerators (e.g., diphenylguanidine (DPG)). One skilled in the art would be able to easily select the amount of cure accelerator to achieve the desired level of cure. Other ingredients

[0059] Other components typically used in rubber compounding may also be added to the rubber composition. These include accelerators, accelerator activators, oils, additive plasticizers, waxes, anti-burn agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids (e.g., stearic acid), deflocculants, and antidegradants (e.g., antioxidants and antiozonants). In certain embodiments, the oils used include those traditionally used as spreader oils. Useful oils or spreaders that may be used include, but are not limited to, aromatic oils, paraffinic oils, naphthenic oils, vegetable oils (other than castor oil), low PCA oils (e.g., MES, TDAE, and SRAE), and heavy naphthenic oils. Suitable low PCA oils also include various plant-derived oils, such as those obtained from vegetables, nuts, and seeds. Non-limiting examples include, but are not limited to, soybean oil, sunflower oil, safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, hemp oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. Metal activators and organic acids

[0060] As noted above, the vulcanizable compositions of the present invention include a metal compound. In one or more embodiments, the metal compound is an activator (i.e., one that aids in the vulcanization or curing of rubber). In other embodiments, the metal activator is a metal oxide. In certain embodiments, the metal activator is zinc oxide. In other embodiments, the metal activator is a zinc species formed in situ through the reaction or interaction between zinc oxide and an organic acid (e.g., stearic acid). In other embodiments, the metal compound is a magnesium compound, such as magnesium hydroxide. In other embodiments, the metal compound is an iron compound, such as iron oxide. In other embodiments, the metal compound is a cobalt compound, such as a cobalt carboxylate.

[0061] In one or more embodiments, zinc oxide is present in an amount of 10 m 2 / g, and in other embodiments, 2 / g, and in other embodiments less than 8m 2 In other embodiments, the zinc oxide is non-functionalized and characterized by a BET surface area of less than 10 m / g. 2 Nano zinc oxide is used, which comprises zinc oxide particles characterized by a BET surface area of greater than 1000 nm / g.

[0062] In one or more embodiments, the organic acid is a carboxylic acid. In certain embodiments, the carboxylic acid is a fatty acid, including saturated and unsaturated fatty acids. In certain embodiments, saturated fatty acids such as stearic acid are used. Other useful acids include, but are not limited to, palmitic acid, arachidic acid, oleic acid, linoleic acid, and arachidonic acid. Ingredient amount rubber

[0063] In one or more embodiments, the vulcanizable composition comprises at least 20 wt. % of the rubber component, and in other embodiments at least 30 wt. %, and in other embodiments at least 40 wt. % of the rubber component, based on the total weight of the composition. In these or other embodiments, the vulcanizable composition comprises up to 90 wt. % of the rubber component, and in other embodiments up to 70 wt. %, and in other embodiments up to 60 wt. % of the rubber component, based on the total weight of the composition. In one or more embodiments, the vulcanizable composition comprises from about 20 to about 90 wt. % of the rubber component, and in other embodiments from about 30 to about 70 wt. %, and in other embodiments from about 40 to about 60 wt. % of the rubber component, based on the total weight of the composition. eutectic composition

[0064] In one or more embodiments, the vulcanizable composition comprises greater than 0.005 parts by weight (pbw) of the eutectic composition per 100 parts by weight of rubber (phr), and in other embodiments greater than 0.01 part by weight, and in other embodiments greater than 0.02 part by weight. In these or other embodiments, the vulcanizable composition comprises less than 3 pbw (phr), and in other embodiments less than 1 pbw (phr), and in other embodiments less than 0.1 pbw (phr). In one or more embodiments, the vulcanizable composition comprises from about 0.005 to about 3 pbw (phr), and in other embodiments from about 0.01 to about 1 pbw (phr), and in other embodiments from about 0.02 to about 0.1 pbw (phr) of the eutectic composition.

[0065] In one or more embodiments, the amount of eutectic solvent can be described based on the loading of metal activator (e.g., zinc oxide). In one or more embodiments, the vulcanizable composition comprises greater than 2 wt. % eutectic solvent, and in other embodiments greater than 3 wt. %, and in other embodiments greater than 5 wt. % eutectic solvent, based on the total weight of eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizable composition. In these or other embodiments, the vulcanizable composition comprises less than 15 wt. % eutectic solvent, and in other embodiments less than 12 wt. %, and in other embodiments less than 10 wt. % eutectic solvent, based on the total weight of eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizable composition. In one or more embodiments, the vulcanizable composition comprises from about 2 to about 15 wt. % eutectic solvent, and in other embodiments from about 3 to about 12 wt. %, and in other embodiments from about 5 to about 10 wt. % eutectic solvent, based on the total weight of eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizable composition. metal compounds

[0066] In one or more embodiments, the vulcanizable composition comprises greater than 0.05 parts by weight (pbw) of metal activator (e.g., zinc oxide) per 100 parts by weight (phr), and in other embodiments greater than 0.1 part by weight, and in other embodiments greater than 0.15 part by weight of metal activator (e.g., zinc oxide). In these or other embodiments, the vulcanizable composition comprises less than 2 pbw (phr), and in other embodiments less than 1 pbw (phr), and in other embodiments less than 0.75 pbw (phr) of metal activator (e.g., zinc oxide). In one or more embodiments, the vulcanizable composition comprises from about 0.05 to about 2 pbw (phr), and in other embodiments from about 0.1 to about 1 pbw (phr), and in other embodiments from about 0.15 to about 0.75 pbw (phr) of metal activator (e.g., zinc oxide). organic acid

[0067] In one or more embodiments, the vulcanizable composition comprises greater than 0.5 parts by weight (pbw) of organic acid (e.g., stearic acid) per 100 parts by weight (phr), and in other embodiments greater than 0.7 parts by weight, and in other embodiments greater than 1.0 parts by weight of organic acid (e.g., stearic acid). In these or other embodiments, the vulcanizable composition comprises less than 5 pbw (phr), and in other embodiments less than 3 pbw (phr), and in other embodiments less than 2 pbw (phr) of organic acid (e.g., stearic acid). In one or more embodiments, the vulcanizable composition comprises from about 0.5 to about 5 pbw (phr), and in other embodiments from about 0.7 to about 3 pbw (phr), and in other embodiments from about 1.0 to about 2 pbw (phr) of organic acid (e.g., stearic acid). Filler

[0068] In one or more embodiments, the vulcanizable composition contains at least 0 parts by weight (pbw) of filler per 100 parts by weight of rubber (phr), and in other embodiments at least 10 parts by weight, and in other embodiments at least 20 parts by weight. In these or other embodiments, the vulcanizable composition contains up to 200 pbw (phr), and in other embodiments up to 100 pbw (phr), and in other embodiments up to 70 pbw (phr). In one or more embodiments, the vulcanizable composition contains from about 0 to about 200 pbw (phr), and in other embodiments from about 10 to about 100 pbw (phr), and in other embodiments from about 20 to about 70 pbw (phr). carbon black

[0069] In one or more embodiments, the vulcanizable composition contains at least 0 parts by weight (pbw) of carbon black per 100 parts by weight of rubber (phr), and in other embodiments at least 10 parts by weight, and in other embodiments at least 20 parts by weight of carbon black. In these or other embodiments, the vulcanizable composition contains up to 200 pbw (phr), and in other embodiments up to 100 pbw (phr), and in other embodiments up to 70 pbw (phr) of carbon black. In one or more embodiments, the vulcanizable composition contains from about 0 to about 200 pbw (phr), and in other embodiments from about 10 to about 100 pbw (phr), and in other embodiments from about 20 to about 70 pbw (phr) of carbon black. silica

[0070] In one or more embodiments, the vulcanizable composition contains at least 5 parts by weight (pbw) silica per 100 parts by weight of rubber (phr), and in other embodiments at least 25 parts by weight, in other embodiments at least 50 parts by weight, and in other embodiments at least 70 parts by weight. In these or other embodiments, the vulcanizable composition contains up to 200 pbw (phr), in other embodiments up to 130 pbw (phr), and in other embodiments up to 80 pbw (phr). In one or more embodiments, the vulcanizable composition contains from about 5 to about 200 pbw (phr), in other embodiments from about 25 to about 130 pbw (phr), and in other embodiments from about 50 to about 80 pbw (phr). Filler Ratio

[0071] In one or more embodiments, the vulcanizable composition can be characterized by the ratio of the amount of the first filler to the amount of the second filler. In one or more embodiments, the carbon black to silica ratio is about 1:1, in other embodiments about 10:1, in other embodiments about 14:1, and in other embodiments about 20:1. In one or more embodiments, the carbon black to silica ratio is about 1:5, in other embodiments about 1:10, in other embodiments about 1:14, and in other embodiments about 1:20. Silica Coupling Agent

[0072] In one or more embodiments, the vulcanizable composition comprises at least 1 part by weight (pbw) of silica coupling agent per 100 parts by weight of silica, and in other embodiments at least 2 parts by weight, and in other embodiments at least 5 parts by weight. In these or other embodiments, the vulcanizable composition comprises at most 20 pbw, in other embodiments at most 15 pbw, and in other embodiments at most 10 pbw of silica coupling agent per 100 parts by weight of silica. In one or more embodiments, the vulcanizable composition comprises from about 1 to about 20 pbw, in other embodiments from about 2 to about 15 pbw, and in other embodiments from about 5 to about 10 pbw of silica coupling agent per 100 parts by weight of silica. resin

[0073] In one or more embodiments, the vulcanizable composition comprises greater than 1 part by weight (pbw) of resin (e.g., hydrocarbon resin) per 100 parts by weight (phr) of rubber, and in other embodiments greater than 15 parts by weight, in other embodiments greater than 25 parts by weight, and in other embodiments greater than 35 parts by weight of resin (e.g., hydrocarbon resin). In these or other embodiments, the vulcanizable composition comprises less than 150 pbw / phr of resin (e.g., hydrocarbon resin), in other embodiments less than 120 pbw / phr, and in other embodiments less than 90 pbw / phr of resin (e.g., hydrocarbon resin). In one or more embodiments, the vulcanizable composition comprises from about 1 to about 150 pbw (phr) of resin (e.g., hydrocarbon resin), in other embodiments from about 15 to about 120 pbw (phr), and in other embodiments from about 25 to about 90 pbw (phr) of resin (e.g., hydrocarbon resin). Process Overview

[0074] In one or more embodiments, the vulcanizable composition is prepared by mixing a vulcanizable rubber with a eutectic solvent to form a masterbatch, followed by adding a curative to the masterbatch. The preparation of the masterbatch may be carried out using one or more auxiliary mixing steps, such as by preparing an initial mixture by mixing two or more components, followed by sequentially adding one or more components to the composition. Additional components may also be added to the vulcanizable composition using conventional techniques, including, but not limited to, carbon black, additional fillers, chemically treated inorganic oxides, silica, silica coupling agents, silica dispersants, processing oils, processing aids (e.g., zinc oxide and fatty acids), and antidegradants (e.g., antioxidants or antiozonants).

[0075] In one or more embodiments, the eutectic composition is prepared prior to its introduction into the vulcanizable rubber. In other words, a first component of the mixture is pre-combined with a second component of the mixture before the mixture is introduced into the vulcanizable composition. In one or more embodiments, the combined components of the mixture are mixed until a homogeneous liquid composition is observed.

[0076] In one or more embodiments, the eutectic composition is precompounded with one or more components of the rubber formulation before introducing the eutectic mixture into the vulcanizable composition. In other words, in one or more embodiments, a component of the vulcanizable composition (e.g., a metal compound such as zinc oxide) is combined with the eutectic mixture to form a precompound or masterbatch, which is then introduced into the mixer where the rubber is mixed. For example, zinc oxide may be dissolved in a eutectic solvent and then introduced into the rubber in the mixer. In other embodiments, the eutectic composition is a minor component of the precompound, and thus the component precompounded with the eutectic composition acts as a carrier for the eutectic composition. For example, the eutectic composition can be combined with a larger volume of zinc oxide, with the zinc oxide acting as a carrier to deliver the solid zinc oxide-eutectic composition compound to the rubber in the mixer. In yet other embodiments, one of the constituent materials of the eutectic pair acts as a solid carrier for the eutectic composition, and thus the combination of the first and second components of the eutectic composition forms a precompound that can be added as a solid to the rubber in the mixer. Those skilled in the art will appreciate that mixtures of this nature are formed by combining an excess amount of one or the other eutectic pair member relative to the other in order to maintain the solid composition at a desired temperature.

[0077] In one or more embodiments, the eutectic solvent is introduced into the vulcanizable rubber as a starting component in forming a rubber masterbatch. The eutectic solvent is then mixed with the rubber at high shear and elevated temperatures. In one or more embodiments, the eutectic solvent is mixed with the rubber at a minimum temperature above 110°C, in other embodiments above 130°C, and in other embodiments above 150°C. In one or more embodiments, the high shear and elevated temperature mixing is carried out at a temperature of from about 110°C to about 170°C.

[0078] In other embodiments, the eutectic solvent is introduced to the vulcanizable rubber along with the sulfur-based vulcanizing agent, either sequentially or all at once. The eutectic solvent is then mixed with the vulcanizable rubber at a maximum temperature of less than 110° C., in other embodiments less than 105° C., and in other embodiments less than 100° C. In one or more embodiments, mixing with the vulcanizing agent is carried out at a temperature of from about 70° C. to about 110° C.

[0079] Similar to the eutectic solvent, the zinc oxide and stearic acid can be added to the rubber masterbatch as starting ingredients, so that these ingredients are mixed at high temperature and high shear. Alternatively, the zinc oxide and stearic acid can be added along with the sulfur-based curative, so that they are mixed only at low temperature.

[0080] In one or more embodiments, the zinc oxide is introduced into the vulcanizable rubber separately and individually from the eutectic solvent. In other embodiments, the zinc oxide and eutectic solvent are precombined to form a zinc oxide masterbatch, which may comprise a solution in which zinc oxide is dissolved or otherwise dispersed in the eutectic solvent. The zinc oxide masterbatch can then be introduced into the vulcanizable rubber. Mixing conditions

[0081] In one or more embodiments, the vulcanizable composition is first prepared by mixing the vulcanizable rubber and the eutectic solvent at a temperature of about 140 to about 180° C., or in other embodiments, about 150 to about 170° C. In certain embodiments, after the initial mixing, the composition (i.e., the masterbatch) is cooled to a temperature below 100° C., or in other embodiments, to a temperature below 80° C., before adding the curatives. Mixing is continued in certain embodiments at a temperature of about 90 to about 110° C., or in other embodiments, at a temperature of about 95 to about 105° C., to prepare the final vulcanizable composition.

[0082] In one or more embodiments, the masterbatch mixing step, or one or more substeps of the masterbatch mixing step, can be characterized by the peak temperature reached by the composition during mixing. This peak temperature may also be referred to as the drop temperature. In one or more embodiments, the peak temperature of the composition during the masterbatch mixing step may be at least 140°C, while in other embodiments it may be at least 150°C, and in other embodiments it may be at least 160°C. In these or other embodiments, the peak temperature of the composition during the masterbatch mixing step may be from about 140 to about 200°C, while in other embodiments it may be from about 150 to about 190°C, and in other embodiments it may be from about 160 to about 180°C. Final Mixing Step

[0083] Following the masterbatch mixing step, a curative or curative system is introduced into the composition and mixing continues to ultimately form the vulcanizable composition. This mixing step may be referred to as the final mix step, the curative mix step, or the product mix step. The product resulting from this mixing step may be referred to as the vulcanizable composition.

[0084] In one or more embodiments, the final mixing step may be characterized by the peak temperature reached by the composition during final mixing. As one skilled in the art will recognize, this temperature may also be referred to as the final drop temperature. In one or more embodiments, the peak temperature of the composition during final mixing may be up to 130°C, while in other embodiments, it may be up to 110°C, and in other embodiments, it may be up to 100°C. In these or other embodiments, the peak temperature of the composition during final mixing may be from about 80 to about 130°C, while in other embodiments, it may be from about 90 to about 115°C, and in other embodiments, it may be from about 95 to about 105°C. mixing equipment

[0085] All components of the vulcanizable composition can be mixed using standard mixing equipment, such as self-contained mixers (e.g., Banbury or Brabender mixers), extruders, kneaders, and two-roll mills. Mixing can be performed singly or in parallel. As suggested above, the components can be mixed in a single stage, or in other embodiments, in two or more stages. For example, in the first stage (i.e., mixing stage), a masterbatch (typically including rubber components and fillers) is prepared. Once the masterbatch is prepared, vulcanizing agents may be introduced and mixed into the masterbatch in a final mixing stage, which is typically performed at a relatively low temperature to reduce the possibility of premature vulcanization. An additional mixing stage (sometimes called a remill) can also be employed between the masterbatch mixing stage and the final mixing stage. Tire Preparation

[0086] The vulcanizable composition can be processed into tire components according to conventional tire manufacturing techniques, including standard rubber molding, molding, and curing techniques. Typically, vulcanization is achieved by heating the vulcanizable composition in a mold. For example, the vulcanizable composition can be heated to about 140 to about 180°C. The cured or crosslinked rubber composition can be referred to as a vulcanizate, which generally contains a thermoset three-dimensional polymer network. Other ingredients (e.g., fillers and processing aids) can be uniformly dispersed throughout the crosslinked network. Pneumatic tires can be made as described in U.S. Patent Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference. Vulcanizate properties

[0087] As noted above, the vulcanizable compositions of the present invention can be cured to prepare various tire components, including, but not limited to, tire treads, tire sidewalls, belt skims, innerliners, and bead apexes.

[0088] According to aspects of the present invention, tire components (which may also be referred to as vulcanizates) are characterized by advantageous cure characteristics while containing relatively low concentrations of metal activators, such as zinc species.

[0089] In one or more embodiments, the vulcanizate is characterized by containing less than 2 pbw zinc per hundred parts by weight of rubber (phr), in other embodiments less than 1 pbw, and in other embodiments less than 0.7 pbw zinc.

[0090] In one or more embodiments, the tire component is a tire tread. As outlined herein, the tread includes only limited concentrations of a metal activator, such as a zinc species, but the tread is still characterized by a 300% modulus greater than 3 MPa, and in other embodiments greater than 5 MPa, and in other embodiments greater than 7 MPa, when measured according to ASTM Standard D-412 at room temperature.

[0091] To demonstrate the practice of the present invention, the following experiments were performed on several vulcanizable compositions. The vulcanizable compositions were prepared by using the ingredients and mixing sequence shown in the table below. All amounts are given in parts by weight per 100 parts by weight of rubber unless otherwise specified. Generally speaking, the amount and point of addition of zinc oxide and eutectic solvent were varied throughout the experiments. The table below also shows the results of several analytical tests performed on the compositions and / or vulcanizates prepared from the compositions. Formation of eutectic solvent I

[0092] A eutectic composition of choline chloride and urea was prepared by mixing 1 mole of choline chloride with 2 moles of urea at 100°C to form a eutectic solvent. The eutectic solvent was considered to be a deep eutectic solvent, which can be referred to as DES-I. The DES-I was allowed to cool to room temperature under standard conditions. Experiment I

[0093] In a first set of experiments, vulcanizable compositions were prepared using the rubber formulations and mixing sequences shown in Table I. The rubber formulations were representative of rubber formulations useful in the manufacture of tire treads. As shown in Table I, the mixing process was a three-step mixing process, including a masterbatch mixing step, a "remill mixing step," and a final mixing step. The various mixing steps were carried out in a Banbury mixer. During the preparation of the masterbatch, the mixer was operated at 75 rpm, and the composition reached a peak temperature of 160°C. At that point, the composition was dropped from the mixer and allowed to cool to less than about 85°C. At this point, the composition was reintroduced into the mixer along with the ingredients identified for the "remill stage," and mixing continued at 75 rpm, with the composition achieving a peak composition temperature of about 160°C. The composition was again dropped from the mixer and allowed to cool to a temperature less than about 50°C. The composition was then reintroduced into the mixer along with the ingredients identified for the "final mix stage." These ingredients, including DES-I and zinc oxide, were introduced separately and individually as shown in Table II. Mixing was continued at 40 rpm with the composition reaching a peak temperature of approximately 100° C. The composition was then dropped from the mixer and samples were obtained from the composition for analytical testing purposes, the results of which are shown in Table II. [Table 1]

[0094] Rheometer measurements were performed using an MDR2000 operating at the temperatures specified in the table. Tensile mechanical properties (maximum stress, modulus, elongation, and toughness) of the vulcanizates were measured by using standard procedures described in ASTM-D412. Dynamic rheological properties (e.g., tan δ) of the vulcanizates were obtained from temperature sweep tests conducted at 10 Hz over the range of about -80°C to about 80°C. [Table 2]

[0095] The data in Table II show that in the presence of the eutectic solvent, the ZnO dosage can be clearly reduced. Experiment II

[0096] In a second experiment, DES-I, prepared using the same procedure as above, was incorporated into a vulcanizable composition prepared using a two-stage mixing process. The components and mixing sequence used are shown in Table III. This rubber compound represents a rubber compound useful for manufacturing tire sidewalls.

[0097] As with the previous experiments, mixing was performed in a Bunbury mixer. During the preparation of the masterbatch, the mixer was operated at 75 rpm and reached a peak temperature of 160°C. At that point, the composition was dropped from the mixer and allowed to cool to below about 85°C. The composition was then reintroduced into the mixer along with the components specified for the "final mix stage," including the amounts of DES-I and zinc oxide as shown in Table IV. Mixing continued at 40 rpm, with the composition reaching a peak temperature of about 100°C. [Table 3]

[0098] As in the previous experiment, the samples were subjected to analytical testing, the results of which are shown in Table IV. [Table 4]

[0099] The data in Table IV show that in the presence of the eutectic solvent, the ZnO dosage can be clearly reduced. Experiment III

[0100] In a third experiment, DES-I, prepared using the same procedure as above, was incorporated into a vulcanizable composition representing a rubber compound useful for the manufacture of innerliners. The mixing conditions were the same as those described above for Experiment II. The components and mixing order used are shown in Table V. [Table 5]

[0101] As in the previous experiment, the samples were subjected to analytical testing, the results of which are shown in Table VI. [Table 6]

[0102] In addition to the MDR, mechanical, and rheological properties, the vulcanizates were analyzed for air permeability according to ASTM D-3985. The data in Table VI show that in the presence of the eutectic solvent, the ZnO dosage can be significantly reduced. Experiment IV

[0103] In a fourth experiment, DES-I, prepared using the same procedure as above, was incorporated into a vulcanizable composition representing a rubber compound useful in the manufacture of tire belt skims. The mixing conditions were the same as those described above for Experiment II. The components and mixing order used are shown in Table VII. [Table 7]

[0104] As in the previous experiment, the samples were subjected to analytical testing, the results of which are shown in Table VIII. [Table 8]

[0105] The data in Table VIII show that in the presence of the eutectic solvent, the ZnO dosage can be clearly reduced. Experiment V

[0106] In the fifth experiment, DES-I, prepared using the same procedure as above, was incorporated into a vulcanizable composition representing a rubber compound useful in the manufacture of tire treads. The mixing conditions were the same as those noted above for Experiment II, except that DES-I was incorporated with the masterbatch components, as shown in Table IX, which lists the components and mixing order used. As in the previous experiment, samples were subjected to analytical testing. The results of the testing are also shown in Table IX. [Table 9]

[0107] The data in Table IX show that in the presence of the eutectic solvent, the ZnO dosage can be clearly reduced. Formation of eutectic solvent II

[0108] A eutectic composition of choline chloride and malonic acid was prepared by mixing 1 mole of choline chloride with 1 mole of malonic acid at 100°C to form a eutectic solvent. This eutectic solvent was considered to be a deep eutectic solvent, which can be designated DES-II. DES-II was allowed to cool to room temperature under standard conditions. Experiment VI

[0109] In the sixth experiment, DES-I prepared using the same procedure as above and DES-II prepared above were incorporated into a vulcanizable composition as shown in Table X. The mixing conditions were the same as those described above for Experiment II, listing the components and mixing order used. [Table 10]

[0110] As in the previous experiment, the samples were subjected to analytical testing, the results of which are also shown in Table XI. [Table 11]

[0111] The data in Table VIII show that in the presence of the eutectic solvent, the ZnO dosage can be clearly reduced.

[0112] Various modifications and alterations that do not depart from the scope and spirit of the invention will be apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.

Claims

1. 1. A method for preparing a vulcanizable composition, comprising: (i) compounding a vulcanizable rubber, a curative, zinc oxide, and a eutectic composition, wherein the vulcanizable composition comprises less than 2 parts by weight (pbw) of the zinc oxide per 100 parts by weight (phr) of the vulcanizable rubber; The eutectic composition has the formula Cat ＋ X － zY (In the formula, Cat ＋ is a cation, and X － is a counter anion, and z represents the number of Y molecules that combine, react or interact with said counter anion; the counter anion is a Lewis acid or a Bronsted acid, the cation is an ammonium, phosphonium, or sulfonium cation, and Y is a hydrogen bond donor, a metal halide, or a metal halide hydrate; The cation is an ammonium cation, and X － is chloride, Y is a hydrogen bond donor and is urea.

2. A vulcanizate prepared from the method for preparing a vulcanizable composition according to claim 1, The vulcanizate is obtained by heating the vulcanizable composition to achieve vulcanization.

3. A rubber vulcanizate comprising a eutectic composition or a residue of a eutectic composition, a vulcanized rubber network containing a metal compound dispersed throughout the rubber network, the metal compound being zinc oxide; containing less than 1 part by weight of zinc oxide per 100 parts by weight of rubber; The eutectic composition has the formula Cat ＋ X － zY (In the formula, Cat ＋ is a cation, and X － is a counter anion, and z represents the number of Y molecules that combine, react or interact with said counter anion; the counter anion is a Lewis acid or a Bronsted acid, the cation is an ammonium, phosphonium, or sulfonium cation, and Y is a hydrogen bond donor, a metal halide, or a metal halide hydrate; The cation is an ammonium cation, and X － is chloride and Y is a hydrogen bond donor and a urea.

4. the rubber vulcanizate is a tire tread; 4. The rubber vulcanizate of claim 3, wherein the rubber vulcanizate is characterized by a 300% modulus of greater than 3 MPa.

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