Modified conjugated diene polymer, polymer composition, crosslinked body, and tire

Abstract

A modified conjugated diene polymer having a polymer chain containing a structural unit derived from a conjugated diene compound, a partial structure derived from a compound (A) represented by formula (1) at a part of a terminal of the polymer chain, a partial structure derived from a compound (C) having at least one element selected from the group consisting of nitrogen, oxygen, and phosphorus and not having a silicon-oxygen bond at a terminal of the polymer chain different from the terminal having the partial structure derived from the compound (A), in the polymer chain, or both.X 1 A group containing a halogenated alkyl group having a carbon number of 1 to 8 or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring, etc.

Description

Technical Field

[0001] [Cross-reference to related applications]

[0002] This application claims priority based on Japanese Patent Application No. 2024-39345, filed on March 13, 2024, the entire contents of which are incorporated herein by reference.

[0003] This disclosure relates to a modified conjugated diene polymer, polymer composition, crosslinker, and tire. Background Technology

[0004] Conjugated diene polymers, obtained by polymerizing conjugated diene compounds, are widely used in various industrial products such as pneumatic tires, vibration damping rubber, and hoses due to their excellent heat resistance, abrasion resistance, mechanical strength, and processability.

[0005] In order to improve the durability or abrasion resistance of rubber compositions used in the tread or sidewall of pneumatic tires, it is known to formulate fillers such as carbon black or silica together with conjugated diene polymers. Furthermore, in the past, to improve the affinity between conjugated diene polymers and fillers, modified conjugated diene polymers (for example, see Patent Documents 1 to 3) have been proposed, in which silicon or heteroatoms such as nitrogen, oxygen, sulfur, and phosphorus are introduced into the conjugated diene polymer.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2008 / 123164

[0009] Patent Document 2: Japanese Patent Application Publication No. 11-349632

[0010] Patent Document 3: International Publication No. 2017 / 221943 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] With the trend towards electric vehicles, cars are becoming heavier, placing higher demands on the rubber used in tires for safety (especially wet grip) and wear resistance. Furthermore, there are also higher requirements for fuel efficiency than ever before.

[0013] This disclosure is made in view of the aforementioned issues, and one of the objectives is to provide a modified conjugated diene polymer that yields a crosslinked polymer with low oil consumption, excellent wet grip, and excellent abrasion resistance.

[0014] Technical means to solve the problem

[0015] According to this disclosure, in one embodiment, a modified conjugated diene polymer is provided having a polymer chain containing structural units derived from a conjugated diene compound, wherein a portion of the end of the polymer chain has a partial structure derived from a compound (A) represented by the following formula (1), and at an end of the polymer chain different from the end having a partial structure derived from the compound (A), or in the polymer chain, or both, a partial structure derived from a compound (C) having at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and not having a silicon-oxygen bond.

[0016] [Chemistry 1]

[0017]

[0018] (In formula (1), X) 1 A is the basis represented by equation (1-1) or equation (1-2) below; 1 It is a hydrocarbon group with a carbon number of 1 to 20 and a valence of (i+k), or has one or both of nitrogen and oxygen atoms, lacks active hydrogen, and is bonded to X by carbon atoms respectively. 1 and the base "-Si(R) 1 ) n (OR 2 ) 3-n The bases with (i+k) valences of carbons 1 to 20; R 1 and R 2 Each group is an independent hydrocarbon group with 1 to 20 carbon atoms; n is an integer from 0 to 2; when n is 0 or 1, multiple ORs 2 Same or different; when n is 2, multiple R 1 Same or different; i and k are independent integers from 1 to 6; where i+k≦10; where i is 2 or higher, multiple X 1 Same or different; when k is greater than 2, multiple bases "-Si(R) 1 ) n (OR 2 ) 3-n (Same or different)

[0019] [Chemistry 2]

[0020]

[0021] (In equation (1-1), R) 5 It is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring; R6 and R 7 Each is an independent hydrocarbon group having 1 to 10 carbon atoms; Q 1 and Q 2 Each is independently a nitrogen atom or -CR 10 -; where, in R 5 In the case of Q being a hydrogen atom, 1 For nitrogen atoms; R 10 It consists of hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms; " represents a bond;

[0022] In equation (1-2), R 8 It is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring; R 9 It is a hydrocarbon group or a trialkylsilyl group having 1 to 20 carbon atoms; wherein, in R 8 In the case of hydrogen atoms, R 9 It consists of hydrocarbon groups with 1 to 20 carbon atoms; "Indicates a bond"

[0023] According to this disclosure, in another embodiment, a method for manufacturing a modified conjugated diene polymer is provided, comprising: a step of polymerizing a monomer in the presence of a compound obtained by mixing a compound represented by formula (1) with a polymerization initiator to obtain a conjugated diene polymer with active ends; and a step of reacting the conjugated diene polymer with active ends with a compound having at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and not having silicon-oxygen bonds.

[0024] According to this disclosure, in another embodiment, a polymer composition is provided comprising: the modified conjugated diene polymer, and a filler. Additionally, according to this disclosure, in another embodiment, a crosslinker is provided, which is formed by crosslinking the polymer composition. Furthermore, according to this disclosure, in another embodiment, a tire is provided that uses the polymer composition to form the tread or sidewall, or both.

[0025] The effects of the invention

[0026] By using the modified conjugated diene polymers disclosed herein, crosslinked polymers with low oil consumption, excellent wet grip, and excellent abrasion resistance can be obtained. Detailed Implementation

[0027] The following provides a detailed description of matters related to the form of this disclosure. Furthermore, the present invention is not limited to the embodiments described below, and should be understood to include various modified embodiments implemented without altering the spirit of the invention. In this specification, the numerical range referred to as "X to Y" indicates a numerical range that includes the value X as a lower limit and the value Y as an upper limit.

[0028] The term "(meth)acrylic acid" encompasses both "acrylic acid" and "methacrylic acid". "(Modified) conjugated diene polymer" includes both unmodified and modified conjugated diene polymers (i.e., modified conjugated diene polymers). Hereinafter, when referred to only as "conjugated diene polymer," unless specifically stated otherwise, it can refer to either unmodified or modified conjugated diene polymers. "Modification" refers to giving a conjugated diene polymer containing structural units derived from hydrocarbons (i.e., unmodified conjugated diene polymers) a partial structure containing heteroatoms such as nitrogen or oxygen, silicon, or phosphorus.

[0029] Modified conjugated diene polymers

[0030] The modified conjugated diene polymer of this disclosure (hereinafter also referred to as "modified conjugated diene polymer (P)") has a polymer chain containing structural units derived from conjugated diene compounds. A portion of the end of the polymer chain of the modified conjugated diene polymer (P) has a partial structure derived from a compound represented by the following formula (1). Furthermore, the modified conjugated diene polymer (P) has a partial structure derived from a compound at a different end in the polymer chain from the end having a partial structure derived from compound (A), in the polymer chain, or in both (i.e., at the end of the polymer chain and in the polymer chain), said compound having at least one element selected from the group consisting of nitrogen, oxygen, and phosphorus and not having silicon-oxygen bonds.

[0031] [Chemistry 3]

[0032]

[0033] (In formula (1), X) 1 A is the basis represented by equation (1-1) or equation (1-2) below; 1 It is a hydrocarbon group with a carbon number of 1 to 20 and a valence of (i+k), or has one or both of nitrogen and oxygen atoms, lacks active hydrogen, and is bonded to X by carbon atoms respectively. 1 and the base "-Si(R) 1 ) n (OR 2 ) 3-nThe bases with (i+k) valences of carbons 1 to 20; R 1 and R 2 Each group is an independent hydrocarbon group with 1 to 20 carbon atoms; n is an integer from 0 to 2; when n is 0 or 1, multiple ORs 2 Same or different; when n is 2, multiple R 1 Same or different; i and k are independent integers from 1 to 6; where i+k≦10; where i is 2 or higher, multiple X 1 Same or different; when k is greater than 2, multiple bases "-Si(R) 1 ) n (OR 2 ) 3-n (Same or different)

[0034] [Chemistry 4]

[0035]

[0036] (In equation (1-1), R) 5 It is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring; R 6 and R 7 Each is an independent hydrocarbon group having 1 to 10 carbon atoms; Q 1 and Q 2 Each is independently a nitrogen atom or -CR 10 -; where, in R 5 In the case of Q being a hydrogen atom, 1 For nitrogen atoms; R 10 It consists of hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms; " represents a bond;

[0037] In equation (1-2), R 8 It is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring; R 9 It is a hydrocarbon group or a trialkylsilyl group having 1 to 20 carbon atoms; wherein, in R 8 In the case of hydrogen atoms, R 9 It consists of hydrocarbon groups with 1 to 20 carbon atoms; "Indicates a bond"

[0038] Hereinafter, matters relating to the form of this disclosure will be described in detail. Hereinafter, the compound represented by the formula (1) will also be referred to as "compound (A)". In addition, a compound having at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and not having a silicon-oxygen bond will also be referred to as "compound (C)".

[0039] <Polymer Chain>

[0040] The modified conjugated diene polymer (P) has a polymer chain containing structural units derived from conjugated diene compounds. Examples of conjugated diene compounds include: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, and 2-chloro-1,3-butadiene. Among these, 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3-butadiene are preferred. One conjugated diene compound may be used alone, or two or more may be used in combination.

[0041] The modified conjugated diene polymer (P) can be a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound and a monomer different from the conjugated diene compound. From the viewpoint of improving the strength of the crosslinked body (i.e., rubber) obtained using the modified conjugated diene polymer (P), the modified conjugated diene polymer (P) is preferably a copolymer of a conjugated diene compound and an aromatic vinyl compound.

[0042] Examples of aromatic vinyl compounds constituting the polymer chain include: styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, vinylxylene, vinylnaphthalene, diphenylethylene, etc. Among these, styrene, α-methylstyrene, or both are preferred.

[0043] Furthermore, the aromatic vinyl compounds constituting the polymer chain may also include compounds having at least one element selected from the group consisting of nitrogen, oxygen, and phosphorus and lacking silicon-oxygen bonds (i.e., compound (C)). As a specific example of such a compound, compounds with a styrene skeleton, such as compound (C2), can be cited. As aromatic vinyl compounds, one may be used alone, or two or more may be used in combination.

[0044] When the modified conjugated diene polymer (P) is a copolymer of a conjugated diene compound and an aromatic vinyl compound, it is preferable to include a copolymer of 1,3-butadiene and styrene in the monomer composition for high reactivity in anionic polymerization. For the purpose of effectively improving hysteresis loss at both low and high temperatures, the modified conjugated diene polymer (P) is preferably a random copolymer with an irregularly distributed random copolymer portion of the conjugated diene compound and aromatic vinyl compound as the main component. Furthermore, the random copolymer may also have block portions containing either a conjugated diene compound or an aromatic vinyl compound at the ends. In the modified conjugated diene polymer (P), the proportion of monomers constituting the random copolymer portion is preferably 65% ​​by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, relative to the total amount of monomers used in the polymerization of the modified conjugated diene polymer (P).

[0045] From the viewpoint of achieving a good balance between low hysteresis loss characteristics (low oil consumption performance) and wet skid resistance in the crosslinked body obtained using the modified conjugated diene polymer (P), or achieving good wear resistance, the proportion of structural units derived from aromatic vinyl compounds in the modified conjugated diene polymer (P) is preferably 3% to 55% by mass relative to the total amount of structural units contained in the modified conjugated diene polymer (P). The proportion of structural units derived from aromatic vinyl compounds is more preferably 5% by mass or more. Furthermore, the proportion of structural units derived from aromatic vinyl compounds is more preferably 50% by mass or less, and even more preferably 45% by mass or less. In addition, the content of structural units derived from aromatic vinyl compounds in the polymer is determined by... 1 H-nuclear magnetic resonance (NMR) 1 H-Nuclear Magnetic Resonance, 1 The value was determined by H-NMR.

[0046] Furthermore, the polymer chain of the modified conjugated diene polymer (P) may also contain structural units (hereinafter referred to as "other structural units") derived from compounds other than conjugated diene compounds and aromatic vinyl compounds. From the viewpoint of achieving a good balance between low hysteresis loss characteristics and wet skid resistance in the crosslinked body obtained using the modified conjugated diene polymer (P), or from the viewpoint of achieving good wear resistance, the proportion of other structural units in the modified conjugated diene polymer (P) is preferably 15% by mass or less, more preferably 10% by mass or less, relative to the total amount of structural units contained in the modified conjugated diene polymer (P).

[0047] The molecular structure of the modified conjugated diene polymer (P) is not particularly limited. That is, the modified conjugated diene polymer (P) can be an aggregate of linear polymers, an aggregate of branched polymers, or a mixture of linear and branched polymers. Specifically, if the modified conjugated diene polymer (P) has a partial structure derived from compound (C) at an end of the polymer chain that is different from the end having a partial structure derived from compound (A), the modified conjugated diene polymer (P) can be a polymer in which one end of the linear polymer chain has a partial structure derived from compound (A) and the other end has a partial structure derived from compound (C). Alternatively, the modified conjugated diene polymer (P) can also be a polymer in which a portion of the ends of a branched polymer chain have a partial structure derived from compound (A), and at least a portion of the remaining ends have a partial structure derived from compound (C).

[0048] <Compound (A)>

[0049] Compound (A) functions as a start-end modifier for modifying the polymerization start-end of conjugated diene polymers. By polymerizing a monomer containing a conjugated diene compound in the presence of a metal amide compound, a portion of the structure derived from compound (A) can be introduced into the polymerization start-end of a polymer chain containing structural units derived from the conjugated diene compound. This metal amide compound is obtained by mixing such compound (A) with at least one (hereinafter also referred to as a "metal compound") selected from the group consisting of alkali metal compounds and alkaline earth metal compounds used as polymerization initiators in the manufacture of modified conjugated diene polymers (P).

[0050] In the above equation (1), in X 1 In the case of R being the basis represented by equation (1-1), 6 and R 7 The alkylene groups representing carbons 1 to 10 are preferably straight-chain or branched alkylides representing carbons 1 to 20, and more preferably methylene or ethylene.

[0051] In Q 1 and Q 2 The base represented is -CR 10 In the case of -R 10 The hydrocarbon group representing 1 to 20 carbon atoms is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Wherein, R 10 Preferably, it contains hydrogen atoms or methyl groups.

[0052] From the viewpoint of achieving good rolling resistance in the obtained crosslinked body, Q 1 and Q 2Preferably, at least one of them is a nitrogen atom, more preferably Q. 1 and Q 2 All are nitrogen atoms. In terms of obtaining a crosslinked body with superior rolling resistance, Q is particularly preferred. 1 and Q 2 Q in 2 It is a tertiary nitrogen atom, or Q 1 and Q 2 All are tertiary nitrogen atoms.

[0053] In equations (1-1) and (1-2), R is used as... 5 and R 8 The alkyl halide represented by the term "1-8 carbon atoms" can be exemplified by groups formed by substituting any hydrogen atom of the alkyl halide with a halogen atom. The alkyl halide with 1-8 carbon atoms substituted with a halogen atom can be linear or branched. The alkyl halide is preferably an alkyl halide with 1-6 carbon atoms, more preferably an alkyl halide with 1-4 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with chlorine or bromine atoms being preferred.

[0054] In R 5 or R 8 The group represented is a monovalent group (hereinafter also referred to as "cyclic group R") having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring. c In the case of "), as a cyclic base R C The aromatic ring it possesses can be, for example, a benzene ring, a naphthalene ring, an anthracene ring, etc., preferably a benzene ring or a naphthalene ring. In the cyclic group R... C In this compound, the aromatic ring may also have a halogen atom and substituents other than a methyl group. Examples of such substituents include N,N-dialkylamino groups. Examples of halogen atoms bonded to the aromatic ring include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, chlorine atoms or bromine atoms are preferred, and bromine atoms are more preferred.

[0055] As R 5 or R 8 The base represented is a cyclic base R. CSpecific examples include: 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-N,N-dimethylamino-3-methylphenyl, 2-N,N-dimethylamino-4-methylphenyl, 2-N,N-dimethylamino-5-methylphenyl, 2-methyl-3-N,N-dimethylaminophenyl, 3-N,N-dimethylamino-4-methylphenyl, 3-N,N-dimethylamino-5-methylphenyl, 2-N,N-dimethylamino-3-bromophenyl, 2-N,N-dimethylamino-4-bromophenyl, 2-N,N-dimethylamino-5-bromophenyl, 2-bromo-3-N,N-dimethylaminophenyl, 3-N,N-dimethylamino-4-bromophenyl, 3-N,N-dimethylamino-5-bromophenyl, 5-bromonaphthyl, 5-bromoanthryl, etc.

[0056] From the perspective of improving the reactivity of the metal compound (A) as a polymerization initiator with compound (A), R 5 Preferably, hydrogen atoms and cyclic groups R C Or a haloalkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom, a monovalent cyclic group having a structure with a bromine atom bonded to an aromatic ring, a bromoalkyl group having 1 to 8 carbon atoms, or a chloroalkyl group having 1 to 8 carbon atoms. R 8 Preferably, cyclic group R C Or a haloalkyl group having 1 to 8 carbon atoms, more preferably a monovalent cyclic group having a structure with bromine atoms bonded to an aromatic ring, a bromoalkyl group having 1 to 8 carbon atoms, or a chloroalkyl group having 1 to 8 carbon atoms.

[0057] R 9 The hydrocarbon group representing 1 to 20 carbon atoms is preferably an alkyl group with 1 to 20 carbon atoms, and more preferably a straight-chain or branched alkyl group with 1 to 20 carbon atoms. Examples of trialkylsilyl groups include trimethylsilyl and triethylsilyl.

[0058] Regarding improving X 1 From the perspective of the reactivity of metal compounds, X 1 Preferably, the base represented by formula (1-1) is used. Furthermore, regarding the possibility of obtaining a crosslinked body with superior rolling resistance, X... 1 More preferably, it has a nitrogen-containing heterocycle, and even more preferably, it has a nitrogen-containing heterocycle containing tertiary nitrogen atoms.

[0059] As A 1 Examples of hydrocarbon groups with a valence of (i+k) include groups formed by removing (i+k) hydrogen atoms from chain hydrocarbons having 1 to 20 carbon atoms, alicyclic hydrocarbons having 3 to 20 carbon atoms, or aromatic hydrocarbons having 6 to 20 carbon atoms. Among these, groups formed by removing (i+k) hydrogen atoms from chain hydrocarbons are preferred.

[0060] As A 1Specific examples of groups having a carbon number of 1 to 20 and a (i+k) valence, having one or both of nitrogen and oxygen atoms and lacking active hydrogen, include heterocyclic groups with an (i+k) valence and groups with an (i+k) valence having a tertiary amine structure. Heterocyclic groups are preferably conjugated, and examples include groups formed by removing (i+k) hydrogen atoms from the ring portion of a monocyclic or condensed ring structure such as pyridine, pyrimidine, pyrazine, quinoline, naphthidine, furan, or a structure formed by multiple linked monocyclic or condensed rings. From the viewpoint of improving processability when preparing polymer compositions containing modified conjugated diene polymers (P), (i+k) is preferably 2 to 6.

[0061] A 1 Using carbon atoms bonded to the base "-Si(R) 1 ) n (OR 2 ) 3-n "and X 1 In terms of obtaining crosslinked bodies with better rolling resistance, A 1 Preferably, the same or different carbon atoms constituting the hydrocarbon group are bonded to the "-Si(R" group. 1 ) n (OR 2 ) 3-n "and X 1 The hydrocarbon group is preferably a hydrocarbon-like group, and more preferably an alkyl diol.

[0062] As R 1 and R 2 Examples of hydrocarbon groups representing 1 to 20 carbon atoms include: alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms. R 1 and R 2 Preferably, it is a straight-chain or branched alkyl group having 1 to 20 carbon atoms, and more preferably a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

[0063] Specific examples of compound (A) include compounds represented by formulas (M1-1) to (M1-50) below, and compounds in these compounds in which the methyl group bonded to the silicon atom is replaced by an alkyl group having 2 to 6 carbon atoms.

[0064] [Chemistry 5]

[0065]

[0066] [Chemistry 6]

[0067]

[0068] [Chemistry 7]

[0069]

[0070] [Chemistry 8]

[0071]

[0072] [Chemistry 9]

[0073]

[0074] [Chemistry 10]

[0075]

[0076] <Compound (C)>

[0077] One form of compound (C) is a stop-end modifier, which modifies the polymer chain (more specifically, the polymerization terminator) by reacting with the active ends of a conjugated diene polymer and stopping the polymerization. Another form of compound (C) is a main-chain modifier, which modifies the polymer chain (more specifically, the polymer backbone) by reacting with the active ends of a conjugated diene polymer and incorporating into the polymer backbone. Specific examples of compound (C) include compounds (C1) and (C2).

[0078] Compound (C1): A compound having at least one element selected from the group consisting of nitrogen, oxygen, and phosphorus, lacking a silicon-oxygen bond, and having a functional group or part of its structure that can react with the active terminals of conjugated diene polymers.

[0079] Compound (C2): A compound having at least one element selected from the group consisting of nitrogen, oxygen, and phosphorus, lacking a silicon-oxygen bond, and having a polymerizable group.

[0080] • About compound (C1)

[0081] Compound (C1) functions as a stop-end modifier for conjugated diene polymers with active ends. There are no particular limitations on the functional groups or partial structures of compound (C1) that can react with the active ends of the conjugated diene polymer. However, in terms of high reactivity with conjugated diene polymers with active ends, compound (C1) preferably has at least one functional group or partial structure selected from the group consisting of epoxy, carbonyl, imino, nitrile, and aromatic heterocyclic structures that can react with the active ends of the conjugated diene polymer.

[0082] Specific examples of compounds (C1) that have an epoxy group include: 1,2-epoxyhexane, ethyl glycidyl ether, 1-methyl-1,2-epoxycyclohexane, styrene oxide, furfuryl glycidyl ether, etc.

[0083] Examples of compounds containing a carbonyl group include: N-methylpyrrolidone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, β-propiolactone, γ-butyrolactone, tetrahydrofuran-3-one, furfuryl glycidyl ether, 4'-acetylbenzo-15-crown-5-ether, etc.

[0084] Examples of compounds containing imino groups include: N-methylenebenzylamine, N-benzylmethylamine, N-benzylethylamine, N-benzylbenzylamine, 2-propyl-2-oxazoline, 1,5-diazabicyclo[4.3.0]-5-nonene, 1-aza-2-methoxy-1-cycloheptene, etc.

[0085] Examples of compounds containing a nitrile group include acetonitrile, propionitrile, butyronitrile, 3-methoxypropionitrile, 3,3-diethoxypropionitrile, benzonitrile, naphthonitrile, 2-cyanopyridine, and benzenemethylene malonitrile.

[0086] Examples of compounds having an aromatic heterocyclic structure include substituted or unsubstituted pyridine, substituted or unsubstituted bipyridine, substituted or unsubstituted terpyridine, and substituted or unsubstituted phenanthroline. When the aromatic heterocycle has a substituent, examples of such substituents include alkyl groups having 1 to 10 carbon atoms and dialkylamino groups having 2 to 10 carbon atoms.

[0087] The compound (C1) is preferably at least one selected from the group consisting of N-methylpyrrolidone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, β-propiolactone, γ-butyrolactone, N-methylenebenzylamine and N-benzylbenzylamine, more preferably at least one selected from the group consisting of benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, N-methylenebenzylamine and N-benzylbenzylamine.

[0088] Regarding compound (C2)

[0089] Compound (C2) can function as a stop-end modifier or a main-chain modifier. In terms of high reactivity with conjugated diene polymers having active ends, compound (C2) is preferably a compound having at least one element selected from the group consisting of nitrogen, oxygen, and phosphorus, lacking silicon-oxygen bonds, and having polymerizable carbon-carbon unsaturated bonds. The polymerizable carbon-carbon unsaturated bonds in compound (C2) are not particularly limited as long as they can copolymerize with the conjugated diene compound. Specific examples of compound (C2) include: (meth)acrylate compounds, (meth)acrylonitrile compounds, styrene compounds, phosphorus-containing vinyl compounds, vinyl compounds having nitrogen-containing heterocycles, and vinyl compounds having alkylene oxides, etc.

[0090] Further specific examples of the compound (C2), as (meth)acrylate compounds, include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, etc.

[0091] Examples of (meth)acrylonitrile compounds include acrylonitrile and methacrylonitrile.

[0092] Examples of styrene compounds include: methoxystyrene, tert-butoxystyrene, vinylbenzyl dimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 4-dimethylaminostyrene, 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene, etc.

[0093] Examples of phosphorus-containing vinyl compounds include dimethyl vinylphosphonate and diethyl vinylphosphonate.

[0094] Examples of vinyl compounds having nitrogen-containing heterocycles include vinylpyridine and compounds represented by the following formula (2).

[0095] [Chemistry 11]

[0096]

[0097] (In equation (2), R) 11 R 12 and R 13 Independently, they are hydrogen atoms, alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, heteroalkyl groups having 1 to 30 carbon atoms, heteroalkenyl groups having 2 to 30 carbon atoms, heteroalkynyl groups having 2 to 30 carbon atoms, cycloalkyl groups having 5 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, or heterocyclic groups having 3 to 30 carbon atoms;

[0098] R 14It is a single bond, a substituted or unsubstituted alkyldiyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; in R 14 When a substituent is present, the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

[0099] R 15 It can be an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms, a heteroalkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 3 to 30 carbon atoms.

[0100] R 16 It is a substituted or unsubstituted alkyldiyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; in R 16 When a substituent is present, the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

[0101] R 17 and R 18 Independently, they are substituted or unsubstituted alkyldiyl groups with 1 to 20 carbon atoms; in R 17 or R 18 When a substituent is present, the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

[0102] R 19 It is a nitrogen atom or an oxygen atom; in R 19 In the case of oxygen atoms, R 20 It does not exist; in R 19 In the case of nitrogen atoms, R 20 It can be a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms, a heteroalkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 3 to 30 carbon atoms;

[0103] a is an integer from 1 to 5, and b is an integer from 0 to 4; where a + b ≦ 5; when a is greater than or equal to 2, R 16 ~R 20 And the monovalent groups represented by nitrogen atoms may be the same or different; when b is 2 or more, multiple R 15 (Same or different)

[0104] As specific examples of compounds represented by the formula (2), compounds represented by the formula (2-1) or formula (2-2) below can be listed.

[0105] [Chemistry 12]

[0106]

[0107] Specific examples of vinyl compounds having alkylene oxides include compounds represented by the following formula (3).

[0108] [Chemistry 13]

[0109]

[0110] (In equation (3), R) 21 It is an alkyldiyl group with 2 or 3 carbon atoms; R 22 It is a hydrocarbon group with 1 to 6 carbon atoms; R 23 (A hydrocarbon group having 1 to 10 carbon atoms or an oxy hydrocarbon group having 2 to 10 carbon atoms; d is an integer from 1 to 10; e is an integer from 0 to 4)

[0111] In the above equation (3), R 21 It can be linear or branched. R 22 The hydrocarbon group representing 1 to 6 carbon atoms is preferably a straight-chain or branched alkyl group representing 1 to 6 carbon atoms. e is preferably 0 or 1, more preferably 0. Specific examples of compounds represented by the formula (3) can be listed as compounds represented by the formulas (3-1) to (3-3) below.

[0112] [Chemistry 14]

[0113]

[0114] (In equations (3-1) to (3-3), d is an integer from 1 to 10)

[0115] The compound (C2) is preferably at least one selected from the group consisting of vinyl compounds having a nitrogen-containing heterocycle, vinyl compounds having phosphorus and vinyl compounds having an alkylene oxide, and more preferably at least one selected from the group consisting of dimethyl vinylphosphonate, diethyl vinylphosphonate, the compound represented by formula (2) and the compound represented by formula (3).

[0116] <Preparation of Modified Conjugated Diene Polymers (P)>

[0117] There is no particular limitation on the method for manufacturing the modified conjugated diene polymer (P). The modified conjugated diene polymer (P) can be obtained, for example, by a method including the following steps: polymerizing monomers in the presence of a metal amide compound obtained by mixing compound (A) with a polymerization initiator (hereinafter also referred to as the "polymerization step"). In this case, by using a monomer composition containing the conjugated diene compound and compound (C2) as the monomers used in the polymerization, a modified conjugated diene polymer (P) can be obtained in which a portion of the polymer chain has a partial structure derived from compound (A), and the polymer chain contains structural units derived from compound (C2).

[0118] Alternatively, the modified conjugated diene polymer (P) can also be obtained by a method comprising the following steps: polymerizing monomers in the presence of a metal amide compound obtained by mixing compound (A) with a polymerization initiator to obtain a conjugated diene polymer with active ends (polymerization step); and reacting the active ends of the conjugated diene polymer obtained by the polymerization step with compound (C) (hereinafter also referred to as the "modification step"). By this method, a modified conjugated diene polymer (P) can be obtained in which a portion of the polymer chain has a partial structure derived from compound (A), and at ends of the polymer chain different from those with the partial structure derived from compound (A) have a partial structure derived from compound (C).

[0119] Polymerization process

[0120] In the polymerization of monomers containing conjugated diene compounds, at least one (metal compound) selected from the group consisting of alkali metal compounds and alkaline earth metal compounds is preferably used as the polymerization initiator. As the metal compound, a compound commonly used as a polymerization initiator in the polymerization reaction of conjugated diene compounds can be suitably used. The metal compound is preferably a compound formed by a hydrocarbon group bonded to an alkali metal element. Examples of such organoalkali metals include: methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, 1,4-dilithiobutane, phenyllithium, lithium stilbene, naphthyllithium, 1,3-bis(1-lithium-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentyl)dilithium, sodium naphthyl, potassium naphthyl, etc.

[0121] The metal compound used to obtain the metal amide compound is preferably a lithium compound, more preferably at least one selected from the group consisting of alkyl lithium and aryl lithium, and particularly preferably alkyl lithium (methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, etc.). One metal compound may be used alone, or two or more may be used in combination.

[0122] Methods A and B are examples of methods for polymerization in the presence of metal amide compounds.

[0123] Method A: A method in which a metal compound is pre-mixed with compound (A) to generate a metal amide compound outside the system, and the obtained metal amide compound is mixed with a monomer and polymerized.

[0124] Method B: A method for generating and polymerizing a metal amide compound by mixing compound (A) with a metal compound in a reactor containing monomers.

[0125] These methods are all included in the embodiment of "polymerizing a monomer containing a conjugated diene compound in the presence of a metal amide compound obtained by mixing a metal compound with compound (A). Method B is preferred from the viewpoint of simplifying operation, while method A is preferred from the viewpoint of sufficiently reducing the rolling resistance of the obtained crosslinked body and improving low oil consumption."

[0126] When using method A as a method for polymerization in the presence of a metal amide compound, compound (A) and the metal compound can be mixed in an organic solvent. The organic solvent used to generate the metal amide compound can be any organic solvent that is inert to both compound (A) and the metal compound. Specifically, examples include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. In method A, the temperature at which compound (A) is mixed with the polymerization initiator is preferably -20°C to 150°C, more preferably 0°C to 120°C.

[0127] When adding a metal amide compound, obtained by pre-mixing compound (A) with a metal compound, to a reactor containing a monomer, the method of adding the metal amide compound to the reactor is not particularly limited. Examples include: adding the metal amide compound simultaneously, adding it in stages, and adding it continuously. Adding the metal amide compound simultaneously to the reactor can narrow the molecular weight distribution of the obtained modified conjugated diene polymer (P), which is advantageous in this respect. Adding the metal amide compound in stages to the reactor tends to improve the efficiency of compound (A) in reaching the polymerization end, while also improving the processability of the obtained modified conjugated diene polymer (P).

[0128] When the metal amide compound is added to the reactor in stages, subsequent additions of the metal amide compound can be made either before or after the polymerization of the monomer. From the viewpoint of improving the efficiency of introducing compound (A) to the end of polymerization, it is preferable to make subsequent additions of the metal amide compound after the polymerization of the monomer has begun; that is, it is preferable to add the metal amide compound to the reactor after polymerization has started via the initial addition. When the metal amide compound is added in stages, the mass ratio of the first addition to the total amount added subsequent times is preferably 9:1 to 1:1.

[0129] The amount of compound (A) used relative to the polymerization initiator can be suitably set depending on the type of polymerization initiator. For example, when using a lithium compound as the metal compound, the amount of compound (A) used is preferably in the range of 0.1 mol to 1.8 mol relative to 1 mol of the lithium compound used in the polymerization. From the viewpoint of suppressing the decrease in processability when preparing a rubber composition containing a modified conjugated diene polymer (P), the amount of compound (A) used is preferably less than 1 mol relative to 1 mol of the lithium compound used in the polymerization, more preferably 0.98 mol or less, and even more preferably 0.95 mol or less. Furthermore, from the viewpoint of sufficiently obtaining the effect of reducing rolling resistance, the amount of compound (A) used is preferably 0.2 mol or more relative to 1 mol of the lithium compound used in the polymerization, more preferably 0.3 mol or more.

[0130] In the polymerization, the amount of metal compound used is preferably 0.01 mmol to 20 mmol, more preferably 0.05 mmol to 15 mmol, relative to 100 g of monomer used in the synthesis of the modified conjugated diene polymer (P).

[0131] In obtaining a modified conjugated diene polymer (P) containing a partial structure derived from compound (C2) in the polymer chain, it is preferable to use compound (C2) in a portion of the monomer. When introducing structural units derived from compound (C2) into the polymer chain, the amount of compound (C2) used is preferably 0.3% by mass or more, more preferably 0.5% by mass to 50% by mass, and even more preferably 1% by mass to 30% by mass, and even more preferably 1% by mass to 10% by mass, relative to the total amount of monomer used in the polymerization.

[0132] When manufacturing modified conjugated diene polymers (P), the polymerization method for the monomer can be any of solution polymerization, gas-phase polymerization, or bulk polymerization. Solution polymerization is particularly preferred. Furthermore, both batch and continuous polymerization can be used as the polymerization form. As an example of a specific polymerization method when using solution polymerization, a method in which a monomer containing a conjugated diene compound is polymerized in a solvent in the presence of an alkali metal compound and, if necessary, a vinyl content modifier.

[0133] Vinyl content modifiers (also known as attributable agents) are used for purposes such as adjusting the vinyl content (hereinafter referred to as "vinyl content") of polymers. Examples of vinyl content modifiers include ether compounds and tertiary amine compounds. Specific examples of vinyl content modifiers include: dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di(2-tetrahydrofuranyl)propane, 2-(2-ethoxyethoxy)-2-methylpropane, triethylamine, pyridine, N-methylmorpholine, tetramethylethylenediamine, etc. One vinyl content modifier can be used alone or in combination of two or more.

[0134] The solvent used in the polymerization (hereinafter also referred to as the "polymerization solvent") can be any solvent that is inert to the reaction. Organic solvents are preferably used as polymerization solvents. Examples of organic solvents include: chain or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, etc. Among these, hydrocarbons having 3 to 8 carbon atoms are preferred, and specific examples include: propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propylene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1-pentene, 2-pentene, cyclohexene, etc. Furthermore, one or more solvents can be used alone or in combination as polymerization solvents.

[0135] In the case of solution polymerization, from the viewpoint of maintaining a balance between productivity and ease of polymerization control, the monomer concentration in the reaction solvent is preferably 5% to 50% by mass, more preferably 10% to 30% by mass. The polymerization temperature is preferably -20°C to 150°C, more preferably 0°C to 120°C. Furthermore, the polymerization reaction is preferably carried out at a pressure sufficient to substantially maintain the monomer in a liquid phase. Through this polymerization reaction, conjugated diene polymers with active ends can be obtained. In this specification, "active ends" refers to portions (e.g., alkali metal ends) existing at the ends of the polymer chain and originating from monomers having carbon-carbon double bonds.

[0136] Modification process

[0137] In the modification process, compound (C) is used as a stop-end modifier, and the conjugated diene polymer obtained through the polymerization process (i.e., the conjugated diene polymer with active ends) is reacted with compound (C). By reacting the polymer with active ends with compound (C), a conjugated diene polymer (i.e., the modified conjugated diene polymer (P)) can be obtained with a partial structure derived from compound (C) at an end different from the end with a partial structure derived from compound (A).

[0138] The reaction of a conjugated diene polymer with an active terminal end to compound (C) can be carried out, for example, in the form of a solution reaction. This solution reaction can be carried out using a solution containing unreacted monomers after the polymerization reaction has completed, or by separating the conjugated diene polymer from the solution and dissolving it in a suitable solvent such as cyclohexane. The reaction can be carried out using either a batch or continuous reaction. In this case, there are no particular limitations on the method of adding compound (C), and examples include: simultaneous addition, partial addition, and continuous addition.

[0139] As compound (C), either compound (C1) or compound (C2) can be used. Alternatively, compound (C1) and compound (C2) can be used together. Furthermore, when compound (C2) is used as a stop-end modifier to react with a conjugated diene polymer having an active end, there is a tendency to obtain a conjugated diene polymer (P) with continuous blocks of structural units derived from compound (C2) at the end of the main chain. Thus, the case of blocks derived from compound (C2) at the end of the main chain is also consistent with the case of partial structures derived from compound (C) at the end of the polymer chain.

[0140] The amount of compound (C) used can be appropriately determined according to the type of compound used in the reaction. When using compound (C1) as compound (C), the amount of compound (C1) used is preferably 0.1 mol equivalent or more, more preferably 0.3 mol equivalent to 1.5 mol equivalent, and even more preferably 0.5 mol equivalent to 1.0 mol equivalent, relative to the metal element of the polymerization initiator that participates in the polymerization reaction. When using compound (C2) as compound (C), the amount of compound (C2) used is preferably 2.0 mol equivalent or more, more preferably 3.0 mol equivalent to 100 mol equivalent, and even more preferably 5.0 mol equivalent to 20 mol equivalent, relative to the metal element of the polymerization initiator that participates in the polymerization reaction.

[0141] In the reaction of conjugated diene polymers with active terminals with compound (C), the reaction temperature is usually the same as the polymerization temperature, preferably -20°C to 150°C, more preferably 0°C to 120°C. If the modification reaction temperature is too low, the viscosity of the polymer solution tends to increase. Conversely, if the modification reaction temperature is too high, the active terminals tend to deactivate easily. The reaction time is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.

[0142] As described above, a portion of the structure derived from compound (C) can be introduced into the conjugated diene polymer through either the polymerization step or the modification step. Regarding the ease of controlling the amount of the portion of the structure derived from compound (C) introduced, thereby further improving the balanced improvement in low fuel consumption, wet grip, and abrasion resistance, the modified conjugated diene polymer (P) is preferably manufactured by a method comprising: a polymerization step using compound (A) as a start-end modifier and polymerizing the monomer; and a modification step using compound (C) as a stop-end modifier.

[0143] The modified conjugated diene polymer (P) can also be a polymer obtained by further reacting the conjugated diene polymer obtained using the polymerization or modification process with an onium salt generating agent. In this case, as the modified conjugated diene polymer (P), a polymer having an onium salt structure at the polymer end can be obtained. By modifying the conjugated diene polymer (P) to have an onium salt structure, the shape retention of the crosslinked body obtained using the modified conjugated diene polymer (P) can be improved, which is preferred in this respect. As the onium salt generating agent, an onium salt generating agent commonly used in the manufacture of oniumized conjugated diene polymers can be suitable.

[0144] When separating modified conjugated diene polymers contained in a reaction solution, this can be done, for example, by known solvent removal methods such as steam stripping and drying operations such as heat treatment.

[0145] <Properties of Modified Conjugated Diene Polymers (P)>

[0146] Next, the physical properties of the modified conjugated diene polymer (P) will be described.

[0147] Mooney viscosity

[0148] The Mooney viscosity of the modified conjugated diene polymer (P) measured at 100°C is preferably 5 or higher and 150 or lower. If the Mooney viscosity of the modified conjugated diene polymer measured at 100°C is less than 5, there is a tendency that the strength, wear resistance, and rolling resistance of the crosslinked body obtained using the modified conjugated diene polymer cannot be improved in a balanced manner. In addition, if the Mooney viscosity of the modified conjugated diene polymer measured at 100°C is higher than 150, there is a tendency that the processability of the modified conjugated diene polymer is poor. From the above point of view, the Mooney viscosity of the modified conjugated diene polymer (P) measured at 100°C is more preferably 10 or higher, and even more preferably 15 or higher. In addition, the Mooney viscosity of the modified conjugated diene polymer (P) measured at 100°C is more preferably 120 or lower, even more preferably 100 or lower, and even more preferably 80 or lower. Furthermore, the Mooney viscosity of the modified conjugated diene polymer (P) was measured according to Japanese Industrial Standards (JIS) K6300-1:2013.

[0149] (Vinyl content)

[0150] The vinyl content of the modified conjugated diene polymer (P) is preferably 10% to 70% by mass. If the vinyl content is 10% by mass or more, the gripping properties of the crosslinked body obtained using the modified conjugated diene polymer (P) are better. Furthermore, if the vinyl content of the modified conjugated diene polymer (P) is 70% by mass or less, the decrease in abrasion resistance of the crosslinked body obtained using the modified conjugated diene polymer (P) can be suppressed, which is preferable in this respect. The vinyl content of the modified conjugated diene polymer (P) is more preferably 12% by mass or more, and even more preferably 15% by mass or more. Furthermore, the vinyl content of the modified conjugated diene polymer (P) is more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. In addition, in this specification, "vinyl content" refers to the proportion of structural units having 1,2-bonds in the conjugated diene polymer relative to all structural units of butadiene, and is determined by... 1 The value was determined by H-NMR.

[0151] (The proportion of structural units derived from aromatic vinyl compounds)

[0152] When the modified conjugated diene polymer (P) has structural units derived from aromatic vinyl compounds, from the viewpoint of achieving a good balance between rolling resistance and wet skid resistance in the crosslinked body obtained using the modified conjugated diene polymer (P), the content of structural units derived from aromatic vinyl compounds in the modified conjugated diene polymer (P) is preferably 3% to 55% by mass relative to the total amount of structural units in the modified conjugated diene polymer (P). The content of structural units derived from aromatic vinyl compounds in the modified conjugated diene polymer (P) is more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, the content of structural units derived from aromatic vinyl compounds in the modified conjugated diene polymer (P) is more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less. In addition, the content of structural units derived from aromatic vinyl compounds in the conjugated diene polymer is determined by... 1 The value was determined by H-NMR.

[0153] (Glass transition temperature)

[0154] The modified conjugated diene polymer (P) preferably exhibits an endothermic peak in the temperature range of -100°C to 20°C in differential scanning calorimetry (DSC) according to JIS K6240:2011. The inflection point of the DSC curve obtained by DSC analysis, i.e., the peak temperature of the differential curve, is the measured value of the glass transition temperature of the modified conjugated diene polymer (P). The modified conjugated diene polymer (P) preferably has a glass transition temperature (measured value) of -100°C to 20°C.

[0155] The glass transition temperature of the modified conjugated diene polymer (P) is more preferably -90°C or higher, and even more preferably -80°C or higher. Furthermore, from the viewpoint of improving wet grip performance, the glass transition temperature of the modified conjugated diene polymer (P) is more preferably below 0°C, even more preferably below -10°C, even more preferably below -20°C, particularly preferably below -30°C, and even more preferably below -40°C. In particular, when the modified conjugated diene polymer (P) exhibits only one endothermic peak in DSC analysis, and the peak temperature of said endothermic peak is within the temperature range of -100°C to 20°C, there is a tendency for the crosslinked body formed using the modified conjugated diene polymer (P) to have improved abrasion resistance and strength.

[0156] (Weight average molecular weight)

[0157] For the modified conjugated diene polymer (P), the preferred weight-average molecular weight (Mw) of polystyrene, determined by gel permeation chromatography (GPC), is 1.0 × 10⁻⁶. 4 ~4.0×10 6 If the Mw of the modified conjugated diene polymer (P) is 1.0 × 10⁻⁶ 4 The above methods yield crosslinked polymers with higher strength, excellent wear resistance, and sufficiently low rolling resistance. Furthermore, if the Mw of the modified conjugated diene polymer (P) is 4.0 × 10⁻⁶... 6 The following results in good processability of the polymer composition containing the modified conjugated diene polymer (P). From the viewpoint of further improving strength, wear resistance, and rolling resistance, the Mw of the modified conjugated diene polymer (P) is more preferably 5.0 × 10⁻⁶. 4 The above, and therefore preferably 1.0 × 10 5 That's all. Furthermore, from a processability perspective, the Mw of the modified conjugated diene polymer (P) is more preferably 2.0 × 10⁻⁶. 6 The preferred value is 1.5 × 10⁻⁶. 6 Below. Furthermore, the weight-average molecular weight (Mw) of the modified conjugated diene polymers represents the weight-average molecular weight (total weight-average molecular weight) based on all peaks of the GPC curve determined using GPC.

[0158] (Molecular weight distribution)

[0159] Regarding the modified conjugated diene polymer (P), from a productive point of view, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) as determined by GPC, is preferably 1.00 to 3.00. The molecular weight distribution (Mw / Mn) of the modified conjugated diene polymer (P) is more preferably 2.00 or less, more preferably 1.80 or less, more preferably 1.70 or less, and particularly preferably 1.65 or less. Furthermore, the molecular weight distribution (Mw / Mn) is more preferably 1.03 or more, and more preferably 1.05 or more.

[0160] Polymer Compositions

[0161] The polymer composition disclosed herein comprises: the modified conjugated diene polymer (P); and a filler. Furthermore, unless otherwise specified, each component in the polymer composition may be used alone or in combination of two or more.

[0162] <filler>

[0163] As a filler, at least one selected from the group consisting of silica, carbon black and the compound represented by the following formula (4) may be used.

[0164] nM 1 ·mSiO k ·iH2O …(4)

[0165] (In equation (4), M) 1 The metal is selected from the group consisting of any one of aluminum, magnesium, titanium, zirconium, and calcium (hereinafter also referred to as "the specific metal"), an oxide of the specific metal, a hydroxide of the specific metal, and a carbonate of the specific metal; n is an integer from 1 to 5, m is an integer from 0 to 10, k is an integer from 2 to 5, and i is an integer from 0 to 10.

[0166] [B]Silica

[0167] There are no particular limitations on the type of silicon dioxide used; examples include wet silicon dioxide (hydrated silicic acid), dry silicon dioxide (anhydrous silicic acid), calcium silicate, and aluminum silicate. Among these, wet silicon dioxide is preferred.

[0168] The Brunauer-Emmett-Teller (BET) specific surface area of ​​silica (determined according to International Organization for Standardization (ISO) 5794 / 1) is preferably 40 m². 2 / g~350 m 2 The range is preferably 80 m / g. 2 / g~300 m 2 The range is preferably 120 m / g. 2 / g~250m 2 The range of / g. Silica with a BET specific surface area in this range has the advantage of balancing dispersibility and rubber-reinforcing properties in modified conjugated diene polymers (P). As such silica, Nipsil AQ (BET specific surface area = 205 m²) manufactured by Tosoh Silica can be used. 2 / g), "Nipsil KQ", and "Ultrasil VN3" manufactured by Degussa (BET specific surface area = 175 m²). 2 Commercially available products such as (g) etc.

[0169] The amount of silica incorporated is preferably in the range of 20 to 160 parts by mass relative to 100 parts by mass of the rubber component containing the modified conjugated diene polymer (P), and more preferably in the range of 30 to 150 parts by mass. If the amount of silica is 20 parts by mass or more relative to 100 parts by mass of the rubber component, the rolling resistance, destructive properties, and abrasion resistance of the crosslinked body obtained from the polymer composition can be sufficiently improved. Furthermore, if the amount of silica is 160 parts by mass or less, the processability of the polymer composition can be sufficiently improved.

[0170] Furthermore, in this specification, the term "rubber component" in a polymer composition refers to a polymer that can be cured to produce a hardened form exhibiting rubber elasticity. The hardened form exhibits the property that it causes large deformation with small forces at room temperature (e.g., stretching to more than twice its original size when stretched at room temperature), and rapidly returns to approximately its original shape when the force is removed.

[0171] [C] Carbon Black

[0172] From the viewpoint of the destructive properties and abrasion resistance of the crosslinked body obtained from the polymer composition, the polymer composition disclosed herein preferably contains carbon black as a filler. There are no particular limitations on the carbon black used; examples include: general purpose furnace black (GPF), fast extruding furnace black (FEF), high abrasion furnace black (HAF), intermediate super abrasion furnace black (ISAF), and super abrasion furnace black (SAF).

[0173] The nitrogen adsorption specific surface area (N2SA) of carbon black is not particularly limited. However, for reasons such as superior performance in achieving the effects of this disclosure, the nitrogen adsorption specific surface area (N2SA) of carbon black is preferably 50 m². 2 / g~200 m 2 / g, more preferably 70 m 2 / g~150 m 2 / g. Furthermore, the nitrogen adsorption specific surface area (N2SA) is a value obtained by determining the amount of nitrogen adsorbed on the surface of carbon black according to JIS K6217-2:2001 "Part 2: Calculation of specific surface area - Nitrogen adsorption method - Single-point method". Carbon black can be used alone or in combination with two or more types.

[0174] When the polymer composition disclosed herein contains carbon black, the carbon black content in the polymer composition is preferably in the range of 1 to 150 parts by mass relative to 100 parts by mass of the rubber component containing the modified conjugated diene polymer (P), and more preferably in the range of 3 to 120 parts by mass.

[0175] [D] The compound represented by formula (4)

[0176] Specific examples of the compounds represented by the formula (4) (hereinafter also referred to as "inorganic compounds (D)") include: aluminum oxide (Al2O3) such as γ-alumina and α-alumina, aluminum oxide monohydrate (Al2O3·H2O) such as boehmite and diaspore, aluminum hydroxide [Al(OH)3] such as gibbsite and bayerite, aluminum carbonate [Al2(CO3)3], magnesium hydroxide [Mg(OH)2], magnesium oxide (MgO), magnesium carbonate (MgCO3), talc (3MgO·4SiO2·H2O), attapulgite (5MgO·8SiO2·9H2O), titanium dioxide (TiO2), titanium black (TiO2). 2n-1 ), calcium oxide (CaO), calcium hydroxide [Ca(OH)2], magnesium aluminum oxide (MgO·Al2O3), clay (Al2O3·2SiO2), kaolin (Al2O3·2SiO2·2H2O), pyrophyllite (Al2O3·4SiO2·H2O), bentonite (Al2O3·4SiO2·2H2O), aluminum silicate (Al2SiO5, Al4·3SiO4·5H2O, etc.), magnesium silicate (Mg2SiO4, MgSiO3, etc.), calcium silicate (Ca2SiO4, etc.), calcium aluminum silicate (Al2O3·CaO·2SiO2, etc.), calcium magnesium silicate (CaMgSiO4), calcium carbonate (CaCO3), zirconium oxide (ZrO2), zirconium hydroxide [ZrO(OH)2·nH2O], zirconium carbonate [Zr(CO3)2], etc.

[0177] In the polymer composition disclosed herein, the filler content is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, relative to 100 parts by mass of the rubber component contained in the polymer composition. Furthermore, the filler content is preferably 160 parts by mass or less, more preferably 120 parts by mass or less. When the filler content in the polymer composition is within the aforementioned range, by applying the polymer composition to the tread of a tire, a greater balance can be achieved between the tire's rolling resistance, braking performance on wet roads, handling performance on dry roads, and wear resistance.

[0178] In addition to the modified conjugated diene polymer (P) and fillers, the polymer compositions disclosed herein may also contain various components as shown below.

[0179] [E] Other rubber components

[0180] The polymer composition disclosed herein preferably further comprises at least one rubber component other than the modified conjugated diene polymer (P) selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, emulsified polymerized styrene-butadiene rubber, solution polymerized styrene-butadiene rubber, hydrogenated butadiene rubber, hydrogenated styrene-butadiene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene rubber, and ethylene-butadiene rubber. Among these, it is preferred to include one or more of natural rubber, butadiene rubber, and styrene-butadiene rubber. The other rubber components are mixed with the modified conjugated diene polymer (P), for example, during mixing in a conventional Banbury mixer, rollers, etc.

[0181] The ratio of the modified conjugated diene polymer (P) to other rubber components is preferably set to a ratio of 5 to 95 parts by mass relative to 100 parts by mass of the total modified conjugated diene polymer (P) and other rubber components. More preferably, the ratio of the modified conjugated diene polymer (P) to other rubber components is set to a ratio of 20 to 90 parts by mass relative to 100 parts by mass of the total modified conjugated diene polymer (P) and other rubber components. In particular, when the modified conjugated diene polymer (P) and other rubber components are formulated such that the modified conjugated diene polymer (P) is 35 to 85 parts by mass relative to 100 parts by mass of the total modified conjugated diene polymer (P) and other rubber components, the resulting polymer composition is preferred as a polymer composition for manufacturing tire rubber.

[0182] [F] resin

[0183] The polymer compositions disclosed herein may also contain thermoplastic or thermosetting resins (hereinafter also simply referred to as "[F] resins"). From the viewpoint of obtaining a crosslinker with superior strength, abrasion resistance, and crack growth resistance, the [F] resin is preferably selected from at least one group consisting of styrene-based resins, α-methylstyrene-based resins, polyethylene, C5-based resins, hydrogenated C5-based resins, C9-based resins, hydrogenated C9 resins, C5 / C9-based resins, hydrogenated C5 / C9-based resins, dicyclopentadiene-based resins, hydrogenated dicyclopentadiene-based resins, dicyclopentadiene-C9-based resins, hydrogenated dicyclopentadiene-C9-based resins, alkylphenol-based resins, coumarone-indene resins, terpene-based resins, and hydrogenated terpene-based resins. [F] The resin is more preferably selected from at least one group consisting of C5 resins, hydrogenated C5 resins, C9 resins, hydrogenated C9 resins, C5 / C9 resins, hydrogenated C5 / C9 resins, dicyclopentadiene resins, hydrogenated dicyclopentadiene resins, dicyclopentadiene-C9 resins, hydrogenated dicyclopentadiene-C9 resins, terpene resins, and hydrogenated terpene resins.

[0184] [F] resin is preferably a thermoplastic resin. When [F] resin is a thermoplastic resin, its softening point is preferably 60°C or higher, more preferably 70°C or higher. Furthermore, its softening point is preferably 180°C or lower, more preferably 170°C or lower.

[0185] When [F] resin is incorporated into the polymer composition, the amount of [F] resin is preferably 1 part by mass or more relative to 100 parts by mass of the rubber component contained in the polymer composition. By incorporating 1 part by mass or more of [F] resin, the improved abrasion resistance, tensile strength, and crack growth resistance resulting from the addition of [F] resin can be sufficiently enhanced in the crosslinked body obtained using the polymer composition. When [F] resin is incorporated into the polymer composition, the proportion of [F] resin is more preferably 5 parts by mass or more relative to 100 parts by mass of the rubber component, and even more preferably 10 parts by mass or more. Furthermore, from the viewpoint of maintaining the various properties of the rubber composition well, the proportion of [F] resin is preferably 100 parts by mass or less relative to 100 parts by mass of the rubber component contained in the polymer composition, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

[0186] [G]Silane coupling agent

[0187] By incorporating a silane coupling agent into the polymer composition disclosed herein, the dispersibility of silica can be further improved. There are no particular limitations on the silane coupling agent, but sulfur-containing silane coupling agents are preferred. Examples of sulfur-containing silane coupling agents include: bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-[ethoxybis(3,6,9,12,15-pentaoxaoctadecane-1-yloxy)silyl]propane-1-thiol (e.g., manufactured by Evonik under the trade name "Si363"), and mercapto-based silane compounds such as NXT and NXT-Z manufactured by Momentive.

[0188] When a silane coupling agent is incorporated into a polymer composition, the content of the silane coupling agent is preferably 1 to 20 parts by mass relative to 100 parts by mass of silica. By setting the content of the silane coupling agent to 1 part by mass or more, the improvement in the dispersibility of silica can be sufficiently obtained. Furthermore, by setting the content of the silane coupling agent to 20 parts by mass or less, the decrease in processability and elongation at break can be suppressed. More preferably, the content of the silane coupling agent is 5 to 15 parts by mass relative to 100 parts by mass of silica.

[0189] [H] Crosslinking agent

[0190] The polymer compositions disclosed herein may contain a crosslinking agent. By including a crosslinking agent in the polymer compositions of this disclosure, crosslinked bodies with improved strength and abrasion resistance can be obtained. Examples of crosslinking agents include sulfur, sulfur halides, organic peroxides, quinone dioximes, organic polyamine compounds, and alkylphenol resins containing hydroxymethyl groups, with sulfur being commonly used. When a crosslinking agent is formulated into the polymer composition, the content of the crosslinking agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total amount of rubber components contained in the polymer composition.

[0191] [G] Process Oil

[0192] In polymer compositions, process oils commonly used for oiling elastomers can be formulated as the oil used for oiling. Process oils can be formulated into polymer compositions, for example, by directly adding oil to the rubber formulation. Preferred process oils include various oils known in the art, such as aromatic oils, paraffinic oils, naphthenic oils, vegetable oils such as soybean oil and sunflower oil, and oils with low polycyclic aromatic compounds (low-polycyclic aromatics (PCA) oils), such as mild extraction solvents (MES), oils obtained by treating aromatic extracts from distillate oils (TDAE), special residual aromatic extracts from residual oils (SRAE), and heavy naphthenic oils, etc. Examples of commercially available MES, TDAE, and SRAE include Catenex SNR (a heavy paraffin wax obtained by dewaxing distillate oil using a solvent) manufactured by Shell as a MES, Vivatec 500 manufactured by H&R Wasag AG as a TDAE, and NC140 manufactured by Japan Energy Corp. as an SRAE. When process oil is incorporated into a polymer composition, the content of process oil is preferably 10 to 100 parts by mass relative to 100 parts by mass of the total amount of rubber components contained in the polymer composition.

[0193] In addition to the aforementioned components, the polymer composition may also contain various additives commonly used in polymer compositions for manufacturing tire rubber, such as anti-aging agents, zinc oxide, stearic acid, softeners, vulcanization accelerators, compatibilizers, vulcanization aids, processing aids, and scorch inhibitors. The amounts of these additives may be appropriately selected based on the various components without impairing the effects of this disclosure.

[0194] The polymer compositions disclosed herein can be used to mix polymer components or fillers, as well as other components formulated as needed, using a mixing machine such as an open mixing machine (e.g., a roller) or a closed mixing machine (e.g., a Banbury mixer), and then crosslinked (vulcanized) after molding, thereby being used as a crosslinked compound in various rubber products. Specifically, the crosslinked materials disclosed herein can be applied to tire applications such as tire tread, under tread, carcass, sidewall, and bead part; sealing materials such as liner, gasket, weatherstrip, and O-ring; inner and outer packaging materials for various vehicles such as automobiles, ships, airplanes, and railways; building materials; vibration damping rubber for industrial machinery or equipment; various hoses and hose covers such as diaphragms, rollers, radiator hoses, and air hoses; belts such as power transmission belts; linings; dust boots; medical machine materials; fenders; electrical wire insulation materials; and other industrial products.

[0195] According to the modified conjugated diene polymer (P), a crosslinker with good physical properties required for tire applications, such as rolling resistance (low fuel consumption), strength, and wear resistance, can be obtained. Therefore, polymer compositions containing the modified conjugated diene polymer (P) are particularly preferred as materials for tire treads, sidewalls, or both.

[0196] Tire manufacturing can be carried out using conventional methods. For example, a polymer composition is mixed using a mixer, and the polymer composition, which is formed into sheets, is placed in a specified position (e.g., the outer side of the frame in the case of the sidewall) and vulcanized according to conventional methods to form tread rubber or sidewall rubber, thereby obtaining a pneumatic tire.

[0197] Based on the above detailed disclosure, the following means are provided.

[0198] [Method 1] A modified conjugated diene polymer having a polymer chain containing structural units derived from a conjugated diene compound, wherein at a portion of the end of the polymer chain, a partial structure derived from a compound (compound (A)) represented by formula (1) is present, and at an end of the polymer chain different from the end having a partial structure derived from compound (A), or in the polymer chain or both, a partial structure derived from a compound (compound (C)) having at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and not having a silicon-oxygen bond.

[0199] [Method 2] The modified conjugated diene polymer according to [Method 1], wherein the weight average molecular weight (Mw) is 1.0 × 10⁻⁶. 4 ~4.0×10 6 .

[0200] [Method 3] The modified conjugated diene polymer according to [Method 1] or [Method 2], wherein the molecular weight distribution (Mw / Mn) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is 1.00 to 3.00.

[0201] [Method 4] A modified conjugated diene polymer according to any one of [Method 1] to [Method 3], wherein the compound (C) has at least one selected from the group consisting of epoxy, carbonyl, imino, nitrile and aromatic heterocyclic structures.

[0202] [Method 5] A modified conjugated diene polymer according to any one of [Method 1] to [Method 3], wherein the compound (C) further has polymerizable carbon-carbon unsaturated bonds.

[0203] [Method 6] A method for manufacturing a modified conjugated diene polymer, comprising: a step of polymerizing a monomer in the presence of a compound obtained by mixing a compound represented by formula (1) with a polymerization initiator to obtain a conjugated diene polymer having active ends; and a step of reacting the conjugated diene polymer having active ends with a compound having at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and not having silicon-oxygen bonds.

[0204] [Method 7] A polymer composition comprising: a modified conjugated diene polymer according to any one of [Method 1] to [Method 5], and a filler.

[0205] [Method 8] The polymer composition according to [Method 7] further comprises a rubber component, said rubber component being at least one selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, emulsified polymerized styrene-butadiene rubber, solution polymerized styrene-butadiene rubber, hydrogenated butadiene rubber, hydrogenated styrene-butadiene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene rubber, and ethylene-butadiene rubber, and is different from said modified conjugated diene polymer.

[0206] [Method 9] The polymer composition according to [Method 7] or [Method 8] further comprises a thermoplastic or thermosetting resin.

[0207] [Method 10] A crosslinker formed by crosslinking a polymer composition according to any one of [Method 7] to [Method 9].

[0208] [Mean 11] A tire, wherein the tread or sidewall or both are formed using a polymer composition according to any one of [Mean 7] to [Mean 9].

[0209] Example

[0210] The following is a detailed description based on examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" in the following synthesis examples, embodiments, and comparative examples are mass references. Methods for determining various physical properties of the polymer are shown below.

[0211] • Bonded styrene content (%): Deuterated chloroform was used as the solvent, and the mixture was passed through a 400 MHz filter. 1 The result is calculated using H-NMR measurements.

[0212] Vinyl content (%): determined by 400 MHz 1 The result is calculated using H-NMR measurements.

[0213] • The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer: Molecular weights based on polystyrene conversion were obtained using gel permeation chromatography (GPC) (GPC curves), and the values ​​were determined based on the obtained curves. Specific GPC determination conditions are described below.

[0214] (GPC measurement conditions)

[0215] Measuring instrument: HLC-8020 (manufactured by Tosoh Corporation)

[0216] Tube String: Two GMH-HR-H tubes (manufactured by Tosoh) connected in series.

[0217] Detector: Differential refractometer RI-8020 (manufactured by Tosoh Corporation)

[0218] Dissolution solution: Tetrahydrofuran

[0219] Column temperature: 40℃

[0220] Flow rate: 1.0 mL / min

[0221] Sample concentration: 10 mg / 20 mL

[0222] Glass transition temperature (°C): According to JIS K6240:2011, the glass transition temperature is determined from the inflection point of the DSC curve within the range of -100°C to 40°C. The specific conditions for determining the glass transition temperature are as follows.

[0223] (DSC measurement conditions)

[0224] Measuring apparatus: Q1000 Differential Scanning Calorimeter (DSC) (manufactured by TA Instruments)

[0225] Heating rate: 10℃ / min

[0226] • Mooney viscosity (ML1+4, 100°C): Measured using a Mooney testing machine (manufactured by Alpha Technology). Determined according to JIS K6300:2013, using an L-shaped rotor, under the conditions of 1 minute preheating, 4 minutes rotor operation time, and 100°C.

[0227] 1. Preparation of modified conjugated diene polymers

[0228] <Example 1>

[0229] In a 5-liter autoclave reactor purged with nitrogen, 2500 g of cyclohexane, 95 mmol of tetrahydrofuran (THF) as a vinyl content adjuster (randomizer), 4.55 mmol of 1-(3-diethyl(tert-amyloxy)silyl)propyl)piperazine (designated "INI-1") as compound (A), and 50 g of styrene and 400 g of 1,3-butadiene as monomers were added. After adjusting the temperature of the reactor contents to 20°C, 5.06 mmol of n-butyllithium was added as a polymerization initiator to begin polymerization. Polymerization was carried out under insulated conditions, with a maximum temperature reaching 75°C.

[0230] After the polymerization conversion reached 99% (25 minutes after the start of polymerization), 50 g of 1,3-butadiene was added as an additional monomer over a 5-minute period. Then, 4.55 mmol of N-benzylmethylamine (compound C) was added, and the reaction was allowed to proceed for another 15 minutes. Finally, 5.06 mmol of methanol was added, and the reaction was allowed to proceed again for another 15 minutes.

[0231] 4.40 g of 2,6-di-tert-butyl-p-cresol was added to the obtained polymer solution. The solvent was then removed by steam stripping, and the solution was dried using a hot roller heated to 110°C to obtain the modified conjugated diene polymer A1-1.

[0232] <Examples 2-5, Example 9, Example 10, Comparative Examples 1-5>

[0233] Except for the types and amounts of reagents shown in Table 1, polymerization, solvent removal, and drying were carried out in the same manner as in Example 1, thereby obtaining modified conjugated diene polymers A1-2 to A1-5, A1-9, A1-10, AC-1 to AC-5.

[0234] <Example 6>

[0235] In a 5-liter autoclave reactor purged with nitrogen, 2500 g of cyclohexane, 95 mmol of tetrahydrofuran as a vinyl content modifier (randomizing agent), 4.55 mmol of INI-1 as compound (A), and 50 g of styrene and 400 g of 1,3-butadiene as monomers were added. After adjusting the temperature of the reactor contents to 20°C, 5.06 mmol of n-butyllithium as a polymerization initiator was added to begin polymerization. Polymerization was carried out under insulated conditions, with the maximum temperature reaching 75°C.

[0236] After the polymerization conversion reached 99% (25 minutes after the start of polymerization), 50 g of 1,3-butadiene was added as an additional monomer over a period of 5 minutes. Then, 50.55 mmol of 1-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-3-vinylbenzene (designated "MOD-1") as compound (C) was added, and the reaction proceeded for 30 minutes. Finally, 5.06 mmol of methanol was added, and the reaction proceeded for another 15 minutes.

[0237] 4.40 g of 2,6-di-tert-butyl-p-cresol was added to the obtained polymer solution. The solvent was then removed by steam stripping, and the solution was dried using a hot roller heated to 110°C to obtain the modified conjugated diene polymer A1-6.

[0238] <Example 7>

[0239] Except for replacing MOD-1 with N,N-dimethyl-4-vinylaniline (designated "MOD-2"), polymerization, solvent removal and drying were performed in the same manner as in Example 6, thereby obtaining the modified conjugated diene polymer A1-7.

[0240] <Example 8>

[0241] Except that dimethyl vinylphosphonate was used instead of MOD-1, polymerization, solvent removal and drying were carried out in the same manner as in Example 6, thereby obtaining the modified conjugated diene polymer A1-8.

[0242] [Table 1]

[0243]

[0244] The abbreviations in Table 1 are as follows.

[0245] INI-1: 1-(3-Diethyl(tert-amyloxy)silyl)propyl)piperazine

[0246] MOD-1: 1-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-3-vinylbenzene

[0247] MOD-2: N,N-Dimethyl-4-vinylaniline

[0248] MOD-3: 3-(N,N-bis(trimethylsilyl)amino)propylmethyldiethoxysilane

[0249] <Example 11>

[0250] In a 16-liter autoclave reactor purged with nitrogen, the following substances were continuously charged at the following rates: 1,3-butadiene as monomer 45.0 g / min, styrene 5.0 g / min, cyclohexane as solvent 237.1 g / min, tetrahydrofuran as vinyl content modifier (randomizer) 9.01 mmol / min, and a mixture (1 / 1, molar ratio) of n-butyllithium as polymerization initiator and INI-1 as compound (A) 0.51 mmol / min, with the reactor temperature controlled at 75°C.

[0251] A polymer solution was continuously discharged from the first reactor at 290.2 g / min, and 4,4'-bis(dimethylamino)benzophenone (compound C) was added at 0.152 mmol / min and line-mixed. The solution was then continuously introduced into a second reactor for reaction. At the outlet of the second reactor, 0.7 parts by mass of di-tert-butyl-p-cresol were added relative to 100 parts by mass of the polymer composition. Subsequently, solvent removal was performed by steam stripping, followed by hot rolling at 110°C, thereby obtaining the modified conjugated diene polymer A1-11.

[0252] The various physical properties of the obtained modified conjugated diene polymers A1-1 to A1-11 and AC-1 to AC-5 are shown in Tables 2 and 3.

[0253] [Table 2]

[0254]

[0255] [Table 3]

[0256]

[0257] 2. Manufacturing of polymer compositions and crosslinkers

[0258] <Examples 12-34, Comparative Examples 6-15>

[0259] The components are prepared according to the formulations shown in Tables 4 to 7, and then melt-blended to produce a polymer composition. The blending is carried out using the following method.

[0260] Using a batch mixer equipped with a temperature control device (manufactured by Toyo Seiki Co., Ltd.; trade name: Labo Plastomill) as the first stage of mixing, the set temperature was adjusted to 100°C, and the mixing was carried out at a speed of 60 rpm for 4 minutes. The rubber components (modified conjugated diene polymer, butadiene rubber, natural rubber, emulsified styrene-butadiene rubber (SBR)), fillers (silica, carbon black, aluminum hydroxide), silane coupling agent, stretching oil, stearic acid, anti-aging agent, and zinc oxide were mixed. Furthermore, in Examples 23-34 and Comparative Examples 11-15, resins were further formulated.

[0261] Next, as the second stage of mixing, the mixture obtained from the first stage of mixing was cooled to room temperature, and then the vulcanization accelerator and sulfur were added to the mixer. The set temperature was adjusted to 70°C, and mixing was carried out at a speed of 60 rpm and a mixing time of 1.5 minutes, thereby obtaining separate formulations. The temperature of the mixtures discharged from the mixer was below 100°C. Next, each formulation was vulcanized at 160°C using vulcanization pressing for a specified time, thereby obtaining vulcanized rubber (crosslinked body). The obtained vulcanized rubber was used to evaluate the following physical properties. These results are shown in Tables 4 to 7.

[0262] [Evaluation methods for blended material properties]

[0263] • Wet grip performance (3%tanδ@0℃)

[0264] Using vulcanized rubber as the test sample, a shear-type dynamic spectrometer (manufactured by TA Instruments) was used to determine the ratio of the loss modulus G'' to the storage modulus G' (0℃ tanδ) under conditions of 100 radians per second, 0°C, and 3% shear strain. For Examples 12-22 and Comparative Examples 7-10, the index is set to 100 (comparative Example 6); for Examples 23-30, the index is set to 100 (comparative Example 11); for Example 31, the index is set to 100 (comparative Example 12); for Example 32, the index is set to 100 (comparative Example 13); for Example 33, the index is set to 100 (comparative Example 14); and for Example 34, the index is set to 100 (comparative Example 15). A higher value indicates better wet grip performance.

[0265] • Rolling resistance (3%tanδ@50℃)

[0266] Using vulcanized rubber as the test sample, a shear-type dynamic spectrometer (manufactured by TA Instruments) was used to determine the ratio of the loss modulus G'' to the storage modulus G' (50°C tanδ) under conditions of 100 radians per second, 50°C, and 3% shear strain. For Examples 12-22 and Comparative Examples 7-10, the values ​​are expressed with Comparative Example 6 set to 100; for Examples 23-30, the values ​​are expressed with Comparative Example 11 set to 100; for Example 31, the values ​​are expressed with Comparative Example 12 set to 100; for Example 32, the values ​​are expressed with Comparative Example 13 set to 100; for Example 33, the values ​​are expressed with Comparative Example 14 set to 100; and for Example 34, the values ​​are expressed with Comparative Example 15 set to 100. A higher value indicates lower rolling resistance and better rolling resistance performance, and also indicates better low-oil consumption performance.

[0267] • Abrasion resistance (German Industrial Standard (Deutsche Industrie Normen, DIN) abrasion resistance)

[0268] Vulcanized rubber was used as the test specimen, and the abrasion tester (manufactured by Toyo Seiki Co., Ltd.) was used according to JIS K6264, with a load of 10 N at 25°C. Regarding the test results, for Examples 12-22 and Comparative Examples 7-10, the index is expressed with Comparative Example 6 set to 100; for Examples 23-30, the index is expressed with Comparative Example 11 set to 100; for Example 31, the index is expressed with Comparative Example 12 set to 100; for Example 32, the index is expressed with Comparative Example 13 set to 100; for Example 33, the index is expressed with Comparative Example 14 set to 100; and for Example 34, the index is expressed with Comparative Example 15 set to 100. A higher value indicates better abrasion resistance.

[0269] [Table 4]

[0270]

[0271] [Table 5]

[0272]

[0273] [Table 6]

[0274]

[0275] [Table 7]

[0276]

[0277] The details of each component in Tables 4 to 7 are as follows.

[0278] 1) Manufactured by ENEOS Materials Co., Ltd., trade name "BR01"

[0279] 2) Silica 1: Manufactured by Solvay, trade name "ZEOSIL 1165MP"; Silica 2: Manufactured by Tosoh Silica, trade name "Nipsil AQ".

[0280] 3) Manufactured by Mitsubishi Chemical Corporation, trade name "DIABLACK N330"

[0281] 4) Manufactured by Evonik, trade name "Si75"

[0282] 5) ENEOS manufactured process oil "T-DAE"

[0283] 6) Ozonone 6C, manufactured by Seiko Chemical Co., Ltd.

[0284] 7) Manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name "Nocceler D".

[0285] 8) Manufactured by Ouchi Shinshin Chemical Industry Co., Ltd., trade name "Nocceler CZ-G"

[0286] 9) Manufactured by ENEOS Materials Co., Ltd., trade name "ESBR1502"

[0287] 10) Manufactured by Nippon Light Metals Co., Ltd., product name "SB92"

[0288] 11) B-1: Manufactured by ENEOS, C5 series resin, trade name "RA100", softening point 99℃

[0289] B-2: Manufactured by ENEOS, C9 series resin, trade name "NEOPOLYMER L-90", softening point 95℃.

[0290] B-3: Manufactured by ENEOS, C5 / C9 series resin, trade name "PR802", softening point 88℃.

[0291] B-4: Manufactured by Arizona Chemical Company, a terpene resin, trade name "Sylvatraxx 4150", softening point 116℃.

[0292] B-5: Manufactured by ENEOS, hydrogenated DCPD / C9 series resin, trade name "PR801", softening point 90℃.

[0293] As shown in Tables 4 to 7, it can be seen that the polymer compositions obtained by formulating the modified conjugated diene polymers obtained in Examples 1 to 11 (Examples 12 to 34) can produce crosslinked bodies with improved low oil consumption, wet grip and abrasion resistance.

Claims

1. A modified conjugated diene polymer having polymer chains containing structural units derived from conjugated diene compounds, At the end of the polymer chain, a portion has a structure derived from compound (A) represented by the following formula (1). The polymer chain has an end that is different from the end having a partial structure derived from compound (A), or the polymer chain has a partial structure derived from compound (C), which has at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and does not have silicon-oxygen bonds. [Chemistry 1] (In formula (1), X) 1 Let A be the basis represented by equation (1-1) or equation (1-2) below. 1 It is a hydrocarbon group with a carbon number of 1 to 20 and a valence of (i+k), or has one or both of nitrogen and oxygen atoms, lacks active hydrogen, and is bonded to X by carbon atoms respectively. 1 and base "-Si(R 1 ) n (OR 2 ) 3-n The base with (i+k) valences of carbons 1 to 20. 1 and R 2 Each group consists of a hydrocarbon group with 1 to 20 carbon atoms, independent of the others. n is an integer from 0 to 2. When n is 0 or 1, multiple ORs... 2 Same or different. When n is 2, multiple R... 1 Same or different. i and k are independent integers from 1 to 6. The condition i+k≦10 is satisfied. In the formula, when i is 2 or higher, multiple X... 1 Same or different. When k is greater than 2, multiple bases "-Si(R) 1 ) n (OR 2 ) 3-n (Same or different) [Chemistry 2] (In equation (1-1), R) 5 R is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring. 6 and R 7 Each group consists independently of a hydrocarbon group having 1 to 10 carbon atoms. Q 1 and Q 2 Each is independently a nitrogen atom or -CR 10 -. Among them, in R 5 In the case of Q being a hydrogen atom, 1 It is a nitrogen atom. R 10 It consists of hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms. " " indicates a bond. In equation (1-2), R 8 R is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring. 9 It is a hydrocarbon group or a trialkylsilyl group having 1 to 20 carbon atoms. Specifically, in R... 8 In the case of hydrogen atoms, R 9 It consists of hydrocarbon groups with 1 to 20 carbon atoms. "Indicates a bond".

2. The modified conjugated diene polymer according to claim 1, wherein the weight average molecular weight (Mw) is 1.0 × 10⁻⁶. 4 ~4.0×10 6 .

3. The modified conjugated diene polymer according to claim 1, wherein the molecular weight distribution (Mw / Mn) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is 1.00 to 3.

00.

4. The modified conjugated diene polymer according to claim 1, wherein the compound (C) has at least one selected from the group consisting of epoxy, carbonyl, imino, nitrile and aromatic heterocyclic structures.

5. The modified conjugated diene polymer according to claim 1, wherein the compound (C) further has polymerizable carbon-carbon unsaturated bonds.

6. A method for manufacturing a modified conjugated diene polymer, comprising: A process of polymerizing monomers in the presence of a compound obtained by mixing a compound represented by formula (1) with a polymerization initiator to obtain a conjugated diene polymer with active ends; and The process of reacting the conjugated diene polymer with active ends with a compound having at least one element selected from the group consisting of nitrogen, oxygen and phosphorus and not having silicon-oxygen bonds. [Chemistry 3] (In formula (1), X) 1 Let A be the basis represented by equation (1-1) or equation (1-2) below. 1 It is a hydrocarbon group with a carbon number of 1 to 20 and a valence of (i+k), or has one or both of nitrogen and oxygen atoms, lacks active hydrogen, and is bonded to X by carbon atoms respectively. 1 and base "-Si(R 1 ) n (OR 2 ) 3-n The base with (i+k) valences of carbons 1 to 20. 1 and R 2 Each group consists of a hydrocarbon group with 1 to 20 carbon atoms, independent of the others. n is an integer from 0 to 2. When n is 0 or 1, multiple ORs... 2 Same or different. When n is 2, multiple R... 1 Same or different. i and k are independent integers from 1 to 6. Among them, i + k ≤ 10. In the formula, when i is 2 or higher, multiple X... 1 Same or different. When k is greater than 2, multiple bases "-Si(R) 1 ) n (OR 2 ) 3-n (Same or different) [Chemistry 4] (In equation (1-1), R) 5 R is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring. 6 and R 7 Each group consists independently of a hydrocarbon group having 1 to 10 carbon atoms. Q 1 and Q 2 Each is independently a nitrogen atom or -CR 10 -. Among them, in R 5 In the case of Q being a hydrogen atom, 1 It is a nitrogen atom. R 10 It consists of hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms. " " indicates a bond. In equation (1-2), R 8 R is a hydrogen atom, a haloalkyl group having 1 to 8 carbon atoms, or a monovalent group having a structure in which a halogen atom or a methyl group is bonded to an aromatic ring. 9 It is a hydrocarbon group or a trialkylsilyl group having 1 to 20 carbon atoms. Specifically, in R... 8 In the case of hydrogen atoms, R 9 It consists of hydrocarbon groups with 1 to 20 carbon atoms. "Indicates a bond".

7. A polymer composition comprising the modified conjugated diene polymer as described in any one of claims 1 to 5, and a filler.

8. The polymer composition according to claim 7, further comprising a rubber component, said rubber component being at least one selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, emulsified polymerized styrene-butadiene rubber, solution polymerized styrene-butadiene rubber, hydrogenated butadiene rubber, hydrogenated styrene-butadiene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene rubber, and ethylene-butadiene rubber, and being different from said modified conjugated diene polymer.

9. The polymer composition according to claim 7, further comprising a thermoplastic or thermosetting resin.

10. A crosslinker formed by crosslinking the polymer composition of claim 7.

11. A tire, wherein the tread or sidewall, or both, is formed using the polymer composition of claim 7.

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