vulcanizing rubber composition containing a solid eutectic mixture

Abstract

A method for preparing a sidewall support, comprising the steps of (i) providing a vulcanizable composition comprising an elastomer, a filler, a curing agent, and a eutectic composition, wherein the eutectic composition is solid; (ii) preparing an environmentally friendly sidewall support from the vulcanizable composition; and (iii) subjecting the environmentally friendly sidewall support to curing conditions.

Description

[Technical Field]

[0001] Embodiments of the present invention relate to vulcanizable compositions prepared using solid eutectic compositions, and vulcanized products produced therefrom. [Background technology]

[0002] In tire manufacturing technology, zinc oxide, along with stearic acid, has played a crucial role in vulcanization. Zinc oxide, or possibly salts formed by a combination of zinc oxide and stearic acid, is thought to interact with sulfur to provide the desired crosslinking density in the rubber matrix. It is also known that the addition of eutectic compositions can reduce the required amount of zinc oxide. For example, International Publication WO2019 / 089788 teaches a vulcanizable rubber composition containing reduced levels of zinc oxide due to the presence of a eutectic solvent. It has been found that vulcanizable compositions containing a small amount of zinc oxide, approximately 0.05 parts per 100 parts of rubber, are useful for preparing tire components in the presence of a eutectic solvent, particularly a deep eutectic solvent such as Reline.

[0003] Those skilled in the art will understand that vulcanizable compositions are often prepared by mixing various components used in the production of vulcanizable compositions, such as, but not limited to, vulcanizable rubber, fillers, and curing agents, in a solid state. Most of these components are solids under standard pressure and temperature conditions, which is useful considering the solid-state mixing techniques used. In other words, those skilled in the art will understand that for one or more reasons, it is advantageous to introduce and mix solid components into vulcanizable compositions as opposed to liquid components. [Overview of the project]

[0004] One or more embodiments of the present invention provide a method for preparing a sidewall support, the method comprising: (i) providing a vulcanizable composition comprising an elastomer, a filler, a curing agent, and a eutectic composition, wherein the eutectic composition is solid; (ii) preparing the vulcanizable composition into an environmentally friendly sidewall support; and (iii) subjecting the environmentally friendly sidewall support to curing conditions.

[0005] Another embodiment of the present invention provides a method for forming a pneumatic tire, which includes arranging a sidewall support formed by a tuning method onto an environmentally friendly tire.

[0006] A further embodiment of the present invention provides a method for forming a pneumatic tire, the method comprising arranging a side wall support formed by a conditioning method onto a hardened tire.

[0007] A further embodiment of the present invention provides a pneumatic tire comprising: (i) a tread; (ii) a carcass; (iii) an optional inner liner layer; and (iv) a pair of sidewall supports disposed on the carcass or optional inner liner layer, wherein, if present, the sidewall supports are prepared from a vulcanizable composition comprising an elastomer, a filler, a curing agent, and a eutectic composition. [Modes for carrying out the invention]

[0008] Embodiments of the present invention are based, at least in part, on the discovery of a process for preparing a vulcanizable composition by combining a vulcanizable rubber, a curing agent, and a fixed eutectic composition. While the prior art attempts to cure rubber compositions in the presence of eutectic compositions, particularly deep eutectic solvents, the present invention offers advantages over the prior art, as the use of a solid eutectic composition provides several advantages over the use of a liquid eutectic composition. For example, solid eutectic compositions are considered easier to handle and disperse better in rubber compositions. In one or more embodiments, the eutectic composition used in carrying out the present invention is a solid deep eutectic, which is eutectic at or near its lowest melting point.

[0009] vulcanizable composition As described above, the vulcanizable composition of the present invention comprises a vulcanizable rubber, a curing agent, and a solid eutectic composition. The composition may also contain other components that are common in the art of producing vulcanizable rubber compositions, such as, but are not limited to, reinforcing fillers, degradation inhibitors, curing activators, curing accelerators, oils, resins, plasticizers, pigments, fatty acids, zinc oxide, and compounding accelerators.

[0010] vulcanized rubber In one or more embodiments, the vulcanizable rubber may also be referred to as an elastomer polymer, rubber polymer, vulcanizable polymer, or simply elastomer, and may include a polymer that can be vulcanized to form a composition having rubber or elastomer properties. These elastomers may include natural rubber and synthetic rubber. Synthetic rubber is typically obtained from polymerization of conjugated diene monomers, copolymerization of conjugated diene monomers with other monomers, such as vinyl-substituted aromatic monomers, or copolymerization of ethylene with one or more α-olefins and optionally one or more diene monomers.

[0011] 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, epichlorohydrin rubber, and mixtures thereof. These elastomers can have countless macromolecular structures, including linear, branched, and star-shaped structures. These elastomers may also contain one or more functional units, which typically include heteroatoms. In certain embodiments, the vulcanizable composition includes a blend of natural rubber and a synthetic diene rubber such as polybutadiene. In other embodiments, the vulcanizable composition includes an olefin rubber such as ethylene-propylene-diene rubber (EPDM).

[0012] Elastomers can be characterized by their number-average molecular weight (Mn), which is measured using gel permeation chromatography with a polystyrene standard and can be adjusted with Marc-Hauink parameters. According to embodiments of the present invention, elastomers can have Mn greater than 120, greater than 150 in other embodiments, and greater than 180 kg / mol in other embodiments. In these or other embodiments, elastomers can have Mn less than 800, less than 600 in other embodiments, and less than 400 kg / mol in other embodiments. In one or more embodiments, elastomers have Mn between about 120 and about 800, between about 150 and about 600 in other embodiments, and greater than 180 and about 400 kg / mol in other embodiments.

[0013] hardening agent A number of rubber curing agents (also called vulcanizing agents) may be used, including sulfur or peroxide-based curing systems. Curing agents are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 20, pgs. 365-468, (3rd Ed. 1982), particularly, Vulcanization Agents and Auxiliary Materials, pgs. 390-402, and A.Y. Coran, Vulcanization, Encyclopedia of Polymer Science and Engineering, (2nd Ed. 1989), which are incorporated herein by reference. In one or more embodiments, the curing agent is a sulfur-containing vulcanizing agent. Examples of suitable sulfur-containing vulcanizing agents include sulfur-donating vulcanizing agents such as "rubbermaker's" soluble sulfur, amine disulfides, polymeric polysulfides, or sulfur olefin adducts, and insoluble polymeric sulfur. The vulcanizing agents may be used alone or in combination. One skilled in the art would be able to readily select the amount of vulcanizing agent to achieve the desired level of curing.

[0014] In one or more embodiments, the curing agent is used in combination with a curing accelerator. In one or more embodiments, an 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 such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazyl-sulfenamide (CBS), and guanidine vulcanization accelerators such as diphenylguanidine (DPG).

[0015] Solid eutectic composition In one or more embodiments, a solid eutectic composition includes a composition formed by combining two or more compounds that provides a resulting combination having a melting point lower than the melting point of each of the compounds being combined, while remaining in the solid phase under normal or standard conditions of temperature and pressure. For the purposes of this specification, a solid eutectic composition may be referred to as a solid eutectic mixture, a solid eutectic complex, or a solid eutectic pair. Each of the compounds being combined may also be referred to, respectively, as a eutectic component, a eutectic constituent, a eutectic member, or a compound for forming a eutectic composition (e.g., a first compound and a second compound). 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 solid eutectic mixture, or a solid eutectic combination, a solid eutectic pair, or a solid eutectic complex includes a combination and reaction product or complex between components that combine to produce a composition having a melting point lower than that of each of the respective components, but that is solid under normal or standard conditions of temperature and pressure. For a given composition, if the relative amounts of the respective components 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 deep eutectic or DES. In one or more embodiments, the eutectic mixture is a composition within + / - 20 molar ratio %, in other embodiments within + / - 10 molar ratio %, and in other embodiments within + / - 5 molar ratio % from the molar ratio that achieves the lowest melting point of the mixture.

[0016] In one or more embodiments, the solid eutectic composition has a melting point above 20 °C at atmospheric pressure (i.e., 1 atm), above 22 °C in other embodiments, above 25 °C in other embodiments, above 30 °C in other embodiments, above 40 °C in other embodiments, above 50 °C in other embodiments, and above 60 °C in other embodiments.

[0017] In one or more embodiments, a useful eutectic composition can be defined by the following Formula I: Cat , + , <color="#FF0000"> - < / color>X - zY In the formula, Cat+ is a cation, and X - is the 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 base). For example, Cat+ can contain an ammonium cation, a phosphonium cation, or a sulfonium cation. - This may include, for example, halide ions. In one or more embodiments, z is a number that realizes a deep eutectic solvent, while in other embodiments, z is a number that realizes a complex having a lower melting point than each eutectic component.

[0018] In one or more embodiments, useful eutectic compositions include combinations of acids and bases, such as Lewis acids and bases, or Brønsted acids and bases. In one or more embodiments, useful eutectic compositions include combinations of quaternary ammonium salts and metal halides (referred to as type I eutectic compositions), combinations of quaternary ammonium salts and metal halide hydrates (referred to as type II eutectic compositions), combinations of quaternary ammonium salts and hydrogen bond donors (referred to as type III eutectic compositions), or combinations of metal halide hydrates and hydrogen bond donors (referred to as type IV eutectic compositions). Similar combinations of sulfonium or phosphonium can be used instead of ammonium compounds, and these can be easily conceived by those skilled in the art.

[0019] Quaternary ammonium salts In one or more embodiments, a useful quaternary ammonium salt, which may also be called an ammonium compound, may be defined by the following formula II: (R1)(R2)(R3)(R4)-N + -Φ - In the formula, each R1, R2, R3, and R4 is individually hydrogen or a monovalent organic group, or alternatively, two of R1, R2, R3, and R4 are bonded together to form a divalent organic group, Φ -is the counter anion. In one or more embodiments, at least one of R1, R2, R3 and R4, in other embodiments at least two, and in other embodiments at least three are not hydrogen.

[0020] In one or more embodiments, the counter anion (e.g., Φ - ) is selected from the group consisting of halide (X - ), nitrate (NO3 - ), tetrafluoroborate (BF4 - ), perchlorate (ClO4 - ), triflate (SO3CF3 - ), trifluoroacetate (COOCF3 - ). In one or more embodiments, Φ - is a halide ion, and in certain embodiments, it is a chloride ion.

[0021] In one or more embodiments, the monovalent organic group comprises a hydrocarbyl group, and the divalent organic group comprises a hydrocarbylene group. In one or more embodiments, the monovalent and divalent organic groups comprise heteroatoms, such heteroatoms being, for example, oxygen and nitrogen, and / or halogen atoms, but not limited to these. Therefore, examples of monovalent organic groups include alkoxy groups, siloxy groups, ether groups, and ester groups, as well as carbonyl or acetyl substituents. In one or more embodiments, the hydrocarbyl and hydrocarbylene groups comprise 1 (or a suitable minimum) to about 18 carbon atoms, 1 to about 12 carbon atoms in other embodiments, and 1 to about 6 carbon atoms in other embodiments. The hydrocarbyl and hydrocarbylene groups may 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 a methyl group, an ethyl group, an octadecyl group, a phenyl group, and a benzyl group. In certain embodiments, the hydrocarbyl group is a methyl group, and the hydrocarbylene group is an ethylene or propylene group.

[0022] Useful types of ammonium compounds include secondary, tertiary, and quaternary ammonium compounds. In these or other embodiments, the ammonium compound is an ammonium halide, such as ammonium chloride, but is not limited to these. In certain embodiments, the ammonium compound is quaternary ammonium chloride (e.g., choline 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.

[0023] In one or more embodiments, the ammonium compound comprises an alkoxy(hydroxyalkyl) group and can be defined by the following formula III: (R1)(R2)(R3)-N + -(R4-OH)Φ - In the formula, each R1, R2, and R3 is either hydrogen or a monovalent organic group individually, or alternatively, two of R1, R2, and R3 are bonded together to form a divalent organic group, and R4 is a divalent organic group, Φ - is a counter anion. In one or more embodiments, R1, R2, R3 and at least one of them, in other embodiments at least two, and in other embodiments at least three are not hydrogen.

[0024] Examples of ammonium compounds defined by formula III include, but are not limited to, N-ethyl-2-hydroxy-N,N-dimethylethaneaminium chloride, 2-hydroxy-N,N,N-trimethylethaneaminium chloride (also known as collinchloride), and N-benzyl-2-hydroxy-N,N-dimethylethaneaminium chloride.

[0025] In one or more embodiments, the ammonium compound comprises a halogen-containing substituent and can be defined by the following formula IV: Φ - -(R1)(R2)(R3)-N + -R4X In the formula, each R1, R2, and R3 is either a hydrogen atom or a monovalent organic group, or alternatively, two of R1, R2, and R3 are bonded together 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 R1, R2, and R3, in other embodiments at least two, and in other embodiments at least three are not hydrogen. In one or more embodiments, X is chlorine.

[0026] Examples of ammonium compounds defined by formula IV include, but are not limited to, 2-chloro-N,N,N-trimethylethaneaminium (also known as choline chloride) and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride.

[0027] Hydrogen bond donor compounds In one or more embodiments, hydrogen-bond donor compounds, which may also be called HBD (hydrogen-bond donor) compounds, include, but are not limited to, amines, amides, carboxylic acids, and alcohols. In one or more embodiments, the hydrogen-bond donor compound comprises hydrocarbon chain components. The hydrocarbon chain components may have a carbon chain length of at least 2, at least 3 in other embodiments, and at least 5 carbon atoms in other embodiments. In these or other embodiments, the hydrocarbon chain components have a carbon chain length of less than 30, less than 20 in other embodiments, and less than 10 in other embodiments.

[0028] In one or more embodiments, useful amines include compounds defined by the following formula: R1-(CH2) x -R2 In the formula, R1 and R2 are -NH2, -NHR3, or -NR3R4, and x is an integer of at least 2. In one or more embodiments, x is between 2 and about 10, in other embodiments it is between about 2 and about 8, and in other embodiments it is between about 2 and about 6.

[0029] Specific examples of useful amines include, but are not limited to, aliphatic amines, ethylenediamines, diethylenetriamines, aminoethylpiperazines, triethylenetetramines, tris(2-aminoethyl)amines, N,N'-bis-(2-aminoethyl)piperazines, piperadinoethylethylenediamines, and tetraethylenepentaamines, propyleneamines, aniline, substituted aniline, and combinations thereof.

[0030] In one or more embodiments, useful amides include compounds defined by the following formula: R-CO-NH2 In the formula, R is H, NH2, CH3, or CF3.

[0031] Specific examples of useful amides include, but are not limited to, urea, 1-methylurea, 1,1-dimethylurea, 1,3-dimethylurea, thiourea, urea, benzamide, acetamide, and combinations thereof.

[0032] In one or more embodiments, useful carboxylic acids include monofunctional, difunctional, and trifunctional organic acids. Examples of these organic acids include alkyl acids, aryl acids, and mixed alkyl-aryl acids.

[0033] Specific examples of useful monofunctional carboxylic acids include, but are not limited to, aliphatic acids, phenylpropionic acid, phenylacetic acid, benzoic acid, and combinations thereof. Specific examples of difunctional carboxylic acids include, but are not limited to, oxalic acid, malonic acid, adipic acid, succinic acid, and combinations thereof. Specific examples of trifunctional carboxylic acids include citric acid, tricarbaryl acid, and combinations thereof.

[0034] Examples of alcohol types include, but are not limited to, monools, diols, and triols. Specific examples of monools include aliphatic alcohols, phenols, substituted phenols, and mixtures thereof. Specific examples of diols include ethylene glycol, propylene glycol, resorcinol, substituted resorcinols, and mixtures thereof. Specific examples of triols include, but are not limited to, glycerol, benzenetriol, and mixtures thereof.

[0035] Metal halides Examples 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 easily envision the corresponding metal halide hydrates.

[0036] 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, iron iodide, and combinations thereof. Those skilled in the art can easily envision corresponding metal halide hydrates. For example, aluminum chloride hexahydrate and copper chloride dihydrate correspond to the above-mentioned halides.

[0037] Eutectic complex formation Those skilled in the art can select appropriate eutectic components in appropriate molar ratios to provide a desired eutectic composition. Those skilled in the art will understand that the molar ratio of a first compound (e.g., a Lewis base) to a second compound (e.g., a Lewis acid) in a pair varies depending on the selected compounds. As those skilled in the art will understand, the melting point suppression of a eutectic solvent includes a eutectic point, which is the molar ratio of the first compound to the second compound that produces maximum melting point suppression (i.e., a deep eutectic solvent). However, the molar ratio of the first compound to the second compound can be varied in various ways, and still, although not the lowest melting point (i.e., not the maximum suppression point), it is possible to suppress the melting point of the eutectic solvent with respect to the individual melting points of the first and second compounds. Therefore, the implementation of one or more embodiments of the present invention involves forming a eutectic solvent at molar ratios outside the eutectic point.

[0038] In one or more embodiments, the eutectic pair compounds, and the molar ratio of the first compound to the second compound in the pair, are selected to maintain the eutectic composition as a solid at temperatures up to at least 20°C, in other embodiments up to at least 22°C, in other embodiments up to at least 25°C, in other embodiments up to at least 30°C, in other embodiments up to at least 40°C, in other embodiments up to at least 50°C, and in other embodiments up to at least 60°C, at atmospheric or standard pressure (i.e., 1 atm). In one or more embodiments, the eutectic pair compounds, 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, 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, the eutectic pairs of compounds, and the molar ratios of the compounds, are selected to produce a mixture with a melting point above 20°C, above 22°C in other embodiments, above 25°C in other embodiments, above 30°C in other embodiments, above 35°C in other embodiments, above 40°C in other embodiments, above 50°C in other embodiments, and above 60°C in other embodiments.

[0039] In one or more embodiments, the compounds of the eutectic pair, and the molar ratio of the first compound to the second compound of the pair, are selected to produce a eutectic solvent having the ability or performance to dissolve a desired metal compound, which may be referred to as solubility or dissolving power. As will be understood by those skilled in the art, this solubility can be quantified based on the weight of the metal compound dissolved in a given weight of the eutectic solvent for a specified time under specified temperature and pressure when preparing a saturated solution. In one or more embodiments, the eutectic solvent of the present invention is selected to achieve a solubility of more than 100 ppm, more than 500 ppm in other embodiments, more than 1000 ppm in other embodiments, more than 1200 ppm in other embodiments, more than 1400 ppm in other embodiments, and more than 1600 ppm in other embodiments when zinc oxide is dissolved at a temperature of 50°C and atmospheric pressure for 24 hours. Here, ppm is measured on a solute weight versus solvent weight basis.

[0040] Filler As suggested above, the sidewall support can be prepared using a vulcanizable composition containing a filler. The filler may include one or more conventional reinforcing or non-reinforcing fillers. For example, useful fillers include carbon black, silica, alumina, and silicates such as calcium silicate, aluminum silicate, and magnesium silicate.

[0041] In one or more embodiments, carbon blacks include furnace black, channel black, and lamp black. More specific examples of carbon blacks include super abrasion furnace (SAF) black, intermediate super abrasion furnace (ISAF) black, high abrasion furnace (HAF) black, fast extrusion furnace (FEF) black, fine furnace (FF) black, semi-reinforcing furnace (SRF) black, intermediate processed channel black, hard processed channel black, conductive channel black, and acetylene black. Representative carbon blacks useful in one or more embodiments may include those specified by ASTM D1765, such as N326, N330, N339, N343, N347, N351, N358, N550, N650, N660, N762, N772, and N774.

[0042] In one or more embodiments, the carbon black is at least 20m 2 / g, in other embodiments, at least 35m 2 / g, in other embodiments, at least 50m 2 / g, in other embodiments, at least 60m 2 It may have a surface area of ​​about 20 to about 110 m². In these or other embodiments, carbon black may have a surface area of ​​about 20 to about 110 m². 2 / g, in other embodiments, about 25 to about 80m 2 / g, in other embodiments, about 30 to about 60m 2 / g, in other embodiments, about 60 to about 110m 2 / g, and in other embodiments, about 40 to about 50m 2It has a surface area of ​​ / g. For the purposes of this specification, unless otherwise specified, the surface area value of carbon black is determined by ASTM D-1765 using the cetyltrimethylammonium bromide (CTAB) technique. Carbon black may be in pelletized form or in unpelleted cotton form. The preferred form of carbon black may depend on the type of mixing equipment used to mix the rubber compound.

[0043] In one or more embodiments, the filler may contain silica. When silica is used as a filler, it may be used in combination with a binder. In these or other embodiments, silica may be used in combination with a silica dispersant.

[0044] In one or more embodiments, useful silica includes, but is not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (amorphous silicic acid), fumed silica, calcium silicate, and the like. Other suitable fillers include aluminum silicate and magnesium silicate. In certain embodiments, the silica is precipitated amorphous wet-treated hydrated silica. In one or more embodiments, these silicas are produced by a chemical reaction in water, thereby precipitating as ultrafine spherical particles. These primary particles are thought to strongly associate to form aggregates, which then combine to form aggregates with less force.

[0045] Some commercially available silica products that may be used include Hi-Sil® 215, Hi-Sil® 233, and Hi-Sil® 190 (PPG Industries, Inc.; Pittsburgh, PA). Other suppliers of commercially available silica include Grace Davison (Baltimore, MD), Degussa Corp. (Parsippany, NJ), Rhodia Silica Systems (Cranbury, NJ), and JMHuber Corp. (Edison, NJ).

[0046] In one or more embodiments, silica can be characterized by its surface area, which serves as a measure of its reinforcing properties. The Brunauer, Emmet, and Teller ("BET") method (described in J.Am.Chem.Soc., vol.60, p.309 et seq.) is a recognized method for determining surface area. The BET surface area of ​​silica is generally 450 m². 2 It is less than / g. The useful range for surface area is approximately 32 to 400 m². 2 / g, about 100~250m 2 / g, and approximately 150-220m 2 / g is one example.

[0047] In one or more embodiments, the pH of the silica may be about 5 to about 7, or slightly above 7, or in other embodiments, about 5.5 to about 6.8.

[0048] In one or more embodiments, useful silica coupling agents include sulfur-containing silica binders. Examples of sulfur-containing silica coupling agents include bis(trialkoxysilylorgano)polysulfides or mercapto-organoalkoxysilanes. Types of bis(trialkoxysilylorgano)polysulfides include bis(trialkoxysilylorgano)disulfide and bis(trialkoxysilylorgano)tetrasulfide. Exemplary silica dispersion aids include, but are not limited to, alkylalkoxysilanes, fatty acid esters of hydrogenated or unhydrogenated C5 or C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated or unhydrogenated C5 or C6 sugars, and mixtures thereof, or mineral or non-mineral additional fillers.

[0049] Processing / Extender Oil In one or more embodiments, the vulcanizing composition of the present invention includes a processing oil, which may also be referred to as an extender oil. In one or more embodiments, the vulcanizing composition does not contain or substantially contains a processing oil.

[0050] In certain embodiments, oils used include those conventionally used as extender oils. Useful oils or extenders 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 oils of various plant origins, such as those extracted from vegetables, nuts, and seeds. Non-limiting examples include, but are not limited to, soy or soybean oil, sunflower oil, safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. As is generally understood in the art, oil refers to a compound having a viscosity that is relatively comparable to other components of a vulcanizing composition, such as a resin.

[0051] Reinforcement resin In one or more embodiments, the vulcanizable composition of the present invention includes a reinforcing resin, which may also be referred to as a thermosetting resin. Examples of reinforcing resins include acrylic resins, alkyd resins, amine resins, amide resins, maleimide resins, maleic acid resins, epoxy resins, furan resins, phenolic resins, phenol-formaldehyde resins, polyamide resins, polyester resins, urethane resins, vinyl resins, vinyl ester resins, cyanoacrylic resins, silicone resins, siloxane resins, melamine resins, urea-formaldehyde resins, and fumaric acid resins. Examples of phenolic resins suitable as reinforcing resins include novolac-type phenolic resins, novolac-type cresol resins, novolac-type xylenol resins, novolac-type resorcinol resins, and oil-modified resins derived therefrom.

[0052] plasticized resin In one or more embodiments, the vulcanizable composition of the present invention may contain one or more plasticizing resins. These resins generally include hydrocarbon resins such as alicyclic resins, aliphatic resins, aromatic resins, terpene resins, and combinations thereof.

[0053] In one or more embodiments, the hydrocarbon resin can be characterized by a glass transition temperature (Tg) of about 30 to about 160°C, in other embodiments by about 35 to about 60°C, and in yet another embodiment by about 70 to about 110°C. In one or more embodiments, the hydrocarbon resin can also be characterized by its softening point being higher than its glass transition temperature (Tg). In certain embodiments, the hydrocarbon resin has a softening point of about 70 to about 160°C, in other embodiments by about 75 to about 120°C, and in yet another embodiment by about 120 to about 160°C.

[0054] Metal activators and organic acids In one or more embodiments, the vulcanizing composition of the present invention comprises a metal compound. In one or more embodiments, the metal compound is an activator (i.e., an agent that assists in the vulcanization or curing of rubber). In other embodiments, the metal activator is a metal oxide. In certain embodiments, the metal activator is a zinc species formed in situ through a 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 cobalt carboxylate.

[0055] In one or more embodiments, zinc oxide is 10m 2 Less than / g, or 9m in other embodiments. 2 Less than / g, in other embodiments 8m 2 It is a non-functionalized zinc oxide characterized by a BET surface area of ​​less than 10 m / g. In other embodiments, 10 m 2 Nano-zinc oxide is used, containing zinc oxide particles characterized by a BET surface area exceeding 1 / g.

[0056] 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, a saturated fatty acid such as stearic acid is used. Other useful acids include, but are not limited to, palmitic acid, arachidic acid, oleic acid, linoleic acid, and arachidonic acid.

[0057] Low molecular weight high vinyl additive In one or more embodiments, the vulcanizable composition comprises a low molecular weight high vinyl polydiene. The polydiene is obtained from the polymerization of conjugated diene monomers, or from the copolymerization of a conjugated diene monomer with other monomers such as vinyl-substituted aromatic monomers. Exemplary low molecular weight high vinyl polydienes include polyisoprene, polybutadiene, polyisobutylene-co-isoprene, poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), and poly(isoprene-co-butadiene), as well as mixtures thereof.

[0058] Low molecular weight high vinyl polydienes can be characterized by their number-average molecular weight (Mn), which is measured using gel permeation chromatography with a polystyrene standard and can be adjusted with the Marc-Hauink parameter. According to embodiments of the present invention, low molecular weight high vinyl polydienes can have Mn greater than 30 kg / mol, greater than 40 kg / mol in other embodiments, and greater than 50 kg / mol in other embodiments. In these or other embodiments, low molecular weight high vinyl polydienes can have Mn less than 120, less than 100 in other embodiments, and less than 80 kg / mol in other embodiments. In one or more embodiments, low molecular weight high vinyl polydienes have Mn about 30 to about 115, about 40 to about 100 in other embodiments, and about 50 to about 80 kg / mol in other embodiments.

[0059] Low molecular weight high vinyl polydienes can be characterized by their molecular weight distribution, which can also be called polydispersity. Low molecular weight high vinyl polydienes are expressed by the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), which is measured using gel permeation chromatography with polystyrene standards and can be adjusted with Marc-Hauink parameters. According to embodiments of the present invention, low molecular weight high vinyl polydienes can have a polyacidity (Mw / Mn) of less than 2.0, less than 1.7 in other embodiments, less than 1.4 in other embodiments, less than 1.3 in other embodiments, less than 1.2 in other embodiments, and less than 1.1 in other embodiments.

[0060] In one or more embodiments, low molecular weight high vinyl polydienes may be characterized by their vinyl content, which may be described as the number of unsaturated 1,2 microstructures relative to the total unsaturation in the polymer chain. As will be understood by those skilled in the art, the vinyl content can be determined by FTIR analysis. In one or more embodiments, the low molecular weight high vinyl polydiene contains more than 40% vinyl, in other embodiments more than 50%, and in other embodiments more than 60% vinyl. In these or other embodiments, the low molecular weight high vinyl polydiene contains less than 95%, in other embodiments less than 90%, and in other embodiments less than 88% vinyl. In one or more embodiments, the low molecular weight high vinyl polydiene contains about 40 to about 95% vinyl, in other embodiments about 50 to about 90%, and in other embodiments about 60 to about 88% vinyl.

[0061] A useful low molecular weight high vinyl polydiene is described in U.S. Patent Application Publication No. 2011 / 0190440, which is incorporated herein by reference.

[0062] Other ingredients Other components typically used in rubber compounding may also be added to the vulcanizing composition used to produce the sidewall support of the present invention. These include waxes, scorch inhibitors, processing aids, peptides, stearic acid, and degradation inhibitors such as antioxidants and ozone degradation inhibitors. In one or more embodiments, one or more additional components may be excluded from the vulcanizing composition of the present invention.

[0063] Ingredient amount rubber In one or more embodiments, the vulcanizable composition contains more than 20% by weight of rubber components based on the total weight of the composition, more than 30% by weight in other embodiments, and more than 40% by weight in other embodiments. In these or other embodiments, the vulcanizable composition contains less than 90% by weight of rubber components based on the total weight of the composition, less than 70% by weight in other embodiments, and less than 60% by weight in other embodiments. In one or more embodiments, the vulcanizable composition contains about 20 to about 90% by weight of rubber components based on the total weight of the composition, about 30 to about 70% by weight in other embodiments, and about 40 to about 60% by weight in other embodiments.

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

[0065] In one or more embodiments, the amount of eutectic solvent can be described in terms of the amount of metal activator (such as zinc oxide) added. In one or more embodiments, the vulcanizing composition contains more than 2% by weight of eutectic solvent, more than 3% by weight in other embodiments, and more than 5% by weight in other embodiments, based on the total weight of the eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizing composition. In these or other embodiments, the vulcanizing composition contains less than 15% by weight of eutectic solvent, less than 12% by weight in other embodiments, and less than 10% by weight in other embodiments, based on the total weight of the eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizing composition. In one or more embodiments, the vulcanizing composition contains about 2 to about 15% by weight of eutectic solvent, about 3 to about 12% by weight in other embodiments, and about 5 to about 10% by weight in other embodiments, based on the total weight of the eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizing composition.

[0066] metal compound In one or more embodiments, the vulcanizing composition contains more than 1.5 parts by weight (pbw) of a metal activator (e.g., zinc oxide) per 100 parts by weight (phr), in other embodiments more than 2.0 pbw, and in other embodiments more than 2.5 pbw of a metal activator (e.g., zinc oxide). In these or other embodiments, the vulcanizing composition contains less than 8 pbw (phr) of a metal activator (e.g., zinc oxide), in other embodiments less than 7 pbw (phr), and in other embodiments less than 6 pbw (phr) of a metal activator (e.g., zinc oxide). In one or more embodiments, the vulcanizing composition contains about 1.5 to about 8.0 pbw (phr) of a metal activator (e.g., zinc oxide), in other embodiments about 2.0 to about 7 pbw (phr), and in other embodiments about 2.5 to about 6 pbw (phr) of a metal activator (e.g., zinc oxide). In one or more embodiments, the vulcanizing composition does not contain or substantially contains a metal activator such as zinc oxide.

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

[0068] Filler In one or more embodiments, the vulcanizable composition contains more than 0 parts by weight (pbw) of filler per 100 parts by weight (phr) of rubber, and in other embodiments, more than 10 pbw, more than 25 pbw, more than 35 pbw, more than 45 pbw, more than 55 pbw, and more than 65 pbw. In these or other embodiments, the vulcanizable composition contains less than 200 pbw (phr) of filler, and in other embodiments, less than 150 pbw (phr), less than 120 pbw (phr), less than 100 pbw (phr), and less than 80 pbw (phr). In one or more embodiments, the vulcanizable composition comprises a filler of about 0 to about 200 pbw(phr), in other embodiments about 35 to about 120 pbw(phr), and in yet another embodiment about 45 to about 100 pbw(phr).

[0069] Carbon Black In one or more embodiments, the vulcanizable composition contains 0 parts by weight (pbw) of carbon black per 100 parts by weight (phr) of rubber, and in other embodiments contains more than 10 pbw, more than 25 pbw, more than 45 pbw, more than 55 pbw, more than 60 pbw, more than 65 pbw, and more than 75 pbw of carbon black. In these or other embodiments, the vulcanizable composition contains less than 200 pbw (phr) of carbon black, in other embodiments less than 150 pbw (phr), and in other embodiments less than 100 pbw (phr) of carbon black. In one or more embodiments, the vulcanizable composition contains about 10 to about 200 pbw (phr) of carbon black, in other embodiments about 40 to about 150 pbw (phr), and in other embodiments about 50 to about 100 pbw (phr) of carbon black.

[0070] silica In one or more embodiments, the vulcanizable composition contains more than 0.1 parts by weight (pbw) of silica per 100 parts by weight (phr) of rubber, more than 2.5 pbw in other embodiments, and more than 5.0 pbw in other embodiments. In these or other embodiments, the vulcanizable composition contains less than 50 pbw (phr) of silica, less than 30 pbw (phr) in other embodiments, less than 25 pbw (phr) in other embodiments, less than 20 pbw (phr) in other embodiments, less than 18 pbw (phr) in other embodiments, less than 15 pbw (phr) in other embodiments, less than 10 pbw (phr) in other embodiments, less than 5 pbw (phr) in other embodiments, less than 3 pbw (phr) in other embodiments, and less than 1 pbw (phr) of silica in other embodiments. In one or more embodiments, the vulcanizable composition contains about 0.1 to about 50 pbw(phr) of silica, in other embodiments about 2.5 to about 30 pbw(phr), and in other embodiments about 3 to about 20 pbw(phr) of silica. In one or more embodiments, the vulcanizable composition does not contain silica or is substantially silica-free.

[0071] Filler ratio In one or more embodiments, the vulcanizable composition can be characterized by the ratio of carbon black to other filler compounds such as silica. In one or more embodiments, carbon black is used in excess of the other filler such as silica. In one or more embodiments, the ratio of the amount of carbon black to silica is greater than 2:1 based on weight ratio, greater than 3:1 in other embodiments, greater than 5:1 in other embodiments, greater than 7:1 in other embodiments, greater than 10:1 in other embodiments, greater than 15:1 in other embodiments, and greater than 20:1 in other embodiments.

[0072] Silica coupling agent In one or more embodiments, the vulcanizable composition contains more than 1 part by weight (pbw) of silica coupling agent per 100 parts by weight of silica, more than 2 pbw in other embodiments, and more than 5 pbw in other embodiments. In these or other embodiments, the vulcanizable composition contains less than 20 pbw of silica coupling agent per 100 parts by weight of silica, less than 15 pbw in other embodiments, and less than 10 pbw in other embodiments. In one or more embodiments, the vulcanizable composition contains about 1 to about 20 pbw of silica coupling agent per 100 parts by weight, about 2 to about 15 pbw in other embodiments, and about 5 to about 10 pbw in other embodiments. In one or more embodiments, the vulcanizable composition does not contain or substantially contains no silica coupling agent.

[0073] resin In one or more embodiments, the vulcanizable composition contains more than 1 part by weight (pbw) of resin (e.g., carbon-hydrogen resin) per 100 parts by weight (phr) of rubber, more than 15 parts by weight (pbw) in other embodiments, and more than 25 parts by weight (pbw) in other embodiments. In these or other embodiments, the vulcanizable composition contains less than 150 pbw (phr) of resin (e.g., carbon-hydrogen resin), less than 120 pbw (phr) in other embodiments, less than 90 pbw (phr) in other embodiments, less than 80 pbw (phr) in other embodiments, less than 60 pbw (phr) in other embodiments, and less than 45 pbw (phr) of resin (e.g., carbon-hydrogen resin). In one or more embodiments, the vulcanizable composition comprises a resin (e.g., a hydrocarbon resin) with a strength of about 1 to about 150 pbw(phr), in other embodiments about 15 to about 100 pbw(phr), and in other embodiments about 25 to about 80 pbw(phr) of resin (e.g., a hydrocarbon resin). In one or more embodiments, the vulcanizable composition contains no resin or is substantially resin-free.

[0074] Processing / Extender Oil In one or more embodiments, the vulcanizing composition contains more than 0.1 parts by weight (pbw) of processing oil (e.g., naphthenic oil) per 100 parts by weight (phr) of rubber, more than 1 part by weight (pbw) in other embodiments, and more than 2 parts by weight (pbw) in other embodiments. In these or other embodiments, the vulcanizing composition contains less than 20 pbw (phr) of processing oil, less than 18 pbw (phr) in other embodiments, less than 15 pbw (phr) in other embodiments, less than 12 pbw (phr) in other embodiments, less than 10 pbw (phr) in other embodiments, and less than 8 pbw (phr) in other embodiments. In one or more embodiments, the vulcanizing composition contains about 0.1 to about 20 pbw(phr) of oil, in other embodiments about 0.5 to about 18 pbw(phr), in other embodiments about 1 to about 15 pbw(phr), and in other embodiments about 2 to about 12 pbw(phr) of oil. In one or more embodiments, the vulcanizing composition contains no oil or is substantially oil-free.

[0075] Plasticizing additives In one or more embodiments, the plasticizing resin and processing oil may be collectively referred to as plasticizing additives, components, or constituent components. In one or more embodiments, the vulcanizable composition of the present invention contains more than 0.1 parts by weight (phr) of plasticizing additive per 100 parts by weight (phr) of rubber, and in other embodiments, more than 1 part by weight (pbw) of plasticizing additive, and in other embodiments, more than 2 parts by weight (pbw) of plasticizing additive. In these or other embodiments, the vulcanizable composition contains less than 15 pbw (phr) of plasticizing additive, in other embodiments less than 12 pbw (phr), in other embodiments less than 10 pbw (phr), in other embodiments less than 7 pbw (phr), in other embodiments less than 5 pbw (phr), and in other embodiments less than 3 pbw (phr) of plasticizing additive. In one or more embodiments, the vulcanizable composition contains a plasticizing additive in an amount of about 0.1 to about 15 pbw(phr), in other embodiments about 0.5 to about 10 pbw(phr), in other embodiments about 1 to about 7 pbw(phr), and in other embodiments about 2 to about 5 pbw(phr).

[0076] Reinforcement resin In one or more embodiments, the vulcanizable composition contains more than 0.1 parts by weight (pbw) of reinforcing resin (e.g., novolac resin) per 100 parts by weight (phr), and in other embodiments, more than 1 part by weight (pbw), and in other embodiments, more than 2 parts by weight (pbw), of reinforcing resin (e.g., novolac resin). In these or other embodiments, the vulcanizable composition contains less than 8 pbw (phr) of reinforcing resin, in other embodiments less than 6 pbw (phr), in other embodiments less than 5 pbw (phr), and in other embodiments less than 4 pbw (phr). In one or more embodiments, the vulcanizable composition contains about 0.1 to about 8 pbw (phr) of reinforcing resin, in other embodiments about 0.5 to about 6 pbw (phr), and in other embodiments about 2 to about 4 pbw (phr) of reinforcing resin. In one or more embodiments, the vulcanizable composition does not contain or substantially contains no reinforcing resin.

[0077] Low molecular weight high vinyl additive In one or more embodiments, the vulcanizable composition contains more than 0.5 parts by weight (pbw) of low molecular weight high vinyl polydiene per 100 parts by weight (phr) of rubber, and in other embodiments, more than 1.5 parts by weight (pbw), and in other embodiments, more than 1.7 parts by weight (pbw) of low molecular weight high vinyl polydiene. In these or other embodiments, the vulcanizable composition contains less than 5.0 parts by weight of low molecular weight high vinyl polydiene per 100 parts by weight of rubber, and in other embodiments, less than 4.0 parts by weight, and in other embodiments, less than 3.0 parts by weight of low molecular weight high vinyl polydiene. In one or more embodiments, the vulcanizable composition contains about 0.5 to about 5.0 parts by weight of low molecular weight high vinyl polydiene per 100 parts by weight of rubber, and in other embodiments, about 1.5 to about 4.0 parts by weight, and in other embodiments, about 1.7 to about 3.0 parts by weight of low molecular weight high vinyl polydiene. In one or more embodiments, the vulcanizable composition does not contain, or substantially does not contain, low molecular weight high vinyl polydienes.

[0078] Method for preparing a side wall support The sidewall support of the present invention can be prepared using conventional rubber processing and curing techniques. For example, the components may be mixed in solid form to form a vulcanizable composition. Next, this composition may be formed into a desired shape to form an environmentally friendly sidewall support. Then, the environmentally friendly sidewall support can be cured.

[0079] In one or more embodiments, the vulcanizable composition is prepared by mixing a vulcanizable rubber with a eutectic solvent to form a masterbatch, and then adding a curing agent to the masterbatch. The preparation of the masterbatch may be carried out using one or more auxiliary mixing steps, in which, for example, an initial mixture may be prepared by mixing two or more components, and then one or more components may be added to the composition sequentially. In addition, additional components may be added to the preparation of the vulcanizable composition using the prior art, and such additional components include, but are 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 degradation inhibitors (or antioxidants or ozone degradation inhibitors).

[0080] In one or more embodiments, the eutectic composition is prepared before introducing the eutectic composition into the vulcanizable rubber. In other words, the first component of the mixture is pre-combined with the second component of the mixture before the mixture is introduced into the vulcanizable composition. In one or more embodiments, the components of the mixture to be combined are mixed until a homogeneous liquid composition is observed.

[0081] In one or more embodiments, the eutectic composition is pre-combined with one or more components of the rubber compound before the eutectic mixture is introduced into the vulcanizing composition. In other words, in one or more embodiments, components of the vulcanizing composition (e.g., a metal compound such as zinc oxide) are combined with the eutectic mixture to form a pre-combination or masterbatch, which is then introduced into a mixer in which the rubber is mixed. For example, zinc oxide may be dissolved in a eutectic solvent before being introduced into the rubber in the mixer. In other embodiments, the eutectic composition is a trace component of the pre-combination, and therefore the component pre-mixed 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, and the zinc oxide acts as a carrier for delivering the combination of zinc oxide and the eutectic composition as a solid to the rubber in the mixer. In yet another embodiment, one of the substances constituting the eutectic pair acts as a solid carrier for the eutectic composition, and therefore the combination of the first and second components of the eutectic composition forms a pre-combination that can be added as a solid to the rubber in the mixer. Those skilled in the art will understand that a mixture of these properties can be formed by combining a first or second eutectic pair of constituent materials in excess of the other eutectic members, in order to maintain a solid composition at a desired temperature.

[0082] In one or more embodiments, the eutectic solvent is introduced into the vulcanizable rubber as an initiating component in the formation of a rubber masterbatch. The eutectic solvent is then mixed with the rubber under high shear and high temperature. In one or more embodiments, the eutectic solvent is mixed with the rubber at a minimum temperature above 110°C, in other embodiments at a minimum temperature above 130°C, and in other embodiments at a minimum temperature above 150°C. In one or more embodiments, the high-shear, high-temperature mixing is carried out at temperatures between approximately 110°C and approximately 170°C.

[0083] In other embodiments, the eutectic solvent is introduced into the vulcanizable rubber either sequentially or in a single step, together with the sulfur-based curing agent. The eutectic solvent is then mixed with the vulcanizable rubber at a maximum temperature below 110°C, in other embodiments at a maximum temperature below 105°C, and in other embodiments at a maximum temperature below 100°C. In one or more embodiments, the mixing with the curing agent is carried out at a temperature of about 70 to about 110°C.

[0084] Similar to eutectic solvents, zinc oxide and stearic acid can be added to the rubber masterbatch as initiating components, and thus these components will undergo high-shear mixing at high temperatures. Alternatively, zinc oxide and stearic acid can be added together with a sulfur-based curing agent, thereby undergoing mixing only at low temperatures.

[0085] In one or more embodiments, zinc oxide is introduced into the vulcanizing rubber separately and individually from the eutectic solvent. In other embodiments, the zinc oxide and the eutectic solvent are pre-combined to form a zinc oxide masterbatch, which may contain 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 vulcanizing rubber.

[0086] In one or more embodiments, polyisoprene rubber (e.g., natural rubber) is first kneaded to achieve desired viscosity and processability properties. After mixing the polyisoprene rubber, other components, such as a eutectic solvent, are introduced into the pre-treated polyisoprene rubber according to one or more embodiments of the present invention.

[0087] Mixing conditions 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, at a temperature of 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, and in other embodiments, to a temperature below 80°C, before adding the curing agent. In certain embodiments, mixing is continued at a temperature of about 90 to about 110°C, and in other embodiments, at a temperature of about 95 to about 105°C, to prepare the final vulcanizable composition.

[0088] 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, at least 150°C in other embodiments, and at least 160°C in other embodiments. In these or other embodiments, the peak temperature of the composition during the masterbatch mixing step may be about 140 to about 200°C, about 150 to about 190°C in other embodiments, and about 160 to about 180°C in other embodiments.

[0089] Final mixing process Following the masterbatch mixing step, a curing agent or curing agent system is introduced into the composition, and mixing is continued to ultimately form a vulcanizable composition. This mixing step may be referred to as the final mixing step, curing agent mixing step, or production mixing step. The product obtained from this mixing step may be referred to as the vulcanizable composition.

[0090] In one or more embodiments, the final mixing step can be characterized by the peak temperature reached by the composition during the final mixing. As those 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 the final mixing may be up to 130°C, up to 110°C in other embodiments, and up to 100°C in other embodiments. In these or other embodiments, the peak temperature of the composition during the final mixing may be about 80 to about 130°C, up to about 90 to about 115°C in other embodiments, and up to about 95 to about 105°C in other embodiments.

[0091] mixing equipment All components of the vulcanizable composition can be mixed using standard mixing equipment, such as built-in mixers (e.g., Banbury or Brabender mixers, extruders, kneaders, and two-roll mills). Mixing can be done individually or in parallel. As described above, the components can be mixed in a single step, or in other embodiments, in two or more steps. For example, in a first step (i.e., a mixing step), a masterbatch (typically containing rubber components and fillers) is prepared. Once the masterbatch is prepared, in a final mixing step, the vulcanizing agent may be introduced into the masterbatch and mixed. This final mixing step is typically carried out at a relatively low temperature to reduce the possibility of premature vulcanization. An additional mixing step, sometimes called a remill, can be employed between the masterbatch mixing step and the final mixing step. [Industrial applicability]

[0092] Tire adjustment The vulcanizable composition can be processed into tire components according to conventional tire manufacturing techniques, including standard rubber molding, shaping, and curing techniques. Typically, vulcanization is carried out by heating the vulcanizable composition in a mold, which may be heated to, for example, about 140°C to about 180°C. The cured or crosslinked rubber composition may also be referred to as a vulcanized product, which generally contains a thermosetting three-dimensional polymer network structure. Other components, such as fillers and processing aids, may be uniformly dispersed throughout the crosslinked network structure. Pneumatic tires can be manufactured as discussed in U.S. Patents 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

[0093] As described above, various tire components can be prepared by curing the vulcanizable composition of the present invention. These tire components include, but are not limited to, the tire tread, tire sidewall, belt skim, inner liner, and bead apex.

[0094] experiment Formation of a liquid eutectic composition A liquid eutectic composition of choline chloride and urea was prepared by mixing 1 mole of choline chloride with 2 moles of urea in an oil bath at 100°C while stirring with a magnetic rod at 60 rpm. The composition, called reline, was liquid under standard temperature and pressure conditions.

[0095] Formation of a solid eutectic composition A solid eutectic composition of choline chloride and thiourea was prepared by mixing 1 mole of choline chloride with 2 moles of thiourea in an oil bath at 100°C while stirring with a magnetic rod at 60 rpm. The composition was referred to as ChCl:thiourea and was determined to have a melting point of 67°C (DSC measurement).

[0096] Formation of vulcanizable compositions A vulcanizable composition was prepared using the rubber compound and mixing sequence provided in Table I. This rubber compound represented a rubber compound useful for the manufacture of tire treads. The mixing procedure was a three-step procedure, including a masterbatch mixing step, a "remilling mixing step," and a final mixing step. The various mixing steps were performed in a 65-gram Banbury-style mixer. During masterbatch preparation, the mixer was operated at 60 rpm for 5 minutes, or until the composition reached its peak temperature of 170°C. At that point, the composition was removed from the mixer and allowed to cool to below approximately 85°C. At this point, the composition was reintroduced into the mixer with additional components for the "remilling step," and mixing was continued at 60 rpm for 5 minutes, or until the composition reached its peak temperature of approximately 170°C. The composition was again removed from the mixer and allowed to cool to below approximately 50°C. Next, the composition was reintroduced into the mixer again with components identified for the "final mixing step." These components included reline or ChCl:thiourea, as provided in Table II. Mixing was continued at 40 rpm for 2.5 minutes, or until the composition reached its peak temperature of approximately 100°C. The composition was then removed from the mixer to obtain a sample for analytical testing. As shown in Table II, the components introduced in the final mixing stage changed as reported in Table II, and Table II also provides the results of the analytical tests.

[0097] [Table 1]

[0098] Rheometer measurements were performed using an MDR2000 operating at the temperatures specified in the table. The tensile mechanical properties (maximum stress, modulus of elasticity, elongation, and toughness) of the vulcanized material were measured using the standard procedure described in ASTM-D412.

[0099] [Table 2]

[0100] The data in Table II demonstrate that a eutectic mixture based on choline chloride and thiourea functions similarly to Reline, while offering the advantage of being in a solid state under standard temperature and pressure conditions.

[0101] Various modifications and changes that do not depart from the scope and spirit of the present invention will be apparent to those skilled in the art. The present invention is not formally limited to the exemplary embodiments described herein.

Claims

1. A method for preparing a side wall support, wherein the method is (i) A step of providing a vulcanizable composition comprising an elastomer, a filler, a curing agent, and a eutectic composition, wherein the eutectic composition is solid, (ii) A step of preparing the vulcanizable composition into an environmentally friendly sidewall support, (iii) A method comprising the step of subjecting the environmentally friendly sidewall support to curing conditions.

2. The method according to claim 1, wherein the eutectic composition is a deep eutectic composition.

3. The method according to claim 1 or 2, wherein the eutectic composition is a deep eutectic composition formed by combining eutectic members into a eutectic pair, and the molar ratio of each member of the pair is within + / - 20% of the lowest melting point of the eutectic pair.

4. The method according to any one of claims 1 to 3, wherein the eutectic composition is solid at atmospheric pressure (i.e., 1 atm) and at a temperature of at least 20°C.

5. The method according to any one of claims 1 to 4, wherein the eutectic composition is solid at atmospheric pressure (i.e., 1 atm) and at a temperature of at least 40°C.

6. The method according to any one of claims 1 to 5, wherein the eutectic composition is a deep eutectic composition formed by combining eutectic members into a eutectic pair, and the molar ratio of each member of the pair is selected to produce a mixture having a melting point above 20°C.

7. The method according to any one of claims 1 to 6, wherein the eutectic composition is a deep eutectic composition formed by combining eutectic members into a eutectic pair, and the molar ratio of each member of the pair is selected to produce a mixture having a melting point above 40°C.

8. The eutectic composition is of formula Cat ＋ X － Defined by zY, in the formula, Cat ＋ However, it is a cation, X － The method according to any one of claims 1 to 7, wherein is a counter anion (e.g., a Lewis base), and z represents the number of Y molecules that interact with the counter anion (e.g., a Lewis base).

9. Cat ＋ However, X is an ammonium cation, a phosphonium cation, or a sulfonium cation. － The method according to any one of claims 1 to 8, wherein the ion is a halide ion.

10. The method according to any one of claims 1 to 9, wherein the eutectic composition is selected from the group consisting of type I, type II, type III, and type IV eutectic compositions.

11. The method according to any one of claims 1 to 10, wherein the eutectic composition is formed by combining an ammonium compound with a metal halide, a metal halide hydrate, or a hydrogen bond donor.

12. The ammonium compound can be defined by formula II. (R １ )(R ２ )(R ３ )(R ４ )-N ＋ -Φ － In the formula, each R １ , R ２ , R ３ , and R ４ However, individually, it may be hydrogen or a monovalent organic group, or alternatively, R １ , R ２ , R ３ , and R ４ Two of them combine to form a divalent organic group, Φ － The method according to any one of claims 1 to 11, wherein the counter anion is

13. The method according to any one of claims 1 to 12, wherein the ammonium compound is selected from the group consisting of N-ethyl-2-hydroxy-N,N-dimethylethaneaminium chloride, 2-hydroxy-N,N,N-trimethylethaneaminium chloride (also known as collinchloride), and N-benzyl-2-hydroxy-N,N-dimethylethaneaminium chloride.

14. The method according to any one of claims 1 to 13, wherein the ammonium compound is selected from the group consisting of 2-chloro-N,N,N-trimethylethaneaminium (also called chlorochloride) and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride.

15. The method according to any one of claims 1 to 14, wherein the hydrogen bond donor is selected from the group consisting of amines, amides, carboxylic acids, and alcohols.

16. The method according to any one of claims 1 to 15, wherein the hydrogen bond donor is selected from the group consisting of aliphatic amines, ethylenediamines, diethylenetriamines, aminoethylpiperazines, triethylenetetramines, tris(2-aminoethyl)amines, N,N'-bis(2-aminoethyl)piperazines, piperadinoethylethylenediamines, tetraethylenepentaamines, propyleneamines, aniline, substituted aniline, and combinations thereof.

17. The method according to any one of claims 1 to 16, wherein the hydrogen bond donor is selected from the group consisting of urea, 1-methylurea, 1,1-dimethylurea, 1,3-dimethylurea, thiourea, urea, benzamide, acetamide, and combinations thereof.

18. The method according to any one of claims 1 to 17, wherein the hydrogen bond donor is selected from the group consisting of phenylpropionic acid, phenylacetic acid, benzoic acid, oxalic acid, malonic acid, adipic acid, succinic acid, citric acid, tricarbaryl acid, and combinations thereof.

19. The method according to any one of claims 1 to 18, wherein the hydrogen bond donor is selected from the group consisting of aliphatic alcohols, phenols, substituted phenols, ethylene glycols, propylene glycols, resorcinols, substituted resorcinols, glycerols, benzenetriols, and mixtures thereof.

20. The method according to any one of claims 1 to 19, wherein the metal halide is selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, zinc chloride, zinc bromide, zinc iodide, tin chloride, tin bromide, tin iodide, iron chloride, iron bromide, iron iodide, and combinations thereof.

21. The method according to any one of claims 1 to 20, wherein the vulcanizable composition contains more than 1.5 ppw of zinc oxide per 100 ppw of rubber.

22. The method according to any one of claims 1 to 21, wherein the vulcanizable composition contains more than 2.0 ppw of zinc oxide per 100 ppw of rubber.

23. The method according to any one of claims 1 to 22, wherein the vulcanizable composition comprises about 0.005 to about 3 ppw of the eutectic composition per 100 ppw of rubber.

24. The method according to any one of claims 1 to 23, wherein the vulcanizable composition comprises about 0.01 to about 1 ppw of the eutectic composition per 100 ppw of rubber.

25. The method according to any one of claims 1 to 24, wherein the vulcanizable composition comprises a low molecular weight high vinyl polydiene.

26. The method according to any one of claims 1 to 25, wherein the eutectic composition is a combination of a quaternary salt and thiourea.

27. The method according to any one of claims 1 to 26, wherein the eutectic composition is a combination of choline chloride and thiourea.

28. A method for forming a pneumatic tire, comprising distributing the side wall support formed by the method of any one of claims 1 to 27 to an environmentally friendly tire.

29. A method for forming a pneumatic tire, comprising arranging the side wall support formed by the method of any one of claims 1 to 27 on a hardened tire.

30. It is a pneumatic tire, (i) Tread and, (ii) Carcass and, (iii) Any inner liner layer, (iv) A pneumatic tire comprising a pair of sidewall supports disposed on the carcass or the optional inner liner layer, wherein, if present, the sidewall supports are prepared from a vulcanizable composition comprising an elastomer, a filler, a curing agent, and a eutectic composition.

31. The tire according to claim 30, wherein the side wall support can substantially support the tire in a run-flat state.

32. The tire according to claim 30 or 31, wherein the tread has a first edge and a second edge, the tire includes a first bead and a second bead, the first reinforcing member of the pair of sidewall supports generally extends from the first edge of the tread to the first bead, and the second reinforcing member of the pair of sidewall supports generally extends from the second edge of the tread to the second bead.

33. The tire according to any one of claims 30 to 32, wherein the side wall support is crescent-shaped.

34. The tire according to any one of claims 30 to 33, wherein the side wall support is made of elastomer material.

35. The sidewall support has a Shore A hardness of over 60 at 100°C, a tandelta at 10 Hz at 100°C less than 0.20, a storage modulus of elasticity of over 6 MPa at 10°C, 52 Hz, and 1% strain, and an elastic modulus of 10 kg / cm². ２ A tire according to any one of claims 30 to 34, characterized by exceeding a certain value.

36. The tire according to any one of claims 30 to 35, wherein the side wall support is characterized by a thickness of more than 6 mm.

37. The tire according to any one of claims 30 to 36, wherein the sidewall support is characterized by a degree of hardening to which less than 5% by weight can be extracted by boiling cyclohexane.

38. The tire according to any one of claims 30 to 37, wherein the eutectic composition is a combination of a quaternary salt and thiourea.

39. The tire according to any one of claims 30 to 38, wherein the eutectic composition is a combination of choline chloride and thiourea.

40. The tire according to any one of claims 30 to 39, wherein the eutectic composition is a deep eutectic composition.

41. The tire according to any one of claims 30 to 40, wherein the eutectic composition is a deep eutectic composition formed by combining eutectic members into a eutectic pair, and the molar ratio of each member of the pair is within + / - 20% of the lowest melting point of the eutectic pair.

42. The tire according to any one of claims 30 to 41, wherein the eutectic composition is solid at atmospheric pressure (i.e., 1 atm) and at a temperature of at least 20°C.

43. The tire according to any one of claims 30 to 42, wherein the eutectic composition is solid at atmospheric pressure (i.e., 1 atm) and at temperatures up to at least 40°C.

44. The tire according to any one of claims 30 to 43, wherein the eutectic composition is a deep eutectic composition formed by combining eutectic members into a eutectic pair, and the molar ratio of each member of the pair is selected to produce a mixture having a melting point above 20°C.

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