Tire components from rubber compositions including guayule rubber and eutectic compositions, and related methods.
A rubber composition combining guayule natural rubber and eutectic compositions addresses performance limitations in tire components by optimizing molecular weights and compositions, enhancing tire tread durability and efficiency.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2022-10-06
- Publication Date
- 2026-04-09
AI Technical Summary
Existing tire components do not effectively utilize guayule natural rubber and eutectic compositions to enhance performance, particularly in tire treads, due to limitations in molecular weight and composition.
A rubber composition comprising guayule natural rubber and a eutectic composition is formulated, incorporating specific molecular weights and ratios of natural rubber, conjugated diene monomer-based rubber, reinforcing fillers, and vulcanizing agents to create tire components with improved properties.
The solution enhances tire performance by leveraging the unique properties of guayule natural rubber and eutectic compositions, resulting in improved tire tread durability and efficiency.
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Abstract
Description
[Technical Field]
[0001] This application relates to tire components comprising a rubber composition comprising guayule natural rubber and a eutectic composition, for the purposes of the relevant method. [Background technology]
[0002] Guayule natural rubber is extracted from the guayule plant (Parthenium argentatum), a woody shrub-like plant that produces rubber and resin. A eutectic composition refers to a mixture of components that can self-associate (for example, through hydrogen bonding interactions) to form a eutectic mixture having a melting point lower than that of each individual component. Such eutectic mixtures are often referred to as deep eutectic solvents (DES). [Overview of the project] [Problems that the invention aims to solve]
[0003] This specification discloses tire components comprising a rubber composition containing guayule natural rubber and a eutectic composition. Related methods for providing or preparing tire components are also disclosed.
[0004] In the first embodiment, a method for providing tire components, preferably a tire tread, is disclosed. The method of the first embodiment comprises preparing a rubber composition, the rubber composition comprising (a)(i) 10 to 100 parts natural rubber, preferably 51 to 90 parts natural rubber, having at least 10% by weight provided by guayule natural rubber having at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and up to 90% by weight provided by Hevea natural rubber, with (a)(i) at least 10% by weight provided by guayule natural rubber having 3,000,000 to 4,000,000 grams / mol of Mw / Mn, and up to 90% by weight provided by Hevea natural rubber. The invention comprises (a), (b), and (c) a cured rubber composition in which (a), (b), and (c) are used in the cured rubber composition to provide tire components. The invention comprises (a), (b), and (c) a natural rubber, (ii) 0 to 90 parts, preferably 10 to 49 parts, of at least one conjugated diene monomer-based rubber, (ii) 100 parts of at least one rubber, (b) of at least one conjugated diene monomer-based rubber, (ii) 0 to 90 parts, preferably 10 to 49 parts, of at least one rubber, (b), and (ii) a cured rubber composition in which (a), (b), and (c) are used in the cured rubber composition to provide tire components.
[0005] In a second embodiment, a tire component comprising a rubber composition, preferably a tire tread, is provided. The rubber composition comprises (a) (i) 10 to 100 parts, preferably 51 to 90 parts, of natural rubber having at least 10% by weight, provided by guayure natural rubber having at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and 3 to 4 Mw / Mn; and (ii) 0 to 90 parts, preferably 10 to 49 parts, of at least one conjugated diene monomer system The cured rubber composition comprises (a), (b), and (c) 100 parts of at least one type of rubber, (b) a reinforcing filler selected from carbon black and silica in an amount of about 30 to about 150 phr, and (c) a sulfur-based vulcanizing agent, at least one vulcanization accelerator, a vulcanization activator, and a eutectic composition, or a residue thereof, preferably in an amount of about 0.005 to about 3 phr, more preferably about 0.01 to about 1 phr, wherein (a), (b), and (c) are used in the cured rubber composition to provide tire components. [Modes for carrying out the invention]
[0006] This specification discloses tire components comprising a rubber composition containing guayule natural rubber and a eutectic composition. Related methods for providing or preparing tire components are also disclosed.
[0007] In the first embodiment, a method for providing tire components, preferably a tire tread, is disclosed. The method of the first embodiment comprises preparing a rubber composition, the rubber composition comprising (a)(i) 10 to 100 parts of natural rubber, preferably 51 to 90 parts, having (a)(i) at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and 3,000,000 to 4,000,000 grams / mol of Mw / Mn, and at least 10% by weight of guayule natural rubber having up to 90% by weight of Hevea natural rubber. The invention comprises (a), (b), and (c) natural rubber, (ii) 100 parts of at least one rubber comprising 0 to 90 parts, preferably 10 to 49 parts, of at least one conjugated diene monomer-based rubber, (b) a reinforcing filler selected from carbon black and silica in an amount of about 30 to about 150 phr, and (c) a cured package comprising a sulfur-based vulcanizing agent, at least one vulcanization accelerator, a vulcanization activator, and a eutectic composition, preferably in an amount of about 0.005 to about 3 phr, more preferably about 0.01 to about 1 phr, wherein (a), (b), and (c) are used in the cured rubber composition to provide tire components.
[0008] In a second embodiment, a tire component comprising a rubber composition, preferably a tire tread, is provided. The rubber composition comprises (a) (i) 10 to 100 parts, preferably 51 to 90 parts, of natural rubber having at least 10% by weight, provided by guayure natural rubber having at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and 3 to 4 Mw / Mn; and (ii) 0 to 90 parts, preferably 10 to 49 parts, of at least one conjugated diene monomer system The cured rubber composition comprises (a), (b), and (c) 100 parts of at least one type of rubber, (b) a reinforcing filler selected from carbon black and silica in an amount of about 30 to about 150 phr, and (c) a sulfur-based vulcanizing agent, at least one vulcanization accelerator, a vulcanization activator, and a eutectic composition, or a residue thereof, preferably in an amount of about 0.005 to about 3 phr, more preferably about 0.01 to about 1 phr, wherein (a), (b), and (c) are used in the cured rubber composition to provide tire components.
[0009] definition The terms used herein are for illustrative purposes only and should not be construed as limiting the invention as a whole.
[0010] As used herein, the terms "BR" or "polybutadiene" refer to a homopolymer of 1,3-butadiene.
[0011] As used herein, the term “majority” means more than 50% (for example, at least 50.1%, at least 50.5%, at least 51%, etc.).
[0012] As used herein, the term “less than half” means less than 50% (e.g., 49.5% or less, 49% or less, etc.).
[0013] Unless otherwise specified herein, the term "Mooney viscosity" refers to Mooney viscosity, ML. 1+4This refers to the Mooney viscosity of a rubber composition, which will be understood by those skilled in the art.
[0014] As used herein, the abbreviation Mn refers to the number-average molecular weight.
[0015] As used herein, the abbreviation Mw refers to the weight-average molecular weight.
[0016] As used herein, the term “natural rubber” means rubber of natural origin, including rubber that can be harvested from raw materials such as the Hevea rubber tree, and rubber that can be harvested from non-Hevea raw materials (e.g., guayule rubber and dandelions such as TKS). In other words, the term “natural rubber” should be interpreted as excluding synthetic polyisoprene.
[0017] As used herein, the term "phr" means parts per 100 parts of rubber. 100 parts of rubber is also referred to herein as 100 parts of elastomer component.
[0018] As used herein, the term “polyisoprene” means synthetic polyisoprene. In other words, the term is used to refer to polymers produced from isoprene monomers and should not be interpreted to include naturally occurring rubbers (e.g., Hevea natural rubber, guayule-derived natural rubber, or dandelion-derived natural rubber). However, the term “polyisoprene” should be interpreted to include polyisoprene produced from natural sources of isoprene monomers.
[0019] As used herein, the term "SBR" means styrene-butadiene copolymer rubber.
[0020] As used herein, the term “tread” means both the portion of the tire that contacts the road under normal inflation and load conditions, and any sub-tread.
[0021] Natural rubber As discussed above, according to the first and second embodiments disclosed herein, the rubber composition comprises (i) 10 to 100 parts (e.g., 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 parts) of natural rubber, preferably 51 to 90 parts (e.g., 51, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 parts) of natural rubber, comprising 100 parts of at least one rubber. The statement that natural rubber is present in the rubber composition in an amount of 10 to 100 parts means that natural rubber may be present in an amount ranging from 10 to a maximum of 100 parts of the total rubber in the rubber composition. The 100 parts of at least one type of rubber and the parts of guayule natural rubber refer to parts by weight.
[0022] At least 10% by weight of the total amount of natural rubber (i) is provided by guayule natural rubber as described below. In preferred embodiments of the first and second embodiments, an increased weight percentage of natural rubber (i), including at least 30% by weight (e.g., 30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 100%), more preferably at least 40% by weight (e.g., 40%, 50%, 60%, 70%, 80%, 90%, or even 100%), is provided by guayule natural rubber as described below. In specific embodiments of the first and second embodiments, at least 50% by weight of natural rubber (i) is provided by guayule natural rubber as described below. Similarly, in specific embodiments of the first and second embodiments, it is specifically assumed that the entirety of natural rubber (i) (i.e., 100% by weight) consists of guayule natural rubber as described below.
[0023] Guayule natural rubber As discussed above, according to the first and second embodiments disclosed herein, at least 10% by weight of natural rubber (i) in the rubber composition comprises guayule natural rubber. According to the first and second embodiments, the guayule natural rubber has at least 1,200,000 grams / mol (e.g., 1,200,000, 1,250,000, 1,300,000, 1,350,000, 1,400,000, 1,450,000, etc.) of Mw and at least 250,000 grams / mol (e.g., 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, etc.) of Mn. In preferred embodiments of the first and second embodiments, the guayule natural rubber has Mw of 1,250,000 to 1,350,000 grams / mol (e.g., 1,250,000, 1,300,000, or 1,350,000) and Mn of 300,000 to 400,000 grams / mol (e.g., 250,000, 300,000, or 350,000). The Mw and Mn values (and thus the Mw / Mn values) referred to herein refer to values measured by GPC using a polystyrene standard.
[0024] According to the first and second embodiments, the resin content of guayule natural rubber can vary. In preferred embodiments of the first and second embodiments, the guayule natural rubber has a resin content of about 2 to about 5% by weight or 2 to 5% by weight (e.g., 2, 2.2, 2.4, 2.5, 2.6, 2.8, 3, 3.2, 3.4, 3.5, 3.6, 3.8, 4, 4.2, 4.4, 4.5, 4.6, 4.8, or 5%). According to the first and second embodiments, the ash content of guayule natural rubber can vary. In preferred embodiments of the first and second embodiments, the guayule natural rubber has an ash content of about 0.1 to about 0.2% by weight or 0.1 to 0.2% by weight (e.g., 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or 0.2%). In particularly preferred embodiments of the first and second embodiments, the guayule natural rubber has a resin content of about 2 to about 5% by weight or 2 to 5% by weight, and an ash content of about 0.1 to 0.2% by weight or 0.1 to 0.2% by weight. The resin content of a natural rubber sample can be measured using an acetone extract; therefore, the term "resin" is used interchangeably with the term "acetone extract". The resin content of purified guayule natural rubber can be determined by following the acetone extraction procedure described below. A 9-10 gram sample of guayure gum is solubilized for 6 hours by Soxhlet extraction in a co-solvent (31 mL of acetone, 170 mL of pentane) to solubilize both the rubber and the resin. The resin is solubilized in the acetone phase. The solubilized rubber (contained in the pentane phase) can be isolated using methanol coagulation, centrifugation, and drying. More specifically, 20 mL of the extract from the Soxhlet extraction is transferred to a centrifuge tube, and 20 mL of methanol is added to coagulate the rubber. The tube and its contents are centrifuged at 1500 rpm for 20 minutes to separate the coagulated rubber from the solvent. The supernatant in the tube is decanted into a flask and saved for resin % measurement. The tube and its coagulated rubber contents are rinsed with an aliquot (10 mL) of acetone, and the acetone is poured from the tube into the flask containing the decanted supernatant. The remaining coagulated rubber in the tube is then dried under vacuum in a vacuum oven preheated to 60°C for 30 minutes. After cooling to room temperature, the tube is weighed and the amount of rubber inside is calculated.The resin content (contained in the acetone phase) is determined by using a flask containing the supernatant and decanted acetone. The solvent is evaporated from the flask in a ventilated hood until nearly dry. The remaining contents are then further dried by placing the flask in an oven at 110°C for 30 minutes. After cooling, the flask is weighed and the amount of resin remaining in the flask is calculated. As used herein, the term “ash” (as used in relation to the solid refined rubber produced by the processes disclosed herein) means the inorganic material (i.e., carbon-free) remaining after ashing the rubber at 550°C ± 25°C.
[0025] According to the first and second embodiments disclosed herein, the Mooney viscosity of guayule natural rubber can vary. In preferred embodiments of the first and second embodiments, the guayule natural rubber has a viscosity of at least 65 (e.g., 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 82, 83, 84, 85, 86, 87, 88, 89, or 90), more preferably at least 70 (e.g., 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 82, 83, 84, 85, 86, 87, 88, 89, or 90) at 100°C. 1+4 It has. According to such embodiments, ML at 100°C 1+4 It should also be understood that this may be within the range encompassed by the aforementioned values, such as 65 to 90, preferably 70 to 90.
[0026] In certain embodiments of the first and second embodiments disclosed herein, guayule natural rubber is functionalized. In such embodiments, guayule natural rubber is functionalized preferably with carbon black reactive functional groups, preferably SBR and BR, as described in detail below.
[0027] additional rubber As discussed above, according to the first and second embodiments disclosed herein, the rubber composition comprises (ii) 0 to 90 parts of at least one conjugated diene monomer rubber. The statement that at least one conjugated diene monomer rubber (ii) is present in the rubber composition in amounts of 0 to 90 parts (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 parts) means that this at least one conjugated diene monomer rubber (ii) is optional, but if present, it can be present in an amount of up to 90 parts of 100 parts of the total rubber in the rubber composition. 100 parts of at least one rubber and parts of at least one conjugated diene monomer rubber refer to parts by weight. In preferred embodiments of the first and second embodiments, at least one conjugated diene monomer-based rubber is present in the rubber composition in an amount of 10 to 49 parts (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 49 parts).
[0028] According to the first and second embodiments, the at least one conjugated diene monomer-based rubber (ii) may be a polymer or copolymer made from (a) at least one conjugated diene monomer selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, and (b) optionally at least one vinyl aromatic monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, and combinations thereof. In preferred embodiments of the first and second embodiments, at least one rubber (ii) is selected from the group consisting of styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, and mixtures thereof. In certain such embodiments, at least one rubber (ii) comprises polybutadiene. A preferred polybutadiene is a high-cis-polybutadiene (which can be considered to have at least 90%, preferably at least 92%, of cis-bonds), and such a high-cis-polybutadiene is optionally functionalized. In other embodiments of the first and second embodiments, at least one rubber (ii) comprises styrene-butadiene rubber, and such styrene-butadiene rubber is optionally functionalized. In other embodiments of the first and second embodiments, at least one rubber (ii) comprises a combination of polybutadiene (preferably high-cis-polybutadiene) and styrene-butadiene rubber, and in certain such embodiments, at least one of the polybutadiene or styrene-butadiene rubber is functionalized.
[0029] In the embodiments of the first and second embodiments, in which at least one conjugated diene monomer rubber comprises a functionalized rubber (e.g., a functionalized polybutadiene and / or functionalized SBR having at least 90% cis-1,4-bond content), the functional groups present can vary. According to the preferred embodiments described above, the functional groups used are carbon black reactive, and in more preferred embodiments, the functional groups include polar groups. Non-limiting examples of preferred carbon black reactive functional groups (for BR and SBR) include, but are not limited to, hydroxyl, carbonyl, ether, ester, halide, amine, imine, amide, nitrile, and oxirane (e.g., epoxy ring) groups. When a functionalized polymer is used, the functional groups may be incorporated into the head and / or tail of the polymer, and / or added along the polymer backbone. Non-limiting examples of functionalization initiators include organoalkali metal compounds (e.g., organolithium compounds) that contain one or more heteroatoms (e.g., nitrogen, oxygen, boron, silicon, sulfur, tin, and phosphorus atoms) or heterocyclic groups containing the above atoms, often further containing one or more nitrogen atoms (e.g., substituted aldimines, ketimines, secondary amines, etc.), and optionally pre-reacted with compounds such as diisopropenylbenzene. Numerous functionalization initiators are known in the art. Examples are disclosed in U.S. Patent Nos. 5,153,159, 5,332,810, 5,329,005, 5,578,542, 5,393,721, 5,698,464, 5,491,230, 5,521,309, 5,496,940, 5,567,815, 5,574,109, 5,786,441, 7,153,919, 7,868,110, and U.S. Patent Application Publication No. 2011-0112263, which are incorporated herein by reference.In certain embodiments of the first and second embodiments, when a functional initiator is used, a functional nitrogen-containing initiator is utilized, and non-limiting examples include cyclic amines, particularly cyclic secondary amines such as azetidine; pyrrolidine; piperidine; morpholine; N-alkyl piperazine; hexamethylene imine; heptamethylene imine, and dodecamethylene imine.
[0030] Eutectic composition As discussed above, according to the first and second embodiments, the rubber composition includes an eutectic composition. The specific amount of the eutectic composition can vary. In a preferred embodiment of the first and second embodiments, the eutectic composition is present in an amount of about 0.005 to about 3 phr or 0.005 to 3 phr (e.g., 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, or 3 phr), more preferably in an amount of about 0.01 to about 1 phr or 0.01 to 1 phr (e.g., 0.01, 0.05, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, or 1 phr).
[0031] In one or more embodiments of the first and second embodiments, the eutectic composition is defined by the following formula I. Cat + X - Y z Wherein, Cat + is a cation, X - is a counter anion (e.g., a Lewis base), and z refers to the number of Y molecules that interact with the counter anion (e.g., a Lewis acid or a Bronsted acid). As will be discussed in more detail below, Cat + can include an ammonium, phosphonium, or sulfonium cation. X - can include a halide ion, and Y can include a hydrogen bond donor, a metal halide, or a metal halide hydrate. In one or more embodiments of the first and second embodiments, z is a number that realizes a deep eutectic solvent, but in other embodiments, z is a number that realizes a complex having a melting point lower than that of each eutectic component in another manner.
[0032] In certain embodiments of the first and second embodiments, the eutectic composition includes a combination of a cation source and an anion source. In preferred embodiments of the first and second embodiments, the eutectic composition includes a combination of a cation source selected from the group consisting of ammonium compounds, phosphonium compounds, sulfonium compounds, and combinations thereof, and an anion source selected from the group consisting of metal halide compounds, metal halide hydrate compounds, hydrogen bond donor compounds, and combinations thereof.
[0033] In certain embodiments of the first and second embodiments, the eutectic composition is selected from ammonium compounds, preferably the following: (i) Formula II: (R 1 )(R 2 )(R 3 )(R 4 ) - N+-Φ - An ammonium compound having the formula, where each R 1 , R 2 , R 3 , and R 4 However, independently selected from hydrogen and monovalent organic groups, R 1 , R 2 , R 3 , and R 4The eutectic composition comprises an ammonium compound, (ii) preferably an ammonium compound having formula IV, selected from the group consisting of N-ethyl-2-hydroxy-N,N-dimethylethaneaminium chloride, 2-hydroxy-N,N,N-trimethylethaneaminium chloride (also known as choline chloride), and N-benzyl-2-hydroxy-N,N-dimethylethaneamine chloride, and combinations thereof, or (iii) preferably a cation source selected from at least one ammonium compound having formula III, selected from the group consisting of 2-chloro-N,N,N-trimethylethaneaminium (also known as chlorocholine chloride), and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride, and combinations thereof. In certain embodiments of the first and second embodiments, the eutectic composition comprises an anion source and a cation source which is an ammonium compound selected from the group described above as (i). In certain embodiments of the first and second embodiments, the eutectic composition comprises an anion source and a cation source which is an ammonium compound selected from the group described above as (ii). In certain embodiments of the first and second embodiments, the eutectic composition comprises an anion source and a cation source which is an ammonium compound selected from the group described above as (iii).
[0034] In certain embodiments of the first and second embodiments, the cation source is an ammonium compound containing a quaternary ammonium salt. Useful eutectic compositions using quaternary ammonium salts include compounds of quaternary ammonium salt and metal halide (referred to as type I eutectic compositions), compounds of quaternary ammonium salt and metal halide hydrate (referred to as type II eutectic compositions), compounds of quaternary ammonium salt and hydrogen bond donor (referred to as type III eutectic compositions), or compounds of metal halide hydrate and hydrogen bond donor (referred to as type IV eutectic compositions). Instead of ammonium compounds, similar compounds of sulfonium or phosphonium can also be used, which can be easily conceived by those skilled in the art.
[0035] In certain embodiments of the first and second embodiments, the quaternary ammonium salt is solid at 20°C. In these or other embodiments, the metal halide and hydrogen bond donor are solid at 20°C.
[0036] In certain embodiments of the first and second embodiments, a useful quaternary ammonium salt, which may also be called an ammonium compound, as discussed above, may be defined by the following formula II: In certain such embodiments, the counter anion (e.g., Φ - ) Halide (X - ), nitrates (NO3 - ), tetrafluoroborate (BF4 - ), perchlorate (ClO4 - ), Triflate (SO3CF3 - ), trifluoroacetate (COOCF3 - Selected from the group consisting of ). In certain such embodiments, Φ - This is a halide ion, and in certain embodiments, a chloride ion.
[0037] In certain embodiments of the first and second embodiments, when the cation source is an ammonium compound having formula (II), the monovalent organic group includes a hydrocarbyl group and the divalent organic group includes a hydrocarbylene group. In certain such embodiments, the monovalent and divalent organic groups include heteroatoms, such as oxygen and nitrogen, and / or halogen atoms, but are not limited to these. Thus, monovalent organic groups include alkoxy groups, siloxy groups, ether groups, and ester groups, as well as carbonyl or acetyl substituents. In certain such embodiments, the hydrocarbyl and hydrocarbylene groups contain 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 methyl groups, ethyl groups, octadecyl groups, phenyl groups, and benzyl groups. In certain embodiments, the hydrocarbyl group is a methyl group, and the hydrocarbylene group is an ethylene or propylene group.
[0038] Generally, useful types of ammonium compounds as cation sources in the first and second embodiments include secondary ammonium compounds, tertiary ammonium compounds, and quaternary ammonium compounds. In certain such 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 a quaternary ammonium chloride. In certain embodiments of the first and second embodiments, when the cation source is an ammonium compound, R 1 , R 2 , R3 , and R 4 is hydrogen, and the ammonium compound is ammonium chloride. In one or more embodiments, the ammonium compound is asymmetric.
[0039] In certain embodiments of the first and second embodiments, where the cation source is an ammonium compound, the ammonium compound comprises an alkoxy group and can be defined by formula III. (R 1 )(R 2 )(R 3 )-N + -(R 4 -OH)Φ - In the formula, each R 1 , R 2 , and R 3 These are individually selected from hydrogen or monovalent organic groups, or alternatively, R 1 , R 2 , and R 3 Two of them combine to form a divalent organic group, R 4 is a divalent organic group, Φ - is a counter anion. In certain such embodiments, R 1 , R 2 , R 3 And at least one of them, at least two in other embodiments, and at least three in other embodiments, is not hydrogen.
[0040] 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-dimethylethanolamine chloride.
[0041] In certain embodiments of the first and second embodiments, the cation source is an ammonium compound comprising a halogen-containing substituent and which can be defined by formula IV. Φ- -(R 1 )(R 2 )(R 3 )-N + -R 4 X In the formula, each R 1 , R 2 , and R 3 These are individually selected from hydrogen or monovalent organic groups, or alternatively, R 1 , R 2 , and R 3 Two of them combine to form a divalent organic group, R 4 is a divalent organic group, X is a halogen atom, and Φ - R is a counter anion. In one or more embodiments, R 1 , R 2 , R 3 And at least one of them, at least two in other embodiments, and at least three in other embodiments, is not hydrogen. In one or more embodiments, X is chlorine.
[0042] Examples of ammonium compounds defined by formula IV include, but are not limited to, 2-chloro-N,N,N-trimethylethaneaminium (also known as chlorochloride) and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride.
[0043] In certain embodiments of the first and second embodiments, the eutectic composition includes a cation source selected from phosphonium compounds. Non-limiting examples of such phosphonium compounds include, but are not limited to, aluminophosphates, cobalt aluminophosphates, and zinc phosphates.
[0044] In certain embodiments of the first and second embodiments, the eutectic composition includes a cation source selected from sulfonium compounds. Non-limiting examples of such sulfonium compounds include, but are not limited to, fluorosulfonates, aluminum sulfonates, and zinc sulfonates.
[0045] In certain embodiments of the first and second embodiments, the eutectic composition comprises an anion source selected from hydrogen bond donor compounds. Various types of hydrogen bond donor compounds, including amines, amides, carboxylic acids, and alcohols, may be useful as anion sources in certain embodiments of the first and second embodiments. 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.
[0046] In preferred embodiments of the first and second embodiments, when the anion ion source is a hydrogen bond donor compound, the anion ion source is: (i) amines, amides, carboxylic acids, alcohols, and mixtures thereof; (ii) amines such as aliphatic amines, ethylenediamine, diethylenetriamine, aminoethylpiperazine, triethylenetetramine, tris(2-aminoethyl)amine, N,N'-bis-(2-aminoethyl)piperazine, piperazinoethylethylenediamine, and tetraethylenepentaamine, propyleneamine, aniline, substituted aniline, and combinations thereof; (iii) urea, 1-methylurine (iv) Preferably, carboxylic acids such as phenylpropionic acid, phenylacetic acid, benzoic acid, oxalic acid, malonic acid, adipic acid, succinic acid, citric acid, tricarbaryl acid, and combinations thereof; or (v) Preferably, at least one of alcohols such as aliphatic alcohols, phenols, substituted phenols, ethylene glycol, propylene glycol, resorcinol, substituted resorcinol, glycerol, benzenetriol, and combinations thereof. In certain embodiments of the first and second embodiments, the eutectic composition comprises a cation source and an anion source which is a hydrogen bond donor compound selected from the group described above as (i). In certain embodiments of the first and second embodiments, the eutectic composition comprises a cation source and an anion source which is a hydrogen bond donor compound selected from the group described above as (ii). In certain embodiments of the first and second embodiments, the eutectic composition comprises a cation source and an anion source which is a hydrogen bond donor compound selected from the group described above as (iii). In certain embodiments of the first and second embodiments, the eutectic composition comprises a cation source and an anion source which is a hydrogen bond donor compound selected from the group described above as (iv). In certain embodiments of the first and second embodiments, the eutectic composition comprises a cation source and an anion source which is a hydrogen bond donor compound selected from the group described above as (v).
[0047] In certain embodiments of the first and second embodiments, when the anion source is an amine, a useful amine can be described as having formula V. R 1 -(CH2) x -R 2 In the formula, R 1 and R 2 -NH2, -NHR 3 , or -NR 3 R 4 The equation is such that x is at least an integer of 2. In one or more embodiments, x is 2 to about 10 or 2 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10), in other embodiments, x is 2 to about 8 or 2 to 8 (e.g., 2, 3, 4, 5, 6, 7, or 8), and in other embodiments, x is 2 to about 6 or 2 to 6 (e.g., 2, 3, 4, 5, or 6).
[0048] In certain embodiments of the first and second embodiments, when the anion source is an amide, a useful amide can be described as having formula VI. R-CO-NH2 In the formula, R is H, NH2, CH3, or CF3.
[0049] In certain embodiments of the first and second embodiments, when the anionic source is a carboxylic acid, useful carboxylic acids include monofunctional, difunctional, and trifunctional organic acids. Examples of such organic acids include alkyl acids, aryl acids, and mixed alkyl-aryl acids.
[0050] In certain embodiments of the first and second embodiments, when the anion source is an alcohol, useful alcohols 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 resorcinol, and mixtures thereof. Specific examples of triols include, but are not limited to, glycerol, benzenetriol, and mixtures thereof.
[0051] In certain embodiments of the first and second embodiments, the eutectic composition is selected from the group consisting of metal halides, and preferably includes an anion source 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, and iron iodide, and combinations thereof.
[0052] In certain embodiments of the first and second embodiments, the eutectic composition includes an anion source selected from metal halide hydrate compounds. Generally, suitable metal halide hydrate compounds for use in certain embodiments of the first and second embodiments include metal halide hydrates corresponding to the metal halides discussed above, such as aluminum halides, zinc halides, tin halides, and iron halides. For example, non-limiting examples include aluminum chloride hexahydrate and copper chloride dihydrate, which correspond to the above halides.
[0053] In preferred embodiments of the first and second embodiments, the eutectic composition comprises a combination of an ammonium compound selected from (ii) above and a hydrogen bond donor compound selected from (iii) above. In particularly preferred embodiments of the first and second embodiments, the eutectic composition comprises a combination of choline chloride and urea. In certain such embodiments, the amount of the eutectic composition is preferably 0.01 to 2 phr or 0.01 to 2 phr (e.g., 0.01, 0.05, 0.1, 0.5, 1, 1.5, or 2 phr), more preferably about 0.1 to about 1 phr (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 phr).
[0054] In certain embodiments of the first and second embodiments, the eutectic composition is prepared before introducing the eutectic composition to the other components of the rubber composition. In other words, according to such embodiments, the first component is pre-combined with the second component and these mixtures (as the eutectic composition) before introducing them to the vulcanizable composition. In one or more embodiments of the first and second embodiments, the combined components are mixed until a homogeneous liquid composition that can be considered to constitute the eutectic composition is observed.
[0055] In certain embodiments of the first and second 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 of the first and second embodiments, a component of the vulcanizing composition (e.g., a metal compound such as zinc oxide) is combined with the eutectic composition to form a pre-compound or masterbatch, and then the pre-compound is introduced into a mixer in which the rubber is mixed. For example, zinc oxide may be dissolved in a eutectic solvent and then introduced into the rubber in the mixer. In preferred embodiments of the first and second embodiments, the eutectic composition is a trace component of the pre-compound, and therefore the component pre-mixed with the eutectic composition can be considered 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 compound of solid zinc oxide and the eutectic composition to the rubber in the mixer. In yet another embodiment, one of the materials constituting the eutectic pair acts as a solid support for the eutectic composition, and therefore the combination of the first and second components of the eutectic composition forms a pre-compound that can be added as a solid to the rubber in the mixer. Those skilled in the art will understand that a mixture of this nature can be formed by combining an excess amount of the constituent material of the first or second eutectic pair with the other eutectic members in order to maintain the solid composition at a desired temperature.
[0056] In one or more embodiments of the first and second 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 of the first and second 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 of the first and second embodiments, the high-shear, high-temperature mixing is carried out at a temperature of approximately 110°C to approximately 170°C.
[0057] In other embodiments of the first and second 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 of less than 110°C, in other embodiments at a maximum temperature of less than 105°C, and in other embodiments at a maximum temperature of less than 100°C. In one or more embodiments of the first and second embodiments, the mixing with the curing agent is carried out at a temperature of about 70 to about 110°C.
[0058] Similar to eutectic solvents, zinc oxide and stearic acid can be added to the rubber masterbatch as initiating components, and thus these components will be mixed at high temperatures and with high shear. Alternatively, in preferred embodiments of the first and second embodiments, zinc oxide and stearic acid may be added together with a sulfur-based curing agent (for example, in the final mixing stage), thereby undergoing only low-temperature mixing.
[0059] In certain embodiments of the first and second embodiments, zinc oxide is introduced into the rubber composition separately from the eutectic solvent. In preferred embodiments of the first and second embodiments, 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 vulcanizable rubber.
[0060] Reinforcing filler As discussed above, according to the first and second embodiments disclosed herein, the rubber composition includes (includes) a reinforcing filler selected from carbon black, silica, and combinations thereof in an amount of about 30 to about 150 phr or 30 to 150 phr (e.g., 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150 phr). The statement that the reinforcing filler is selected from carbon black, silica, and combinations thereof means that embodiments include those in which the reinforcing filler is carbon black only, those in which the reinforcing filler is silica only, and those in which the reinforcing filler includes both carbon black and silica. As will be discussed in more detail below, when both carbon black and silica are present, the relative amounts of each can vary. In certain embodiments of the first and second embodiments, the rubber composition includes a reinforcing filler selected from carbon black, silica, and combinations thereof in an amount of about 30 to about 60 phr or 30 to 60 phr (e.g., 30, 35, 40, 45, 50, 55, or 60 phr). In certain other embodiments of the first and second embodiments, the rubber composition includes a reinforcing filler selected from carbon black, silica, and combinations thereof in an amount of about 50 to about 150 phr or 50 to 150 phr (e.g., 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 phr).
[0061] In the embodiments of the first and second embodiments, where the carbon black filler is present as part (or all) of the reinforcing filler, one or more carbon blacks may be present. According to the first and second embodiments, the specific type of carbon black used may vary. Generally, suitable carbon blacks for use as reinforcing fillers in the rubber compositions of the specific embodiments in the first and second embodiments are at least about 20 m 2 / g (at least 20m) 2 (including / g), and more preferably at least about 35m 2 / g ~ up to approximately 200m2 / g, or higher (35m 2 / g~200m 2 This includes any commercially available carbon black having a surface area of (including / g). The surface area values used herein for carbon black are determined by ASTM D-1765 using the cetyltrimethyl-ammonium bromide (CTAB) technique. Useful carbon blacks include furnace black, channel black, and lamp black. More specifically, examples of useful carbon blacks include super abrasion furnace (SAF) black, high abrasion furnace (HAF) black, fast extrusion furnace (FEF) black, fine furnace (FF) black, intermediate super abrasion furnace (ISAF) black, semi-reinforcing furnace (SRF) black, moderately processable channel black, difficult-to-process channel black, and conductive channel black. Other carbon blacks that may be used include acetylene black. In certain embodiments of the first and second embodiments, the rubber composition comprises a mixture of two or more of the above-described blacks. Preferably, according to the first and second embodiments, if a carbon black filler is present, it consists of only one type (or grade) of reinforcing carbon black. Typical carbon blacks suitable for use in the specific embodiments of the first and second embodiments are N-110, N-220, N-339, N-330, N-351, N-550, and N-660, as specified by ASTM D-1765-82a. The carbon black used can be in pelletized form or in non-pelletized cotton-like form. Preferably, non-pelletized carbon black is preferred for a more homogeneous mixture.
[0062] In the embodiments of the first and second embodiments in which the silica filler is present as part of the reinforcing filler, one or more silica particles may be present. Additionally, in the embodiments of the first and second embodiments in which the silica filler is present, the surface area of the reinforcing silica filler may vary. According to the first and second embodiments, there may be a variety of specific types of silica for at least one type of reinforcing silica filler. Non-limiting examples of reinforcing silica fillers suitable for use in the specific embodiments of the first and second embodiments include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, calcium silicate, and the like. Other reinforcing silica fillers suitable for use in specific embodiments of the first and second embodiments include, but are not limited to, aluminum silicate, magnesium silicate (Mg2SiO4, MgSiO3, etc.), calcium magnesium silicate (CaMgSiO4), calcium silicate (Ca2SiO4, etc.), aluminum silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), and calcium aluminum silicate (Al2O3.CaO2, SiO2, etc.). Among the enumerated reinforcing silica fillers, precipitation amorphous wet processes and hydrated silica fillers are preferred. Such reinforcing silica fillers are produced by chemical reactions in water, from which they are strongly bound to aggregates and subsequently precipitated as ultrafine spherical particles with primary particles that are slightly more strongly bound to aggregates. Surface area, measured by the BET method, is a preferred measure that characterizes the reinforcing properties of various reinforcing silica fillers. In specific embodiments of the first and second embodiments disclosed herein, the rubber composition is approximately 100 m 2 / g~about 400m 2 / g, 100m 2 / g~400m 2 / g (for example, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, or 400m) 2 / g), about 100 m 2 / g to about 350 m 2 / g, or 100 m 2 / g to 350 m 2 / g (e.g., 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, or 350 m 2 / g) of a reinforcing silica filler having a surface area (measured by the BET method). In certain embodiments of the first and second embodiments disclosed herein, the rubber composition is about 110 m 2 / g to about 200 m 2 / g, 110 m 2 / g to 200 m 2 / g (e.g., 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 m 2 / g), about 110 to about 140 m 2 / g, 110 to 140 m 2 / g (e.g., 110, 115, 120, 125, 130, 135, or 140 m 2 / g), 180 m 2 / g to about 200 m 2 / g, and 180 m 2 / g to 200 m 2 / g (e.g., 180, 185, 190, 195, or 200 m 2 / g) of a reinforcing silica filler having a BET surface area within the range, and in certain such embodiments, the only silica filler present in the rubber composition has a BET surface area within one of the前述 ranges. In other embodiments of the first and second embodiments disclosed herein, the rubber composition is about 210 m 2 / g to about 320 m 2 / g, 210 m 2 / g to 320 m 2 / g (e.g., 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, or 320 m 2 / g), about 220 m2 / g~about 300m 2 / g, and 220m 2 / g~300m 2 / g (for example, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, or 300m) 2The rubber composition comprises a reinforcing silica filler having a BET surface area containing ( / g). In certain such embodiments, the only silica filler present in the rubber composition has a BET surface area within one of the aforementioned ranges. In certain embodiments of the first and second embodiments disclosed herein, the rubber composition comprises a reinforcing silica filler having a pH of about 5.5 to about 8, 5.5 to 8 (e.g., 5.5, 5.7, 5.9, 6.1, 6.3, 6.5, 6.7, 6.9, 7.1, 7.3, 7.5, 7.7, 7.9, or 8), about 6 to about 8, 6 to 8 (e.g., 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, or 8), about 6 to about 7.5, 6 to about 7.5, about 6.5 to about 8, 6.5 to 8, about 6.5 to about 7.5, 6.5 to 7.5, about 5.5 to about 6.8, or 5.5 to 6.8. Some commercially available reinforcing silica fillers that can be used in specific embodiments of the first and second embodiments include Hi-Sil® EZ120G, Hi-Sil® EZ120G-D, Hi-Sil® 134G, Hi-Sil® EZ 160G, Hi-Sil® EZ 160G-D, Hi-Sil® 190, Hi-Sil® 190G-D, Hi-Sil® EZ 200G, and Hi-Sil® EZ, manufactured by PPG Industries (Pittsburgh, Pa.). Examples include, but are not limited to, 200G-D, Hi-Sil® 210, Hi-Sil® 233, Hi-Sil® 243LD, Hi-Sil® 255CG-D, Hi-Sil® 315-D, Hi-Sil® 315G-D, Hi-Sil® HDP 320G, etc.Similarly, many useful commercial grades of different reinforcing silica fillers are also available from Evonik Corporation (e.g., Ultrasil® 320 GR, Ultrasil® 5000 GR, Ultrasil® 5500 GR, Ultrasil® 7000 GR, Ultrasil® VN2 GR, Ultrasil® VN2, Ultrasil® VN3, Ultrasil® VN3 GR, Ultrasil® 7000 GR, Ultrasil® 7005, Ultrasil® 7500 GR, Ultrasil® 7800 GR, Ultrasil® 9500 GR, Ultrasil® 9000 G, Ultrasil® 9100 Available from GR) and Solvay (e.g., Zeosil® 1115MP, Zeosil® 1085GR, Zeosil® 1165MP, Zeosil® 1200MP, Zeosil® Premium, Zeosil® 195HR, Zeosil® 195GR, Zeosil® 185GR, Zeosil® 175GR, and Zeosil® 165GR).
[0063] Silica coupling agent In certain embodiments of the first and second embodiments disclosed herein, if a silica filler is present, one or more silica coupling agents may also be used (optionally). In preferred embodiments of the first and second embodiments, if a silica filler is present, at least one silica coupling agent is used. Silica coupling agents are useful for preventing or reducing the aggregation of silica fillers in the rubber composition. Aggregation of silica filler particles is thought to increase the viscosity of the rubber composition; therefore, preventing this aggregation reduces viscosity and improves the processability and blendability of the rubber composition.
[0064] In general, any type of conventional silica coupling agent can be used, such as silanes and their constituent components, or those having a portion that can react with polymers, particularly vulcanizable polymers. The silica coupling agent acts as a linking crosslink between silica and polymers. Suitable silica coupling agents for use in the specific embodiments of the first and second embodiments disclosed herein include silica coupling agents containing groups such as alkylalkoxy, mercapto, blocked mercapto, sulfide-containing (e.g., monosulfide-based alkoxy-containing, disulfide-based alkoxy-containing, tetrasulfide-based alkoxy-containing), amino, vinyl, epoxy, and combinations thereof. In certain embodiments, the silica coupling agent may be added to the rubber composition in the form of pre-treated silica. The pre-treated silica is pre-surface-treated with silane before being added to the rubber composition. The use of pre-treated silica makes it possible to add two components (i.e., silica and silica coupling agent) to one component, which generally tends to facilitate the compounding of rubbers.
[0065] Alkylalkoxysilanes have the general formula R 10 p Si(OR 11 ) 4-p It has each R 11 These are independently monovalent organic groups, and p is an integer from 1 to 3, but at least one R 10 The condition is that is an alkyl group. Preferably, p is 1. Generally, each R 10 These are independently C1~C 20 Aliphatic, C5~C 20 cyclic aliphatic, or C6~C 20 Contains aromatic compounds, each R 11 These independently include C1-C6 aliphatic atoms. In certain exemplary embodiments, each R 10 It is independently C6~C 15 Includes aliphatic elements, and in further embodiments, each R 10 It is independently C8~C 14 It contains aliphatic compounds. Mercaptosilane has the general formula HS-R 13 -Si(R14 )(R 15 ) has 2, R 13 is a divalent organic group, R 14 R is a halogen atom or an alkoxy group, and each R 15 These are independently a halogen, an alkoxy group, or a monovalent organic group. The halogen is chlorine, bromine, fluorine, or iodine. The alkoxy group preferably has 1 to 3 carbon atoms. Blocked mercaptosilanes have the general formula BSR. 16 It has -Si-X3, the silyl group is available for reaction with silica in silica-silane reactions, and the blocking group B substitutes a mercapto hydrogen atom to block the reaction between the sulfur atom and the polymer. In the general formula above, B is a blocking group that can be in the form of an unsaturated heteroatom or a carbon directly bonded to sulfur via a single bond. 16 X is a C1-C6 linear or branched alkylidene, where each X is independently selected from the group consisting of C1-C4 alkyl or C1-C4 alkoxy.
[0066] Non-limiting examples of alkylalkoxysilanes suitable for use in specific embodiments of the first and second embodiments include octyltriethoxysilane, octyltrimethoxysilane, trimethylethoxysilane, cyclohexyltriethoxysilane, isobutyltriethoxysilane, ethyltrimethoxysilane, cyclohexyltributoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, propyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane Examples include, but are not limited to, siliane, dodecyltriethoxysilane, tetradecyltriethoxysilane, octadecyltriethoxysilane, methyloctyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, octadecyl-trimethoxysilane, methyloctyldimethoxysilane, and mixtures thereof.
[0067] Non-limiting examples of bis(trialkoxysilylorgano) polysulfides suitable for use in specific embodiments of the first and second embodiments include bis(trialkoxysilylorgano) disulfides and bis(trialkoxysilylorgano) tetrasulfides. Specific non-limiting examples of bis(trialkoxysilylorgano) disulfides include, but are not limited to, 3,3'-bis(triethoxysilylpropyl) disulfide, 3,3'-bis(trimethoxysilylpropyl) disulfide, 3,3'-bis(tributoxysilylpropyl) disulfide, 3,3'-bis(tri-t-butoxysilylpropyl) disulfide, 3,3'-bis(trihexoxysilylpropyl) disulfide, and 2,2'-bis(dimethyl Examples include methoxysilylethyl disulfide, 3,3'-bis(diphenylcyclohexoxysilylpropyl) disulfide, 3,3'-bis(ethyl-di-sec-butoxysilylpropyl) disulfide, 3,3'-bis(propyldiethoxysilylpropyl) disulfide, 12,12'-bis(triisopropoxysilylpropyl) disulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, and mixtures thereof. Non-limiting examples of bis(trialkoxysilylorgano)tetrasulfide silica coupling agents suitable for use in specific embodiments of the first and second embodiments include, but are not limited to, bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropyl-benzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, and mixtures thereof.Bis(3-triethoxysilylpropyl)tetrasulfide is commercially available as Si69® from Evonik Degussa Corporation.
[0068] Non-limiting examples of mercaptosilanes suitable for use in specific embodiments of the first and second embodiments disclosed herein include, but are not limited to, 1-mercaptomethyltriethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltripropoxysilane, 18-mercaptooctadecyldiethoxychlorosilane, and mixtures thereof.
[0069] Non-limiting examples of blocked mercaptosilanes suitable for use in the specific embodiments of the first and second embodiments disclosed herein include, but are not limited to, those described in U.S. Patents 6,127,468, 6,204,339, 6,528,673, 6,635,700, 6,649,684, and 6,683,135 (these disclosures are incorporated herein by reference). Representative examples of blocked mercaptosilanes include 2-triethoxysilyl-1-ethylthioacetate, 2-trimethoxysilyl-1-ethylthioacetate, 2-(methyldimethoxysilyl)-1-ethylthioacetate, 3-trimethoxysilyl-1-propylthioacetate, triethoxysilylmethylthioacetate, trimethoxysilylmethylthioacetate, triisopropoxysilylmethylthioacetate, methyldiethoxysilylmethylthioacetate, methyldimethoxysilylmethylthioacetate, methyldiisopropoxysilylmethylthioacetate, dimethylethoxysilylmethylthioacetate, dimethylmethoxysilylmethylthioacetate, dimethylisopropoxysilylmethylthioacetate, 2-triisopropoxysilyl-1-ethylthioacetate, 2-(methyldiethoxysilyl)-1-ethylthioacetate, 2-( Methyldiisopropoxysilyl)-1-ethylthioacetate, 2-(dimethylethoxysilyl-1-ethylthioacetate, 2-(dimethylmethoxysilyl)-1-ethylthioacetate, 2-(dimethylisopropoxysilyl)-1-ethylthioacetate, 3-triethoxysilyl-1-propylthioacetate, 3-triisopropoxysilyl-1-propylthioacetate, 3-methyldiethoxysilyl-1-propyl- Oacetate, 3-methyldimethoxysilyl-1-propylthioacetate, 3-methyldiisopropoxysilyl-1-propylthioacetate, 1-(2-triethoxysilyl-1-ethyl)-4-thioacetylcyclohexane, 1-(2-triethoxysilyl-1-ethyl)-3-thioacetylcyclohexane, 2-triethoxysilyl-5-thioacetylnorbornene, 2-triethoxysilyl-4-thioacetylnorbornene,2-(2-triethoxysilyl-1-ethyl)-5-thioacetylnorbornene, 2-(2-triethoxy-silyl-1-ethyl)-4-thioacetylnorbornene, 1-(1-oxo-2-thia-5-triethoxysilylphenyl)benzoic acid, 6-triethoxysilyl-1-hexylthioacetate, 1-triethoxysilyl-5-hexylthioacetate, 8-triethoxysilyl-1-octylthioacetate, 1-triethoxysilyl-7-octylthioacetate, 6-triethoxysilyl-1-hexylthioacetate, 1- Triethoxysilyl-5-octylthioacetate, 8-trimethoxysilyl-1-octylthioacetate, 1-trimethoxysilyl-7-octylthioacetate, 10-triethoxysilyl-1-decylthioacetate, 1-triethoxysilyl-9-decylthioacetate, 1-triethoxysilyl-2-butylthioacetate, 1-triethoxysilyl-3-butylthioacetate, 1-triethoxysilyl-3-methyl-2-butylthioacetate, 1-triethoxysilyl-3-methyl-3-butylthioacetate, 3- Dimethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propyl-1-propylthiopalmitate, 3-triethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propylthiobenzoate, 3-triethoxysilyl-1-propylthio-2-ethylhexanoate, 3-methyldiacetoxysilyl-1-propylthioacetate, 3-triacetoxysilyl-1-propylthioacetate, 2-methyldiacetoxysilyl-1-ethylthioacetate, 2-triacetoxysilyl Lyl-1-ethylthioacetate, 1-methyldiacetoxysilyl-1-ethylthioacetate, 1-triacetoxysilyl-1-ethyl-thioacetate, tris-(3-triethoxysilyl-1-propyl)trithiophosphate, bis-(3-triethoxysilyl-1-propyl)methyldithiophosphonate, bis-(3-triethoxysilyl-1-propyl)ethyldithiophosphonate, 3-triethoxysilyl-1-propyldimethylthiophosphinate, 3-triethoxysilyl-1-propyldiethylthiophosphinate,Tris-(3-triethoxysilyl-1-propyl)tetrathiophosphate, bis-(3-triethoxysilyl-1-propyl)methyltrithiophosphonate, bis-(3-triethoxysilyl-1-propyl)ethyltrithiophosphonate, 3-triethoxysilyl-1-propyldimethyldithiophosphinate, 3-triethoxysilyl-1-propyldiethyldithiophosphinate, Tris-(3-methyldimethoxysilyl-1-propyl)trithiophosphate, bis-(3-methyldimethoxysilyl-1-propyl)-methyldithiophosphonate, bis-(3-methyldimethoxysilyl-1-propyl)-ethyldithiophosphonate, 3-methyldimethoxysilyl-1-propyldimethylthiophosphinate, 3-methyldimethoxysilyl-1-propyldiethylthiophosphinate, 3-triethoxysilyl-1-propylmethyl The following are selected from the group consisting of thiosulfates, 3-triethoxysilyl-1-propylmethanethiosulfate, 3-triethoxysilyl-1-propylethanethiosulfate, 3-triethoxysilyl-1-propylbenzenethiosulfate, 3-triethoxysilyl-1-propyltoluenethiosulfate, 3-triethoxysilyl-1-propylnaphthalenthiosulfate, 3-triethoxysilyl-1-propylxylentiosulfate, triethoxysilylmethylmethylthiosulfate, triethoxysilylmethylmethanethiosulfate, triethoxysilylmethylethanethiosulfate, triethoxysilylmethylbenzenethiosulfate, triethoxysilylmethyltoluenethiosulfate, triethoxysilylmethylnaphthalenthiosulfate, triethoxysilylmethylxylentiosulfate, and the like. Various mixtures of blocked mercaptosilanes can be used. A further example of a blocked mercaptosilane suitable for use in specific exemplary embodiments is NXT® silane (3-octanoylthio-1-propyltriethoxysilane), available from Momentive Performance Materials Inc. (Albany, NY).
[0070] Examples of pre-treated silica (i.e., silica pre-surface-treated with silane) suitable for use in specific embodiments of the first and second embodiments disclosed herein include, but are not limited to, Ciptane® 255 LD and Ciptane® LP (PPG Industries) silica pre-treated with mercaptosilane, and Coupsil® 8113 (Degussa), a product of the reaction between organosilane bis(triethoxysilylpropyl) polysulfide (Si69) and Ultrasil® VN3 silica. Other examples include Coupsil 6508, Agilon 400® silica (PPG Industries), Agilon 454® silica (PPG Industries), and 458® silica (PPG Industries). In embodiments in which the silica includes pre-treated silica, the pre-treated silica is used in amounts already disclosed for the silica filler (i.e., 81–120 phr or about 90–about 120 phr, etc.).
[0071] In one embodiment of the first and second embodiments, when a silica coupling agent is used, the amount used may vary. In certain embodiments of the first and second embodiments, the rubber composition does not contain a silica coupling agent. In other preferred embodiments of the first and second embodiments, the silica coupling agent is present in sufficient quantity such that the ratio of the total amount of silica coupling agent to the silica filler is about 0.1:100 to about 1:5 (i.e., about 0.1 to about 20 parts by weight per 100 parts of silica) (including 0.1:100 to 1:5), about 1:100 to about 1:10, 1:100 to 1:10, about 1:100 to about 1:20, 1:100 to 1:20, about 1:100 to about 1:25, 1:100 to 1:25, and about 1:100 to about 0:100 and 1:100 to 0:100. In preferred embodiments of the first and second embodiments, the ratio of the total amount of silica coupling agent to the silica packing agent is in the range of 1:10 to 1:20 (i.e., 10 to 5 parts by weight per 100 parts of silica).In the specific embodiments of the first and second embodiments, the rubber composition comprises about 0.1 to about 15 phr of silica coupling agent, which includes 0.1 to 15 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), about 0.1 to about 12 phr, 0.1 to about 12 phr, and about 0.1 to about 10 phr, 0.1~10 phr, approximately 0.1~7 phr, 0.1~7 phr, approximately 0.1~5 phr, 0.1~5 phr, approximately 0.1~3 phr, 0.1~3 phr, approximately 1~15 phr, 1~15 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), approximately 1~12 phr, 1~12 phr (e.g., 1, 2 , 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 phr), approximately 1 to approximately 10 phr, 1 to 10 phr (for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 phr), approximately 1 to approximately 7 phr, 1 to 7 phr, approximately 1 to approximately 5 phr, 1 to 5 phr, approximately 1 to approximately 3 phr, 1 to 3 phr, This includes approximately 3 to approximately 15 phr, 3 to 15 phr, approximately 3 to approximately 12 phr, 3 to 12 phr, approximately 3 to approximately 10 phr, 3 to 10 phr, approximately 3 to approximately 7 phr, 3 to 7 phr, approximately 3 to approximately 5 phr, 3 to 5 phr, approximately 5 to approximately 15 phr, 5 to 15 phr, approximately 5 to approximately 12 phr, 5 to 12 phr, approximately 5 to approximately 10 phr, 5 to 10 phr, approximately 5 to approximately 7 phr, or 5 to 7 phr. In the preferred embodiments of the first and second embodiments, the rubber composition comprises 8 to 12 phr, or one of the aforementioned ranges within this range, of the silica coupling agent.
[0072] Hardened package As discussed above, according to the first and second embodiments disclosed herein, the rubber composition comprises a cured package comprising (including) a sulfur-based vulcanizing agent, at least one vulcanization accelerator, a vulcanization activator, and a eutectic composition (discussed in detail below). The eutectic composition is generally added during the final mixing stage (together with the sulfur-based vulcanizing agent and at least one vulcanization accelerator), and is therefore included in the description of the cured package.
[0073] According to the first and second embodiments disclosed herein, the curing package of the rubber composition includes a sulfur-based vulcanizing agent. The specific sulfur-based vulcanizing agent used can vary. In preferred embodiments of the first and second embodiments, the vulcanizing agent consists of a sulfur-based curing agent (only). Examples of specific preferred sulfur-based vulcanizing agents include sulfur-donating curing agents such as soluble sulfur, disulfide amines, polymeric polysulfides, or sulfur olefin adducts from "rubbermaker," and insoluble polymeric sulfur. Preferably, the sulfur-based vulcanizing agent is soluble sulfur, or a mixture of soluble sulfur polymer and insoluble sulfur polymer. For a general disclosure of suitable curing agents and other components used in curing (e.g., vulcanization inhibitors and scorch inhibitors), refer to Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., Wiley Interscience, NY 1982, Vol. 20, pp. 365-468, in particular Vulcanization Agents and Auxiliary Materials, pp. 390-402, or Vulcanization by AYCoran (Encyclopedia of Polymer Science and Engineering, Second Edition (1989 John Wiley & Sons, Inc.)), both of which are incorporated herein by reference. Sulfur-based vulcanizing agents can be used alone or in combination. In general, in the first and specific embodiments of the second embodiment, the sulfur-based vulcanizing agent may be used in amounts ranging from 0.1 to 10 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr), including 1 to 7.5 phr, including 1 to 5 phr, preferably 1 to 3.5 phr (e.g., 1, 1.5, 2, 2.5, 3, or 3.5 phr).
[0074] According to the first and second embodiments, the rubber composition comprises at least one vulcanization accelerator. The vulcanization accelerator is used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized product. Examples of vulcanization accelerators suitable for use in specific embodiments of the first and second embodiments disclosed herein include, but are not limited to, thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, 2,2'-dithiobis(benzothiazole) (MBTS), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), guanidine vulcanization accelerators such as diphenyl guanidine (DPG), thiram vulcanization accelerators, and carbamic acid vulcanization accelerators. Generally, the amount of vulcanization accelerator used is in the range of 0.1 to 10 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr), preferably 1 to 6 phr (e.g., 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 phr).Preferably, any vulcanization accelerator used in the rubber composition in the first and second embodiments excludes any thiuram such as thiuram monosulfide and thiuram polysulfide (examples include TMTM (tetramethyl thiuram monosulfide), TMTD (tetramethyl thiuram disulfide), DPTT (dipentamethylene thiuram tetrasulfide), TETD (tetraethyl thiuram disulfide), TiBTD (tetraisobutyl thiuram disulfide), and TBzTD (tetrabenzyl thiuram disulfide)), in other words, the rubber composition in the first and second embodiments preferably does not contain a thiuram accelerator (i.e., 0 phr).
[0075] As described above, according to the first and second embodiments, the rubber composition includes a vulcanization activator. A vulcanizing agent or vulcanization activator is an additive used to assist in vulcanization. Generally, vulcanization activators include both inorganic and organic components. Zinc oxide is the most widely used inorganic vulcanization activator. Various organic vulcanization activators, including stearic acid, palmitic acid, lauric acid, and the respective zinc salts mentioned above, are commonly used. Generally, in the specific embodiments of the first and second embodiments, the amount of vulcanization activator used is in the range of 0.1 to 6 phr (e.g., 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 phr), preferably 0.5 to 4 phr (e.g., 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 4 phr). In certain embodiments of the first and second embodiments, both zinc oxide and stearic acid are used as vulcanization activators, and the total amount used falls within one of the aforementioned ranges. In certain such embodiments, the only vulcanization activators used are zinc oxide and stearic acid.
[0076] In certain embodiments of the first and second embodiments, the curing package of the rubber composition also includes (further includes) a vulcanization inhibitor. Vulcanization inhibitors are generally used to control the vulcanization process, typically by delaying or inhibiting vulcanization until a desired time and / or temperature is reached. Common vulcanization inhibitors include, but are not limited to, PVI, cyclohexylthiophthalmide, manufactured by Santogard. Generally, in specific embodiments of the first and second embodiments, the amount of vulcanization inhibitor is 0.01 to 1 phr (e.g., 0.01, 0.015, 0.02, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 phr), preferably 0.01 to 0.3 phr (e.g., 0.01, 0.015, 0.02, 0.025, or 0.3 phr).
[0077] Plasticizing components In certain embodiments of the first and second embodiments, the rubber composition also includes (and further includes) a plasticizing component. If present, the plasticizing component may include one or more components selected from plasticizing oils and resins. According to the first and second embodiments, if the rubber composition includes a plasticizing component, the rubber composition includes a plasticizing component comprising 0 to 50 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 phr) of at least one plasticizing oil having a Tg of at least 30°C and 0 to 60 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 phr) of at least one hydrocarbon resin. In other words, such a rubber composition may include a plasticizing oil, a hydrocarbon resin, or a combination thereof. In other embodiments of the first and second embodiments, at least one of the plasticizing oil or hydrocarbon resin is present in the rubber composition. In certain embodiments of the first and second embodiments, the plasticizing component comprises a plasticizing oil of 0 to 30 phr (e.g., 0, 5, 10, 15, 20, 25, or 30 phr) and a hydrocarbon resin of 5 to 60 phr (e.g., 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 phr), more preferably a plasticizing oil of 0 to 15 phr and a hydrocarbon resin of 5 to 50 phr. In certain embodiments of the third embodiment, the plasticizing oil is present in an amount of at least 1 phr (e.g., 1 to 50 phr, 1 to 30 phr, 1 to 15 phr, 1 to 10 phr, 1 to 5 phr, etc.).
[0078] According to the first and second embodiments, when a plasticizing oil is present in the rubber composition, various types of plasticizing oils may be used, including, but are not limited to, aromatic oils, naphthenic oils, and low-PCA oils (ester plasticizers). Preferably, the plasticizing oil is liquid (injectable) at 25°C. Suitable low-PCA oils include those having a polycyclic aromatic content of less than 3% by weight, as measured by the IP346 method. The IP346 procedure can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum (UK). Suitable low-PCA oils include light extract solvates (MES), treated distillate aromatic extracts (TDAE), TRAE, and heavy naphthenic systems. Suitable MES oils are commercially available as CATENEX SNR (SHELL), PROREX 15 and FLEXON 683 (EXXONMOBIL), VIVATEC 200 (BP), PLAXOLENE MS (TOTAL FINA ELF), TUDALEN 4160 / 4225 (DAHLEKE), MES-H (REPSOL), MES (Z8), and OLIO MES S201 (AGIP). Suitable TDAE oils are available as TYREX 20 (EXXONMOBIL), VIVATEC 500, VIVATEC 180, and ENERTHENE 1849 (BP), and EXTENSOIL 1996 (REPSOL). Suitable heavy naphthenic oils are available as SHELLFELX 794, ERGON BLACK OIL, ERGON H2000, CROSS C2000, CROSS C2400, and SAN JOAQUIN 2000L. Suitable low PCA oils also include various plant-derived oils, such as those extracted from vegetables, nuts, and seeds.Non-limiting examples include, but are not limited to, soybean oil, sunflower oil (including high-oleic sunflower oil having an oleic acid content of at least 60%, at least 70%, or at least 80%), 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. In certain embodiments of the first and second embodiments, the tire rubber composition contains a small amount of oil, such as less than 10 phr (e.g., 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0 phr), less than 5 phr, 1 to less than 5 phr, or even 0 phr.
[0079] As described above, in certain embodiments of the first and second embodiments, the plasticizing component includes a plasticizing oil in the form of an ester plasticizer, which is a type of plasticizer that is generally liquid at room temperature. Although not strictly considered an oil, ester plasticizers are considered herein together with plasticizing oils because they can serve similar plasticizing purposes in the rubber compositions of the first and second embodiments. Suitable ester plasticizers are known to those skilled in the art and include, but are not limited to, phosphate esters, phthalate esters, adipic esters, and oleate esters (i.e., derived from oleic acid). Considering that esters are chemical compounds derived from acids in which at least one -OH group is substituted with an -O-alkyl group, a variety of alkyl groups can be used in suitable ester plasticizers for use in tread rubber compositions, including C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20) or generally linear or branched alkyl groups of C6-C12. Certain of the aforementioned esters are based on acids having two or more -OH groups and can therefore accommodate one or more O-alkyl groups (e.g., trialkyl phosphates, dialkyl phthalates, dialkyl adipates). Non-limiting examples of suitable ester plasticizers include trioctyl phosphate, dioctyl phthalate, dioctyl adipicate, nonyl oleate, octyl oleate, and combinations thereof. The use of one or more of the aforementioned ester plasticizers may be beneficial to the snow or ice performance of tires made from tread rubber compositions containing such ester plasticizers, at least in part due to the relatively low Tg of the ester plasticizers. In specific embodiments of the first and second embodiments, the tread rubber composition comprises one or more ester plasticizers having a Tg of -40°C to -70°C (e.g., -40, -45, -50, -55, -60, -65, or -70°C) or -50°C to -65°C (e.g., -50, -51, -52, -53, -54, -55, -56, -57, -58, -59, -60, -61, -62, -63, -64, or -65°C).In the embodiments of the first and second embodiments, one or more ester plasticizers are used, and the amounts used may vary. In the specific embodiments of the first and second embodiments, the one or more ester plasticizers used may be 1 to 25 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 phr), 1 to 20 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 1 It is used in total amounts of 5, 16, 17, 18, 19, or 20 phr), 1 to 15 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), 1 to 10 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr), 2 to 6 phr (e.g., 2, 3, 4, 5, or 6 phr), or 2 to 5 phr (e.g., 2, 3, 4, or 5 phr). In certain preferred embodiments of the first and second embodiments, the amount of ester plasticizer is 15 phr or less or 12 phr or less. In certain embodiments of the first and second embodiments, if the oil is present in an amount of less than 1 to 10 phr or 1 to 5 phr, one or more ester plasticizers are used in combination with the oil (in one of the aforementioned amounts). In the first and other embodiments of the second embodiment, one or more ester plasticizers are used in the absence of any oil in the tread rubber composition (i.e., 0 phr of oil) (one of the amounts described above).
[0080] When hydrocarbon resins are used in the rubber compositions of the first and second embodiments, the specific types of hydrocarbon resins used in the plasticizing components can vary and may include, in particular, plastic resins. As used herein, the term plastic resin refers to a compound that is solid at room temperature (23°C) and is typically miscible in the rubber composition in amounts used that are at least 5 phr. Generally, plastic resins act as diluents and can be in contrast to tacky resins, which are generally miscible, and can migrate to impart viscosity to the surface of the rubber composition. In certain embodiments of the first and second embodiments in which plastic resins are used, the plastic resin includes a hydrocarbon resin and can be aliphatic, aromatic, or aliphatic / aromatic depending on the monomers contained therein. Examples of plastic resins suitable for use in the rubber compositions of the third embodiment include, but are not limited to, cyclopentadiene (often abbreviated as CPD) or dicyclopentadiene (often abbreviated as DCPD) homopolymer or copolymer resins. Examples include, but are not limited to, terpene homopolymer or copolymer resins, phenol homopolymer or copolymer resins, C5 or C9 partial homopolymer or copolymer resins, alpha-methylstyrene homopolymer or copolymer resins, and combinations thereof. Such resins can be used, for example, individually or in combination. In a particular embodiment of the third embodiment, a plastic resin is used that satisfies at least one of the following: Tg above 30°C (preferably above 40°C and / or 120°C or below or 100°C), number-average molecular weight (Mn) of 400 to 2000 g / mol (preferably 500 to 2000 g / mol), and polydispersity index (PI) of less than 3 (preferably less than 2) (PI = Mvv / Mn, where Mvv is the weight-average molecular weight of the resin). The Tg of the resin can be measured by differential scanning calorimetry (DSC) in accordance with ASTM D3418 (1999).The Mw, Mn, and PI of the resin can be determined by size exclusion chromatography (SEC) using a solution filtered through a filter with a porosity of 0.45 μm before injection at THF, 35°C, a concentration of 1 g / 1, a flow rate of 1 ml / min, Moore calibration with polystyrene standards, a set of three "Waters" columns ("Styragel" HR4E, HR1, and HR0.5), a differential refractometer ("Waters 2410"), and its associated operating software ("Waters Empower").
[0081] Other ingredients Various other components that may be optionally added to the rubber compositions of the first and second embodiments disclosed herein include waxes (which may be antioxidants), processing aids, reinforcing resins, compounding accelerators, and antioxidants / degradation inhibitors. Components that are degradation inhibitors may be classified as ozone degradation inhibitors or antioxidants, such as those selected from N,N'-disubstituted-p-phenylenediamines, for example, N-1,3-dimethylbutyl-N'phenyl-p-phenylenediamine (6PPD), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), N-phenyl-N-isopropyl-p-phenylenediamine (IPPD), and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (HPPD). Other examples of degradation inhibitors include acetone diphenylamine condensation products, 2,4-trimethyl-1,2-dihydroquinoline, octylated diphenylamine, 2,6-di-t-butyl-4-methylphenol, and certain waxes. In certain other embodiments of the first and second embodiments, the tire tread rubber composition may not contain, or is essentially without, degradation inhibitors such as antioxidants or ozone degradation inhibitors.
[0082] Properties of rubber compositions In certain embodiments of the first and second embodiments, the rubber composition can be described as having improved properties compared to a comparative rubber composition in which guayule rubber is replaced with Hevea natural rubber (preferably viscosity-stabilized TSR grade). In certain such embodiments, the cured rubber composition (cured at 145°C for 33 minutes) has the following physical properties: (a) elongation at break at 23°C is higher than that of a comparative cured rubber composition using Hevea natural rubber instead of guayule rubber, preferably at least 3% higher (e.g., 3% higher, 4% higher, 5% higher, 6% higher, 7% higher, 8% higher, or more); (b) tensile strength at 23°C is higher than that of a comparative cured rubber composition using Hevea natural rubber instead of guayule rubber, preferably at least 5% higher (e.g., 5% higher, 6% higher, 7% higher, 8% higher, 9% higher, 10% higher, or more); The rolling resistance, as demonstrated by the tan delta at 60°C, is lower than (c) a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber, preferably at least 3% lower (e.g., 3% lower, 4% lower, 5% lower, 6% lower, 7% lower, or less), and has at least one of these. In certain embodiments of the embodiments described above, the cured rubber composition has properties (a) to (d) and the following physical properties (when cured at 145°C for 33 minutes): (d) is higher than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber, preferably at least 2% higher (e.g., 2% higher, 3% higher, 4% higher, 5% higher, or more), and also has coefficients selected from M50, M100, M300, and combinations thereof. In certain embodiments of the first and second embodiments, each of (a) to (c) is preferably satisfied by their preferred ranges. In other embodiments of the first and second embodiments, each of (a) to (d) is preferably satisfied by their preferred ranges. In certain such embodiments, the coefficient is selected from M50 or M100, and is preferably M100.
[0083] As will be discussed in more detail below, in certain embodiments of the first and second embodiments, the tire component is for a TBR tire tread, preferably for the road contact portion of the TBR tread. In certain such embodiments, the cured rubber composition of the TBR tread has the following physical properties (when cured at 145°C for 33 minutes): (a) elongation at break at 23°C of at least about 250% or at least 250% (e.g., 250%, 275%, 300%, 325%, 350%, 375%, 400%, 425%, 450%, 475%, 500%, 525%, 550%, 575%, or so (a) (i) at least about 18 MPa or at least 18 MPa (i) at least about 18 MPa (i) at least about 18 MPa (i) at least about 18 MPa (i) at least 18 MPa, (c) Tensile strength (Tb) at 23°C at approximately 18 MPa to approximately 35 MPa or 18 MPa to 35 MPa (for example, 18 MPa, 20 MPa, 22 MPa, 24 MPa, 26 MPa, 28 MPa, 30 MPa, 32 MPa, 34 MPa, or 35 MPa), or (c) approximately 0.21 or less or 0.21 or less (for example, 0. It has at least one of the rolling resistances, as demonstrated by the tan delta at 60°C, which is approximately 0.06 to approximately 0.21 or 0.06 to 0.21 (e.g., 0.21, 0.2, 0.18, 0.16, 0.14, 0.12, 0.1, 0.08, 0.06, or less).In a specific embodiment of the above embodiment, the cured rubber composition of the TBR tread has properties (a) to (d), and the following physical properties (when cured at 145°C for 33 minutes): (i) M50 of at least about 1.3 MPa or at least 1.3 MPa (e.g., 1.3 MPa, 1.5 MPa, 1.7 MPa, 1.8 MPa, 2 MPa, 2.2 MPa, 2.4 MPa, 2.5 MPa, 2.6 MPa, or higher), preferably about 1.3 MPa to about 2. (ii) 5 MPa or 1.3 MPa to 2.5 MPa (e.g., 1.3 MPa, 1.5 MPa, 1.7 MPa, 1.8 MPa, 2 MPa, 2.2 MPa, 2.4 MPa, 2.5 MPa), (ii) M100 at least about 2.3 MPa or at least 2.3 MPa (e.g., 2.3 MPa, 2.5 MPa, 2.7 MPa, 2.9 MPa, 3 MPa, 3.2 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.8 MPa, 4 MPa, 4.2 MPa, 4. 4MPa, 4.5MPa, 4.6MPa, 4.8MPa, 5MPa, 5.2MPa, or higher), preferably about 2.3MPa to about 5MPa or 2.3MPa to 5MPa (for example, 2.3MPa, 2.5MPa, 2.7MPa, 2.9MPa, 3MPa, 3.2MPa, 3.4MPa, 3.5MPa, 3.6MPa, 3.8MPa, 4MPa, 4.2MPa, 4.4MPa, 4.5MPa, 4.6MPa, 4.8MPa, 5MPa), or (iii) The coefficient also has at least about 12 MPa or M300 of at least 12 MPa (e.g., 12 MPa, 14 MPa, 15 MPa, 16 MPa, 18 MPa, 20 MPa, 22 MPa, 24 MPa, or higher), preferably selected from at least one of about 12 MPa to about 22 MPa or 12 MPa to 22 MPa (e.g., 12 MPa, 14 MPa, 15 MPa, 16 MPa, 18 MPa, 20 MPa, 22 MPa).
[0084] Tire components As discussed above, the first embodiment disclosed herein relates to a method for providing tire components, and the second embodiment disclosed herein relates to tire components. According to the first and second embodiments, the specific tire components can vary. Exemplary tire components according to the first and second embodiments include, but are not limited to, the tire tread, base tread, belt, and sidewall. In preferred embodiments of the first and second embodiments, the tire component is the tire tread, more preferably the road contact tread. In specific embodiments of the first and second embodiments, the tire component is the tire sidewall. In yet other embodiments of the first and second embodiments, the tire component is the belt.
[0085] Tire type According to the first and second embodiments, the type of tire on which the tire components are designed can vary. According to the first and second embodiments, the tire components can be designed for truck and bus radial tires (TBR tires) or for passenger car and light truck tires (PSR tires). In the preferred embodiments described above, the tire components are either TBR treads or PSR treads, most preferably road-contact TBR treads or road-contact PSR treads. As those skilled in the art will understand, the specific amount of total natural rubber, the amount of at least one conjugated diene monomer-based rubber (ii) (if present), and the amount of reinforcing fillers can vary depending on whether the tire components are intended for use in TBR or PSR tires. Generally, the amount of total natural rubber, the amount of substitution with guayule natural rubber, the amount of at least one conjugated diene monomer-based rubber (ii), and the amount of reinforcing fillers for either TBR or PSR tire components fall within the ranges considered above. However, as will be discussed in detail below, the following sub-ranges described above may be particularly useful for either TBR or PSR tire components including treads.
[0086] In certain embodiments of the first and second embodiments, the type of tire for which the tire components are designed is a TBR tire. In the preferred embodiments described above, the tire components are treads, i.e., treads for TBR tires. In those embodiments of the first and second embodiments in which the tire components are TBR treads, the rubber composition comprises carbon black, silica, and a reinforcing filler selected from a combination thereof, preferably in an amount of about 30 to about 60 phr or 30 to 60 phr (e.g., 30, 35, 40, 45, 50, 55, or 60 phr). In certain such embodiments of the first and second embodiments, the tread is for a first type of TBR tire, and the reinforcing filler comprises 0 to 20 wt% silica (e.g., 0%, 5%, 10%, 15%, or 20%), which can be considered to include amounts within the aforementioned ranges such as 0% silica and up to 20 wt% silica, as well as 0 to 10 wt% silica (e.g., 0%, 5%, or 10%), 1 to 10 wt% silica (e.g., 1%, 5%, or 10%), 5 to 20 wt% silica (e.g., 5%, 10%, 15%, or 20%), 5 to 15 wt% silica (e.g., 5%, 10%, or 15%), and 10 to 20 wt% silica (e.g., 10%, 15%, or 20%), with the remainder of the reinforcing filler comprising carbon black.In other embodiments of the first and second embodiments, the tire component is a tread for a second type of TBR tire, preferably comprising about 30 to about 60 phr of reinforcing filler, the reinforcing filler being 0 to 60% by weight (e.g., 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%), 1 to 60% by weight (e.g., 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or It contains up to 60% by weight silica, including 60%, 5-50% by weight (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%), 10-60% by weight (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%), and 20-60% by weight (e.g., 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%), with the remainder of the reinforcing filler consisting of carbon black. In certain embodiments of the first and second embodiments, where the tire component is a TBR tread, the rubber composition preferably includes 1 to 10 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr) of plasticizing components, or an amount within the aforementioned range such as 1 to 5 phr or 5 to 9 phr, and in certain such embodiments, the plasticizing components include 1 to 8 phr of resin (e.g., 1, 2, 3, 4, 5, 6, 7, or 8 phr) and 1 to 5 phr (e.g., 1, 2, 3, 4, or 5 phr) of plasticizing oil, and the total amount of plasticizing components is 1 to 10 phr.
[0087] In certain embodiments of the first and second embodiments, the type of tire for which the tire components are designed is a PSR tire. In the preferred embodiments described above, the tire components are treads, i.e., treads for PSR tires. In those embodiments of the first and second embodiments in which the tire components are PSR treads, the rubber composition includes carbon black, silica, and a combination thereof, preferably in a reinforcing filler of about 50 to about 150 phr or 50 to 150 phr (e.g., 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 phr). The amount of reinforcing filler 50-150 phr should be considered to include amounts within the aforementioned ranges such as 50-100 phr, 50-90 phr, 50-80 phr, 50-70 phr, 70-120 phr, 70-100 phr, 90-150 phr, 90-140 phr, 90-130 phr, and 90-120 phr. In certain embodiments of the first and second embodiments, where the tire component is a PSR tread, the reinforcing filler is present in an amount of about 50-150 phr or 50-150 phr, and silica constitutes the majority of the weight of the reinforcing filler (e.g., 51%, 60%, 70%, 80%, 85%, 90%, 95%, or more), including amounts within the aforementioned ranges such as 51-95%, 60-90%, and 70-90%.
[0088] Preparation of rubber composition The specific steps involved in the preparation of the rubber compositions in the first and second embodiments disclosed herein are generally steps of conventionally practiced methods, which include mixing the components in at least one non-production masterbatch step and a final production mixing step. In the specific embodiments of the first and second embodiments, the rubber compositions are prepared by mixing the components of the rubber compositions (disclosed above) by methods known in the art, such as kneading the components together in a barb mixer or milling rolls. Such methods generally include at least one non-production masterbatch mixing step and a final production mixing step. The term non-production masterbatch step is known to those skilled in the art and is generally understood to be a mixing step (one or more steps) in which no vulcanizing agent or vulcanization accelerator is added. The term final production mixing step is also known to those skilled in the art and is generally understood to be a mixing step in which vulcanizing agents and vulcanization accelerators are added to the rubber composition. In the specific embodiments of the first and second embodiments, the rubber compositions are prepared by a process that includes a plurality of non-production masterbatch mixing steps.
[0089] In certain preferred embodiments of the first and second embodiments, the rubber composition is prepared by a process in which the masterbatch mixing step comprises at least one of tandem mixing or intermeshing mixing. Tandem mixing can be understood as comprising the use of a mixer having two mixing chambers, each chamber having a pair of mixing rotors, generally the two mixing chambers stacked together with an upper mixer which is a primary mixer, and the lower mixer receives batches from the upper or primary mixer. In certain embodiments, the primary mixer utilizes intermeshing rotors, and in other embodiments, the primary mixer utilizes tangential rotors. Preferably, the lower mixer utilizes intermeshing rotors. Intermeshing mixing can be understood as comprising the use of a mixer having intermeshing rotors. Intermeshing rotors refer to a set of rotors in which the larger diameter of one rotor in the set interacts with the smaller diameter of an opposing rotor in the set, so that the rotors intermesh each other. The intermeshing rotors must be driven at a uniform speed due to the interaction between the rotors. In contrast to meshing rotors, tangential rotors refer to a pair of rotors in which each rotor rotates independently of the others within a cavity that may be called a side. Generally, mixers with tangential rotors include a ram, which is not necessary for mixers with meshing rotors.
[0090] Generally, rubber (or polymer) and at least one reinforcing filler (and optional silane coupling agents, liquid plasticizers, and resins) are added during the non-production or masterbatch mixing stage (or multiple stages). Generally, at least the vulcanizing agent and vulcanization accelerator components of the cured package will be added during the final or production mixing stage.
[0091] In certain embodiments of the first and second embodiments, the rubber composition is prepared using a process in which at least one non-production masterbatch mixing step is carried out at a temperature of about 130°C to about 200°C. In certain embodiments of the first and second embodiments, the rubber composition is prepared using a final production mixing step carried out at a temperature below the vulcanization temperature to avoid undesirable pre-curing of the rubber composition. Thus, the temperature of the production or final mixing step should not exceed about 120°C, and is typically about 40°C to about 120°C, or about 60°C to about 110°C, particularly about 75°C to about 100°C. In certain embodiments of the first and second embodiments, the rubber composition is prepared by a process comprising at least one non-production mixing step and at least one production mixing step. The use of silica fillers may optionally require a separate re-grinding step to separately add some or all of such fillers. This stage is often performed at temperatures similar to those used in the masterbatch stage, but frequently slightly lower, typically between approximately 90°C and 150°C, which is the drop temperature. [Examples]
[0092] The following examples illustrate specific and exemplary embodiments and / or features of the embodiments of the present disclosure. The examples are provided for illustrative purposes only and should not be construed as limiting the present disclosure. Many modifications to these specific examples are possible without departing from the spirit and scope of the embodiments of the present disclosure. It should be specifically understood that the rubber compositions according to the first and second embodiments disclosed herein can be prepared using different rubbers (as discussed above), different combinations and amounts of reinforcing fillers, different components or amounts of plasticizing elements (as discussed above), and different specific curing package components and amounts (as discussed above).
[0093] Examples A-H: Rubber compositions were prepared using the components listed in Table 1 below. As can be seen from the examination in Table 1, the compositions utilized either high-cis-polybutadiene (hereinafter abbreviated as BR) and either Hevea natural rubber (viscosity stabilizer TSR grade), hereinafter abbreviated as Hevea NR, or guayule natural rubber, hereinafter abbreviated as GR. The guayule natural rubber (GR) used had 1,300,000 g / mol Mw, 350,000 g / mol Mn, 2-5 wt% resin, and 0.1-0.2 wt% ash. The eutectic mixture used was a commercially available product purchased from Scionix Ltd. (sold under the trade name Reline), which was a combination of choline chloride and urea. The rubber composition of Example G is considered to be the present invention, and other rubber compositions (i.e., Examples A-F and H) are provided for comparison, as will be discussed in detail below. All components in Table 1 are listed by PHR, and the mixing procedure used to prepare the rubber composition was as provided in Table 2 (using a 6-pound Brabender mixer).
[0094] [Table 1] 1=N-cyclohexyl-2-benzothiazole-sulfenamide
[0095] [Table 2]
[0096] As listed in Table 2, the properties listed in Table 3 were determined for each rubber composition A to H as follows. Eb and Tb were measured using a dumbbell-shaped specimen with a cross-sectional width of 4 mm and a central thickness of 1.9 mm, following the standard procedure described in ASTM D-412, but not limited to the guidelines. During measurement, the specimen was deformed at a constant rate (20% per second), and the resulting force was recorded as a function of elongation (strain). Eb and Tb measured at 23°C are sometimes referred to as room temperature measurements. The coefficient measurements at 50%, 100%, and 300% (in MPa) are also referred to as M50, M100, and M300, respectively, and measure the tensile stress of a rubber composition specimen at 50%, 100%, and 300% elongation, respectively. These coefficient measurements are not true coefficient measurements and can be measured using the same method as described for Eb and Tb. The tanδ value was measured by a strain sweep test performed using the Advanced Rheometric Expansion System (ARES) manufactured by TA Instruments. The test specimen had a cylindrical shape with a length of 14.4 mm and a diameter of 7.8 mm. The test was performed using a frequency of 10 Hz. The temperature was swept from -120°C to 120°C under a constant strain of 2%. Measurements at 0°C and 60°C were recorded for each rubber composition. The tanδ index of the rubber composition at 60°C is an indicator of its rolling resistance when incorporated into a tire tread. The tanδ index of the rubber composition at 0°C indicates its wet traction when incorporated into a tire tread. Generally, a lower tanδ value at 60°C is considered an improvement, and a higher tanδ value at 0°C is also considered an improvement.
[0097] [Table 3]
[0098] As is evident from examining the data provided in Table 3, rubber composition G of the present invention exhibited best (highest) Tb and best (highest) Eb in all rubber compositions. Similarly, rubber composition G of the present invention exhibited best (lowest) tanδ or rolling resistance at 60°C in all rubber compositions. The effect of adding the eutectic composition is demonstrated by comparing rubber composition G of the present invention with control rubber composition C (which differs from G only in that it lacks the eutectic composition), and rubber composition G exhibits improved Tb, Eb, M50, M100, M300, and rolling resistance. When comparing rubber composition G of the present invention with control rubber composition F (which differs from G only in that it uses Hevea natural rubber instead of guayule rubber), it is clear that rubber composition G has a Tb that is more than 5% higher (about 9% higher), an Eb that is more than 5% higher, and improved / lower (about 3.3% lower) rolling resistance. When comparing rubber composition G of the present invention with control rubber composition F, it is clear that the M50 and M100 values of rubber composition G are almost the same as the corresponding values of F, differing by only 0.01 MPa. It is also noteworthy that rubber composition G of the present invention exhibited improved Eb, Tb, and rolling resistance compared to rubber composition E, which lacks any eutectic composition (and guayure rubber) but instead utilizes increased amounts of vulcanization accelerator (15% higher) and increased amounts of sulfur (15% higher) compared to rubber composition G (in general, the effects of increased amounts of vulcanization accelerator and sulfur can be observed in comparative or control examples by comparing rubber compositions E and E'). Therefore, it was determined that by using a eutectic composition, it is not necessary to increase the amount of vulcanization accelerator or sulfur to account for the resin of guayure rubber. Similarly, by using a eutectic composition (as in rubber composition G) instead of increased amounts of vulcanization accelerator and sulfur (composition E), M50, M100, and M300 were all improved by more than 10%.
[0099] The following exemplary embodiments of the present invention are specifically envisioned.
[0100] Embodiment 1: A method for providing a tire component, preferably a tire tread, the method comprising preparing a rubber composition, the rubber composition having (a)(i) at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and 3,000,000 to 4,000,000 grams / mol of Mw / Mn, and at least 10% by weight of guayure natural rubber having up to 90% by weight of Hevea natural rubber. A method comprising (a), (b), and (c) used in a cured rubber composition to provide tire components, wherein (a), (b), and (c) are used in a cured rubber composition, comprising (a), (b), and (c) in an amount of about 0.005 to about 3 phr, more preferably about 0.01 to about 1 phr, a cured package containing (a), (b), and (c) 00 parts of natural rubber, preferably 51 to 90 parts of natural rubber, and (ii) 0 to 90 parts of at least one conjugated diene monomer-based rubber, (b) in an amount of about 30 to about 150 phr, and (c) in an amount of about 0.005 to about 3 phr, and (a), (b), and (c).
[0101] Embodiment 2: The method according to Embodiment 1, wherein 51 to 90 parts of (i) of natural rubber are provided by guayule natural rubber.
[0102] Embodiment 3: The method according to Embodiment 1 or 2, wherein (ii) is present in an amount of 10 to 49 parts.
[0103] Embodiment 4: The method according to any one of Embodiments 1 to 3, wherein the eutectic composition is present in an amount of about 0.005 to about 3 phr.
[0104] Embodiment 5: The method according to any one of Embodiments 1 to 4, wherein the eutectic composition is present in an amount of about 0.01 to about 1 phr.
[0105] Embodiment 6: The method according to any one of Embodiments 1 to 5, wherein the guayule natural rubber provides at least 20% by weight of natural rubber.
[0106] Embodiment 7: The method according to any one of Embodiments 1 to 5, wherein the guayule natural rubber provides at least 30% by weight of natural rubber.
[0107] Embodiment 8: The method according to any one of Embodiments 1 to 5, wherein the guayule natural rubber provides at least 40% by weight of natural rubber.
[0108] Embodiment 9: The method according to any one of Embodiments 1 to 5, wherein guayure natural rubber provides the majority of the weight in natural rubber.
[0109] Embodiment 10: The method according to any one of Embodiments 1 to 5, wherein the guayule natural rubber provides at least 70% by weight of natural rubber.
[0110] Embodiment 11: The method according to any one of Embodiments 1 to 5, wherein the guayule natural rubber is more preferably at least 80% by weight of natural rubber.
[0111] Embodiment 12: The method according to any one of Embodiments 1 to 5, wherein the guayule natural rubber provides 100% by weight natural rubber.
[0112] Embodiment 13: The method according to any one of Embodiments 1 to 12, wherein guayule natural rubber is preferably functionalized with carbon black reactive functional groups.
[0113] Embodiment 14: The method according to any one of Embodiments 1 to 13, wherein the guayule natural rubber has a resin content of about 2 to about 5% by weight and an ash content of about 0.1 to about 0.2% by weight.
[0114] Embodiment 15: The method according to any one of Embodiments 1 to 14, wherein rubber (iii) is a polymer or copolymer made from at least one conjugated diene monomer selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, and optionally at least one vinyl aromatic monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, and combinations thereof.
[0115] Embodiment 16: The method according to Embodiment 15, wherein the conjugated diene is 1,3-butadiene.
[0116] Embodiment 17: The method according to Embodiment 15, wherein the conjugated diene is 1,3-butadiene and the aromatic vinyl monomer is styrene.
[0117] Embodiment 18: The method according to any one of Embodiments 1 to 17, wherein rubber(ii) is selected from the group consisting of styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, and mixtures thereof.
[0118] Embodiment 19: The method according to Embodiment 18, wherein rubber (ii) comprises a functionalized high-cis-polybutadiene rubber, preferably a high-cis-polybutadiene rubber functionalized with carbon black reactive functional groups.
[0119] Embodiment 20: The method according to any one of Embodiments 1 to 19, wherein the eutectic composition comprises a combination of a cation source selected from the group consisting of ammonium compounds, phosphonium compounds, sulfonium compounds, and combinations thereof, and an anion source selected from the group consisting of metal halide compounds, metal halide hydrate compounds, hydrogen bond donor compounds, and combinations thereof.
[0120] Embodiment 21: The cation source is selected from the group consisting of ammonium compounds, preferably the following: (i) Formula II: (R 1 )(R 2 )(R 3 )(R 4 )-N + -Φ - An ammonium compound having the formula, where each R 1 , R 2 , R 3 , and R 4 However, independently selected from hydrogen and monovalent organic groups, R 1 , R 2 , R 3 , and R 4 The method according to Embodiment 20, wherein two of the ammonium compounds can be linked to form a divalent organic group, and Φ is a counter anion, (ii) preferably an ammonium compound having formula IV selected from the group consisting of N-ethyl-2-hydroxy-N,N-dimethylethaneaminium chloride, 2-hydroxy-N,N,N-trimethylethaneaminium chloride, and N-benzyl-2-hydroxy-N,N-dimethylethaneamine chloride, and combinations thereof, or (iii) preferably at least one ammonium compound having formula III selected from the group consisting of 2-chloro-N,N,N-trimethylethaneaminium, and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride, and combinations thereof.
[0121] Embodiment 22: The anion source is selected from the group consisting of hydrogen bond donor compounds, preferably the following: (i) amines, amides, carboxylic acids, alcohols, and mixtures thereof; (ii) preferably amines selected from aliphatic amines, ethylenediamines, diethylenetriamines, aminoethylpiperazines, triethylenetetramines, tris(2-aminoethyl)amines, N,N'-bis-(2-aminoethyl)piperazines, piperadinoethylethylenediamines, and tetraethylenepentaamines, propyleneamines, anilines, substituted anilines, and combinations thereof; (iii) preferably urea, 1-methylurea, 1,1-dimethylurea, 1, (iv) Preferably, an amide selected from 3-dimethylurea, thiourea, benzamide, acetamide, and combinations thereof; (iv) Preferably, a carboxylic acid selected from phenylpropionic acid, phenylacetic acid, benzoic acid, oxalic acid, malonic acid, adipic acid, succinic acid, citric acid, tricarbaryl acid, and combinations thereof; or (v) Preferably, the method according to Embodiment 20 or 21, selected from at least one of aliphatic alcohols, phenols, substituted phenols, ethylene glycol, propylene glycol, resorcinol, substituted resorcinol, glycerol, benzenetriol, and combinations thereof.
[0122] Embodiment 23: The method according to Embodiment 20 or 21, wherein the anion source is selected from the group consisting of metal halides, preferably 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, and iron iodide, and combinations thereof.
[0123] Embodiment 24: The method according to any one of Embodiments 1 to 23, wherein the eutectic composition comprises a combination of choline chloride and urea.
[0124] Embodiment 25: The method according to any one of Embodiments 1 to 24, wherein the tire tread is a tire tread having one of the following physical properties: (a) elongation at break at 23°C which is higher, preferably at least 3%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber; (b) tensile strength (Tb) at 23°C which is higher, preferably at least 5%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber; or (c) rolling resistance which is lower, preferably at least 3%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber, as demonstrated by the tan delta at 60°C.
[0125] Embodiment 26: The method according to Embodiment 25, wherein the tire components are a tire tread having characteristics (a) to (c) and the following physical characteristics: (d) a coefficient selected from M50, M100, M300, and combinations thereof, which is higher, preferably at least 2%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber.
[0126] Embodiment 27: The method according to Embodiment 26, wherein each of (a) to (d) is satisfied, and the coefficient is selected from M50 or M100, preferably M100.
[0127] Embodiment 28: The method according to any one of Embodiments 1 to 27, wherein the tire component is a tire tread, preferably a tire tread for a truck or bus radial tire, and the cured rubber composition has at least one of the following physical properties: (a) elongation at break at 23°C of at least about 250%, preferably about 250% to about 550%, (b) tensile strength (Tb) at 23°C of at least about 18 MPa, preferably about 18 MPa to about 35 MPa, and (c) rolling resistance as demonstrated by the tan delta at 60°C of about 0.21 or less, preferably about 0.06 to about 0.21.
[0128] Embodiment 29: The method according to Embodiment 28, wherein the cured rubber composition has properties (a) to (c) and the following physical properties: (d) below: (i) M50 of at least about 1.3 MPa, preferably about 1.3 MPa to about 2.5 MPa, (ii) M100 of at least about 2.3 MPa, preferably about 2.3 MPa to about 5 MPa, or (iii) M300 of at least about 12 MPa, preferably about 12 MPa to about 22 MPa.
[0129] Embodiment 30: The method according to Embodiment 29, wherein each of (a) to (d) is satisfied, and the coefficient is selected from M50 or M100, preferably M100.
[0130] Embodiment 31: The method according to any one of Embodiments 1 to 30, wherein the eutectic composition is premixed with a solid support.
[0131] Embodiment 100: A tire component comprising a rubber composition, preferably a tire tread, wherein the rubber composition comprises (a) (i) 10 to 100 parts, preferably 51 to 90 parts of natural rubber having at least 10% by weight, provided by guayule natural rubber having at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and 3 to 4 Mw / Mn, and (ii) 0 to 90 parts, preferably 10 to 49 parts A tire component comprising: (a), (b), and (c) 100 parts of at least one rubber, including at least one conjugated diene monomer rubber; (b) a reinforcing filler selected from carbon black and silica in an amount of about 30 to about 150 phr; and (c) a cured package containing a sulfur-based vulcanizing agent, at least one vulcanization accelerator, a vulcanization activator, and a eutectic composition, or a residue thereof, preferably in an amount of about 0.005 to about 3 phr, more preferably about 0.01 to about 1 phr, wherein (a), (b), and (c) are used in the cured rubber composition to provide a tire component.
[0132] Embodiment 101: The tire component according to Embodiment 100, wherein the tire component is a tire tread.
[0133] Embodiment 102: The tire component according to Embodiment 100 or 101, wherein 51 to 90 parts of (i) of natural rubber are provided by guayule natural rubber.
[0134] Embodiment 103: A tire component according to any one of Embodiments 100 to 102, wherein (ii) is present in an amount of 10 to 49 parts.
[0135] Embodiment 104: A tire component according to any one of Embodiments 100 to 103, wherein the eutectic composition is present in an amount of about 0.005 to about 3 phr.
[0136] Embodiment 105: A tire component according to any one of Embodiments 100 to 104, wherein the eutectic composition is present in an amount of about 0.01 to about 1 phr.
[0137] Embodiment 106: A tire component according to any one of Embodiments 100 to 105, wherein guayure natural rubber provides at least 20% by weight of natural rubber.
[0138] Embodiment 107: A tire component according to any one of Embodiments 100 to 105, wherein guayure natural rubber provides at least 30% by weight of natural rubber.
[0139] Embodiment 108: A tire component according to any one of Embodiments 100 to 105, wherein guayure natural rubber provides at least 40% by weight of natural rubber.
[0140] Embodiment 109: A tire component according to any one of Embodiments 100 to 105, wherein guayule natural rubber provides the majority of the weight in natural rubber.
[0141] Embodiment 110: A tire component according to any one of Embodiments 100 to 105, wherein guayure natural rubber provides at least 70% by weight of natural rubber.
[0142] Embodiment 111: The tire component according to any one of Embodiments 100 to 105, wherein the guayule natural rubber is more preferably at least 80% by weight of natural rubber.
[0143] Embodiment 112: A tire component according to any one of Embodiments 100 to 105, wherein guayule natural rubber provides 100% by weight of natural rubber.
[0144] Embodiment 113: A tire component according to any one of Embodiments 100 to 112, wherein the guayule natural rubber has a resin content of about 2 to about 5% by weight and an ash content of about 0.1 to about 0.2% by weight.
[0145] Embodiment 114: A tire component according to any one of Embodiments 100 to 113, wherein rubber (iii) is a polymer or copolymer made from at least 100 conjugated diene monomers selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, and optionally at least one vinyl aromatic monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, and combinations thereof.
[0146] Embodiment 115: The tire component according to Embodiment 114, wherein the conjugated diene is 1,3-butadiene.
[0147] Embodiment 116: The tire component according to Embodiment 114, wherein the conjugated diene is 1,3-butadiene and the aromatic vinyl monomer is styrene.
[0148] Embodiment 117: A tire component according to any one of Embodiments 100 to 116, wherein rubber(ii) is selected from the group consisting of styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, and mixtures thereof.
[0149] Embodiment 118: The tire component according to Embodiment 117, wherein rubber (ii) comprises a functionalized high-cis-polybutadiene rubber, preferably a high-cis-polybutadiene rubber functionalized with carbon black reactive functional groups.
[0150] Embodiment 119: A tire component according to any one of Embodiments 100 to 118, wherein the eutectic composition comprises a combination of a cation source selected from the group consisting of ammonium compounds, phosphonium compounds, sulfonium compounds, and combinations thereof, and an anion source selected from the group consisting of metal halide compounds, metal halide hydrate compounds, hydrogen bond donor compounds, and combinations thereof.
[0151] Embodiment 120: The cation source is selected from the group consisting of ammonium compounds, preferably the following: (i) Formula II: (R 1 )(R 2 )(R 3 )(R 4 )-N + -Φ - An ammonium compound having the formula, where each R 1 , R 2 , R 3 , and R 4 However, independently selected from hydrogen and monovalent organic groups, R 1 , R 2 , R 3 , and R 4The tire component according to Embodiment 119, wherein two of the ammonium compounds can be linked to form a divalent organic group, and Φ is a counter anion, (ii) preferably an ammonium compound having formula IV selected from the group consisting of N-ethyl-2-hydroxy-N,N-dimethylethaneaminium chloride, 2-hydroxy-N,N,N-trimethylethaneaminium chloride, and N-benzyl-2-hydroxy-N,N-dimethylethaneamine chloride, and combinations thereof, or (iii) preferably at least one ammonium compound having formula III selected from the group consisting of 2-chloro-N,N,N-trimethylethaneaminium, and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride, and combinations thereof.
[0152] Embodiment 121: The anion source is selected from the group consisting of hydrogen bond donor compounds, preferably the following: (i) amines, amides, carboxylic acids, alcohols, and mixtures thereof; (ii) preferably amines selected from aliphatic amines, ethylenediamines, diethylenetriamines, aminoethylpiperazines, triethylenetetramines, tris(2-aminoethyl)amines, N,N'-bis-(2-aminoethyl)piperazines, piperadinoethylethylenediamines, and tetraethylenepentaamines, propyleneamines, anilines, substituted anilines, and combinations thereof; (iii) preferably urea, 1-methylurea, 1,1-dimethylurea, 1, (iv) Preferably, a carboxylic acid selected from phenylpropionic acid, phenylacetic acid, benzoic acid, oxalic acid, malonic acid, adipic acid, succinic acid, citric acid, tricarbaryl acid, and combinations thereof; or (v) Preferably, a tire component according to Embodiment 120, selected from at least one of aliphatic alcohols, phenols, substituted phenols, ethylene glycol, propylene glycol, resorcinol, substituted resorcinol, glycerol, benzenetriol, and combinations thereof.
[0153] Embodiment 122: The tire component according to Embodiment 120 or 121, wherein the anion source is selected from the group consisting of metal halides, preferably 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, and iron iodide, and combinations thereof.
[0154] Embodiment 123: A tire component according to any one of Embodiments 100 to 122, wherein the eutectic composition comprises a combination of choline chloride and urea.
[0155] Embodiment 124: A tire tread according to any one of Embodiments 100 to 123, wherein the tire component is a tire tread having one of the following physical properties: (a) elongation at break at 23°C, which is higher, preferably at least 3%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber; (b) tensile strength (Tb) at 23°C, which is higher, preferably at least 5%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber; or (c) rolling resistance, which is lower, preferably at least 3%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber, as demonstrated by the tan delta at 60°C.
[0156] Embodiment 125: The tire component according to Embodiment 124, wherein each of (a) to (c) is satisfied, and the tire tread also has the following additional property: (d) a coefficient selected from M50, M100, M300, and combinations thereof, which is higher, preferably at least 2%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber.
[0157] Embodiment 126: The tire component according to Embodiment 125, wherein each of (a) to (d) is satisfied, and the coefficient is selected from M50 or M100, preferably M100.
[0158] Embodiment 127: A tire component according to any one of Embodiments 100 to 123, wherein the tire component is a tire tread, preferably a tire tread for a truck or bus radial tire, and the cured rubber composition has at least one of the following physical properties: (a) elongation at break at 23°C of at least about 250%, preferably about 250% to about 550%, (b) tensile strength (Tb) at 23°C of at least about 18 MPa, preferably about 18 MPa to about 35 MPa, and (c) rolling resistance as demonstrated by the tan delta at 60°C of about 0.21 or less, preferably about 0.06 to about 0.21.
[0159] Embodiment 128: A tire component according to Embodiment 127, wherein the cured rubber composition has properties (a) to (c), and the following physical properties: (d) below: (i) M50 of at least about 1.3 MPa, preferably about 1.3 MPa to about 2.5 MPa, (ii) M100 of at least about 2.3 MPa, preferably about 2.3 MPa to about 5 MPa, or (iii) M300 of at least about 12 MPa, preferably about 12 MPa to about 22 MPa.
[0160] Embodiment 129: A tire component according to any one of Embodiments 100 to 128, wherein the eutectic composition is premixed with a solid carrier.
[0161] Embodiment 200: A tire tread comprising a rubber composition, wherein the rubber composition comprises (a) (i) 10 to 100 parts, preferably 51 to 90 parts, of natural rubber having at least 10% by weight, provided by guayule natural rubber having at least 1,200,000 grams / mol, preferably 1.25 to 1.35 grams / mol of Mw, at least 250,000 grams / mol, preferably 300,000 to 400,000 grams / mol of Mn, and 3 to 4 Mw / Mn; and (ii) 0 to 90 parts, preferably 10 to 49 parts, of at least one combined A tire tread comprising (a), (b), and (c) 100 parts of at least one rubber, including a diene monomer-based rubber; (b) a reinforcing filler selected from carbon black and silica in an amount of about 30 to about 150 phr; and (c) a cured package containing a sulfur-based vulcanizing agent, at least one vulcanization accelerator, vulcanization activator, and a eutectic composition, or a residue thereof, preferably in an amount of about 0.005 to about 3 phr, more preferably about 0.01 to about 1 phr, wherein (a), (b), and (c) are used in the cured rubber composition to provide tire components.
[0162] Embodiment 201: The tire tread according to Embodiment 200, wherein the tire component is a tire tread.
[0163] Embodiment 202: The tire tread according to Embodiment 200 or 201, wherein 51 to 90 parts of (i) of natural rubber are provided by guayule natural rubber.
[0164] Embodiment 203: A tire tread according to any one of Embodiments 200 to 202, wherein (ii) is present in an amount of 10 to 49 parts.
[0165] Embodiment 204: A tire tread according to any one of Embodiments 200 to 203, wherein the eutectic composition is present in an amount of about 0.005 to about 3 phr.
[0166] Embodiment 205: A tire tread according to any one of Embodiments 200 to 204, wherein the eutectic composition is present in an amount of about 0.01 to about 1 phr.
[0167] Embodiment 206: A tire tread according to any one of Embodiments 200 to 205, wherein guayure natural rubber provides at least 20% by weight of natural rubber.
[0168] Embodiment 207: A tire tread according to any one of Embodiments 200 to 205, wherein guayure natural rubber provides at least 30% by weight of natural rubber.
[0169] Embodiment 208: A tire tread according to any one of Embodiments 200 to 205, wherein guayure natural rubber provides at least 40% by weight of natural rubber.
[0170] Embodiment 209: A tire tread according to any one of Embodiments 200 to 205, wherein guayure natural rubber provides the majority of the weight in natural rubber.
[0171] Embodiment 210: A tire tread according to any one of Embodiments 200 to 205, wherein guayure natural rubber provides at least 70% by weight of natural rubber.
[0172] Embodiment 211: The tire tread according to any one of Embodiments 200 to 205, wherein the guayule natural rubber is more preferably at least 80% by weight of natural rubber.
[0173] Embodiment 212: A tire tread according to any one of Embodiments 100 to 205, wherein guayure natural rubber provides 200% by weight of natural rubber.
[0174] Embodiment 213: A tire tread according to any one of Embodiments 200 to 212, wherein the guayule natural rubber has a resin content of about 2 to about 5% by weight and an ash content of about 0.1 to about 0.2% by weight.
[0175] Embodiment 214: A tire tread according to any one of Embodiments 200 to 213, wherein rubber (iii) is a polymer or copolymer made from at least 200 conjugated diene monomers selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, and optionally at least one vinyl aromatic monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, and combinations thereof.
[0176] Embodiment 215: The tire tread according to Embodiment 214, wherein the conjugated diene is 1,3-butadiene.
[0177] Embodiment 216: The tire tread according to Embodiment 214, wherein the conjugated diene is 1,3-butadiene and the aromatic vinyl monomer is styrene.
[0178] Embodiment 217: A tire tread according to any one of Embodiments 200 to 216, wherein rubber(ii) is selected from the group consisting of styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, and mixtures thereof.
[0179] Embodiment 218: The tire tread according to Embodiment 217, wherein rubber (ii) comprises a functionalized high-cis-polybutadiene rubber, preferably a high-cis-polybutadiene rubber functionalized with carbon black reactive functional groups.
[0180] Embodiment 219: A tire tread according to any one of Embodiments 200 to 218, wherein the eutectic composition comprises a combination of a cation source selected from the group consisting of ammonium compounds, phosphonium compounds, sulfonium compounds, and combinations thereof, and an anion source selected from the group consisting of metal halide compounds, metal halide hydrate compounds, hydrogen bond donor compounds, and combinations thereof.
[0181] Embodiment 220: The cation source is selected from the group consisting of ammonium compounds, preferably the following: (i) Formula II: (R 1 )(R 2 )(R 3 )(R 4 )-N + -Φ - An ammonium compound having the formula, where each R 1 , R 2 , R 3 , and R 4 However, independently selected from hydrogen and monovalent organic groups, R 1 , R 2 , R 3 , and R 4 A tire tread according to Embodiment 219, wherein two of the ammonium compounds can be linked to form a divalent organic group, and Φ is a counter anion, (ii) preferably an ammonium compound having formula IV selected from the group consisting of N-ethyl-2-hydroxy-N,N-dimethylethaneaminium chloride, 2-hydroxy-N,N,N-trimethylethaneaminium chloride, and N-benzyl-2-hydroxy-N,N-dimethylethaneamine chloride, and combinations thereof, or (iii) preferably at least one ammonium compound having formula III selected from the group consisting of 2-chloro-N,N,N-trimethylethaneaminium, and 2-(chlorocarbonyloxy)-N,N,N-trimethylethaneaminium chloride, and combinations thereof.
[0182] Embodiment 221: The anion source is selected from the group consisting of hydrogen bond donor compounds, preferably the following: (i) amines, amides, carboxylic acids, alcohols, and mixtures thereof; (ii) preferably amines selected from aliphatic amines, ethylenediamines, diethylenetriamines, aminoethylpiperazines, triethylenetetramines, tris(2-aminoethyl)amines, N,N'-bis-(2-aminoethyl)piperazines, piperadinoethylethylenediamines, and tetraethylenepentaamines, propyleneamines, anilines, substituted anilines, and combinations thereof; (iii) preferably urea, 1-methylurea, 1,1-dimethylurea, 1, (iv) Preferably, a carboxylic acid selected from phenylpropionic acid, phenylacetic acid, benzoic acid, oxalic acid, malonic acid, adipic acid, succinic acid, citric acid, tricarbaryl acid, and combinations thereof; or (v) Preferably, a tire tread according to Embodiment 220, selected from at least one of aliphatic alcohols, phenols, substituted phenols, ethylene glycol, propylene glycol, resorcinol, substituted resorcinol, glycerol, benzenetriol, and combinations thereof.
[0183] Embodiment 222: The tire tread according to Embodiment 220 or 221, wherein the anion source is selected from the group consisting of metal halides, preferably 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, and iron iodide, and combinations thereof.
[0184] Embodiment 223: A tire tread according to any one of Embodiments 200 to 222, wherein the eutectic composition comprises a combination of choline chloride and urea.
[0185] Embodiment 224: A tire tread according to any one of Embodiments 200 to 223, wherein the tread tire is for truck or bus radial tires.
[0186] Embodiment 225: A tire tread according to any one of Embodiments 200 to 223, wherein the tire tread is for pneumatic tires, preferably for passenger cars or light trucks.
[0187] Embodiment 226: A tire tread according to any one of Embodiments 200 to 225, having one of the following physical properties: (a) elongation at break at 23°C, which is higher, preferably at least 3%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber; (b) tensile strength (Tb) at 23°C, which is higher, preferably at least 5%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber; or (c) rolling resistance, which is lower, preferably at least 3%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber, as demonstrated by the tan delta at 60°C.
[0188] Embodiment 227: The tire tread according to Embodiment 226, wherein each of (a) to (c) is satisfied, and the tire tread also has the following additional property: (d) a coefficient selected from M50, M100, M300, and combinations thereof, which is higher, preferably at least 2%, than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber.
[0189] Embodiment 228: The tire tread according to Embodiment 227, wherein each of (a) to (d) is satisfied and the coefficient is selected from M50 or M100, preferably M100.
[0190] Embodiment 229: A tire tread for truck or bus radial tires, wherein the cured rubber composition has at least one of the following physical properties: (a) elongation at break at 23°C of at least about 250%, preferably about 250% to about 550%, (b) tensile strength (Tb) at 23°C of at least about 18 MPa, preferably about 18 MPa to about 35 MPa, and (c) rolling resistance as demonstrated by the tan delta at 60°C of about 0.21 or less, preferably about 0.06 to about 0.21, according to any one of Embodiments 200 to 228.
[0191] Embodiment 230: A tire tread according to Embodiment 229, wherein the cured rubber composition has properties (a) to (c), and the following physical properties: (d) below: (i) M50 of at least about 1.3 MPa, preferably about 1.3 MPa to about 2.5 MPa, (ii) M100 of at least about 2.3 MPa, preferably about 2.3 MPa to about 5 MPa, or (iii) M300 of at least about 12 MPa, preferably about 12 MPa to about 22 MPa.
[0192] Embodiment 231: A tire tread according to any one of Embodiments 200 to 230, wherein the eutectic composition is premixed with a solid carrier.
[0193] This application discloses several numerical range limits that support any range within the disclosed numerical range, even when explicit range limits are not explicitly mentioned in the specification, because embodiments of the compositions and methods disclosed herein can be performed across the entire numerical range disclosed. With regard to the use of substantially any plural or singular terminology herein, those skilled in the art can substitute plurals for singulars or singulars for plurals as appropriate to the context or application. Various singular or plural substitutions may be explicitly stated herein for brevity.
[0194] In general, those skilled in the art will understand that the terms used herein and in particular in the appended claims are generally intended to be “open” terms. For example, the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” and the term “listed” should be interpreted as “listed but not limited to.” Furthermore, those skilled in the art will understand that if a particular number is intended in the description of a preceding claim, such intention will be explicitly stated in that claim, and if there is no such statement, such intention does not exist. For example, to aid understanding, the following appended claims may include the use of the prefix phrases “at least one” and “one or more” to prefix the description of the claims. However, the use of such phrases should not be interpreted as meaning that the indefinite article "a" or "an" preamble to a claim, even if the same claim includes the preamble "one or more" or "at least one" and an indefinite article such as "a" or "an," limits any particular claim containing the description of the claim in such a preamble to an invention containing only one such description (for example, "a" or "an" should typically be interpreted as meaning "at least one" or "one or more"), and the same applies to the use of definite articles used to preamble claims. In addition, even if a specific number is explicitly stated in the description of a preamble claim, a person skilled in the art will understand that such a description should typically be interpreted as meaning at least the number described (for example, "two descriptions," which is an obvious description without other modifiers, typically means at least two descriptions or two or more descriptions).Furthermore, when using conventional expressions similar to "at least one of A, B, and C," such constructions are generally intended to be understood by those skilled in the art (for example, "a system having at least one of A, B, and C" could include, but not limited to, A only, B only, C only, A and B together, A and C together, B and C together, and / or a system having A, B, and C together). Furthermore, those skilled in the art will understand that any disjunct word or phrase indicating two or more alternative terms should be understood, whether in the specification, claims, or drawings, as intended to include the possibility of including one of these terms, either of these terms, or both of these terms. For example, the phrase "A or B" would be understood to include the possibility of "A" or "B" or "A and B." All references, including but not limited to patents, patent applications, and non-patent literature, are incorporated herein by reference in their entirety. While various aspects and embodiments of compositions and methods have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are illustrative and are not intended to limit the true scope and spirit set forth in the claims.
Claims
1. A tire component comprising a rubber composition, wherein the rubber composition is (a) (i) 10 to 100 parts by weight of natural rubber provided by guayule natural rubber having at least 1,200,000 grams / mol Mw, at least 250,000 grams / mol Mn, and 3 to 4 Mw / Mn, and (ii) 100 parts of at least one rubber comprising 0 to 90 parts of at least one conjugated diene monomer-based rubber, (b) A reinforcing filler selected from carbon black and silica in an amount of 30 to 150 phr, (c) A cured package comprising a sulfur-based vulcanizing agent, at least one vulcanization accelerator, a vulcanization activator, and a eutectic composition, wherein the eutectic composition is present in an amount of 0.005 to 3 phr, (a), (b), and (c) are used in a cured rubber composition to provide the tire components, A tire component comprising a eutectic composition comprising a combination of a cation source selected from the group consisting of ammonium compounds, phosphonium compounds, sulfonium compounds, and combinations thereof, and an anion source selected from the group consisting of metal halide compounds, metal halide hydrate compounds, hydrogen bond donor compounds, and combinations thereof.
2. The tire component according to claim 1, wherein the guayule natural rubber has a resin content of 2 to 5% by weight and an ash content of 0.1 to 0.2% by weight, and has a Mooney viscosity of at least 65 (ML1+4 at 100°C).
3. The tire component according to claim 1 or 2, wherein the cation source is selected from ammonium compounds and the anion source is selected from hydrogen bond donor compounds.
4. The aforementioned tire components have the following physical characteristics: (a) Elongation at break at 23°C that is at least 3% higher than that of a comparative cured rubber composition using Hevea natural rubber instead of the guayule natural rubber, (b) Tensile strength (Tb) at 23°C that is at least 5% higher than that of a comparative cured rubber composition using Hevea natural rubber instead of the guayule natural rubber, (c) Rolling resistance as demonstrated by the tan delta at 60°C, which is at least 3% lower than that of a comparative cured rubber composition using Hevea natural rubber instead of the guayule natural rubber, and (d) A tire tread having a coefficient selected from M50, M100, and M300 that is at least 2% higher than a comparative cured rubber composition using Hevea natural rubber instead of guayule natural rubber.
5. The tire component is a tire tread for a truck or bus radial tire, and the cured rubber composition has the following physical properties: (a) At least 250% elongation at break at 23°C, (b) Tensile strength (Tb) at 23°C at least 18 MPa, (c) Rolling resistance as demonstrated by tan delta at 60°C, which is 0.21 or less, and (d) i. M50 of at least 1.3 MPa, ii. M100 of at least 2.3 MPa, or iii. A tire component according to any one of claims 1 to 4, having each of the coefficients selected from at least one of M300, which is at least 12 MPa.
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