Vulcanized rubber compositions comprising a

Abstract

A method of making a sidewall support, the method 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 a solid; (ii) making the vulcanizable composition into a green sidewall support; and (iii) subjecting the green sidewall support to curing conditions.

Description

Technical Field

[0001] Embodiments of the present invention relate to vulcanizable compositions and vulcanizates produced therefrom, which are prepared by using solid eutectic compositions. Background Technology

[0002] In tire manufacturing, zinc oxide, along with stearic acid, plays a crucial role in vulcanization. It is believed that zinc oxide, or a salt formed from a combination of zinc oxide and stearic acid, interacts with sulfur to provide the desired crosslinking density of the rubber matrix. It is also known that adding a eutectic composition can reduce the amount of zinc oxide required. For example, WO 2019 / 089788 discloses a vulcanizable rubber composition containing reduced levels of zinc oxide due to the presence of a eutectic solvent. In the presence of a eutectic solvent, particularly a deep eutectic solvent such as reline, it has been found that only 0.05 parts of zinc oxide per 100 parts of rubber are required for the preparation of tire components in a vulcanizable composition.

[0003] Those skilled in the art will understand that vulcanizable compositions are typically prepared by mixing various components (such as, but not limited to, vulcanizable rubber, fillers, and curing agents) used to prepare the vulcanizable composition in a solid state. Most of these components are solid under standard temperature or pressure conditions, which is useful for the solid mixing techniques used. In other words, those skilled in the art will understand that it is advantageous to introduce and mix solid components (rather than liquid components) into the vulcanizable composition for one or more reasons. Summary of the Invention

[0004] One or more embodiments of the present invention provide a method for preparing a sidewall support, the method 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 a solid; (ii) manufacturing the vulcanizable composition into a green sidewall support; and (iii) subjecting the green sidewall support to curing conditions.

[0005] Other embodiments of the present invention provide a method for forming a pneumatic tire, the method comprising placing a sidewall support formed by one method into a green tire.

[0006] Other embodiments of the present invention provide a method for forming a pneumatic tire, the method comprising placing a sidewall support formed by one method into a cured tire.

[0007] Other embodiments of the invention provide a pneumatic tire comprising (i) a tread; (ii) a carcass; (iii) an optional inner liner; and (iv) a pair of sidewall supports disposed on the carcass or, if present, the optional inner liner, wherein the sidewall supports are made of a vulcanizable composition comprising an elastomer, filler, curing agent, and eutectic composition. Detailed Implementation

[0008] Embodiments of the present invention are based, at least in part, on the discovery of a method for preparing a vulcanizable composition by combining a vulcanizable rubber, a curing agent, and a solid eutectic composition. While the prior art considers curing rubber compositions in the presence of a eutectic composition, particularly a deep eutectic solvent, the present invention offers advantages over the prior art because using a solid eutectic composition has several advantages compared to using a liquid eutectic composition. For example, solid eutectic compositions are easier to handle and are believed to disperse better in the rubber composition. In one or more embodiments, the eutectic composition used in the practice of the present invention is a solid deep eutectic that is in a eutectic state at or near its lowest melting point.

[0009] Vulcanizable Composition

[0010] As described above, the vulcanizable composition of the present invention comprises vulcanizable rubber, a curing agent, and a solid eutectic composition. The composition may also contain other components, such as those commonly found in the field of preparing vulcanizable rubber compositions, including, but not limited to, reinforcing fillers, anti-degradation agents, curing activators, curing accelerators, oils, resins, plasticizers, pigments, fatty acids, zinc oxide, and adhesive solvents.

[0011] Vulcanizable rubber

[0012] In one or more embodiments, vulcanizable rubber (also referred to as elastomeric polymer, rubber polymer, vulcanizable polymer, or simply elastomer) may include those polymers that can be vulcanized to form compositions having rubber or elastomer properties. These elastomers may include natural rubber and synthetic rubber. Synthetic rubber is typically derived from the 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.

[0013] Exemplary elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-coisoprene, chloroprene rubber, poly(ethylene-copropylene), poly(styrene-cobutadiene), poly(styrene-coisoprene), poly(styrene-coisoprene-cobutadiene), poly(isoprene-cobutadiene), poly(ethylene-copropylene-cobutadiene), polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers can have a wide variety of macromolecular structures, including linear, branched, and star-shaped structures. These elastomers may also contain one or more functional units, which typically include heteroatoms. In a particular embodiment, the vulcanizable composition comprises a blend of natural rubber and synthetic diene rubbers such as polybutadiene. In other embodiments, the vulcanizable composition comprises an olefin rubber such as ethylene propylene diene monomer (EPDM).

[0014] The elastomers are characterized by their number-average molecular weight (Mn), which can be measured using polystyrene standards via gel permeation chromatography and adjusted using Mark-Houwink parameters. According to embodiments of the invention, the elastomers may have an Mn greater than 120 kg / mol, greater than 150 kg / mol in other embodiments, and greater than 180 kg / mol in other embodiments. In these or other embodiments, the elastomers may have an Mn less than 800 kg / mol, less than 600 kg / mol in other embodiments, and less than 400 kg / mol in other embodiments. In one or more embodiments, the elastomers have an Mn of about 120 kg / mol to about 800 kg / mol, about 150 kg / mol to about 600 kg / mol in other embodiments, and about 180 kg / mol to about 400 kg / mol in other embodiments.

[0015] curing agent

[0016] Many types of rubber curing agents (also known as vulcanizing agents) can be used, including sulfur-based or peroxide-based curing systems. Curing agents are described in the following literature: Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 20, pgs.365-468 (3rd edition, 1982), particularly Vulcanization Agents and Auxiliary Materials, pgs.390-402; and AYCoran, Vulcanization, Encyclopedia of Polymer Science and Engineering (2nd edition, 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 soluble sulfur from "rubber manufacturers"; sulfur-containing vulcanizing agents such as amine disulfides, polymeric polysulfides, or sulfur olefin adducts; and insoluble polymeric sulfur. Vulcanizing agents can be used alone or in combination. Those skilled in the art will be able to easily select the amount of vulcanizing agent to achieve the desired level of curing.

[0017] In one or more embodiments, a curing agent and a curing accelerator are used in combination. 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 vulcanizate. Examples of accelerators include thiazole vulcanization accelerators, such as 2-mercaptobenzothiazole, dibenzothiazole disulfide, N-cyclohexyl-2-benzothiazole sulfinamide (CBS), etc.; and guanidine vulcanization accelerators, such as diphenylguanidine (DPG), etc.

[0018] Solid eutectic composition

[0019] In one or more embodiments, a solid eutectic composition includes those compositions formed by combining two or more compounds, the resulting combination having a melting point lower than that of the respective compounds being combined, while remaining solid under normal or standard temperature and pressure conditions. 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 be referred to, respectively, as a eutectic component, eutectic element, eutectic member, or compound used to form the eutectic composition (e.g., first compound and second compound). It is not intended to be bound by any particular theory that eutectic components combine, or otherwise react or interact to form a complex. Therefore, any reference to a solid eutectic mixture or solid eutectic combination, solid eutectic pair, or solid eutectic complex will include the combination and reaction products or complexes between the combined components, and the resulting composition having a melting point lower than that of the respective components, but remaining solid under normal or standard temperature and pressure conditions. For a given composition, when 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 be referred to as a deep eutectic or DES. In one or more embodiments, the eutectic mixture is a composition within + / - 20 molar percentages of the molar ratio that achieves the lowest melting point of the mixture, within + / - 10 molar percentages in other embodiments, and within + / - 5 molar percentages in other embodiments.

[0020] In one or more embodiments, the solid eutectic composition has a melting point at standard pressure (i.e., 1 atm) above 20°C, 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.

[0021] In one or more embodiments, the available eutectic composition can be defined by Formula I:

[0022]

[0023] in It is a cation. To counter anion (e.g., a Lewis base), and z refers to the number of Y molecules that interact with that counter anion (e.g., a Lewis base). For example, It may include ammonium, phosphonium, or sulfonium cations. It may include, for example, halide ions. In one or more embodiments, z is the amount of solvent that achieves deep eutectic, or in other embodiments, the amount of complexes with melting points lower than the corresponding eutectic components, obtained in other ways.

[0024] In one or more embodiments, the available eutectic compositions comprise combinations of acids and bases, wherein the acids and bases may comprise Lewis acids and Lewis bases or Brønsted acids and Brønsted bases. In one or more embodiments, the available eutectic compositions comprise 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, instead of ammonium compounds, may also be used and are readily conceived by those skilled in the art.

[0025] Quaternary ammonium salts

[0026] In one or more embodiments, the available quaternary ammonium salt (also referred to as an ammonium compound) can be defined by Formula II:

[0027]

[0028] 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. To counteract anions. In one or more embodiments, at least one of R1, R2, R3, and R4 is not hydrogen, in other embodiments at least two are not hydrogen, and in other embodiments at least three are not hydrogen.

[0029] In one or more embodiments, counteracting anions (e.g.) Select free halide ions ( ), nitrate ( ), tetrafluoroborate ( ), perchlorate ( ), trifluoromethanesulfonate ( ), trifluoroacetate ( A group consisting of ) . In one or more embodiments, It is a halide ion, and in some embodiments, it is a chloride ion.

[0030] In one or more embodiments, the monovalent organic group includes a hydrocarbon group, and the divalent organic group includes an alkylene group. In one or more embodiments, the monovalent and divalent organic groups include heteroatoms, such as, but not limited to, oxygen and nitrogen, and / or halogen atoms. Thus, the monovalent organic group may include alkoxy groups, silanoxy groups, ether groups, and ester groups, as well as carbonyl or acetyl substituents. In one or more embodiments, the hydrocarbon group and the alkylene group comprise one (or a suitable minimum number) to about 18 carbon atoms, in other embodiments one to about 12 carbon atoms, and in other embodiments one to about 6 carbon atoms. The hydrocarbon group and the alkylene group may be branched, cyclic, or linear. Exemplary types of hydrocarbon groups include alkyl, cycloalkyl, aryl, and alkylaryl groups. Exemplary types of alkylene groups include alkylene, cycloalkylene, aryl, and alkylarylene groups. In a particular embodiment, the hydrocarbon group is selected from the group consisting of methyl, ethyl, octadecyl, phenyl, and benzyl groups. In some embodiments, the hydrocarbon group is a methyl group, and the hydrocarbon group is an ethylene or propylene group.

[0031] Available types of ammonium compounds include secondary ammonium compounds, tertiary ammonium compounds, and quaternary ammonium compounds. In these or other embodiments, the ammonium compound includes ammonium halides, such as, but not limited to, ammonium chloride. In a particular embodiment, the ammonium compound is a quaternary ammonium chloride (e.g., choline chloride). In some 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.

[0032] In one or more embodiments, the ammonium compound comprises an alkoxy (hydroxyalkyl) group and may be defined by Formula III:

[0033]

[0034] Each of R1, R2, and R3 is independently a hydrogen or 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. To counteract anions. In one or more embodiments, at least one of R1, R2, and R3 is not hydrogen, in other embodiments at least two are not hydrogen, and in other embodiments at least three are not hydrogen.

[0035] Examples of ammonium compounds defined by Formula III include, but are not limited to, N-ethyl-2-hydroxy-N,N-dimethylethylammonium chloride, 2-hydroxy-N,N,N-trimethylethylammonium chloride (also known as choline chloride), and N-benzyl-2-hydroxy-N,N-dimethylethylammonium chloride.

[0036] In one or more embodiments, the ammonium compound includes a halogen-containing substituent and may be defined by Formula IV:

[0037]

[0038] Each of R1, R2, and R3 is independently a 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... To counteract anions. In one or more embodiments, at least one of R1, R2, and R3 is not hydrogen, in other embodiments at least two are not hydrogen, and in other embodiments at least three are not hydrogen. In one or more embodiments, X is chlorine.

[0039] Examples of ammonium compounds defined by Formula IV include, but are not limited to, 2-chloro-N,N,N-trimethylethylammonium (also known as choline chloride) and 2-(chlorocarbonyloxy)-N,N,N-trimethylethylammonium chloride.

[0040] Hydrogen bond donor compounds

[0041] In one or more embodiments, the hydrogen bond donor compound (which may also be referred to as an HBD compound) includes, but is not limited to, amines, amides, carboxylic acids, and alcohols. In one or more embodiments, the hydrogen bond donor compound comprises a hydrocarbon chain component. The hydrocarbon chain component may include a carbon chain length having at least 2 carbon atoms, at least 3 carbon atoms in other embodiments, and at least 5 carbon atoms in other embodiments. In these or other embodiments, the hydrocarbon chain component has a carbon chain length of less than 30 carbon atoms, less than 20 carbon atoms in other embodiments, and less than 10 carbon atoms in other embodiments.

[0042] In one or more embodiments, the available amines include those compounds defined by the following formula:

[0043] R1-(CH2) x -R2

[0044] 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 2 to about 10, in other embodiments it is about 2 to about 8, and in still other embodiments it is about 2 to about 6.

[0045] Specific examples of amines that may be used include, but are not limited to, aliphatic amines, ethylenediamine, diethylenetriamine, aminoethylpiperazine, triethylenetetramine, tri(2-aminoethyl)amine, N,N'-bis-(2-aminoethyl)piperazine, piperazine ethyl ethylenediamine and tetraethylenepentamine, acrylamine, aniline, substituted anilines and combinations thereof.

[0046] In one or more embodiments, available amides include those compounds defined by the following formula:

[0047] R-CO-NH2

[0048] Where R is H, NH2, CH3 or CF3.

[0049] Specific examples of available amides include, but are not limited to, urea, 1-methylurea, 1,1-dimethylurea, 1,3-dimethylurea, thiourea, urea, benzamide, acetamide, and combinations thereof.

[0050] In one or more embodiments, the available carboxylic acids include monofunctional, difunctional, and trifunctional organic acids. These organic acids may include alkyl acids, arylic acids, and mixtures of alkyl-arylic acids.

[0051] Specific examples of 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, mesonic acid tricarboxylic acid, and combinations thereof.

[0052] The types of alcohols include, but are not limited to, monohydric alcohols, dihydric alcohols, and trihydric alcohols. Specific examples of monohydric alcohols include fatty alcohols, phenols, substituted phenols, and mixtures thereof. Specific examples of dihydric alcohols include ethylene glycol, propylene glycol, resorcinol, substituted resorcinols, and mixtures thereof. Specific examples of trihydric alcohols include, but are not limited to, glycerol, glycerol, and mixtures thereof.

[0053] metal halides

[0054] The 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 conceive of corresponding metal halide hydrates.

[0055] Specific examples of available 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, ferric chloride, ferric bromide, ferric iodide, and combinations thereof. Those skilled in the art can readily conceive of corresponding metal halide hydrates. For example, aluminum chloride hexahydrate and copper chloride dihydrate correspond to the above-mentioned halides.

[0056] Formation of eutectic complexes

[0057] Those skilled in the art can select appropriate eutectic members at suitable molar ratios to provide a desired eutectic composition. Those skilled in the art 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 selected compounds. As should also be understood by those skilled in the art, melting point suppression of the eutectic solvent includes the eutectic point, which is the molar ratio of the first to the second compound that produces maximum melting point suppression (i.e., deep eutectic solvent). However, the molar ratio of the first to the second compound can be varied to produce melting point suppression of the eutectic solvent relative to the individual melting points of the first and second compounds, which is not the minimum melting point (i.e., not the maximum suppression point). Therefore, operation of one or more embodiments of the invention involves forming the eutectic solvent at a molar ratio other than the eutectic point.

[0058] 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 keep the eutectic composition in a solid state at atmospheric pressure or standard pressure (i.e., 1 atm), 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 in other embodiments, and up to at least 60°C in other embodiments. 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 mixtures with melting points below 130°C, below 110°C in other embodiments, below 100°C in other embodiments, below 80°C in other embodiments, below 60°C in other embodiments, below 40°C in other embodiments, and below 30°C in other embodiments. In these or other embodiments, the compounds of the eutectic pair and the molar ratio of the compounds are selected to produce mixtures with melting points 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.

[0059] In one or more embodiments, compounds of a eutectic pair and the molar ratio of a first compound to a second compound of the pair are selected to produce a eutectic solvent having the ability or capacity to dissolve a desired metal compound, which may be referred to as solubility or dissolving capacity. As those skilled in the art will understand, when preparing a saturated solution, this solubility can be quantified based on the weight of the metal compound dissolved in a given weight of the eutectic solvent at a specified temperature and pressure over a specified time. In one or more embodiments, the eutectic solvent of the present invention is selected to achieve a solubility of zinc oxide greater than 100 ppm over 24 hours at 50°C and atmospheric pressure, 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 in other embodiments, and greater than 1600 ppm in other embodiments, wherein ppm is measured based on the ratio of solute weight to solvent weight.

[0060] filler

[0061] As described above, sidewall supports can be prepared using vulcanizable compositions including fillers. The fillers may include one or more conventional reinforcing or non-reinforcing fillers. For example, usable fillers include carbon black, silica, alumina, and silicates such as calcium silicate, aluminum silicate, and magnesium silicate.

[0062] In one or more embodiments, carbon black includes furnace black, channel black, and lamp black. More specific examples of carbon black include super abrasion-resistant furnace black (SAF), medium super abrasion-resistant furnace black (ISAF), high abrasion-resistant furnace black (HAF), fast extrusion furnace black (FEF), fine furnace black (FF), semi-reinforced furnace black (SRF), medium-process channel black, difficult-to-process channel black, conductive channel black, and acetylene black. Representative carbon blacks available in one or more embodiments may include those designated by ASTM D1765 as N326, N330, N339, N343, N347, N351, N358, N550, N650, N660, N762, N772, and N774.

[0063] In one or more embodiments, the carbon black may have a particle size of at least 20 μm. 2 / g, at least 35m in other embodiments 2 / g, at least 50m in other embodiments 2 / g, and at least 60m in other embodiments 2 / g surface area. In these or other embodiments, the carbon black has a surface area of ​​about 20m². 2 / g to approximately 110m 2 / g, approximately 25m in other embodiments 2 / g to approximately 80m 2 / g, approximately 30m in other embodiments 2 / g to approximately 60m 2 / g, approximately 60m in other embodiments 2 / g to approximately 110m 2 / g, and approximately 40m in other embodiments 2 / g to approximately 50m 2 / g surface area. For the purposes of this specification, and unless otherwise specified, the carbon black surface area value is determined by ASTM D-1765 using the cetyltrimethylammonium bromide (CTAB) technique. Carbon black may be in granular or non-granular flocculent form. The preferred form of carbon black may depend on the type of mixing equipment used to mix the rubber compounds.

[0064] In one or more embodiments, the filler may include silica. When silica is used as a filler, it may be used in combination with a coupling agent. In these or other embodiments, silica may be used in combination with a silica dispersant.

[0065] In one or more embodiments, the silica used includes, but is not limited to, precipitated amorphous silica, wet silica (hydrated silica), dry silica (anhydrous silica), pyrolytic silica, and calcium silicate. Other suitable fillers include aluminum silicate, magnesium silicate, etc. In a particular embodiment, the silica is precipitated amorphous wet-processed silica hydrate. In one or more embodiments, this silica is produced by a chemical reaction in water, from which silica precipitates as ultrafine spherical particles. It is believed that these primary particles strongly associate into aggregates, which then less strongly bind together into clusters.

[0066] Some commercially available silica that can be used includes Hi-Sil (™) 215. Hi-Sil (™) 233 and Hi-Sil (™) 190 (PPG Industries, Inc., Pittsburgh, PA). Other commercially available suppliers of silica include Grace Davison, Baltimore, MD; Degussa Corp, Parsippany, NJ; Rhodia Silica Systems, Cranbury, NJ; and JMHuber Corp., Edison, NJ.

[0067] In one or more embodiments, silica can be characterized by its surface area, which provides 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 typically less than 450 m². 2 / g. The useful range of surface area includes approximately 32m². 2 / g to approximately 400m 2 / g, approximately 100m 2 / g to approximately 250m 2 / g, and about 150m 2 / g to approximately 220m 2 / g.

[0068] In one or more embodiments, the pH of the silica may be from about 5 to about 7 or slightly above 7, or in other embodiments from about 5.5 to about 6.8.

[0069] In one or more embodiments, the available silica coupling agents include sulfur-containing silica coupling agents. Examples of sulfur-containing silica coupling agents include bis(trialkoxysilyl)polysulfides or mercapto-organoalkoxysilanes. Types of bis(trialkoxysilyl)polysulfides include bis(trialkoxysilyl)disulfides and bis(trialkoxysilyl)tetrasulfides. Exemplary silica dispersing aids include, but are not limited to, alkylalkoxysilanes, fatty acid esters of hydrogenated or non-hydrogenated C5 or C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated or non-hydrogenated C5 or C6 sugars, and mixtures thereof, or inorganic or non-inorganic additional fillers.

[0070] Processing oil / volume-enhancing oil

[0071] In one or more embodiments, the vulcanizable composition of the present invention comprises a processing oil, which may also be referred to as a increment oil. In one or more embodiments, the vulcanizable composition contains no or substantially no processing oil.

[0072] In certain embodiments, the oils used include those commonly used as extender oils. Available oils or extenders include, but are not limited to, aromatic oils, paraffinic oils, naphthenic oils, vegetable oils other than castor oil, low-PCA oils (including MES, TDAE, and SRAE), and heavy naphthenic oils. Suitable low-PCA oils also include oils of various plant sources, such as those harvested from vegetables, nuts, and seeds. Non-limiting examples include, but are not limited to, soybean oil or yellow soybean oil, sunflower oil, safflower oil, corn oil, flaxseed oil, cottonseed oil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia oil, coconut oil, and palm oil. As commonly understood in the art, oil refers to those compounds that have a relative viscosity compared to other components of the vulcanizable composition, such as resins.

[0073] Reinforced resin

[0074] In one or more embodiments, the vulcanizable composition of the present invention comprises a reinforcing resin, which may also be referred to as a thermosetting resin. Exemplary 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, polyurethane resins, vinyl resins, vinyl ester resins, cyanoacrylate resins, silicone resins, siloxane resins, melamine resins, urea-formaldehyde resins, and fumaric acid resins. Examples of phenolic resins suitable as reinforcing resins include phenolic varnish-type phenolic resins, phenolic varnish-type cresol resins, phenolic varnish-type xylenol resins, phenolic varnish-type resorcinol resins, and oil-modified resins obtained therefrom.

[0075] Plasticized resin

[0076] In one or more embodiments, the vulcanizable compositions of the present invention may include one or more plasticizing resins. These resins typically include hydrocarbon resins, such as alicyclic resins, aliphatic resins, aromatic resins, terpene resins, and combinations thereof.

[0077] In one or more embodiments, the hydrocarbon resin is characterized by a glass transition temperature (Tg) of about 30°C to about 160°C, in other embodiments about 35°C to about 60°C, and in other embodiments about 70°C to about 110°C. In one or more embodiments, the hydrocarbon resin is also characterized by a softening point higher than its Tg. In some embodiments, the hydrocarbon resin has a softening point of about 70°C to about 160°C, in other embodiments about 75°C to about 120°C, and in other embodiments about 120°C to about 160°C.

[0078] Metal activators and organic acids

[0079] In one or more embodiments, the vulcanizable composition of the present invention comprises a metal compound. In one or more embodiments, the metal compound is an activator (i.e., one that facilitates the vulcanization or curing of the rubber). In other embodiments, the metal activator is a metal oxide. In a particular embodiment, the metal activator is a zinc substance formed in situ by 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.

[0080] In one or more embodiments, the zinc oxide is unfunctionalized zinc oxide, characterized in that its BET surface area is less than 10 m². 2 / g, less than 9m in other implementations 2 / g, and less than 8m in other implementations. 2 / g. In other embodiments, nano-zinc oxide is used, characterized by a BET surface area greater than 10m². 2 Those zinc oxide particles per g.

[0081] In one or more embodiments, the organic acid is a carboxylic acid. In a particular embodiment, the carboxylic acid is a fatty acid, including both saturated and unsaturated fatty acids. In a particular embodiment, a saturated fatty acid, such as stearic acid, is used. Other available acids include, but are not limited to, palmitic acid, arachidic acid, oleic acid, linoleic acid, and arachidonic acid.

[0082] Low molecular weight high vinyl additives

[0083] In one or more embodiments, the vulcanizable composition comprises a low molecular weight, high-vinyl polydiene. The polydiene is derived from the polymerization of a conjugated diene monomer or 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), and mixtures thereof.

[0084] Low molecular weight high-vinyl polydienes are characterized by their number-average molecular weight (Mn), which can be measured using a polystyrene standard via gel permeation chromatography and adjusted using Mark-Houwink parameters. According to embodiments of the invention, low molecular weight high-vinyl polydienes may have an 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 may have an Mn less than 120 kg / mol, less than 100 kg / mol in other embodiments, and less than 80 kg / mol in other embodiments. In one or more embodiments, low molecular weight high-vinyl polydienes have an Mn of about 30 kg / mol to about 115 kg / mol, about 40 kg / mol to about 100 kg / mol in other embodiments, and about 50 kg / mol to about 80 kg / mol in other embodiments.

[0085] Low molecular weight high-vinyl polydienes are characterized by their molecular weight distribution, also known as polydispersity, and is expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). This ratio can be measured using gel permeation chromatography with polystyrene standards and adjusted using Mark-Houwink parameters. According to embodiments of the invention, low molecular weight high-vinyl polydienes may have a polydispersity (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.

[0086] In one or more embodiments, the low molecular weight high vinyl polydiene is characterized by a vinyl content, which can be described as the number of unsaturated groups in the 1,2 microstructure relative to the total number of unsaturated groups within the polymer chain. As those skilled in the art will understand, 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%, more than 50%, and more than 60% vinyl in other embodiments. In these or other embodiments, the low molecular weight high vinyl polydiene contains less than 95%, less than 90%, and less than 88%. In one or more embodiments, the low molecular weight high vinyl polydiene contains about 40% to about 95%, about 50% to about 90%, and about 60% to about 88% vinyl in other embodiments.

[0087] Useful low molecular weight high vinyl polydienes are described in U.S. Publication No. 2011 / 0190440, which is incorporated herein by reference.

[0088] Other ingredients

[0089] Other components commonly used in rubber compounding may also be added to the vulcanizable composition used to manufacture the sidewall support of the present invention. These components may include waxes, scorch inhibitors, processing aids, plasticizers, stearic acid, and anti-degradation agents, such as antioxidants and anti-ozone agents. In one or more embodiments, one or more of these other components may be excluded from the vulcanizable composition of the present invention.

[0090] Component amount

[0091] rubber

[0092] In one or more embodiments, the vulcanizable composition comprises, based on the total weight of the composition, greater than 20% by weight, greater than 30% by weight in other embodiments, and greater than 40% by weight of rubber component. In these or other embodiments, the vulcanizable composition comprises, based on the total weight of the composition, less than 90% by weight, less than 70% by weight in other embodiments, and less than 60% by weight of rubber component. In one or more embodiments, the vulcanizable composition comprises, based on the total weight of the composition, about 20% by weight to about 90% by weight, about 30% by weight to about 70% by weight in other embodiments, and about 40% by weight to about 60% by weight of rubber component.

[0093] Eutectic composition

[0094] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0.005 parts by weight (pbw), greater than 0.01 pbw in other embodiments, and greater than 0.02 pbw in other embodiments of a eutectic composition. In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 3 pbw, less than 1 pbw in other embodiments, and less than 0.1 pbw in other embodiments of a eutectic composition. In one or more embodiments, the vulcanizable composition comprises, based on pr, about 0.005 pbw to about 3 pbw, about 0.01 pbw to about 1 pbw in other embodiments, and about 0.02 pbw to about 0.1 pbw in other embodiments of a eutectic composition.

[0095] In one or more embodiments, the amount of eutectic solvent may be described with reference to the loading of a metal activator (such as zinc oxide). In one or more embodiments, the vulcanizable composition contains more than 2% by weight, more than 3% by weight in other embodiments, and more than 5% by weight of eutectic solvent, based on the total weight of the eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizable composition. In these or other embodiments, the vulcanizable composition contains less than 15% by weight, less than 12% by weight in other embodiments, and less than 10% by weight of eutectic solvent, based on the total weight of the eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizable composition. In one or more embodiments, the vulcanizable composition contains about 2% by weight to about 15% by weight, about 3% by weight to about 12% by weight in other embodiments, and about 5% by weight to about 10% by weight of eutectic solvent, based on the total weight of the eutectic solvent and metal activator (e.g., zinc oxide) present in the vulcanizable composition.

[0096] Metal compounds

[0097] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 1.5 parts by weight (pbw), greater than 2.0 pbw in other embodiments, and greater than 2.5 pbw in other embodiments, a metal activator (e.g., zinc oxide). In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 8 pbw, less than 7 pbw in other embodiments, and less than 6 pbw in other embodiments, a metal activator (e.g., zinc oxide). In one or more embodiments, the vulcanizable composition comprises, based on pr, about 1.5 pbw to about 8.0 pbw, about 2.0 pbw to about 7 pbw in other embodiments, and about 2.5 pbw to about 6 pbw in other embodiments, a metal activator (e.g., zinc oxide). In one or more embodiments, the vulcanizable composition contains no or substantially no metal activator, such as zinc oxide.

[0098] organic acids

[0099] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0.5 parts by weight (pbw), greater than 0.7 pbw in other embodiments, and greater than 1.0 pbw in other embodiments of an organic acid (e.g., stearic acid). In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 5 pbw, less than 3 pbw in other embodiments, and less than 2 pbw in other embodiments of an organic acid (e.g., stearic acid). In one or more embodiments, the vulcanizable composition comprises, based on pr, about 0.5 pbw to about 5 pbw, about 0.7 pbw to about 3 pbw in other embodiments, and about 1.0 pbw to about 2 pbw in other embodiments of an organic acid (e.g., stearic acid).

[0100] filler

[0101] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0 parts by weight (pbw), greater than 10 pbw in other embodiments, greater than 25 pbw in other embodiments, greater than 35 pbw in other embodiments, greater than 45 pbw in other embodiments, greater than 55 pbw in other embodiments, and greater than 65 pbw in other embodiments. In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 200 pbw, less than 150 pbw in other embodiments, less than 120 pbw in other embodiments, less than 100 pbw in other embodiments, and less than 80 pbw in other embodiments. In one or more embodiments, the vulcanizable composition comprises, based on pr, about 0 pbw to about 200 pbw, about 35 pbw to about 120 pbw in other embodiments, and about 45 pbw to about 100 pbw in other embodiments.

[0102] carbon black

[0103] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0 parts by weight (pbw), greater than 10 pbw in other embodiments, greater than 25 pbw in other embodiments, greater than 45 pbw in other embodiments, greater than 55 pbw in other embodiments, greater than 60 pbw in other embodiments, greater than 65 pbw in other embodiments, and greater than 75 pbw of carbon black in other embodiments. In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 200 pbw, less than 150 pbw in other embodiments, and less than 100 pbw of carbon black. In one or more embodiments, the vulcanizable composition comprises, based on pr, about 10 pbw to about 200 pbw, about 40 pbw to about 150 pbw in other embodiments, and about 50 pbw to about 100 pbw of carbon black in other embodiments.

[0104] silicon dioxide

[0105] In one or more embodiments, the vulcanizable composition comprises more than 0.1 parts by weight (pbw), more than 2.5 pbw in other embodiments, and more than 5.0 pbw of silica per 100 parts by weight of rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 50 pbw, less than 30 pbw in other embodiments, less than 25 pbw in other embodiments, less than 20 pbw in other embodiments, less than 18 pbw in other embodiments, less than 15 pbw in other embodiments, less than 10 pbw in other embodiments, less than 5 pbw in other embodiments, less than 3 pbw in other embodiments, and less than 1 pbw of silica per pr. In one or more embodiments, the vulcanizable composition comprises about 0.1 pbw to about 50 pbw, about 2.5 pbw to about 30 pbw in other embodiments, and about 3 pbw to about 20 pbw of silica per pr. In one or more embodiments, the vulcanizable composition contains no or substantially no silica.

[0106] Filler ratio

[0107] In one or more embodiments, the vulcanizable composition may 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 relative to other fillers such as silica. In one or more embodiments, the weight ratio of carbon black to silica is greater than 2:1, 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.

[0108] Silica coupling agent

[0109] In one or more embodiments, the vulcanizable composition comprises more than 1 part by weight (pbw), more than 2 pbw in other embodiments, and more than 5 pbw of silica coupling agent per 100 parts by weight of silica. In these or other embodiments, the vulcanizable composition comprises less than 20 pbw, less than 15 pbw in other embodiments, and less than 10 pbw of silica coupling agent per 100 parts by weight of silica. In one or more embodiments, the vulcanizable composition comprises about 1 pbw to about 20 pbw, about 2 pbw to about 15 pbw in other embodiments, and about 5 pbw to about 10 pbw of silica coupling agent per 100 parts by weight of silica. In one or more embodiments, the vulcanizable composition contains no or substantially no silica coupling agent.

[0110] resin

[0111] In one or more embodiments, the vulcanizable composition comprises more than 1 part by weight (pbw), more than 15 pbw in other embodiments, and more than 25 pbw of resin (e.g., hydrocarbon resin) per 100 parts by weight of rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 150 pbw, less than 120 pbw in other embodiments, less than 90 pbw in other embodiments, less than 80 pbw in other embodiments, less than 60 pbw in other embodiments, and less than 45 pbw of resin (e.g., hydrocarbon resin) per pbw. In one or more embodiments, the vulcanizable composition comprises about 1 pbw to about 150 pbw, about 15 pbw to about 100 pbw in other embodiments, and about 25 pbw to about 80 pbw of resin (e.g., hydrocarbon resin) per pbw in other embodiments. In one or more embodiments, the vulcanizable composition contains no or substantially no resin.

[0112] Processing oil / volume-enhancing oil

[0113] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0.1 parts by weight (pbw), greater than 1 pbw in other embodiments, and greater than 2 pbw in other embodiments, processing oil (e.g., naphthenic oil). In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 20 pbw, less than 18 pbw in other embodiments, less than 15 pbw in other embodiments, less than 12 pbw in other embodiments, less than 10 pbw in other embodiments, and less than 8 pbw in other embodiments, processing oil. In one or more embodiments, the vulcanizable composition comprises, based on pr, about 0.1 pbw to about 20 pbw, about 0.5 pbw to about 18 pbw in other embodiments, about 1 pbw to about 15 pbw in other embodiments, and about 2 pbw to about 12 pbw in other embodiments, oil. In one or more embodiments, the vulcanizable composition contains no or substantially no oil.

[0114] Plasticizers

[0115] In one or more embodiments, the plasticizing resin and processing oil may be collectively referred to as plasticizing additives, ingredients, or components. In one or more embodiments, the vulcanizable composition of the present invention comprises more than 0.1 parts by weight (pbw), more than 1 pbw in other embodiments, and more than 2 pbw of plasticizing additives, based on 100 parts by weight of rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 15 pbw, less than 12 pbw in other embodiments, less than 10 pbw in other embodiments, less than 7 pbw in other embodiments, less than 5 pbw in other embodiments, and less than 3 pbw of plasticizing additives, based on pbw. In one or more embodiments, the vulcanizable composition comprises about 0.1 pbw to about 15 pbw, about 0.5 pbw to about 10 pbw in other embodiments, about 1 pbw to about 7 pbw in other embodiments, and about 2 pbw to about 5 pbw of plasticizing additives, based on pbw.

[0116] Reinforced resin

[0117] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0.1 parts by weight (pbw), greater than 1 pbw in other embodiments, and greater than 2 pbw in other embodiments, a reinforcing resin (e.g., phenolic varnish resin). In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 8 pbw, less than 6 pbw in other embodiments, less than 5 pbw in other embodiments, and less than 4 pbw in other embodiments, a reinforcing resin. In one or more embodiments, the vulcanizable composition comprises, based on pr, about 0.1 pbw to about 8 pbw, about 0.5 pbw to about 6 pbw in other embodiments, and about 2 pbw to about 4 pbw in other embodiments, a reinforcing resin. In one or more embodiments, the vulcanizable composition contains no or substantially no reinforcing resin.

[0118] Low molecular weight high vinyl additives

[0119] In one or more embodiments, the vulcanizable composition comprises, based on 100 parts by weight of rubber (phr), greater than 0.5 parts by weight (pbw), greater than 1.5 pbw in other embodiments, and greater than 1.7 pbw in other embodiments of low molecular weight high-vinyl polydiene. In these or other embodiments, the vulcanizable composition comprises, based on pr, less than 5.0 pbw, less than 4.0 pbw in other embodiments, and less than 3.0 pbw of low molecular weight high-vinyl polydiene. In one or more embodiments, the vulcanizable composition comprises, based on pr, about 0.5 pbw to about 5.0 pbw, about 1.5 pbw to about 4.0 pbw in other embodiments, and about 1.7 pbw to about 3.0 pbw of low molecular weight high-vinyl polydiene. In one or more embodiments, the vulcanizable composition contains no or substantially no low molecular weight high-vinyl polydiene.

[0120] Method for preparing sidewall support

[0121] The sidewall support of the present invention can be prepared using conventional rubber processing and curing techniques. For example, the components can be mixed in a solid state to form a vulcanizable material composition. The composition can then be shaped into a desired form to create a green sidewall support. The green sidewall support can then be cured.

[0122] 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 curing agent to the masterbatch. The preparation of the masterbatch may be carried out using one or more sub-mixing steps, wherein, for example, one or more components may be added sequentially to the composition after an initial mixture is prepared by mixing two or more ingredients. Additionally, using conventional techniques, additional components may be added to the preparation of the vulcanizable composition, such as, but not limited to, carbon black, additional fillers, chemically treated inorganic oxides, silica, silica coupling agents, silica dispersants, processing oils, processing aids such as zinc oxide and fatty acids, and anti-degradation agents such as antioxidants or anti-ozone agents.

[0123] In one or more embodiments, the eutectic composition is prepared before being introduced into the vulcanizable rubber. In other words, a first component of the mixture is pre-combined with a second component of the mixture before being 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.

[0124] In one or more embodiments, the eutectic composition is pre-combined with one or more components of the rubber formulation before the eutectic mixture is introduced 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 pre-composition or masterbatch before the pre-composition is 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 within the mixer. In other embodiments, the eutectic composition is a minor component of the pre-composition, and thus the component pre-mixed with the eutectic composition acts as a carrier for the eutectic composition. For example, the eutectic composition may be combined with a larger volume of zinc oxide, and the zinc oxide will act as a carrier for delivering the combination of zinc oxide and the eutectic composition in solid form to the rubber within the mixer. In still other embodiments, one member 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 pre-composition that can be added to the rubber within the mixer in solid form. Those skilled in the art should understand that a mixture with this property can be formed by combining an excess of the first or second eutectic member relative to the other eutectic members, thereby maintaining the solid composition at the desired temperature.

[0125] In one or more embodiments, a eutectic solvent is introduced into the vulcanizable rubber as an initial component in the formation of the rubber masterbatch. Therefore, the eutectic solvent and rubber are mixed under high shear and high temperature. In one or more embodiments, the eutectic solvent and rubber are mixed at a minimum temperature exceeding 110°C, in other embodiments exceeding 130°C, and in other embodiments exceeding 150°C. In one or more embodiments, the high shear and high temperature mixing is carried out at a temperature from about 110°C to about 170°C.

[0126] In other embodiments, the eutectic solvent and the sulfur-based curing agent are introduced sequentially or simultaneously into the vulcanizable rubber. Thus, the eutectic solvent and the vulcanizable rubber are mixed at a maximum temperature below 110°C, below 105°C in other embodiments, and below 100°C in still other embodiments. In one or more embodiments, mixing with the curing agent is carried out at a temperature of about 70°C to about 110°C.

[0127] Similar to eutectic solvents, zinc oxide and stearic acid can be added as initial components to rubber masterbatches, thus undergoing high-temperature, high-shear mixing. Alternatively, zinc oxide and stearic acid can be added together with sulfur-based curing agents, resulting in only low-temperature mixing.

[0128] In one or more embodiments, zinc oxide and the eutectic solvent are introduced separately into the vulcanizable rubber. In other embodiments, zinc oxide and the eutectic solvent are pre-combined to form a zinc oxide masterbatch, which may comprise a solution of zinc oxide dissolved or otherwise dispersed in the eutectic solvent. The zinc oxide masterbatch can then be introduced into the vulcanizable rubber.

[0129] In one or more embodiments, polyisoprene rubber (e.g., natural rubber) is first plasticized to achieve desired viscosity and processability properties. After mixing the polyisoprene rubber, other components, such as a eutectic solvent, are introduced into the pre-processed polyisoprene rubber according to one or more embodiments of the invention.

[0130] Mixed conditions

[0131] In one or more embodiments, a vulcanizable composition is prepared by first mixing a vulcanizable rubber with a eutectic solvent at a temperature of about 140°C to about 180°C, or in other embodiments, at a temperature of about 150°C to about 170°C. In some embodiments, after initial mixing, the composition (i.e., the masterbatch) is cooled to a temperature below 100°C, or in other embodiments, cooled to a temperature below 80°C, and a curing agent is added. In some embodiments, mixing is continued at a temperature of about 90°C to about 110°C, or in other embodiments, mixing is continued at a temperature of about 95°C to about 105°C, to prepare the final vulcanizable composition.

[0132] In one or more embodiments, the masterbatch mixing step or one or more sub-steps of the masterbatch mixing step can be characterized by a peak temperature achieved by the composition during mixing. This peak temperature may also be referred to as the dripping temperature. In one or more embodiments, the peak temperature of the composition during the masterbatch mixing step can be at least 140°C, in other embodiments at least 150°C, and in other embodiments at least 160°C. In these or other embodiments, the peak temperature of the composition during the masterbatch mixing step can be from about 140°C to about 200°C, in other embodiments from about 150°C to about 190°C, and in other embodiments from about 160°C to about 180°C.

[0133] Final mixing step

[0134] Following the masterbatch mixing step, a curing agent or curing agent system is introduced into the composition, and mixing continues to ultimately form a vulcanizable composition. This mixing step may be referred to as the final mixing step, the curing mixing step, or the production mixing step. The product obtained from this mixing step may be referred to as a vulcanizable composition.

[0135] In one or more embodiments, the final mixing step can be characterized by the peak temperature achieved by the composition during final mixing. Those skilled in the art will recognize that this temperature may also be referred to as the final dripping temperature. In one or more embodiments, the peak temperature of the composition during final mixing can be up to 130°C, in other embodiments up to 110°C, and in other embodiments up to 100°C. In these or other embodiments, the peak temperature of the composition during final mixing can be from about 80°C to about 130°C, in other embodiments about 90°C to about 115°C, and in other embodiments about 95°C to about 105°C.

[0136] mixing equipment

[0137] All components of a vulcanizable composition can be mixed using standard mixing equipment such as internal mixers (e.g., Banbury mixers or Brabender mixers), extruders, kneaders, and two-roll mills. Mixing can be performed individually or sequentially. As mentioned above, components can be mixed in a single stage, or in two or more stages in other embodiments. For example, in the first stage (i.e., the mixing stage), a masterbatch is prepared, which typically contains rubber components and fillers. Once the masterbatch is prepared, a vulcanizing agent can be introduced and mixed into the masterbatch in the final mixing stage, which is typically carried out at a relatively low temperature to reduce the chance of premature vulcanization. An additional mixing stage, sometimes referred to as re-mixing, can be employed between the masterbatch mixing stage and the final mixing stage.

[0138] Industrial applicability

[0139] Tire manufacturing

[0140] Vulcanizable compositions can be processed into tire parts using common tire manufacturing techniques, including standard rubber molding, forming, and curing techniques. Vulcanization is typically achieved by heating the vulcanizable composition in a mold; for example, it can be heated to approximately 140°C to approximately 180°C. The cured or crosslinked rubber composition, referred to as a vulcanizate, typically contains a thermosetting three-dimensional polymer network. Other components, such as fillers and processing aids, can be uniformly dispersed throughout the crosslinked network. Pneumatic tires can be manufactured as described in U.S. Patents 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

[0141] As described above, the vulcanizable compositions of the present invention can be cured to prepare various tire components. These tire components include, but are not limited to, tire treads, tire sidewalls, belt layers, inner liners, and tread cores.

[0142] experiment

[0143] Formation of liquid eutectic compositions

[0144] A liquid eutectic composition of choline chloride and urea was prepared by mixing 1 mole of choline chloride and 2 moles of urea in an oil bath at 100°C while stirring with a magnetic rod at 60 rpm. The composition, referred to as reline, is a liquid under standard temperature and pressure conditions.

[0145] Formation of solid eutectic compositions

[0146] A solid eutectic composition of choline chloride and thiourea was prepared by mixing 1 mole of choline chloride and 2 moles of thiourea in an oil bath at 100°C while stirring with a magnetic rod at 60 rpm. The composition, referred to as ChCl:thiourea, was determined to have a melting temperature of 67°C (DSC measurement).

[0147] Formation of vulcanizable compositions

[0148] Vulcanizable compositions were prepared using the rubber formulations and mixing sequence provided in Table I. The rubber formulation indicates a rubber formulation suitable for manufacturing tire treads. The mixing procedure was a three-step process, comprising a masterbatch mixing step, a “re-mixing” step, and a final mixing step. Each mixing step was carried out in a 65g Banbury-style mixer. During masterbatch preparation, the mixer was operated at 60 rpm for five minutes, or until a peak composition temperature of 170°C was achieved. At this point, the composition was dripped from the mixer and allowed to cool to below approximately 85°C. At this point, the composition was then reintroduced into the mixer along with additional ingredients for the “re-mixing” stage and mixed at 60 rpm for five minutes, or until the peak composition temperature of approximately 170°C was reached. The composition was again dripped from the mixer and allowed to cool to below approximately 50°C. The composition was then again reintroduced into the mixer along with the ingredients identified for the “final mixing” stage. These ingredients included reline or ChCl:thiourea, as provided in Table II. Continue mixing at 40 rpm for two and a half minutes, or until the peak composition temperature of approximately 100°C is reached. The composition is then dripped from the mixer, and a sample is obtained from the composition for analytical testing purposes. As shown in Table II, the components introduced during the final mixing stage change as reported in Table II, and the results of the analytical tests are provided in the table.

[0149]

[0150] Rheometer measurements were performed using an MDR 2000 operating at the temperatures specified in the table. The tensile mechanical properties (maximum stress, modulus, elongation, and toughness) of the vulcanizate were measured using the standard procedure described in ASTM-D412.

[0151]

[0152] The data in Table II show that the eutectic mixture based on choline chloride and thiourea has performance comparable to reline, while also having the advantage of being solid under standard temperature and pressure conditions.

[0153] Various modifications and alterations without departing from the scope and spirit of the invention will be apparent to those skilled in the art. The invention should not be unduly limited to the exemplary embodiments shown herein.

Claims

1. A method for manufacturing a sidewall support member, the method comprising the following steps: (i) Provide a vulcanizable composition comprising an elastomer, a filler, a curing agent, and a eutectic composition, wherein the eutectic composition is a solid; (ii) Manufacturing the vulcanizable composition into a green sidewall support; and (iii) subjecting the green 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 any one of the preceding claims, wherein the eutectic composition is a deep eutectic composition formed by combining eutectic members into eutectic pairs, and wherein the molar ratio of the respective members of the pair is within + / - 20% of the molar ratio of the lowest melting point of the eutectic pair.

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

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

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

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

8. The method according to any one of the preceding claims, wherein the eutectic composition is composed of the formula... Define, where It is a cation. The term refers to 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).

9. The method according to any one of the preceding claims, wherein It is an ammonium, phosphonium, or sulfonium cation, and It is a halide ion.

10. The method according to any one of the preceding claims, 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 the preceding claims, 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 method according to any one of the preceding claims, wherein the ammonium compound is defined by Formula II: 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. To counteract anions.

13. The method according to any one of the preceding claims, wherein the ammonium compound is selected from the group consisting of N-ethyl-2-hydroxy-N,N-dimethylethylammonium chloride, 2-hydroxy-N,N,N-trimethylethylammonium chloride (also known as choline chloride), and N-benzyl-2-hydroxy-N,N-dimethylethylammonium chloride.

14. The method according to any one of the preceding claims, wherein the ammonium compound is selected from the group consisting of 2-chloro-N,N,N-trimethylethylammonium (also known as chlorocholine chloride) and 2-(chlorocarbonyloxy)-N,N,N-trimethylethylammonium chloride.

15. The method according to any one of the preceding claims, 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 the preceding claims, wherein the hydrogen bond donor is selected from the group consisting of: aliphatic amines, ethylenediamine, diethylenetriamine, aminoethylpiperazine, triethylenetetramine, tri(2-aminoethyl)amine, N,N'-bis-(2-aminoethyl)piperazine, piperazine ethyl ethylenediamine and tetraethylenepentamine, acrylamine, aniline, substituted aniline and combinations thereof.

17. The method according to any one of the preceding claims, 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 the preceding claims, 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, mesoneprolic acid, and combinations thereof.

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

20. The method according to any one of the preceding claims, 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, ferric chloride, ferric bromide, ferric iodide, and combinations thereof.

21. The method according to any one of the preceding claims, wherein the vulcanizable composition comprises more than 1.5 pbw of zinc oxide based on 100 pbw of rubber.

22. The method according to any one of the preceding claims, wherein the vulcanizable composition comprises more than 2.0 pbw of zinc oxide based on 100 pbw of rubber.

23. The method according to any one of the preceding claims, wherein the vulcanizable composition comprises about 0.005 pbw to about 3 pbw of the eutectic composition based on 100 pbw of rubber.

24. The method according to any one of the preceding claims, wherein the vulcanizable composition comprises about 0.01 pbw to about 1 pbw of the eutectic composition based on 100 pbw of rubber.

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

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

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

28. A method of forming a pneumatic tire, the method comprising placing the sidewall support formed by the method according to any one of the preceding claims into a green tire.

29. A method of forming a pneumatic tire, the method comprising placing the sidewall support formed by the method according to any one of the preceding claims into a cured tire.

30. A pneumatic tire, the pneumatic tire comprising: (i) Tread; (ii) The fetus; (iii) Optional inner lining layer; and (iv) A pair of sidewall supports disposed on the carcass or, if present, the optional inner liner, wherein the sidewall supports are made of a vulcanizable composition comprising an elastomer, filler, curing agent and eutectic composition.

31. The tire according to any one of the preceding claims, wherein the sidewall support is substantially capable of supporting the tire in a leak-proof condition.

32. The tire according to any one of the preceding claims, wherein the tread has a first edge and a second edge, and the tire includes a first bead and a second bead, wherein a first reinforcing member of the sidewall support pair generally extends from the first edge of the tread to the first bead, and wherein a second reinforcing member of the sidewall support pair generally extends from the second edge of the tread to the second bead.

33. The tire according to any one of the preceding claims, wherein the sidewall support is crescent-shaped.

34. The tire according to any one of the preceding claims, wherein the sidewall support is an elastomer.

35. The tire according to any one of the preceding claims, wherein the sidewall support is characterized in that it has a Shore hardness A greater than 60 at 100°C, a loss tangent less than 0.20 at 100°C and 10Hz, a storage modulus greater than 6 MPa at 10°C, 52Hz and 1% strain, and an elastic modulus greater than 10 kg / cm². 2 .

36. The tire according to any one of the preceding claims, wherein the sidewall support is characterized by a thickness greater than 6 mm.

37. The tire according to any one of the preceding claims, wherein the sidewall support is characterized in that it has a degree of curing such that less than 5% by weight can be extracted by boiling cyclohexane.

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

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

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

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

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

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

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

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