Method of using rubber compositions and polyphenylene ether

Abstract

An object of the present application is to obtain a rubber composition which is excellent in processability, low fuel consumption, wet grip performance, and ice grip performance, and in which a balance among the above-mentioned properties is exhibited at a high level. In order to achieve the above-mentioned object, the present application is characterized by comprising: a polyphenylene ether having a glass transition temperature of -100°C or higher and less than 0°C based on differential scanning calorimetry (DSC); and a diene-based elastomer.

Description

Technical Field

[0001] This invention relates to the use of rubber compositions and polyphenylene ethers. Background Technology

[0002] Rubber compositions have long been widely used in industrial components such as automotive parts, tire components, liners, gaskets, sealing materials, vibration damping rubber, vibration-proof rubber, shock-absorbing materials, shoe outsoles, and shoe midsoles.

[0003] The tire tread, as a component of the tire, requires higher levels of reduction in rolling resistance (low fuel consumption) and improvement in handling stability on wet roads (wet grip). However, generally speaking, low fuel consumption and wet grip are inversely related and difficult to achieve simultaneously.

[0004] Furthermore, winter tires require excellent handling stability (ice grip) at low temperatures and on icy and snowy roads. Increasing the contact area between the tire rubber and ice / snow is effective in improving ice grip, thus requiring high flexibility in the tire rubber. Petroleum-based softeners are used to impart this flexibility. However, the addition of oil causes seepage, leading to a decline in ice grip over the years. Therefore, additives to replace oils have been proposed.

[0005] For example, reference 1 discloses a rubber composition containing rubber components and farnesene resin in a specific ratio, which describes good grip on ice and wear resistance, and minimal changes in hardness.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2014-218631 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, although the tire grip appears to have been improved in Patent Document 1, it is not sufficient. Furthermore, there is no record of low fuel consumption. From the viewpoint of obtaining a rubber composition with excellent balance of properties, further improvements are expected.

[0011] The present invention was made in view of the above-mentioned problems, and its object is to provide a rubber composition that takes into account a high level of processability, low fuel consumption, wet grip and ice grip.

[0012] Methods for solving problems

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that a rubber composition containing polyphenylene ether with a specific glass transition temperature can solve the problems of the prior art, thereby completing the present invention.

[0014] That is, the present invention is as follows.

[0015] [1] A rubber composition, characterized in that it comprises: Polyphenylene ether (A) with a glass transition temperature above -100°C and below 0°C, as determined by differential scanning calorimetry (DSC); and Diene-based elastomers (B).

[0016] [2] The rubber composition according to [1] is characterized in that, The above-mentioned polyphenylene ether (A) comprises repeating units derived from phenol of formula (1) and repeating units derived from phenol of formula (2). The total percentage of repeating units in formula (1) and formula (2) below is 100 mol%, and the percentage of repeating units derived from phenol in formula (1) below is 31 mol% to 100 mol%, and the percentage of repeating units derived from phenol in formula (2) below is more than 0 mol% and less than 69 mol%.

[0017] [Chemical Formula 1]

[0018] (In equation (1), R) 13 R is a saturated or unsaturated hydrocarbon group with or without substituents and 15 carbon atoms. 11 and R 12 Each of the following is independently a hydrogen atom, a straight-chain saturated hydrocarbon group having 1 to 12 carbon atoms, and any of the substituents shown in formula (3) below.

[0019] [Chemical Formula 2]

[0020] (In equation (3), R) 31 Each independently forms a straight-chain alkyl group with or without substituents, having 1 to 8 carbon atoms, or 2 R groups. 31 The atoms contained therein are bonded together to form cyclic alkyl groups with 1 to 8 carbon atoms, R 32 Each is an alkylene group having 1 to 8 carbon atoms, with or without substituents; b is independently 0 or 1; R 33 It can be a hydrogen atom, an alkyl group with 1 to 8 carbon atoms (with or without substituents), or a phenyl group (with or without substituents).

[0021] [Chemical Formula 3]

[0022] (In equation (2), R) 21 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, with or without substituents, or an aryl or halogen atom with 6 to 12 carbon atoms, with or without substituents. R 22 Each of the following is independently a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms (with or without substituents), or an aryl or halogen atom with 6 to 12 carbon atoms (with or without substituents).

[0023] [3] The rubber composition according to [1] or [2] is characterized in that the viscosity of the polyphenylene ether (A) at 80°C is less than 1 million cP.

[0024] [4] The rubber composition according to any one of [1] to [3] is characterized in that the number average molecular weight of the polyphenylene ether (A) is less than 5500.

[0025] [5] The rubber composition according to any one of [1] to [4] is characterized in that the polyphenylene ether (A) contains a monomer derived from biomass.

[0026] [6] The rubber composition according to any one of [1] to [5] is characterized in that the biomass-derived monomer is CNSL.

[0027] [7] The rubber composition according to any one of [1] to [6] is characterized in that it contains 0.01 to 65 parts by mass of the polyphenylene ether (A) relative to 100 parts by mass of the diene elastomer (B).

[0028] [8] The rubber composition according to any one of [1] to [7] is characterized in that it contains 10 to 115 parts by mass of silicon dioxide relative to 100 parts by mass of the diene elastomer (B).

[0029] [9] A method of using polyphenylene ether, characterized in that a polyphenylene ether having a glass transition temperature of -100°C or higher and less than 0°C as determined by differential scanning calorimetry (DSC) is used as a raw material for a tire composition.

[0030]

[10] A method for manufacturing vulcanized rubber, characterized in that, The method includes: The process of mixing a diene-based elastomer (B) with a polyphenylene ether (A) having a glass transition temperature of -100°C or higher and less than 0°C, as determined by differential scanning calorimetry (DSC), to obtain a rubber composition; and The process of vulcanizing the above rubber composition. The polyphenylene ether (A) has unsaturated hydrocarbon groups in its side chain, and the diene elastomer (B) undergoes a crosslinking reaction with the polyphenylene ether (A).

[0031] Invention Effects

[0032] According to the present invention, a rubber composition that balances processability, low fuel consumption, wet grip and ice grip at a high level can be obtained.

[0033] Furthermore, according to the present invention, a new method of using polyphenylene ether can be provided. Detailed Implementation

[0034] Hereinafter, a detailed description will be given of the method for carrying out the present invention (hereinafter referred to as "this embodiment").

[0035] The following embodiments are illustrative of the present invention. The present invention is not limited to these embodiments and can be implemented by appropriate modifications within the scope of its spirit.

[0036] <Rubber Composition>

[0037] The rubber composition of this embodiment contains polyphenylene ether (A) and diene elastomer (B).

[0038] ((A) Polyphenylene ether)

[0039] The rubber composition of this embodiment contains polyphenylene ether, which is a polyphenylene ether based on DSC with a glass transition temperature of -100°C or higher and less than 0°C.

[0040] The glass transition temperature of the aforementioned polyphenylene ether based on DSC needs to be -100°C or higher, preferably -80°C or higher, and more preferably -50°C or higher. If the glass transition temperature of the aforementioned polyphenylene ether based on DSC is -100°C or higher, the aforementioned properties of the obtained rubber composition are well balanced at a high level.

[0041] Furthermore, the glass transition temperature of the aforementioned polyphenylene ether obtained by DSC is required to be less than 0°C, preferably less than -5°C, and more preferably less than -10°C. When the glass transition temperature of the polyphenylene ether is less than 0°C, the resulting rubber composition exhibits excellent wet grip and ice grip.

[0042] It is speculated that if the glass transition temperature of the polyphenylene ether is within the above range, its compatibility with diene-based elastomers will be higher, and the resulting rubber composition will exhibit the above-mentioned effects.

[0043] Furthermore, the compatibility of the aforementioned polyphenylene ether with the diene-based elastomer can be inferred from the height of the tanδ of the rubber composition of this embodiment. When the compatibility is good, the height of the tanδ of the rubber composition of this embodiment will not be significantly reduced compared to the height of the tanδ of a rubber composition without the aforementioned polyphenylene ether.

[0044] In addition, the above-mentioned polyphenylene ether (A) can be used alone or in combination with two or more types.

[0045] It should be noted that, as a method for adjusting the glass transition temperature based on DSC, the glass transition temperature can be lowered by, for example, by weakening the interactions between polymer chains through molecular design and making the polymer chains more mobile. For example, introducing repeating units with long-chain alkyl groups into polyphenylene ether can lower the glass transition temperature, but it is not limited to this. In addition, by appropriately adjusting the introduction ratio of repeating units with long-chain alkyl groups and the chain length of the long-chain alkyl groups, the glass transition temperature based on DSC can be adjusted.

[0046] Furthermore, there are no particular limitations on the measuring apparatus used for differential scanning calorimetry (DSC), and commercially available apparatus can be used. For example, the TA Instruments DSC250 can be used as the aforementioned differential scanning calorimetry measuring apparatus.

[0047] Furthermore, from the viewpoint of improving the vulcanization reactivity with the rubber composition, the aforementioned polyphenylene ether (A) preferably contains repeating units derived from phenol of the following formula (1). In polyphenylene ethers containing repeating units derived from phenol of the following formula (1), since there are multiple reaction sites on the side chains protruding outward from the main molecular chain, there is less steric hindrance, the frequency of collisions between molecules increases, and therefore high reactivity. By improving vulcanization reactivity, the vulcanization rate can be increased, resulting in improved vulcanization adhesion during retreading, and consequently, excellent oil consumption, wet grip, ice grip, tensile strength, and elongation at break of the rubber composition.

[0048] [Chemical Formula 4]

[0049] In equation (1) above, R 13 R is a saturated or unsaturated hydrocarbon group with or without substituents and 15 carbon atoms. 11 and R 12 Each is independently selected from the group consisting of at least one of the following: a straight-chain saturated hydrocarbon group with 1 to 12 carbon atoms and a substituent shown in formula (3).

[0050] As the preferred R 11 and R 12Each of the following is independently selected from at least one of hydrogen atoms, methyl, ethyl, and substituents represented by formula (3). Further preferred is R. 11 The substituent is shown in formula (3). R is particularly preferred. 11 The substituents shown in equation (3), and R 12 It is a hydrogen atom.

[0051] [Chemical Formula 5]

[0052] (In equation (3), R) 31 Each is independently a straight-chain alkyl group having 1 to 8 carbon atoms, with or without substituents, or with 2 R groups. 31 The atoms contained therein are bonded together to form cyclic alkyl groups with 1 to 8 carbon atoms, R 32 Each is an alkylene group having 1 to 8 carbon atoms, with or without substituents; b is independently 0 or 1; R 33 (The atom is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms with or without substituents, or a phenyl group having or without substituents.)

[0053] Furthermore, the substituents shown in formula (3) above are preferably groups containing secondary and / or tertiary carbons, such as isopropyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, 2,2-dimethylpropyl, cyclohexyl, and groups formed by replacing the hydrogen of the terminal hydrocarbon group with a phenyl group. Tert-butyl and cyclohexyl are more preferred substituents shown in formula (3), and tert-butyl is even more preferred. In addition, the atoms contained therein can bond together to form a cyclic structure.

[0054] Furthermore, in the rubber composition of this embodiment, R in formula (1) above is preferred. 11 It is tert-butyl, and R 12 It is in the form of hydrogen atoms.

[0055] It should be noted that in the above formula (1), R 13 It is a saturated or unsaturated hydrocarbon group with or without substituents, preferably R. 13 By C 15 H 31-2n (n is an independent integer from 0 to 3) represents this.

[0056] Furthermore, from the perspective of the heat resistance of the obtained rubber composition, the above-mentioned polyphenylene ether may include repeating units derived from phenol of formula (2) on the basis of including repeating units derived from phenol of formula (1).

[0057] [Chemical Formula 6]

[0058] (In equation (2), R) 21 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, with or without substituents; an aryl group with 6 to 12 carbon atoms, with or without substituents; or a halogen atom, R. 22 Each of the following is independently a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms (with or without substituents), an aryl group with 6 to 12 carbon atoms (with or without substituents), or a halogen atom.

[0059] In addition, in the above equation (2), R 21 Each of the following groups is preferably a saturated hydrocarbon group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms, more preferably methyl or phenyl, and even more preferably methyl. Furthermore, in formula (2) above, two R groups are preferred. 21 They all have the same structure.

[0060] Furthermore, in equation (2) above, R 22 Each of the two R groups is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group. In formula (2) above, the two R groups are... 22 They can be the same or different.

[0061] As a preferred approach, two Rs can be cited. 22 The arrangement can be either a hydrogen atom or a hydrocarbon group (more preferably methyl) consisting of one hydrogen atom and the other a hydrocarbon group with 1 to 6 carbon atoms.

[0062] It should be noted that in this embodiment, the structure of polyphenylene ether can be identified by analyzing it using methods such as NMR and mass spectrometry.

[0063] As a specific method for identifying the structure of the aforementioned polyphenylene ether, field desorption mass spectrometry (FD-MS), a method known to be less prone to fragmentation, can be performed to estimate repeating units based on the intervals of the detected ions. Furthermore, a method can be employed to estimate the structure of polyphenylene ether by combining electron ionization (EI) with fragment ion peak analysis and NMR-based structural analysis. Additionally, for example, [further methods can be used]. 1 The results were obtained using analytical methods such as H NMR.

[0064] In addition, in the above-mentioned polyphenylene ether (A), the content ratio of the repeating unit derived from phenol of the above formula (1) and the repeating unit derived from phenol of the above formula (2) is preferably 31 mol% or more and 100 mol% or less, relative to the total 100 mol% of the repeating unit derived from phenol of the above formula (1), and the content ratio of the repeating unit derived from phenol of the above formula (2) is more than 0 mol% and 69 mol% or less.

[0065] Furthermore, from the viewpoint of improving the processability, low oil consumption, wet grip, and ice grip of the obtained rubber composition, and balancing the aforementioned properties, the content ratio of the phenol-derived repeating unit of formula (1) is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, relative to a total of 100 mol% of the repeating unit derived from phenol in formula (1) and the repeating unit derived from phenol in formula (2). On the other hand, there is no upper limit to the content ratio of formula (1).

[0066] Furthermore, the content of the repeating unit derived from phenol in formula (2) above can be appropriately selected according to the application. For example, if it is desirable to improve heat resistance, it is preferable to have more repeating units derived from phenol in formula (2) above.

[0067] The total molar ratio of the polyphenylene ether 100 mol% of this embodiment to the repeating unit derived from phenol of formula (1) and the repeating unit derived from phenol of formula (2) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and may also be 100 mol%.

[0068] The molar ratio of the repeating units derived from phenol in formula (1) to the repeating units derived from phenol in formula (2) totaling 100 mol% can be used, for example, as a percentage of the total repeating units derived from phenol in formula (2). 1 H-NMR, 13 The determination can be made using analytical methods such as C-NMR, or more specifically, by methods described in the examples below.

[0069] In addition, the polyphenylene ether (A) described above may contain repeating units derived from phenol of the following formula (4). In this case, since the Tg of the rubber composition can be reduced, wet grip and ice grip can be further improved.

[0070] [Chemical Formula 7]

[0071] In equation (4) above, R 41 R 42 R 43 Each is independently a straight-chain saturated hydrocarbon group having 1 to 12 carbon atoms, and an organic group having 7 to 25 carbon atoms, with or without substituents, having one or more atoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms. R 41 R 42 R 43One or more of them are organic groups with 7 to 25 carbon atoms, having one or more atoms selected from the group consisting of nitrogen, oxygen and sulfur atoms.

[0072] In addition, in equation (4) above, R 41 R 42 R 43 One or more of the organic groups are preferably organic groups with 8 to 20 carbon atoms having sulfur atoms, and more preferably organic groups with 9 to 15 carbon atoms having sulfur atoms.

[0073] Furthermore, the phenol in the above formula (4) is preferably 4,6-bis(octylthiomethyl)o-cresol or 4,6-bis(dodecylthiomethyl)o-cresol.

[0074] In addition, the polyphenylene ether of this embodiment may include repeating units derived from phenol of formula (2) above, in addition to including repeating units derived from phenol of formula (4).

[0075] In the polyphenylene ether of this embodiment, the content ratio of the repeating unit derived from phenol of formula (4) and the repeating unit derived from phenol of formula (2) is preferably 7 to 50 mol% relative to a total of 100 mol%.

[0076] From the viewpoint of the processability of the obtained rubber composition, the content ratio of the phenol-derived repeating unit of formula (4) to the total 100 mol% of the repeating unit derived from phenol of formula (2) is preferably 7 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more.

[0077] Furthermore, from the viewpoint of low oil consumption, wet grip and ice grip of the obtained rubber composition, the content ratio of the phenol-derived repeating unit of formula (4) is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, relative to the total 100 mol% of the repeating unit derived from phenol of formula (4) and the repeating unit derived from phenol of formula (2).

[0078] The total molar ratio of the polyphenylene ether 100 mol% in this embodiment to the phenol-derived repeating unit of formula (4) and the phenol-derived repeating unit of formula (2) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and may also be 100 mol%.

[0079] The polyphenylene ether in this embodiment may have at least one partial structure selected from the group consisting of partial structures of formula (10), formula (11), formula (12), and formula (13).

[0080] [Chemical Formula 8]

[0081] [Chemical Formula 9]

[0082] [Chemical Formula 10]

[0083] (In equation (12), R) 4 It consists of a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms. The aforementioned saturated or unsaturated hydrocarbons can be in R... 4 (Substituents are present in the range of 1 to 10 carbon atoms.)

[0084] [Chemical Formula 11]

[0085] (In equation (13), R) 5 It is a saturated or unsaturated divalent hydrocarbon group with 1 to 10 carbon atoms. The aforementioned saturated or unsaturated divalent hydrocarbons can be in R... 5 The total number of carbon atoms is in the range of 1 to 10, and it has substituents, R 6 It is a saturated or unsaturated hydrocarbon group with 1 to 10 hydrogen atoms or carbon atoms, and the saturated or unsaturated hydrocarbon can be in R 6 (The total number of carbon atoms is in the range of 1 to 10, and it contains substituents.)

[0086] It should be noted that at least one partial structure selected from the group consisting of partial structures of formula (10), partial structures of formula (11), partial structures of formula (12), and partial structures of formula (13) can be introduced through the modification process described later, and can be directly bonded to the oxygen atoms of the hydroxyl groups contained in polyphenylene ether.

[0087] (Viscosity)

[0088] From the perspective of the processability of the obtained rubber composition, the viscosity of the above-mentioned polyphenylene ether (A) at 80°C is preferably less than 1 million cP, more preferably less than 500,000 cP, and even more preferably less than 300,000 cP.

[0089] By adjusting the viscosity to the aforementioned range, the polyphenylene ether melts during the mixing process in the production of the rubber composition, which optimizes the compatibility with the fillers contained in the rubber composition described later, resulting in a rubber composition with excellent low oil consumption, wet grip, ice grip, tensile strength, and elongation. The method for adjusting the viscosity is not particularly limited; for example, it can be adjusted by the molecular weight of the polyphenylene ether (A) or the ratio of repeating units in the polyphenylene ether (A).

[0090] (molecular weight)

[0091] From the perspective of the processability of the obtained rubber composition, the number average molecular weight (Mn) of the above-mentioned polyphenylene ether (A) is preferably less than 5500, more preferably less than 5000, and even more preferably less than 4500.

[0092] By melting polyphenylene ether during the mixing process in the production of rubber compositions, the compatibility with fillers contained in the rubber compositions described later can be optimized, resulting in rubber compositions with excellent low oil consumption, wet grip, ice grip, tensile strength, and elongation.

[0093] (Specific viscosity)

[0094] From the perspective of the processability of the obtained rubber composition, the specific viscosity (ηsp / c) of the above-mentioned polyphenylene ether (A) in a chloroform solution with a concentration of 0.5 g / dL at 30°C, as measured by an Ubbelohde viscometer, is preferably 0.03 to 0.90 dL / g, more preferably 0.05 to 0.60 dL / g.

[0095] By melting polyphenylene ether during the mixing process in the production of rubber compositions, the compatibility with fillers contained in the rubber compositions described later can be optimized, resulting in rubber compositions with excellent low oil consumption, wet grip, ice grip, tensile strength, and elongation.

[0096] (Manufacturing method of polyphenylene ether)

[0097] The polyphenylene ether (A) of this embodiment is obtained, for example, by a method comprising at least the following steps, wherein a monobasic raw material phenol comprising phenol of formula (1) above is subjected to oxidative polymerization. Furthermore, the step of performing the oxidative polymerization is preferably a step of oxidatively polymerizing a raw material phenol comprising phenol of formula (1) above and phenol of formula (2) above.

[0098] Examples of phenols according to formula (1) include 3-pentadecanylphenol, commercially available cashew phenol, modified 3-pentadecanylphenol with a straight-chain saturated hydrocarbon group having 1 to 12 carbon atoms or a substituent shown in formula (3) introduced into it, and modified cashew phenol with a straight-chain saturated hydrocarbon group having 1 to 12 carbon atoms or a substituent shown in formula (3) introduced into it. From the viewpoint of suppressing multibranching and gelation, it is preferable that the substituent introduced into the 3-pentadecanylphenol or commercially available cashew phenol is R. 11 The introduction of tert-butyl or cyclohexyl as bulk substituents into R, or in R 11 With R 12 A methyl group is introduced into both. As a precursor to R... 11 and R 12 Methods for introducing substituents include A) reacting haloalkyl groups in the presence of Lewis acids, and B) reacting isobutylene in the presence of Brønsted acids.

[0099] The phenol in formula (1) can be used alone or in combination of multiple types.

[0100] Examples of phenols that can be represented by formula (2) above include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, and 2-ethyl-6- 2-Chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6-xylylphenol, 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6-dimethyl-3-tert-butylphenol, etc. Among these, 2,6-dimethylphenol, 2,3,6-trimethylphenol, and 2,6-diphenylphenol are particularly preferred due to their low cost and easy availability.

[0101] The phenol in formula (2) above can be used alone or in combination of multiple types.

[0102] Alternatively, polyphenylene ether (A) can be obtained, for example, by a method that includes at least a step of oxidative polymerization of phenol, a monobasic raw material containing phenol of formula (4) above. The step of oxidative polymerization is preferably a step of oxidative polymerization of raw material phenol containing phenol of formula (4) above and phenol of formula (2) above.

[0103] As the phenol in formula (4) above, 4,6-bis(octylthiomethyl)o-cresol and 4,6-bis(dodecylthiomethyl)o-cresol are preferred as commercially available products.

[0104] (Biomass, CNSL)

[0105] From the perspective of reducing the environmental impact of the resulting rubber composition, the aforementioned polyphenylene ether preferably contains monomers derived from biomass. If biomass-derived raw materials are used in even a portion of the rubber composition, the amount of fossil fuel used can be reduced compared to existing technologies.

[0106] Regarding the biomass content in the aforementioned polyphenylene ether, the biomass-derived carbon content can be determined by measuring radioactive carbon (C14). It is known that atmospheric carbon dioxide contains C14 in a certain proportion (105.5 pMC), therefore, plants grown using atmospheric carbon dioxide, such as corn, also contain approximately 105.5 pMC of C14. Furthermore, it is known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 in all carbon atoms in the polyphenylene ether, the proportion of biomass-derived carbon can be calculated.

[0107] Here, "biomass" refers to living organisms, especially plant materials such as wood, bamboo, coconut, and cashew shells; polysaccharides such as cellulose, starch, pullulan, dextrin, oligosaccharides such as sucrose and maltose, monosaccharides such as fructose and glucose, lignin, and hemicellulose. Furthermore, it includes various lignocellulosic materials such as woody waste from the wood and pulp industries, thinning materials, building dismantling materials, straw, bean pods, and bagasse, as well as resource rice, old rice, and food industry waste. Unless otherwise specified, all these substances are referred to as biomass in this specification.

[0108] For example, cashew nut shell liquid (CNSL) can be cited as a phenolic compound derived from biomass.

[0109] Cashews are a naturally occurring tropical plant. The cashew kernel, its fruit, contains protein and carbohydrates, and is used in snacks and dishes, often mixed with other nuts. Cashew kernels are a natural fruit and, when considered as a resource, are a renewable biomass resource.

[0110] The main component of CNSL is cashew phenol, which is an oily liquid contained in the non-edible part of the cashew shell, obtained as a byproduct during the harvesting of natural cashew kernels used for food purposes.

[0111] Natural CNSL is a mixture of cashew acid, cashew phenol, cashew diol and 2-methyl cashew diol, as shown in formulas (2) to (5) below, each component being an organic compound containing a phenolic moiety and a straight-chain hydrocarbon moiety R.

[0112] [Chemical Formula 12]

[0113] The straight-chain hydrocarbon moiety R of each component has any of the structures shown below. That is, there are four possible structures with 0, 1, 2, or 3 unsaturated bonds, and an average of 2 double bonds. R: -(CH2) 14 CH3

[0114] -(CH2)7CH=CH(CH2)5CH3

[0115] -(CH2)7CH=CHCH2CH=CH(CH2)2CH3

[0116] -(CH2)7CH=CHCH2CH=CHCH2CH=CH2

[0117] Each compound shown in formulas (2) to (5) consists of a single compound or two or more compounds with different R values.

[0118] Natural CNSL is mainly composed of cashew acid, as shown in formula (2) above. For industrial use, this natural CNSL undergoes decarbonation treatment, and cashew phenol, as shown in formula (3) above, becomes the main component. The proportions of each component in industrial CNSL vary depending on the origin, but are approximately cashew phenol (3): 70-80% by mass, cashew diol (4): 15-25% by mass, and 2-methyl cashew diol (5): less than 5% by mass. The proportion of cashew phenol can be increased by distilling industrial CNSL.

[0119] In addition, regarding CNSL, which is used as a raw material for manufacturing phenol in this embodiment, a product obtained by pre-hydrogenating (adding hydrogen) the unsaturated bonds of the straight-chain hydrocarbon portion R located on the side chains of each component shown in formulas (2) to (5) above, or a product obtained by chemical modification (modification) can be used.

[0120] In the manufacturing method of polyphenylene ether (A), in the oxidative polymerization step, an aromatic solvent that is a good solvent for polyphenylene ether can be used as the polymerization solvent.

[0121] Here, a good solvent for polyphenylene ether refers to a solvent that can dissolve polyphenylene ether. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including ortho, meta, and para isomers), ethylbenzene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, nitro compounds such as nitrobenzene, and so on.

[0122] As the polymerization catalyst used in this embodiment, a known catalyst system commonly used in the manufacture of polyphenylene ether can be used. Commonly known catalyst systems include those consisting of a transition metal ion with redox capabilities and an amine compound capable of forming a complex with that transition metal ion; examples include catalyst systems consisting of copper compounds and amine compounds, catalyst systems consisting of manganese compounds and amine compounds, and catalyst systems consisting of cobalt compounds and amine compounds. The polymerization reaction proceeds efficiently under slightly alkaline conditions; therefore, a certain amount of base or further amine compounds are sometimes added.

[0123] In this embodiment, the preferred polymerization catalyst is a catalyst that includes copper compounds, halogen compounds and amine compounds as constituent components of the catalyst, and more preferably a catalyst that includes a diamine compound as shown in the following formula (14) as an amine compound.

[0124] [Chemical Formula 13]

[0125] (In equation (14), R) 14 R 15 R 16 R 17 Each alkyl group consists independently of hydrogen atoms and is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, but not all of them are simultaneously hydrogen atoms. R 18 It is a straight-chain alkylene group with 2 to 5 carbon atoms or a methyl-branched alkylene group.

[0126] Examples of copper compounds used as catalyst components are given herein. Preferred copper compounds include monovalent copper compounds, divalent copper compounds, or mixtures thereof. Examples of divalent copper compounds include copper chloride, copper bromide, copper sulfate, and copper nitrate. Examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Particularly preferred metal compounds are cuprous chloride, copper chloride, cuprous bromide, and copper bromide. Furthermore, these copper salts can be synthesized in use from halogens or acids corresponding to oxides (e.g., cuprous oxide), carbonates, hydroxides, etc. A commonly used method is to prepare them by mixing the previously exemplified cuprous oxide with hydrogen halide (or a solution of hydrogen halide).

[0127] Examples of the aforementioned halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. Furthermore, they can be used in the form of aqueous solutions or solutions using suitable solvents. These halogen compounds can be used as components alone or in combination of two or more. Preferred halogen compounds are aqueous solutions of hydrogen chloride and hydrogen bromide.

[0128] The amount of these compounds used is not particularly limited, but relative to the molar number of copper atoms, it is preferably in the range of 2 to 20 times, more preferably in the range of 2 to 15 times, and even more preferably in the range of 2 to 10 times, based on the number of halogen atoms. Relative to 100 moles of phenol compound added in the polymerization reaction, the preferred amount of copper atoms used is in the range of 0.02 to 0.6 moles, more preferably in the range of 0.02 to 0.5 moles, and even more preferably in the range of 0.02 to 0.4 moles.

[0129] Next, examples of diamine compounds that are catalyst components are given. Examples include N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N-diethylethylenediamine, N,N-diethylethylenediamine, N-ethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-N-ethylethylenediamine, N-n-propylethylenediamine, N,N'-n-propylethylenediamine, N-isopropylethylenediamine, N, N'-Isopropylethylenediamine, N-n-Butylethylenediamine, N,N'-n-Butylethylenediamine, N-Isobutylethylenediamine, N,N'-Isobutylethylenediamine, N-tert-Butylethylenediamine, N,N'-tert-Butylethylenediamine, N,N,N'-Tetramethyl-1,3-Diaminopropane, N,N,N'-Trimethyl-1,3-Diaminopropane, N,N'-Dimethyl-1,3-Diaminopropane, N-Methyl-1,3-Diaminopropane, N,N,N',N'-Tetramethyl-1,3-Diamino-1-Methylpropane, N,N,N',N'-Tetramethyl-1,3-Diamino-2-Methylpropane, N,N,N',N'-Tetramethyl-1,4-Diaminobutane, N,N,N',N'-Tetramethyl-1,5-Diaminopentane, etc. In this embodiment, the preferred diamine compound is a diamine compound with 2 or 3 carbon atoms in the alkylene group connected to 2 nitrogen atoms. The amount of these diamine compounds used is not particularly limited, but is preferably in the range of 0.01 to 10 moles relative to 100 moles of phenol compound added in the polymerization reaction, more preferably in the range of 0.01 to 8.0 moles, and even more preferably in the range of 0.01 to 6 moles.

[0130] In this embodiment, the polymerization catalyst may contain primary amines and secondary monoamines. Examples of secondary monoamines include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-tert-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2',6'-dimethylphenyl)ethanolamine, N-(p-chlorophenyl)ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, and diphenylamine.

[0131] In addition, tertiary monoamine compounds may also be included as components of the aforementioned polymerization catalyst. Tertiary monoamine compounds are aliphatic tertiary amines containing alicyclic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyl diethylamine, dimethyl n-butylamine, diethylisopropylamine, and N-methylcyclohexylamine. These tertiary monoamines can be used alone or in combination of two or more. Their usage is not particularly limited, but is preferably 15 moles or less, more preferably 14 moles or less, and even more preferably 13 moles or less, relative to 100 moles of phenol compound added in the polymerization reaction.

[0132] It should be noted that in this embodiment, there are no restrictions on the addition of existing surfactants known to enhance polymerization activity. Examples of such surfactants include, for instance, trioctylmethylammonium chloride, known by trade names such as Aliquat336 and Capriquat. The amount used is preferably no more than 0.1% by mass relative to 100% of the total polymerization reaction mixture.

[0133] In addition to pure oxygen, the oxygen-containing gas used in the polymerization of this embodiment can also be a gas formed by mixing oxygen with inert gases such as nitrogen in any proportion, or air, or a gas formed by mixing air with inert gases such as nitrogen in any proportion. Atmospheric pressure is sufficient within the system during the polymerization reaction, but depressurization or pressurization can be used as needed.

[0134] There is no particular limitation on the polymerization temperature. If it is too low, the reaction is difficult to proceed. In addition, if it is too high, the reaction selectivity may decrease and gel may form. Therefore, the temperature range is 0~60℃, preferably 10~40℃.

[0135] Alternatively, in the above-mentioned method for manufacturing polyphenylene ether (A), polymerization can also be carried out in undesirable solvents such as alcohols.

[0136] In this embodiment, there are no particular limitations on the post-treatment method after the polymerization reaction. Typically, acids such as hydrochloric acid and acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, hypozinogenyltriacetic acid and its salts, are added to the reaction solution to deactivate the catalyst. Furthermore, methods known in the art can be used to remove the byproducts of the diphenols produced by the polymerization of polyphenylene ether. As mentioned above, if the metal ions acting as the catalyst are substantially deactivated, decolorization can be achieved simply by heating the mixture. Alternatively, a method of adding a necessary amount of a known reducing agent can be used. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0137] In the above-described method for manufacturing polyphenylene ether (A), water can be added to extract the compound that deactivates the copper catalyst. After liquid-liquid separation in the organic and aqueous phases, the aqueous phase is removed, thereby removing the copper catalyst from the organic phase. This liquid-liquid separation process is not particularly limited, and methods such as static separation or separation using a centrifuge can be cited. Known surfactants can be used to facilitate this liquid-liquid separation.

[0138] Next, in the above-mentioned method for manufacturing polyphenylene ether (A), the organic phase containing the above-mentioned polyphenylene ether after liquid-liquid separation can be concentrated and dried by evaporating the solvent.

[0139] There are no particular limitations on the method for evaporating the solvent contained in the organic phase. Examples include concentrating the organic phase by distilling off the solvent in a high-temperature concentration tank, or concentrating it by distilling off toluene using a rotary evaporator or similar machine. From the viewpoint of suppressing thermal degradation caused by heating, low-temperature concentration under reduced pressure is more preferred.

[0140] The drying temperature in the drying process is preferably at least 60°C or higher, more preferably at 80°C or higher, and even more preferably at 110°C or higher. Drying polyphenylene ether at a temperature of 60°C or higher can effectively reduce the content of high-boiling-point volatile components in the polyphenylene ether powder. From the viewpoint of preventing heat-induced deterioration, it is preferably below 200°C, more preferably below 180°C, and even more preferably below 160°C.

[0141] To obtain the aforementioned polyphenylene ether with high efficiency, methods such as increasing the drying temperature, increasing the vacuum level in the drying atmosphere, and stirring during drying are effective. From a manufacturing efficiency perspective, methods that increase the drying temperature are particularly preferred. A dryer with a mixing function is preferably used in the drying process. Examples of dryers with agitation or rotary mixing functions include stirred dryers. This increases throughput and maintains higher productivity.

[0142] (Residual solvent)

[0143] From the perspective of reducing the odor of the obtained polyphenylene ether, the total amount of solvent remaining in the above-mentioned polyphenylene ether (A) is preferably less than 1% by mass, more preferably less than 0.6% by mass, even more preferably less than 0.5% by mass, particularly preferably less than 0.3% by mass, and particularly preferably less than 0.1% by mass.

[0144] (Residual metal)

[0145] From the perspective of suppressing the degradation of the obtained polyphenylene ether due to heat, the residual metal catalyst content of the above-mentioned polyphenylene ether (A) is preferably less than 1.0 ppm, more preferably less than 0.5 ppm.

[0146] (Residual amines)

[0147] From the perspective of reducing the odor of the obtained polyphenylene ether, the total amount of amines remaining in the above-mentioned polyphenylene ether (A) is preferably less than 1.0% by mass, more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass. The amine balance mentioned here refers to the amount of amines remaining in the total amount of amines contained in the polyphenylene ether after the drying process, after removing the amines chemically bonded to the polyphenylene ether.

[0148] (Residual monomer)

[0149] From the perspective of reducing the odor of the obtained polyphenylene ether, the residual monomer content of the above-mentioned polyphenylene ether (A) is preferably less than 5% by mass, more preferably less than 4% by mass, and even more preferably less than 3% by mass.

[0150] The aforementioned polyphenylene ether (A) can also be produced by a redistribution reaction in which a polyphenylene ether derived from the phenol of formula (2) is balanced with a phenol compound of formula (1) in the presence of an oxidant. Redistribution reactions are well known in this art, for example, as described in U.S. Patent No. 3,496,236 to Cooper et al. and U.S. Patent No. 5,880,221 to Liska et al.

[0151] It should be noted that there is no limitation on the method of introducing functional groups into the hydroxyl groups of unmodified polyphenylene ether. For example, it can be obtained by reacting the hydroxyl groups of unmodified polyphenylene ether with the ester bond of a carboxylic acid (hereinafter referred to as carboxylic acid) having a carbon-carbon double bond.

[0152] In addition, ester bond formation can be achieved using various known methods. Examples include: a. reaction of carboxylic acid halides with the terminal hydroxyl groups of polymers; b. ester bond formation based on reaction with carboxylic anhydrides; c. direct reaction with carboxylic acids; and d. transesterification.

[0153] The reaction with carboxylic acid halides is one of the most common methods. Chlorides and bromides are commonly used as carboxylic acid halides, but other halogens are also acceptable. The reaction can be either a direct reaction with a hydroxyl group or a reaction with an alkali metal salt of a hydroxyl group. The direct reaction of carboxylic acid halides with hydroxyl groups produces acids such as hydrogen halides; therefore, to capture the acid, weak bases such as amines can coexist.

[0154] In the reactions with carboxylic anhydrides (b) and carboxylic acids (c), it is acceptable to allow compounds such as carbodiimides and dimethylaminopyridine to coexist in order to activate the reaction sites and promote the reaction.

[0155] In the case of transesterification reaction d, it is preferable to remove the generated alcohol as needed. Alternatively, known metal catalysts can be used to promote the reaction. After the reaction, to remove byproducts such as amine salts, washing can be performed with water, acidic or alkaline aqueous solutions. Alternatively, the polymer solution can be added dropwise to a poor solvent such as an alcohol, and the target compound can be recovered by reprecipitation. Alternatively, after washing the polymer solution, the solvent can be removed by distillation under reduced pressure to recover the polymer.

[0156] The method for manufacturing modified polyphenylene ether is not limited to the method for manufacturing multifunctional modified polyphenylene ether described in this embodiment. The order and number of times of the above-mentioned oxidative polymerization process, copper extraction and by-product removal process, liquid-liquid separation process, and concentration / drying process can be appropriately adjusted.

[0157] It should be noted that the substance can also be obtained as follows: after oxidative polymerization of 3-pentadecanylphenol or commercially available cashew phenol and optionally 2,6-dimethylphenol as phenol of formula (2) above, the resulting polyphenylene ether is obtained by introducing at least one partial structure selected from the group consisting of formula (10), formula (11), formula (12) and formula (13) above; in addition, the polyphenylene ether of this embodiment can be obtained by modifying 3-pentadecanylphenol or modified cashew phenol as phenol of formula (1) above, and as any The substance obtained by oxidative polymerization of 2,6-dimethylphenol of the phenol selected in formula (2) above, further exemplified by the polyphenylene ether of this embodiment, can also be a substance obtained by oxidative polymerization of modified 3-pentadecanylphenol or modified cashew phenol as phenol of formula (1) above, and 2,6-dimethylphenol as optional phenol of formula (2) above, and then introducing at least one partial structure selected from the group consisting of formula (10), formula (11), formula (12), and formula (13) above into the resulting polyphenylene ether.

[0158] In addition, by way of example, the polyphenylene ether of this embodiment may also be a substance obtained as follows: after oxidative polymerization of 4,6-bis(octylthiomethyl)o-cresol, 4,6-bis(dodecylthiomethyl)o-cresol, which is phenol of the above formula (4), and 2,6-dimethylphenol, which is optionally phenol of the above formula (2), the resulting polyphenylene ether is introduced with at least one partial structure selected from the group consisting of the above formula (10), the above formula (11), the above formula (12), and the above formula (13).

[0159] (B) Diene-based elastomers)

[0160] Diene elastomer (B) is selected from at least one of synthetic rubber and natural rubber. In addition, one type of synthetic rubber and one type of natural rubber may be used alone, or two or more types may be used in combination.

[0161] It should be noted that the weight-average molecular weight of the diene elastomer (B) in this embodiment is preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 150,000 or more.

[0162] Examples of the aforementioned synthetic rubbers include styrene-butadiene rubber (hereinafter also referred to as "SBR"), butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene-diene rubber, butadiene-acrylonitrile polymer rubber, and chloroprene rubber. Among these, SBR, isoprene rubber, and butadiene rubber are preferred, and SBR and butadiene rubber are more preferred. One type may be used alone, or two or more types may be used in combination.

[0163] It should be noted that the diene-based elastomer in this embodiment does not contain polymer blocks composed solely of vinyl aromatic monomer units.

[0164] Styrene-butadiene rubber (SBR)

[0165] As the aforementioned SBR, a conventional SBR used in tire applications can be used. Specifically, the styrene content is preferably 0.1 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 5 to 50% by mass. In addition, the vinyl content is preferably 0.1 to 80% by mass, more preferably 5 to 70% by mass.

[0166] It should be noted that the vinyl content of SBR in this specification refers to the content of vinyl monomer units among all butadiene units contained in the SBR. Similarly, the vinyl content of the diene elastomer (B) described above refers to the actual content of vinyl monomer units relative to the total amount of vinyl monomer units that can have vinyl according to the bonding morphology.

[0167] The weight-average molecular weight (Mw) of the SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and even more preferably 150,000 to 1,500,000. When the weight-average molecular weight (Mw) of the SBR is within the above range, the processability of the rubber composition is improved, and the ice grip of the tire obtained from the rubber composition is improved, thereby improving mechanical strength, wear resistance, and handling stability. Furthermore, the weight-average molecular weight (Mw) in this specification is a value measured by GPC.

[0168] The glass transition temperature (Tg) of the SBR determined by differential thermal analysis is preferably -95 to 0°C, more preferably -95 to -5°C, even more preferably -95 to -10°C, even more preferably -95 to -15°C, and even more preferably -95 to -20°C. When the glass transition temperature is within the above range, the viscosity of the rubber composition can be suppressed, and the operation becomes easier.

[0169] Furthermore, there are no particular restrictions on the manufacturing method of the SBR mentioned above. Any one of emulsion polymerization, solution polymerization, gas-phase polymerization, or bulk polymerization can be used, with emulsion polymerization and solution polymerization being particularly preferred.

[0170] (i) Emulsion polymerized styrene-butadiene rubber (E-SBR)

[0171] E-SBR can be manufactured by conventional emulsion polymerization, for example, by emulsifying and dispersing a specified amount of styrene and butadiene monomers in the presence of an emulsifier, and then carrying out emulsion polymerization using a free radical polymerization initiator. As an emulsifier, long-chain fatty acid salts or rosin salts with 10 or more carbon atoms are used, for example. Specific examples include potassium or sodium salts of fatty acids such as decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid. Water is typically used as the dispersion medium, and water-soluble organic solvents such as methanol and ethanol may be included, provided they do not impede the stability of the polymerization. Examples of free radical polymerization initiators include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide. Chain transfer agents can also be used to adjust the molecular weight of the resulting E-SBR. Examples of chain transfer agents include thiols such as tert-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride; mercaptoacetic acid; diterpenes; terpinene; γ-terpinene; and α-methylstyrene dimers. The temperature of emulsion polymerization can be appropriately selected according to the type of free radical polymerization initiator used, typically preferably 0~100℃, more preferably 0~60℃. The polymerization method can be either continuous polymerization or batch polymerization. The polymerization reaction can be terminated by adding a polymerization terminator. Examples of polymerization terminators include amine compounds such as isopropyl hydroxylamine, diethyl hydroxylamine, and hydroxylamine; quinone compounds such as hydroquinone and benzoquinone; and sodium nitrite. After the polymerization reaction stops, an anti-aging agent can be added as needed. After the polymerization reaction stops, unreacted monomers are removed from the obtained latex as needed. Then, salts such as sodium chloride, calcium chloride, and potassium chloride are used as coagulants, and acids such as nitric acid and sulfuric acid are added as needed. While adjusting the pH of the coagulation system to a specified value, the polymer is coagulated. Then, the dispersion solvent is separated, thereby recovering the polymer in the form of granules. The granules are washed with water, then dehydrated, and dried using a belt dryer or the like to obtain E-SBR. It should be noted that during solidification, the latex can be premixed with the filler oil used to make the emulsion dispersion as needed, and then recycled in the form of oil-extended rubber.

[0172] (ii) Solution-polymerized styrene-butadiene rubber (S-SBR)

[0173] S-SBR can be manufactured by conventional solution polymerization methods, such as using an active metal capable of anionic polymerization in a solvent, and polymerizing styrene and butadiene in the presence of a polar compound as needed.

[0174] Examples of active metals suitable for anionic polymerization include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide rare earth metals such as lanthanum and neodymium. Alkali metals and alkaline earth metals are preferred, with alkali metals being more preferred. Furthermore, among alkali metals, organoalkali metal compounds are more preferred. Examples of solvents include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents are preferably used in the range of 1 to 50% by mass of the monomer concentration.

[0175] Examples of organoalkali metal compounds include, for instance, monolithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, phenyllithium, and stilbene; multifunctional organolithium compounds such as dilithium methane, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, and 1,3,5-trilithiumbenzene; and sodium naphthalene and potassium naphthalene. Among these, organolithium compounds are preferred, and monolithium compounds are more preferred. The amount of organoalkali metal compound used is appropriately determined based on the required molecular weight of the S-SBR. Organoalkali metal compounds can also react with secondary amines such as dibutylamine, dihexylamine, and dibenzylamine to be used as organoalkali metal amides. As polar compounds, there are no particular restrictions as long as they do not deactivate the reaction in anionic polymerization and are usually used to adjust the microstructure of the butadiene site and the distribution of styrene in the polymer chain. Examples include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.

[0176] The polymerization temperature is typically -80 to 150°C, preferably 0 to 100°C, and more preferably 30 to 90°C. The polymerization can be either batch or continuous. Furthermore, since this increases the random copolymerization of styrene and butadiene, it is preferable to continuously or intermittently supply styrene and butadiene to the reaction solution to maintain a specific styrene-to-butadiene ratio within a certain range in the polymerization system. The polymerization reaction can be terminated by adding alcohols such as methanol or isopropanol as polymerization terminators. Before adding the polymerization terminator, coupling agents such as tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tetraglycidyl-1,3-diaminomethylcyclohexane, and 2,4-toluene diisocyanate, as well as polymerization terminator modifiers such as 4,4'-bis(diethylamino)benzophenone and N-vinylpyrrolidone, which can react with the active polymerization terminator, can be added. After the polymerization reaction is stopped, the polymerization solution can be separated by direct drying, stripping, or other solvent separation methods to recover the target S-SBR. It should be noted that the polymerization solution can be premixed with filler oil before removing the solvent, and then recycled in the form of oil-extended rubber.

[0177] (iii) Modified styrene-butadiene rubber (modified SBR)

[0178] Alternatively, in this embodiment, a modified SBR in which functional groups are introduced can also be used. Examples of functional groups include amino, alkoxysilyl, hydroxyl, epoxy, and carboxyl groups. Examples of methods for manufacturing the modified SBR include adding coupling agents such as tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-diaminomethylcyclohexane, and 2,4-toluene diisocyanate, polymerization terminator modifiers such as 4,4'-bis(diethylamino)benzophenone and N-vinylpyrrolidone, or other modifiers described in Japanese Patent Application Publication No. 2011-132298. In this modified SBR, the location of the polymer in which the functional groups are introduced can be either the polymerization terminus or a side chain of the polymer chain.

[0179] Isoprene rubber

[0180] As the aforementioned isoprene rubber, for example, Ziegler-based catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel can be used; lanthanide rare earth metal catalysts such as triethylaluminum-neodymium organic acid-Lewis acid can be used; or commercially available isoprene rubber polymerized using organoalkali metal compounds, similar to S-SBR. Isoprene rubber polymerized using Ziegler-based catalysts has a high cis content and is therefore preferred. Alternatively, isoprene rubber with an ultra-high cis content obtained using lanthanide rare earth metal catalysts can also be used.

[0181] The vinyl content of the aforementioned isoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. When the vinyl content exceeds 50% by mass, the low oil consumption tends to deteriorate. There is no particular limitation on the lower limit of the vinyl content. Furthermore, the glass transition temperature varies depending on the vinyl content, and is preferably -20°C or less, more preferably -30°C or less. The weight-average molecular weight (Mw) of the isoprene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When the weight-average molecular weight of the isoprene rubber is within the above range, the processability of the rubber composition is improved, and the ice grip is improved, thereby improving the handling stability. A portion of the isoprene rubber may have a branched structure or polar functional groups formed by using a multifunctional modifier, such as tin tetrachloride, silicon tetrachloride, alkoxysilanes with intramolecular epoxy groups, or alkoxysilanes containing amino groups.

[0182] Butadiene rubber

[0183] As butadiene rubber, Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel can be used; lanthanide rare earth metal catalysts such as triethylaluminum-neodymium organic acid-Lewis acid can be used; or commercially available butadiene rubber polymerized using organoalkali metal compounds, similar to S-SBR. Butadiene rubber polymerized using Ziegler catalysts is preferred for its high cis content. Alternatively, butadiene rubber with an ultra-high cis content (e.g., cis content of 95% or more) obtained using lanthanide rare earth metal catalysts can also be used. The vinyl content of the butadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. When the vinyl content exceeds 50% by mass, there is a tendency for low fuel consumption performance to deteriorate. The lower limit of the vinyl content is not particularly limited. Furthermore, the glass transition temperature varies depending on the vinyl content, and is preferably -40°C or less, more preferably -50°C or less.

[0184] The weight-average molecular weight (Mw) of the aforementioned butadiene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When the weight-average molecular weight (Mw) of the butadiene rubber is within the above range, the processability of the rubber composition is improved, and the grip on ice and handling stability are also improved. A portion of the butadiene rubber may have a branched structure or polar functional groups formed by using a multifunctional modifier, such as tin tetrachloride, silicon tetrachloride, alkoxysilanes with intramolecular epoxy groups, or alkoxysilanes containing amino groups. It can be used with at least one of SBR, isoprene rubber, and butadiene rubber, or one or more of butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, butadiene acrylonitrile polymer rubber, chloroprene rubber, etc. Furthermore, their manufacturing methods are not particularly limited, and commercially available products can be used.

[0185] Natural rubber

[0186] Natural rubber used in the aforementioned diene-based elastomers (B) can include, for example, SMR, SIR, STR, and other natural rubbers commonly used in the tire industry such as TSR and RSS, high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, and grafted natural rubber. Among these, SMR20, STR20, and RSS#3 are preferred due to their lower quality deviations and ease of acquisition. They can be used individually or in combination of two or more.

[0187] Furthermore, from the viewpoint of processability, low oil consumption, wet grip, and ice grip of the obtained rubber composition, it is preferable to contain 0.01 to 65 parts by mass of the polyphenylene ether (A) relative to 100 parts by mass of the diene elastomer (B), more preferably 0.01 to 60 parts by mass, and even more preferably 0.01 to 55 parts by mass. It should be noted that rubber compositions containing more than 65 parts by mass of the polyphenylene ether (A) relative to 100 parts by mass of the diene elastomer (B) tend to have poor low oil consumption, poor wet grip, and poor ice grip.

[0188] (Other ingredients)

[0189] Provided that the effects of the present invention are not compromised, the rubber composition of this embodiment may also contain fillers, silane coupling agents, vulcanizing agents, vulcanization accelerators, vulcanization aids and other components in addition to the polyphenylene ether and diene elastomers described above.

[0190] As for the filler mentioned above, there are no particular restrictions as long as it is a filler commonly used in rubber compositions. From the viewpoint of improving the dispersibility of the filler in the rubber composition, improving low oil consumption performance and grip, it is preferable to contain at least one selected from silica and carbon black.

[0191] ·Silicon oxide

[0192] Examples of silica include wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, and aluminum silicate. From the viewpoint of further improving the low oil consumption and grip of the rubber composition, wet silica is preferred. One type can be used alone, or two or more types can be used in combination.

[0193] Furthermore, from the viewpoint of improving the processability, low oil consumption, molding processability, abrasion resistance, and grip of the rubber composition, the average particle size of the aforementioned silica is preferably 0.5 nm or more, more preferably 2 nm or more, further preferably 5 nm or more, even more preferably 8 nm or more, even more preferably 10 nm or more, and preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, even more preferably 50 nm or less, even more preferably 30 nm or less, and even more preferably 20 nm or less. It should be noted that the average particle size of the silica can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating their average value.

[0194] Carbon black

[0195] As the aforementioned carbon black, examples include furnace black, channel black, thermal cracking black, acetylene black, and Ketjen black. Among these, furnace black is preferred from the viewpoint of improving the low oil consumption performance and grip of the rubber composition.

[0196] Commercially available furnace blacks that can be used in this embodiment include, for example, "DIABLACK" manufactured by Mitsubishi Chemical Corporation and "SEAST" manufactured by Tokai Carbon Co., Ltd. Commercially available acetylene blacks include, for example, "DENKA BLACK" manufactured by Denki Kagaku Kogyo Co., Ltd. Commercially available Ketjen blacks include, for example, "ECP600JD" manufactured by Lion Corporation.

[0197] Furthermore, from the viewpoint of improving the low oil consumption performance, molding processability, abrasion resistance, and grip of the rubber composition, the average particle size of the carbon black is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, and preferably 100 nm or less, more preferably 80 nm or less, even more preferably 70 nm or less, and even more preferably 60 nm or less. It should be noted that the average particle size of the carbon black can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating their average value. The particle size of the carbon black can be adjusted by pulverization, etc. Pulverization of carbon black can be performed using high-speed rotary mills (hammer mills, pin mills, cage mills), various ball mills (roller mills, vibratory mills, planetary mills), stirred mills (bead mills, grinding mills, flow-through mills, annular mills), etc.

[0198] From the viewpoint of improving the wettability and dispersibility of polyphenylene ether (A) and diene elastomer (B), carbon black can be subjected to acid treatment using nitric acid, sulfuric acid, hydrochloric acid, or mixtures thereof, or surface oxidation treatment using heat treatment in the presence of air. Furthermore, from the viewpoint of improving mechanical strength, in the present invention, heat treatment can be performed at 2,000 to 3,000 °C in the presence of a graphitization catalyst. It should be noted that, as the graphitization catalyst, boron, boron oxides (e.g., B₂O₂, B₂O₃, B₄O₃, B₄O₅, etc.), boron oxyacids (e.g., orthoboric acid, metaboric acid, tetraboric acid, etc.) and their salts, boron carbides (e.g., B₄C, B₆C, etc.), boron nitride (BN), and other boron compounds are preferably used.

[0199] Other fillers

[0200] In this invention, fillers other than silica and carbon black may be included to improve the mechanical strength of the rubber composition and to reduce manufacturing costs by incorporating fillers as extenders. Examples of fillers other than silica and carbon black include organic fillers, clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium dioxide, glass fiber, fibrous fillers, and inorganic fillers such as glass beads. These fillers may be used individually or in combination of two or more.

[0201] Furthermore, when the aforementioned filler is incorporated into the rubber composition of this embodiment, the content of the filler relative to 100 parts by weight of the diene elastomer (B) is preferably 20 to 150 parts by weight. When the amount of filler is within the aforementioned range, the low oil consumption performance, molding processability, abrasion resistance, and grip of the rubber composition can be further improved. From the same viewpoint, the content of the filler relative to 100 parts by weight of the diene elastomer (B) is preferably 30 parts by weight or more, more preferably 40 parts by weight or more, further preferably 45 parts by weight or more, even more preferably 50 parts by weight or more, even more preferably 55 parts by weight or more, even more preferably 60 parts by weight or more, even more preferably 65 parts by weight or more, and preferably 120 parts by weight or less, more preferably 100 parts by weight or less, even more preferably 90 parts by weight or less, even more preferably 85 parts by weight or less, even more preferably 80 parts by weight or less, and even more preferably 75 parts by weight or less.

[0202] Furthermore, when using silica as the filler, from the viewpoint of improving the low fuel consumption performance and ice grip of tires that partially use tire tread rubber compositions, the content of silica relative to 100 parts by mass of the diene elastomer (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and preferably 115 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, and even more preferably 65 parts by mass or less.

[0203] Furthermore, when carbon black is used as the filler, from the viewpoint of improving the low oil consumption performance, abrasion resistance and grip of the rubber composition, the content of carbon black relative to 100 parts by weight of the diene elastomer (B) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, even more preferably 15 parts by weight or more, even more preferably 20 parts by weight or more, even more preferably 25 parts by weight or more, even more preferably 30 parts by weight or more, and preferably 75 parts by weight or less, more preferably 65 parts by weight or less, even more preferably 55 parts by weight or less, even more preferably 45 parts by weight or less, even more preferably 40 parts by weight or less, and even more preferably 35 parts by weight or less.

[0204] ·Silane coupling agent

[0205] The rubber composition of this embodiment may further contain a silane coupling agent. Examples of silane coupling agents include thioether compounds, mercapto compounds, vinyl compounds, amino compounds, epoxypropoxy compounds, nitro compounds, and chlorine compounds.

[0206] Examples of the aforementioned thioether compounds include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, and 3-trimethoxysilylpropyl-N. N-Dimethylthiocarbamoyl tetrasulfide, 3-Triethoxysilylpropyl-N,N-Dimethylthiocarbamoyl tetrasulfide, 2-Trimethoxysilylethyl-N,N-Dimethylthiocarbamoyl tetrasulfide, 3-Trimethoxysilylpropylbenzothiazole tetrasulfide, 3-Triethoxysilylpropylbenzothiazole tetrasulfide, 3-Triethoxysilylpropyl methacrylate monosulfide, 3-Trimethoxysilylpropyl methacrylate monosulfide, etc.

[0207] Examples of the aforementioned thiol compounds include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.

[0208] Examples of the aforementioned vinyl compounds include vinyltriethoxysilane and vinyltrimethoxysilane.

[0209] Examples of the aforementioned amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0210] Examples of the aforementioned epoxypropoxy compounds include γ-epoxypropoxypropyltriethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, and γ-epoxypropoxypropylmethyldimethoxysilane.

[0211] Examples of the aforementioned nitro compounds include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.

[0212] Examples of the aforementioned chlorinated compounds include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.

[0213] It should be noted that these silane coupling agents can be used alone or in combination of two or more. From the perspective of maximizing the reinforcing effect, sulfur-containing silane coupling agents such as thioether compounds and mercapto compounds are preferred.

[0214] Furthermore, when the rubber composition of this embodiment contains a silane coupling agent, its content relative to 100 parts by weight of the diene elastomer (B) is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 15 parts by weight. When the amount of silane coupling agent is within the above range, the abrasion resistance of the rubber composition is improved.

[0215] Vulcanizing agent

[0216] The rubber composition of this embodiment preferably contains a vulcanizing agent. Examples of vulcanizing agents include sulfur and sulfur compounds. They can be used alone or in combination of two or more.

[0217] When the rubber composition of this embodiment contains a vulcanizing agent, its content relative to 100 parts by weight of the diene elastomer (B) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 0.8 to 5 parts by weight.

[0218] • Vulcanization accelerator

[0219] The rubber composition of this embodiment may contain a vulcanization accelerator. Examples of vulcanization accelerators include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamate compounds, aldehyde-amine compounds, aldehyde-amine compounds, imidazoline compounds, and xanthate compounds. One or more of these compounds may be used alone or in combination.

[0220] When the rubber composition of this embodiment contains a vulcanization accelerator, its content is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the diene elastomer (B), and more preferably 0.1 to 10 parts by mass.

[0221] Vulcanizing aids

[0222] The rubber composition of this embodiment may contain a vulcanizing aid. Examples of such vulcanizing aids include fatty acids such as stearic acid, metal oxides such as zinc oxide, and fatty acid metal salts such as zinc stearate. One or more of these aids may be used individually or in combination.

[0223] When the rubber composition of this embodiment contains a vulcanizing aid, its content is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the diene elastomer (B) described above.

[0224] ·other

[0225] To improve processability and flowability, rubber compositions may contain, as needed, processing oils such as silicone oil, aromatic oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (Residual Aromatic Extracts), paraffin oil, and naphthenic oil; resin components such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 series resins, rosin-based resins, coumarone-indene series resins, and phenolic resins; and liquid polymers such as low molecular weight polybutadiene, low molecular weight polyisoprene, low molecular weight styrene-butadiene polymers, and low molecular weight styrene-isoprene polymers as softeners.

[0226] When the above-mentioned processing oil, resin components, and liquid polymer are used as softeners, from the viewpoint of bleed resistance, their content relative to 100 parts by weight of the above-mentioned diene elastomer (B) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 15 parts by weight or less.

[0227] Furthermore, in order to improve weather resistance, heat resistance, and oxidation resistance, the rubber composition of this embodiment may contain one or more additives such as anti-aging agents, antioxidants, waxes, lubricants, light stabilizers, anti-scorching agents, processing aids, pigments, colorants, flame retardants, antistatic agents, matting agents, anti-blocking agents, ultraviolet absorbers, release agents, foaming agents, antibacterial agents, mildew inhibitors, and fragrances.

[0228] Examples of such antioxidants include hindered phenolic compounds, phosphorus compounds, lactone compounds, and hydroxyl compounds.

[0229] Examples of anti-aging agents include amine-ketone compounds, imidazole compounds, amine compounds, phenolic compounds, sulfur compounds, and phosphorus compounds.

[0230] It should be noted that the rubber composition of this embodiment may contain a crosslinking agent in addition to the vulcanizing agent. Examples of crosslinking agents include oxygen, organic peroxides, phenolic resins, amino resins, quinones and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides, organometallic halides, and silane compounds. One or more of these agents may be used alone or in combination. The amount of crosslinking agent is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the diene elastomer (B).

[0231] <Method for manufacturing rubber composition for tire tread>

[0232] There are no limitations on the method for manufacturing rubber compositions for tire treads, as long as the above-mentioned components can be mixed uniformly. Examples of methods for uniform mixing include kneaders, Brabender plasticizers, Banbury internal mixers, tangential or interlocking closed mixers such as internal mixers, single-screw extruders, twin-screw extruders, mixing rollers, and rollers, which can generally be carried out in a temperature range of 30 to 270°C.

[0233] The preferred tire tread rubber composition is used as a vulcanized rubber by vulcanization. There are no particular restrictions on the vulcanization conditions and methods, but it is preferred to use a vulcanization mold and carry out the vulcanization at a vulcanization temperature of 120~200°C and a vulcanization pressure of 0.5~20MPa.

[0234] Polyphenylene ether (A) containing repeating units derived from phenol of the above formula (1) has multiple reaction sites with diene elastomer (B) during vulcanization on the side chains that protrude outward from the main molecular chain. Therefore, there is less steric hindrance and the frequency of collisions between molecules is higher, resulting in high crosslinking reactivity.

[0235] <Instructions for using polyphenylene ether>

[0236] In the method of using polyphenylene ether in this embodiment, polyphenylene ether with a glass transition temperature of -100°C or higher and less than 0°C, as determined by differential scanning calorimetry (DSC), is used as a raw material for the tire composition.

[0237] As described above, by using polyphenylene ether with a glass transition temperature of -100°C or higher and less than 0°C as determined by differential scanning calorimetry (DSC) in the rubber composition, a rubber composition that balances processability, low oil consumption, wet grip and ice grip at a high level can be obtained.

[0238] It should be noted that the composition of the polyphenylene ether described above is the same as that described in the rubber composition of the present invention.

[0239] The rubber composition of this embodiment is preferably used in automotive parts, and more preferably in tire components.

[0240] Specifically, it can be suitable for at least one component among the following: tread portion, sidewall portion, shoulder portion, carcass portion, belt layer portion, bead portion, rim buffer portion, run-flat reinforcing liner portion, and other reinforcing rubber portions. When the rubber composition of this embodiment is used, for example, in the tread of a tire, it can be extruded into the shape of the tire tread portion in an uncured stage, and then bonded on a tire forming machine using conventional methods to form an uncured tire. Then, the uncured tire is heated and pressurized in a vulcanizing machine to obtain a tire. Furthermore, in this embodiment, "tire" refers to a pneumatic tire, which can be used in passenger cars, trucks, buses, heavy machinery, etc.

[0241]

Example

[0242] The following describes this embodiment in more detail based on the examples, but this embodiment is not limited to the following examples.

[0243] The following describes the methods for determining the various properties of polyphenylene ether.

[0244] (1) Number-average molecular weight and weight-average molecular weight of polyphenylene ether

[0245] As the measuring apparatus, gel permeation chromatography (LC-2030C Plus, manufactured by Shimadzu Corporation) was used. A standard curve was prepared using standard polystyrene and ethylbenzene, and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the obtained modified polyphenylene ether were determined using this standard curve. Polystyrene with molecular weights of 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, and 550 was used as the standard.

[0246] The column used was a K-805L column manufactured by Showa Denko Corporation connected in series. Chloroform was used as the solvent, with a flow rate of 1.0 mL / min and a column temperature of 40°C. A 1 g / L chloroform solution of polyphenylene ether was prepared as the sample for testing. The UV wavelength of the detection section was 254 nm for standard polystyrene and 283 nm for polyphenylene ether. Based on the above measurement data, the number-average molecular weight and weight-average molecular weight were calculated from the proportion of peak areas on the curve representing the molecular weight distribution obtained by GPC.

[0247] (2) Determination of glass transition temperature

[0248] The glass transition temperature of polyphenylene oxide (PPE) was determined using a differential scanning calorimeter (DSC250, TA Instruments). Under a nitrogen atmosphere, the PPE was heated from -120°C to 250°C at a heating rate of 10°C per minute, then cooled back to -120°C at a cooling rate of 20°C per minute. The glass transition temperature was then measured again at a heating rate of 10°C per minute.

[0249] (3) Viscosity determination at 80℃

[0250] The viscosity of polyphenylene ether at 80°C was measured using an EMS viscometer (EMS-1000S, manufactured by Kyoto Electronics Industry Co., Ltd.), with a Φ4.7mm spherical probe, a motor speed of 1,000 rpm, and a measurement time of 5 minutes. The following parameters were used for interpretation.

[0251] ○: Viscosity at 80℃ is less than 500,000 cP

[0252] △: Viscosity at 80℃ is above 500,000 cP and less than 1,000,000 cP

[0253] ×: Viscosity at 80℃ is above 1 million cP or not melted

[0254] (4) Determination of residual solvent content (PPE-4)

[0255] 1 g of polyphenylene ether was dissolved in 5 g of chloroform and then solidified with 5 g of methanol. The amount of residual solvent in 1 μL of the solution after the solid components were removed was determined by gas chromatography (manufactured by Shimadzu Corporation: GC-2010 Plus).

[0256] (5) Determination of remaining catalyst amount (PPE-4)

[0257] 30g of n-butanol was added to 3g of polyphenylene ether to disperse the polyphenylene ether. Then, 30g of toluene was added to dissolve the polyphenylene ether. 10g of 1N-HCl was added, and the mixture was stirred vigorously at 40°C for 10 minutes. After standing, the aqueous layer was recovered. Another 10g of 1N-HCl was added to the organic layer, and the mixture was stirred vigorously at 40°C for another 10 minutes. After standing, the aqueous layer was recovered. The two aqueous layers were combined, their weights were measured, and the residual copper content was determined using an atomic absorption spectrophotometer (Shimadzu Corporation AA-7800).

[0258] (6) Determination of residual amine content (PPE-4)

[0259] 1 g of polyphenylene ether was dissolved in 5 g of chloroform and then solidified with 5 g of methanol. The residual amine content was determined by gas chromatography (GC-2010 Plus, manufactured by Shimadzu Corporation) of 1 μL after the solid components were removed.

[0260] (7) Determination of residual monomer content (PPE-4)

[0261] 0.5 g of polyphenylene ether was diluted to 10 ml with chloroform and then solidified with 10 ml of acetonitrile. The solution containing the solid component was then used. High-performance liquid chromatography (HPLC) (Extrema, Nippon Spectrophotometry Co., Ltd.) was used as the analytical apparatus. A Waters XBridge BEH C18 column (130 Å, 5 μm, 4.6 mm x 150 mm, 1 / pk) was used. The mobile phase was 0.1 vol% formic acid-acetonitrile, with a solvent flow rate of 0.5 ml / min, and the column temperature was 40 °C. The UV wavelength of the detection unit was 280 nm. Based on the above measurement data, the residual monomer amount was calculated from the peak area obtained by HPLC.

[0262] Synthesis of Polyphenylene Ethers (PPE-1~PPE9)

[0263] In the various examples and comparative examples described below, the polyphenylene ethers (PPE-1 to PPE9) obtained below were used.

[0264] (Synthesis of modified cashew nut shell extract)

[0265] Cashew nut shell hydrate (trade name NX-2026, manufactured by Cardolite, 345 g) obtained from CNSL and p-toluenesulfonic acid monohydrate (5.9 g) were added sequentially to a 1 L flask connected to a Dewar condenser at -10 °C, and stirred with a stirrer blade. The external temperature was then set to 80 °C using an aluminum block heating device. Isobutylene (100 g) was slowly introduced over 10 hours. The isobutylene supply was stopped, and stirring continued at 80 °C for 15 hours. The reaction solution temperature was lowered to 40 °C, and toluene (300 g) was added. A 5% sodium hydroxide aqueous solution (27 g) was further added dropwise. Ion-exchanged water (320 g) was added, and the reaction solution temperature was raised to 70 °C. After stirring for 30 minutes, the organic layer was recovered using a separatory funnel. Ion-exchanged water (760 g) was added to the recovered organic layer, and the reaction solution temperature was raised to 70 °C. After stirring for 30 minutes, the mixture was allowed to stand. The organic layer was recovered using a separatory funnel. The organic layer obtained after washing was concentrated using a rotary evaporator to obtain a pale yellow oily modified cashew phenol (370g).

[0266] The structure of the obtained compound was identified. 1 The H-NMR was performed. The results showed that cashew phenol with a tert-butyl group introduced at the 2-position was the main component in the cashew phenol raw material before the reaction.

[0267] Cashew phenol raw material: 1H-NMR(CDCl3) δ7.15-7.10(m, 1H), 6.78-6.73(m, 1H), 6.68-6.62(m, 2H), 5.88-5.77(m, 0.37H), 5.50-5.29(m, 3.44H), 5.10-4.95(m, 0.80H),4.81-4.64(m, 1H), 2.88-2.75(m, 2.14H), 2.55(t, 2.13H), 2.08-1.98(m, 3.31H),1.69-1.53(m, 3.15H), 1.51-1.12(m, 14.10H), 0.94-0.85(m, 1.95H)

[0268] Modified cashew phenol (product): 1 H-NMR(CDCl3) δ7.16(d, 1H), 6.69(dd, 1H), 6.49(d,1H), 5.88-5.77(m, 0.39H), 5.50-5.29(m, 3.56H), 5.10-4.95(m, 0.80H), 4.64(s,1H), 2.87-2.75(m, 2.12H), 2.56-2.46(m, 2.22H), 2.12-1.95(m, 3.60), 1.65-1.53(m, 2.62H), 1.43-1.24(m, 23.42H), 0.96-0.80(m, 2.20H)

[0269] (Synthesis of polyphenylene ether 1 (PPE-1))

[0270] In a 1.5-liter jacketed reactor equipped with a nitrogen inlet at the top, an oxygen-containing gas inlet at the bottom, stirring turbine blades and baffles, and a reflux cooler on the exhaust line at the top, nitrogen was introduced at a rate of 1.24 L / min. Simultaneously, a pre-prepared mixture of 0.064 g of cuprous oxide and 0.482 g of 47% hydrogen bromide, 0.154 g of N,N'-di-tert-butylethylenediamine, 2.28 g of dimethyl-n-butylamine, 0.748 g of di-n-butylamine, 80.0 g of modified cashew nut shell powder, 0.05 g of methyltri-n-octylammonium chloride, and 716 g of toluene were added. Then, air was introduced into the reactor through the nozzle at a rate of 0.84 L / min while vigorous stirring. The polymerization temperature was maintained at 35°C by regulating the heat transfer medium through the jacket. 120 minutes after the initial air introduction, the air supply was stopped, and the reactor was purged with nitrogen. Then, 0.689 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (a reagent prepared by Tongjin Chemical Research Institute) was added as an aqueous solution (80.0 g of water). The mixture was heated to 70°C and copper extraction was performed at 70°C for 2 hours. The mixture was then separated by static separation into a polyphenylene ether solution (organic phase) and an aqueous phase containing the transferred catalyst metal. The solvent in the organic phase was removed using a rotary evaporator.

[0271] The obtained liquid polyphenylene ether was subjected to various determinations using the methods described above. The analytical results are shown in Table 1.

[0272] (Synthesis of polyphenylene ether 2 (PPE-2))

[0273] In a 1.5-liter jacketed reactor equipped with a nitrogen inlet at the top, an oxygen-containing gas inlet at the bottom, stirring turbine blades and baffles, and a reflux cooler on the exhaust line at the top, nitrogen was introduced at a rate of 1.24 L / min. Simultaneously, a pre-prepared mixture of 0.074 g of cuprous oxide and 0.555 g of 47% hydrogen bromide, 0.178 g of N,N'-di-tert-butylethylenediamine, 2.62 g of dimethyl-n-butylamine, 0.861 g of di-n-butylamine, 6.31 g of 2,6-dimethylphenol, 73.7 g of modified cashew phenol, 0.05 g of methyltri-n-octylammonium chloride, and 716 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the nozzle while vigorous stirring. The polymerization temperature was maintained at 35°C by regulating the heat transfer medium through the jacket. 120 minutes after the initial air introduction, the air supply was stopped, and the reactor was purged with nitrogen. Then, 0.794 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (a reagent prepared by Tongjin Chemical Research Institute) was added as an aqueous solution (80.0 g water). The mixture was heated to 70°C and copper extraction was performed at 70°C for 2 hours. The mixture was then separated by static separation into a polyphenylene ether solution (organic phase) and an aqueous phase containing the transferred catalyst metal. The solvent in the organic phase was removed using a rotary evaporator.

[0274] The obtained liquid polyphenylene ether was subjected to various determinations using the methods described above. The analytical results are shown in Table 1.

[0275] (Synthesis of polyphenylene ether 3 (PPE-3))

[0276] A 1.0-liter jacketed reactor, equipped with a nitrogen inlet at the top, an oxygen-containing gas inlet nozzle at the bottom, stirring turbine blades and baffles, and a reflux cooler on the exhaust line at the top, was filled with nitrogen at a rate of 1.16 L / min. Simultaneously, a pre-prepared mixture of 0.068 g of cuprous oxide and 0.511 g of 47% hydrogen bromide, 0.164 g of N,N'-di-tert-butylethylenediamine, 2.41 g of dimethyl-n-butylamine, 0.793 g of di-n-butylamine, 43.8 g of 2,6-dimethylphenol, 31.2 g of 4,6-bis(octylthiomethyl)-o-cresol, 0.05 g of methyltri-n-octylammonium chloride, and 421 g of toluene were added. Then, while vigorously stirring, air was introduced into the reactor through the nozzle at a rate of 0.79 L / min. The polymerization temperature was regulated by passing a heat medium through a jacket to maintain a temperature of 40°C. After 120 minutes of initial air introduction, air supply was stopped, and the reactor was purged with nitrogen. Then, 0.73 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (a reagent prepared by Tongjin Chemical Research Institute) was added as an aqueous solution of 50.0 g of water. The mixture was heated to 70°C and copper extraction was performed at 70°C for 2 hours. The mixture was then separated by static separation into a polyphenylene ether solution (organic phase) and an aqueous phase containing the transferred catalyst metal. The solvent in the organic phase was removed using a rotary evaporator.

[0277] The obtained liquid polyphenylene ether was subjected to various determinations using the methods described above. The analytical results are shown in Table 1.

[0278] (Synthesis of polyphenylene ether 4 (PPE-4))

[0279] Liquid polyphenylene ether was obtained under the same conditions as in Manufacturing Example 3, except that 10.2 g of 2,6-dimethylphenol and 69.8 g of modified cashew phenol were used.

[0280] The obtained liquid polyphenylene ether was subjected to various determinations using the above method. The analytical results are shown in Table 1. Additionally, the residual solvent content was 0.084% by mass, the residual catalyst content was 0.02 ppm, the residual amine content was 300 ppm, and the residual monomer content was 1.5% by mass.

[0281] (Synthesis of polyphenylene ether 5 (PPE-5))

[0282] Liquid polyphenylene ether was obtained under the same conditions as in Manufacturing Example 3, except that 27.1 g of 2,6-dimethylphenol and 52.9 g of modified cashew phenol were used.

[0283] The obtained liquid polyphenylene ether was subjected to various determinations using the methods described above. The analytical results are shown in Table 1.

[0284] (Synthesis of polyphenylene ether 6 (PPE-6))

[0285] Except for using 80.0 g of 2,6-dimethylphenol, polyphenylene ether in a dry state was obtained in the same manner as in Manufacturing Example 6.

[0286] The obtained polyphenylene ether was subjected to various determinations using the methods described above. The analytical results are shown in Table 1.

[0287] (Synthesis of polyphenylene ether 7 (PPE-7))

[0288] Poly(2,6-dimethyl-1,4-phenylene ether): Noryl TM SA120 (manufactured by Sabic), number average molecular weight (Mn) = 2350 g / mol

[0289] (Synthesis of polyphenylene ether 8 (PPE-8))

[0290] Poly(2,6-dimethyl-1,4-phenylene ether): Xyron TM S201A (manufactured by Asahi Kasei Corporation), number average molecular weight (Mn) = 19000 g / mol

[0291] (Synthesis of polyphenylene ether 9 (PPE-9))

[0292] Poly(2,6-dimethyl-1,4-phenylene ether): Noryl TM SA90 (manufactured by Sabic), number average molecular weight (Mn) = 1800 g / mol

[0293] (Synthesis of polyphenylene ether 10 (PPE-10))

[0294] 1kg of Noryl TM SA120 (PPE, manufactured by Sabic) was mixed with 3 kg of toluene at 60 °C. The mixture was stirred until the PPE was completely dissolved. Then, 20 kg of methanol was added, and the mixture was stirred for 30 minutes to homogenize. The suspension was cooled to room temperature, and the precipitate was separated from the supernatant to remove the solvent. The recovered product powder had a Mn content of 950 g / mol.

[0295] (Synthesis of polyphenylene ether 11 (PPE-11))

[0296] 1kg of Noryl TM SA90 (PPE, manufactured by Sabic) was mixed with 3 kg of toluene at 60 °C. The mixture was stirred until the PPE was completely dissolved. Then, 42.8 kg of methanol was added, and the mixture was stirred for 30 minutes to homogenize. The suspension was cooled to room temperature, and the precipitate was separated from the supernatant to remove the solvent. The recovered product powder had a Mn content of 950 g / mol.

[0297] [Table 1]

[0298] [Examples 1-16, Comparative Examples 1-7]

[0299] According to the formulation shown in Table 2 below, the components are mixed using the materials and methods described below to prepare a sample of the rubber composition. Components other than polyphenylene ether (A) are formulated in a uniform manner as shown below.

[0300] It should be noted that, regarding the mixing of the components constituting the rubber composition, a closed mixer (0.5L capacity) equipped with a temperature control device was used as the first stage of mixing. The materials, excluding sulfur and vulcanization accelerators, were mixed under conditions of 65% filler and a rotor speed of 50-90 rpm. At this time, the temperature of the closed mixer was controlled, and the compound was obtained at an outlet temperature of 150-160°C.

[0301] Next, as a second stage of mixing, the obtained complex is cooled to room temperature and then mixed again to improve the dispersion of the reinforcing filler. In this case, the discharge temperature of the complex is also adjusted to 150~160°C by controlling the temperature of the mixer.

[0302] After cooling, as the third stage of mixing, vulcanization accelerator and sulfur are added and mixed using an open roller set to 70°C to obtain an unvulcanized rubber composition.

[0303] Then, molding is performed, and the rubber is vulcanized at 160°C for the specified vulcanization time using a vulcanizing press to obtain the vulcanized rubber composition. The vulcanization time is 90% of the vulcanization time of the unvulcanized rubber composition plus 5 minutes.

[0304] (polyphenylene ether (A))

[0305] Using the PPE1~PPE9 obtained above as shown in Table 1, the types and proportions were changed and mixed into rubber compositions.

[0306] (Diene-based elastomers (B))

[0307] Styrene-butadiene rubber (SBR (Asahi Kasei Corporation HS265)): 70 parts by weight

[0308] Butadiene rubber (BR (trade name "U150" manufactured by Ube Industries): 30 parts by weight)

[0309] (Other ingredients)

[0310] • Silica (trade name "Ultrasil 7000GR" manufactured by Evonik Degussa, with a nitrogen adsorption specific surface area of ​​170 m²) 2 / g): 5 parts by weight, 15.0 parts by weight, 50.0 parts by weight, 75.0 parts by weight, 100.0 parts by weight, 120.0 parts by weight

[0311] • Silane coupling agent (manufactured by Evonik Degussa, "Si75", bis(triethoxysilylpropyl) disulfide): 6.0 parts by weight

[0312] • Carbon black (manufactured by Tokai Carbon Co., Ltd., SEAST KH(N339)): 5.0 parts by weight

[0313] • Softener (TDAE oil (manufactured by H&R, trade name "V500"): 32 parts by weight

[0314] Zinc oxide: 2.5 parts by weight

[0315] Stearic acid: 2.0 parts by weight

[0316] Wax, Sunnock: 1.5 parts by weight

[0317] • Anti-aging agent (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine): 2.0 parts by weight

[0318] • Sulfur: 2.2 parts by weight

[0319] • Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazole sulfinamide): 1.7 parts by weight

[0320] • Vulcanization accelerator 2 (diphenylguanidine): 2.0 parts by weight

[0321] <Evaluation>

[0322] The obtained rubber compositions and vulcanized rubber compositions were evaluated as follows. The evaluation results are shown in Table 2.

[0323] (1) Hardness

[0324] For samples of the vulcanized rubber compositions obtained in the examples and comparative examples, the values ​​of the A-type hardness tester were determined according to JIS K6253.

[0325] (2) Tensile strength and elongation at break

[0326] For samples of the vulcanized rubber compositions obtained in the examples and comparative examples, tensile strength and elongation at break were determined according to the tensile test method of JIS K6251.

[0327] (3) Processability (Mounney viscosity (ML viscosity) of the rubber composition)

[0328] The uncured rubber composition obtained above was used as a sample. Using a Mooney viscometer (trade name "VR1132" manufactured by Uejima Manufacturing Co., Ltd.), following ISO 289, after preheating at 130°C for 1 minute, the viscosity was measured after rotating the rotor at 2 revolutions per minute for 4 minutes. The following indicators were used for evaluation.

[0329] ○: ML viscosity less than 100

[0330] △: ML viscosity is above 100 and less than 150

[0331] ×: ML viscosity is above 150

[0332] (4) Low fuel consumption (tanδ at 50℃)

[0333] For the samples of the vulcanized rubber compositions obtained in the examples and comparative examples, the torsional mode was measured using a viscoelastic testing machine "ARES" manufactured by RheometricScientific at 50°C with a frequency of 10 Hz and a strain of 3%. The obtained tanδ was used as an indicator of low oil consumption. It should be noted that the value of tanδ was judged according to the following indicators, and the smaller the value, the better the low oil consumption.

[0334] ○: tanδ at 50℃ is less than 0.120

[0335] △: tanδ at 50℃ is greater than 0.120 and less than 0.130.

[0336] ×: The tanδ at 50℃ is above 0.130.

[0337] (5) Wet grip (tanδ at 0℃)

[0338] For the samples of the vulcanized rubber compositions obtained in the examples and comparative examples, the torsional mode was measured using a viscoelasticity testing machine "ARES" manufactured by RheometricScientific at 0°C with a frequency of 10 Hz and a strain of 1%. The obtained tanδ was used as an indicator of wet grip. It should be noted that the value of tanδ was judged according to the following indicators, with a larger value indicating better wet grip.

[0339] ○: The tanδ at 0℃ is above 0.180.

[0340] △: tanδ at 0℃ is greater than 0.170 and less than 0.180.

[0341] ×: tanδ at 0℃ is less than 0.170

[0342] (6) Ice grip (tanδ at -20℃)

[0343] For the samples of the vulcanized rubber compositions obtained in the examples and comparative examples, the torsional mode was measured using a viscoelastic testing machine "ARES" manufactured by RheometricScientific at -20°C with a frequency of 10 Hz and a strain of 1%. The obtained tanδ was used as an indicator of ice grip. It should be noted that the value of tanδ was judged according to the following indicators, with a larger value indicating better ice grip.

[0344] ○: The tanδ at -20℃ is above 0.302.

[0345] △: tanδ at -20℃ is greater than 0.275 and less than 0.302.

[0346] ×: tanδ at -20℃ is less than 0.275

[0347] (7) Vulcanization rate

[0348] For the rubber composition obtained above, according to JIS K6300-2 "Method for determining vulcanization characteristics using a vibration vulcanization testing machine", a rotorless vulcanization testing machine, which is used as a rheometer, was used to measure the vulcanization curve with the obtained torque as the vertical axis and the vulcanization time as the horizontal axis at a temperature of 160°C. In the obtained vulcanization curve, the vulcanization time required from the start of vulcanization to the maximum torque MH is set as tc(max). According to JIS K6300-2, the difference between the minimum torque ML and the maximum torque MH is set as ME (ME=MH-ML), and the vulcanization time from the start of the test to reaching ML+90%ME is set as T90 (unit: minutes), which is used as the vulcanization rate for measurement.

[0349] (8) Performance Balance

[0350] Considering the aforementioned low fuel consumption (tanδ at 50°C), wet grip performance (tanδ at 0°C), and ice grip performance (tanδ at -20°C), the performance balance of the vulcanized rubber compositions obtained in the Examples and Comparative Examples was evaluated according to the following indicators.

[0351] ○: Fuel efficiency, wet grip, and ice grip are all ○.

[0352] △: Any one of the following: fuel efficiency, wet grip, or ice grip is △

[0353] ×: Any one of the following: fuel efficiency, wet grip, or ice grip is ×

[0354] [Table 2]

[0355] As shown in Table 2, in Examples 1 to 16, the hardness, tensile strength, elongation at break, processability, low oil consumption, wet grip, ice grip and vulcanization speed are excellent, and the above properties are well balanced.

[0356] In Comparative Examples 1-7, any one or a balance of hardness, tensile strength, elongation at break, processability, low fuel consumption, wet grip, ice grip, and vulcanization rate was worse than in the Examples.

[0357] [Industrial Applicability]

[0358] The rubber composition of this embodiment is industrially applicable as a constituent material for tires such as truck tires, bus tires, automobile tires, motorcycle tires, off-road tires, and aircraft tires; a material for tire constituent elements such as treads, sidewalls, bead wraps, tire rubber layers, reinforcing cord coating materials, and buffer layers; industrial components such as fibers, films, laminates, automotive parts, and medical parts; molded articles such as equipment housings, consumer products, and packaging; belts such as tire curing capsules, inner tubes, air jackets, hoses, conveyor belts or automotive belts, solid tires, retread tires, footwear constituent elements, rollers for graphic arts applications, vibration damping devices, pharmaceutical devices, adhesives, caulking materials, sealing materials, glass-mounted compounds, protective coatings, air cushions, air springs, air bellows, liquid storage bags, and various airbags used in liquid storage and curing methods; and a material for molded rubber parts such as automotive suspension bumpers, automotive exhaust pipe hangers, and body supports.

Claims

1. A rubber composition, characterized in that, Include: Polyphenylene ether (A) with a glass transition temperature above -100°C and below 0°C, as determined by differential scanning calorimetry (DSC); and Diene-based elastomers (B).

2. The rubber composition according to claim 1, characterized in that, The polyphenylene ether (A) comprises repeating units derived from phenol of formula (1) and repeating units derived from phenol of formula (2). The percentage of phenol-derived repeating units from formula (1) to formula (2) is 31 mol% to 100 mol% relative to the total 100 mol% of the repeating units in formula (1), and the percentage of phenol-derived repeating units from formula (2) is more than 0 mol% and less than 69 mol%. [Chemical Formula 1] In equation (1), R 13 R is a saturated or unsaturated hydrocarbon group with or without substituents and 15 carbon atoms. 11 and R 12 Each of the following is an independent substituent consisting of a hydrogen atom, a straight-chain saturated hydrocarbon group having 1 to 12 carbon atoms, and any of the substituents shown in formula (3) below. [Chemical Formula 2] In equation (3), R 31 Each independently forms a straight-chain alkyl group with or without substituents, having 1 to 8 carbon atoms, or 2 R groups. 31 The atoms contained therein are bonded together to form cyclic alkyl groups with 1 to 8 carbon atoms, R 32 Each is an alkylene group having 1 to 8 carbon atoms, with or without substituents; b is independently 0 or 1; R 33 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms with or without substituents, or a phenyl group having or without substituents. [Chemical Formula 3] In equation (2), R 21 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, with or without substituents, or an aryl or halogen atom with 6 to 12 carbon atoms, with or without substituents. R 22 Each is independently a hydrogen atom, a hydrocarbon group with or without substituents having 1 to 6 carbon atoms, or an aryl or halogen atom with or without substituents having 6 to 12 carbon atoms.

3. The rubber composition according to claim 1 or 2, characterized in that, The polyphenylene ether (A) has a viscosity of less than 1 million cP at 80°C.

4. The rubber composition according to claim 1 or 2, characterized in that, The number-average molecular weight of the polyphenylene ether (A) is less than 5500.

5. The rubber composition according to claim 1 or 2, characterized in that, The polyphenylene ether (A) contains monomers derived from biomass.

6. The rubber composition according to claim 1 or 2, characterized in that, The monomer derived from biomass is CNSL.

7. The rubber composition according to claim 1 or 2, characterized in that, The product contains 0.01 to 65 parts by weight of polyphenylene ether (A) relative to 100 parts by weight of the diene elastomer (B).

8. The rubber composition according to claim 1 or 2, characterized in that, The diene elastomer (B) contains 10 to 115 parts by mass of silicon dioxide relative to 100 parts by mass.

9. A method of using polyphenylene ether, characterized in that, Polyphenylene ether with a glass transition temperature of -100°C or higher and less than 0°C, as determined by differential scanning calorimetry (DSC), is used as a raw material for tire compositions.

10. A method for manufacturing vulcanized rubber, characterized in that, The method includes: The process of mixing a diene-based elastomer (B) with a polyphenylene ether (A) having a glass transition temperature of -100°C or higher and less than 0°C, as determined by differential scanning calorimetry (DSC), to obtain a rubber composition; and The process of vulcanizing the rubber composition. The polyphenylene ether (A) has unsaturated hydrocarbon groups in its side chain, and the diene elastomer (B) undergoes a crosslinking reaction with the polyphenylene ether (A).

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