JP2009120757A - Method for producing modified conjugated diene-based polymer, modified conjugated diene-based polymer, and rubber composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a modified conjugated diene-based polymer which can suitably be used as a raw material for vulcanized rubbers excellent in a low heat-generating property and an abrasion-resistant property and is good in cold flow characteristics. <P>SOLUTION: This method for producing the modified conjugated diene-based polymer comprises polymerizing a conjugated diene-based compound in the presence of a polymerization catalyst composition containing a metallocene type complex containing at least one group 3 element or a bis(phosphinophenyl)amide type complex containing at least one group 3 element to obtain a conjugated diene-based polymer having a cis-1,4-bond content of ≥75%, and then reacting the obtained conjugated diene-based polymer with a modifying agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, and a rubber composition. More specifically, a method for producing a modified conjugated diene polymer that can be suitably used as a vulcanized rubber material excellent in heat generation and wear resistance and has good cold flow characteristics, that is, hardly undergoes plastic deformation. The present invention relates to a modified conjugated diene polymer obtained by the method and a rubber composition.

  The conjugated diene polymer is a polymer having an extremely important role industrially, and is produced by polymerizing a conjugated diene compound in the presence of a polymerization catalyst. Conventionally, many proposals have been made on this polymerization catalyst. For example, a composite catalyst polymerization catalyst containing a transition metal compound containing a transition metal such as nickel, cobalt, or titanium as a main component has been proposed. Some of them are already widely used industrially as polymerization catalysts such as butadiene and isoprene (see, for example, Patent Document 1 and Non-Patent Document 1).

  In addition to the above composite catalyst polymerization catalyst, a polymerization catalyst using a neodymium compound and methylalumoxane has been proposed. When this polymerization catalyst is used, it exhibits high polymerization activity and has a narrow molecular weight distribution. It has been reported that a conjugated diene polymer can be obtained (see, for example, Patent Documents 2 to 4). However, when a polymerization catalyst using the above neodymium compound and methylalumoxane is used, in order to obtain a conjugated diene polymer having a sufficient molecular activity and a narrow molecular weight distribution, a large amount of methylalumoxane is used. Need to use. For this reason, there is a problem that it is necessary to remove a large amount of metal (mainly aluminum) remaining in the polymerization reaction solution after the conjugated diene compound is polymerized to produce a conjugated diene polymer.

  In addition, the price of methylalumoxane has a problem that it is more expensive than conventional polymerization catalysts such as organoaluminum compounds. Furthermore, the conjugated diene compound produced has a problem in practical use because of its large cold flow, that is, poor storage (storage) stability.

  In response to these problems, a conjugated diene polymer polymerized in the presence of a polymerization catalyst using a neodymium compound and methylalumoxane is obtained, and the obtained conjugated diene polymer is converted into a hetero three-membered ring compound or a halogenated compound. It has been reported that modification with a compound such as a metal compound or metal carboxylate suppresses an increase in cold flow (see, for example, Patent Documents 5 and 6). Further, a conjugated diene compound is polymerized in the presence of a specific catalyst to obtain a conjugated diene polymer, and the resulting conjugated diene polymer has at least one epoxy group and / or isocyanate group in the molecule. A modified conjugated diene polymer production method has been proposed in which a modified conjugated diene polymer is produced by reacting with an alkoxysilane compound having two or more specific compounds (see, for example, Patent Document 7). .

Japanese Patent Publication No. 37-8198 JP-A-6-221916 JP-A-6-306113 JP-A-8-73515 Japanese Patent Laid-Open No. 10-306113 Japanese Patent Laid-Open No. 11-35633 JP 2001-139633 A Ind. Eng. Chem. , 48, 784 (1956)

  However, in order to suppress the cold flow by the methods described in Patent Documents 5 and 6, there is a problem that the catalyst level is high and the amount of alumoxane used cannot be reduced to a practical level. In addition, although the production method described in Patent Document 7 has an effect of suppressing the cold flow of the resulting modified conjugated diene polymer, when a vulcanized rubber is produced using the modified conjugated diene polymer, There was a problem that the low heat build-up and wear resistance of the vulcanized rubber were insufficient. Note that low heat buildup and wear resistance are important characteristics for vulcanized rubber.

  The present invention has been made in order to solve the above-described problems of the prior art, and can be suitably used as a vulcanized rubber material excellent in low heat buildup and wear resistance, and has a cold flow characteristic. A method for producing a modified conjugated diene polymer having good cold flow properties, that is, in addition to good plastic deformation hardly occurring, ie, cold flow suppression, modified conjugated diene obtained by this production method A polymer and a rubber composition are provided.

  As a result of intensive studies to solve the above problems, the present inventors obtained a conjugated diene polymer by polymerizing a conjugated diene compound in the presence of a specific polymerization catalyst composition, and the obtained conjugated diene system. It has been found that the above problem can be solved by reacting a polymer with a modifier, and the present invention has been completed.

  Specifically, the present invention provides the following modified conjugated diene polymer production method, modified conjugated diene polymer, and rubber composition.

[1] In the presence of a polymerization catalyst composition comprising a conjugated diene compound comprising a metallocene type complex containing at least one group 3 element or a bis (phosphinophenyl) amide type complex containing at least one group 3 element. A method for producing a modified conjugated diene polymer comprising polymerizing to obtain a conjugated diene polymer having a cis-1,4-bond content of 75% or more and reacting the resulting conjugated diene polymer with a modifier.

[2] The method for producing a modified conjugated diene polymer according to [1], wherein the modifier includes at least one compound selected from the group consisting of the following components (a) to (g).
(A) Component: Alkoxysilane compound containing in its molecular structure at least one group selected from the group consisting of an epoxy group and an isocyanate group (b) Component: General formula (1) R ¹ _n M ¹ At least one compound selected from the group consisting of compounds represented by X _4-n , general formula (2) M ¹ X ₄ , and general formula (3) M ² X ₃ (provided that the general formula (1) R ¹ is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms. In the general formulas (1) and (2), M ¹ is a tin atom, a silicon atom, or a germanium atom, respectively. In the general formula (3), M ² is a phosphorus atom, in the general formulas (1) to (3), each X is a halogen atom, and in the general formula (1), n is 0 to 0, respectively. (It is an integer of 3)
(C) Component: a compound having a structure represented by the general formula (4) Y = C = Z in the molecular structure (wherein Y is a carbon atom, oxygen atom, nitrogen atom in the general formula (4)) Or a sulfur atom, and Z is an oxygen atom, a nitrogen atom, or a sulfur atom)
Component (d): A compound having a structure represented by the following general formula (5) in its molecular structure (however, in the general formula (5), Z is an oxygen atom, a nitrogen atom, or a sulfur atom).

(E) Component: Compound having a structure represented by general formula (6) N = C—X in the molecular structure (f) Component: General formula (7) R ⁴ (COOH) _m , General formula (8 ₎ ^R 4 (COX) _m, the general formula ^{(9) R 4 (COO-} R 4) m, the general formula ^{(10) R 4 -OCOO-R} 4, the general formula ^{(11) R 4 (COOCO-} R 4) m , At least one compound selected from the group consisting of compounds represented by the following general formula (12) and the following general formula (13) (provided that, in the general formulas (7) to (12), R ⁴ represents It is the same or different, It is a C1-C50 hydrocarbon group, In said general formula (8), X is a halogen atom, In said general formula (7), (8) and (11), m is respectively an integer from 1 to 5, in the general formula (13), R ⁵ is optionally contain a substituent alkyl Is down based on, h is an integer of 1 to 50)

Component (g): General formula _{^{(14) R 6 l M 3}} (OCOR 6) 4-l, formula _{^{(15) R 6 l M 3}} (OCOR 6 -COOR 6) 4-l, and the following formula At least one compound selected from the group consisting of compounds represented by (16) (provided that, in the general formulas (14) to (16), each R ⁶ is the same or different and is a hydrocarbon having 1 to 20 carbon atoms) And M ³ is a tin atom, a silicon atom, or a germanium atom, l is an integer of 0 to 2, and J is 0 or 1)

[3] The polymerization catalyst composition according to [1] or [2], wherein the polymerization catalyst composition further contains at least one catalyst selected from the group consisting of the following catalysts (α) to (γ) as a promoter component. A method for producing a modified conjugated diene polymer.
Catalyst (α): ionic compound composed of non-coordinating anion and cation Catalyst (β): Aluminoxane Catalyst (γ): Organoaluminum compound represented by formula (17) AlR ⁷ R ⁷ R ⁸ However, in said general formula (17), R < ⁷ > is the same or different, respectively, and is a hydrogen atom or a C1-C10 hydrocarbon group, R < ⁸ > is the same or different C1-C10 hydrocarbon as R < ⁷ >. Base)

[4] The metallocene complex is composed of scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), and lutetium (Lu). And containing at least one element selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), and neodymium. (Nd), samarium (Sm), gadolinium (Gd), and at least one element selected from the group consisting of lutetium (Lu) A method for producing a modified conjugated diene polymer.

[5] The above [1] to [4], wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. The manufacturing method of the modified conjugated diene type polymer in any one.

[6] The conjugated diene polymer has a cis-1,4-bond content of 99% or more and a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by gel permeation chromatography. The method for producing a modified conjugated diene polymer according to any one of [1] to [5], wherein the ratio (Mw / Mn) is 2.0 or less.

[7] A modified conjugated diene polymer produced by the method for producing a modified conjugated diene polymer according to any one of [1] to [6].

[8] A rubber composition comprising the modified conjugated diene polymer according to [7].

  According to the method for producing a modified conjugated diene-based polymer of the present invention, a modified conjugated diene-based polymer that can be suitably used as a vulcanized rubber material excellent in low heat buildup and wear resistance and has good cold flow characteristics. The effect is that a polymer can be produced.

  The modified conjugated diene polymer of the present invention can be suitably used as a vulcanized rubber material excellent in low heat buildup and wear resistance, and has the effect of good cold flow characteristics.

  The rubber composition of the present invention has an effect that a vulcanized rubber excellent in low heat buildup and wear resistance can be formed.

  Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

[1] Method for producing modified conjugated diene polymer:
In one embodiment of the method for producing a modified conjugated diene polymer of the present invention, the conjugated diene compound is converted into a metallocene complex containing at least one group 3 element or bis (phosphino) containing at least one group 3 element. Polymerization is carried out in the presence of a polymerization catalyst composition containing a phenyl) amide type complex to obtain a conjugated diene polymer having a cis-1,4-bond content of 75% or more (hereinafter referred to as “(A) step”. In some cases, the resulting conjugated diene polymer is allowed to react with a modifier (hereinafter may be referred to as “step (B)”).

  As described above, by using a conjugated diene polymer obtained by polymerization in the presence of a polymerization catalyst composition, a modifier is reacted with the conjugated diene polymer, thereby maintaining low heat buildup and wear resistance. In addition to being able to provide vulcanized rubber, it is possible to produce a modified conjugated diene polymer having good cold flow characteristics (hard to cause plastic deformation).

[1-1] Step (A):
In the production method of the modified conjugated diene polymer of this embodiment, first, a conjugated diene compound is converted into a metallocene-type complex containing at least one group 3 element or bis (phosphinophenyl) containing at least one group 3 element. ) Polymerization is carried out in the presence of a polymerization catalyst composition containing an amide type complex to obtain a conjugated diene polymer having a cis-1,4-bond content of 75% or more.

  Thus, by polymerizing the conjugated diene compound in the presence of the polymerization catalyst composition, the resulting conjugated diene polymer has the advantage that the molecular weight distribution is narrow and the cis-1,4-bond content is high. .

[1-1-1] Conjugated diene compound:
The conjugated diene compound used in the method for producing the modified conjugated diene polymer of this embodiment is a substituted or unsubstituted conjugated diene compound, for example, a linear or branched conjugated diene having 4 to 20 carbon atoms. A compound can be mentioned. Specifically, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, myrcene (7 -Methyl-3-methylideneocta-1,7-diene), cyclo-1,3-pentadiene and the like. Among these, at least one selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene is preferable.

[1-1-2] Polymerization catalyst composition:
The polymerization catalyst composition used in the method for producing the modified conjugated diene polymer of this embodiment is a metallocene-type complex containing at least one group 3 element or bis (phosphinophenyl) containing at least one group 3 element. Including amide type complex. Examples of the metallocene complex (hereinafter sometimes referred to as “first complex”) include, for example, general formula (18): (R ⁹ ) _a M (X ² ) _b · L _c , or general formula (19). : (R ⁹ ) _a M (X ² ) _b Q (X ² ) _b (wherein, in the above general formulas (18) and (19), M is a Group 3 element, R ⁹ is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group, and X ² is a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amide group, or a carbon atom having 1 to 20 carbon atoms It is a hydrogen group, L is a Lewis basic compound, Q is a group 13 element, a is 1 or 2, b is an integer of 0 to 2, and c is an integer of 0 to 2. If a is 2, the two R ⁹ may be the same or different If .b or c is 2, the two X ² or L, and the like each organic metal compound represented by may also be.) To be the same or different.

  In the general formulas (18) and (19), M is not particularly limited as long as it is a Group 3 element. Among Group 3 elements, scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr) ), Neodymium (Nd), samarium (Sm), gadolinium (Gd), or lutetium (Lu).

  That is, the metallocene complex is composed of scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), and lutetium (Lu). It is preferable to contain at least one element selected from the group, and examples of the bis (phosphinophenyl) amide type complex include scandium (Sc), yttrium (Y), lanthanum (La), and praseodymium (Pr). , Neodymium (Nd), samarium (Sm), gadolinium (Gd), and at least one element selected from the group consisting of lutetium (Lu) is preferable.

In the general formulas (18) and (19), the type, number and substitution position of the substituents in the substituted cyclopentadienyl group, substituted indenyl group and substituted fluorenyl group represented by R ⁹ are not particularly limited. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, phenyl group, benzyl group; silicon atoms such as trimethylsilyl group The hydrocarbon group to contain etc. can be mentioned. R ⁹ may be bonded to each other through a crosslinking group such as a dimethylsilyl group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, or a substituted ethylene group.

Specific examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, a benzylcyclopentadienyl group, a vinylcyclopentadienyl group, a 2-methoxyethylcyclopentadienyl group, and a trimethylsilylcyclopentadienyl group. Enyl group, tert-butylcyclopentadienyl group, ethylcyclopentadienyl group, phenylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1, 3-di (tert-butyl) cyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group 1-ethyl-2,3,4,5-tetramethylcyclopentadienyl group, Zyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trimethylsilyl-2,3,4,5- Examples thereof include a tetramethylcyclopentadienyl group and a 1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl group. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. Can be mentioned. R ⁹ is preferably a pentamethylcyclopentadienyl group.

In the general formulas (18) and (19), examples of the halogen atom represented by X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom or an iodine atom is preferable. .

In the general formulas (18) and (19), examples of the alkoxy group represented by X ² include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Aliphatic alkoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentyl Examples thereof include aryloxy groups such as phenoxy group and 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

In the general formulas (18) and (19), examples of the thiolate group represented by X ² include a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, thio an aliphatic thiolate group such as a tert-butoxy group; a thiophenoxy group, a 2,6-di-tert-butylthiophenoxy group, a 2,6-diisopropylthiophenoxy group, a 2-tert-butyl-6-isopropylthiophenoxy group, Aryl thiolate groups such as 2-tert-butyl-6-neopentylthiophenoxy group, 2-isopropyl-6-neopentylthiophenoxy group, 2,4,6-triisopropylthiophenoxy group, etc., among these, 2,4,6-triisopropylthiophenoxy group is preferred.

In the general formulas (18) and (19), the amide group represented by X ² is an aliphatic amide group such as a dimethylamide group, a diethylamide group, or a diisopropylamide group; a phenylamide group, 2,6-di-tert -Butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenyl Examples thereof include arylamide groups such as an amide group, 2-isopropyl-6-neopentylphenylamide group, and 2,4,6-tert-butylphenylamide group. Among these, 2,4,6-tert-butyl A phenylamide group is preferred.

In the general formulas (18) and (19), examples of the hydrocarbon having 1 to 20 carbon atoms represented by X ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, linear or branched aliphatic hydrocarbon groups such as sec-butyl group, tert-butyl group, neopentyl group, hexyl group and octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group and naphthyl group; benzyl And an aralkyl group such as a group; a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group or a bistrimethylsilylmethyl group. Among these, a methyl group, an ethyl group, an isobutyl group, and a trimethylsilylmethyl group are preferable.

  In the general formula (18), L is not particularly limited as long as it is a Lewis basic compound capable of coordinating with a Group 3 element, and may be either an inorganic compound or an organic compound. Examples of Lewis basic compounds include ether compounds, ester compounds, ketone compounds, amine compounds, phosphine compounds, silyloxy compounds, and the like.

  In the general formula (19), Q represents a group 13 element, and specific examples include boron, aluminum, gallium, and the like. Among these, aluminum is preferable.

  Specific examples of the organometallic compound represented by the general formula (18) include, for example, bispentamethylcyclopentadienylbistetrahydrofuran samarium, methylbispentamethylcyclopentadienyltetrahydrofuran samarium, chlorobispentamethylcyclopentadi Specific examples of the organometallic compound represented by the general formula (19) include, for example, dimethylaluminum (μ-dimethyl) bis (pentamethyl), such as eniltetrahydrofuran samarium and iodobispentamethylcyclopentadienyltetrahydrofuran samarium. And cyclopentadienyl) samarium, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium, and the like.

  The first complexes include bispentamethylcyclopentadienylbistetrahydrofuran samarium, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) samarium, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadiene). Enyl) gadolinium is preferred.

  The amount of the first complex used is preferably 0.01 μmol to 2.0 mmol, more preferably 0.1 μmol to 0.2 mmol, and more preferably 1 μmol to 0.02 mmol, with respect to 100 g of the conjugated diene compound. It is particularly preferred that There exists a possibility that a polymerization reaction may not advance that the usage-amount of a 1st complex is less than 0.01 micromol. On the other hand, if it exceeds 2.0 mmol, the catalyst concentration becomes high and a deashing step may be required, which may make the manufacturing process complicated.

  Examples of the bis (phosphinophenyl) amide type complex (hereinafter sometimes referred to as “second complex”) contained in the polymerization catalyst composition include, for example, an organometallic compound represented by the following general formula (20) Etc.

（但し、上記一般式（２０）中、Ｍは３族元素であり、Ｒ^１０は置換されてもよい、アルキル基、シクロアルキル基、アリール基、アラルキル基であり、Ｘ^３は水素原子、ハロゲン原子、アルコキシ基、チオラート基、アミド基、又は炭素数１から２０の炭化水素基であり、Ｌはルイス塩基性化合物である。ｄは１又は２であり、ｅは０〜３の整数である。ｄが２である場合、２個のＸ^３は同一でも異なっていてもよい。ｅが２または３である場合、Ｌはそれぞれ同一でも異なっていてもよい。）

(In the general formula (20), M is a Group 3 element, R ¹⁰ is an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, which may be substituted, and X ³ is a hydrogen atom or a halogen atom. An atom, an alkoxy group, a thiolate group, an amide group, or a hydrocarbon group having 1 to 20 carbon atoms, L is a Lewis basic compound, d is 1 or 2, and e is an integer of 0 to 3. When d is 2, two X ³ may be the same or different.When e is 2 or 3, L may be the same or different.)

  In the general formula (20), M is not particularly limited as long as it is a Group 3 element. Among Group 3 elements, scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium ( Nd), samarium (Sm), gadolinium (Gd), or lutetium (Lu) is preferred.

In the general formula (20), when the alkyl group, cycloalkyl group, aryl group, or aralkyl group represented by R ¹⁰ has a substituent, the type, number and substitution position of the substituent are not particularly limited. Contains silicon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, phenyl, benzyl; trimethylsilyl, etc. A hydrocarbon group etc. can be mentioned.

In the general formula (20), examples of the halogen atom represented by X ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom or an iodine atom is preferable.

In the general formula (20), the alkoxy group represented by X ³ is an aliphatic alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group. Phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2 Examples include aryloxy groups such as -isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

In the general formula (20), the thiolate group represented by X ³ includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, and a thiotert-butoxy group. Aliphatic thiolate groups such as thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert- Examples include arylthiolate groups such as butyl-6-neopentylthiophenoxy group, 2-isopropyl-6-neopentylthiophenoxy group, 2,4,6-triisopropylthiophenoxy group, and among these, A 6-triisopropylthiophenoxy group is preferred.

In the general formula (20), the amide group represented by X ³ includes aliphatic amide groups such as dimethylamide group, diethylamide group, diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide. Group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2 And arylamide groups such as isopropyl-6-neopentylphenylamide group and 2,4,6-tert-butylphenylamide group, among which 2,4,6-tert-butylphenylamide group is preferable. .

In the general formula (20), the hydrocarbon having 1 to 20 carbon atoms represented by ^{X 3,} methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group , Tert-butyl group, neopentyl group, hexyl group, octyl group or the like linear or branched aliphatic hydrocarbon group; phenyl group, tolyl group, naphthyl group or other aromatic hydrocarbon group; benzyl group or other aralkyl group In addition to groups, hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group can be mentioned. Among these, a methyl group, an ethyl group, an isobutyl group, and a trimethylsilylmethyl group are preferable.

  In the general formula (20), L is not particularly limited as long as it is a Lewis basic compound capable of coordinating with a Group 3 element, and may be either an inorganic compound or an organic compound. Examples of Lewis basic compounds include ether compounds, ester compounds, ketone compounds, amine compounds, phosphine compounds, silyloxy compounds, and the like.

Specific examples of the second complex include the formula ((2- (C ₆ H ₅ ) ₂ P) C ₆ H ₄ ) ₂ N) Y (CH ₂ Si (CH ₃ ) ₃ ) ₂ (C ₄ H ₈ compounds represented by _{O), ((2- (C} 6 H 5) 2 P) C 6 H 4) 2 N) Lu (CH 2 Si (CH 3) 3) 2 (C 4 H 8 O), ( (2- (C ₆ H ₅ ) ₂ P) C ₆ H ₄ ) ₂ N) Sc (CH ₂ Si (CH ₃ ) ₃ ) _{2 and the} like can be mentioned. Among them, the formula _{((2- (C 6 H 5} ) 2 P) C 6 H 4) 2 N) Y (CH 2 Si (CH 3) 3) 2 (C 4 H 8 O) a compound represented by Is preferred.

  The amount of the second complex used is preferably 0.01 μmol to 2.0 mmol, more preferably 0.1 μmol to 0.2 mmol, and more preferably 1 μmol to 0.02 mmol, with respect to 100 g of the conjugated diene compound. It is particularly preferred that There exists a possibility that a polymerization reaction may not advance that the usage-amount of a 2nd complex is less than 0.01 micromol. On the other hand, if it exceeds 2.0 mmol, the catalyst concentration becomes high and a deashing step may be required, which may make the manufacturing process complicated.

[1-1-3] Cocatalyst component:
The polymerization catalyst composition preferably further contains at least one compound selected from the group consisting of the following catalysts (α) to (γ) as a promoter component.
Catalyst (α): ionic compound composed of non-coordinating anion and cation Catalyst (β): Aluminoxane Catalyst (γ): Organoaluminum compound represented by formula (17) AlR ⁷ R ⁷ R ⁸ However, in said general formula (17), R < ⁷ > is respectively the same or different and is a hydrogen atom or a C1-C10 hydrocarbon group, and R < ⁸ > is the same or different C1-C10 hydrocarbon as R < ⁷ >. Base)

  The catalyst (α) is an ionic compound composed of a non-coordinating anion and a cation. Non-coordinating anions include, for example, tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (penta Fluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, trideca Examples thereof include hydride-7,8-dicarboundeborate.

  Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.

  Examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

  Examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like, N, N-diethylanilinium cations, N, Examples thereof include N, N-dialkylanilinium cations such as N-2,4,6-pentamethylanilinium cation, dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

  Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

  In addition, what was arbitrarily selected and combined from the non-coordinating anion and cation can be used for the said ionic compound, respectively. For example, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium Tetrakis (pentafluorophenyl) borate and the like are preferable. The ionic compounds may be used alone or in combination of two or more.

  In the polymerization catalyst composition, the mixing ratio of the first complex or the second complex and the ionic compound (first complex or second complex / ionic compound) is 1 / 0.1 to 0.1 in molar ratio. It is preferably 1/10, more preferably 1 / 0.2 to 1/5, and particularly preferably 1 / 0.5 to 1/2.

  The catalyst (β) is aluminoxane. Aluminoxane (hereinafter sometimes referred to as “alumoxane”) is a compound whose structure is represented by the following general formula (21) or (22). In addition, Fine Chemical, 23, (9), 5 (1994), J. Org. Am. Chem. Soc. 115, 4971 (1993); Am. Chem. Soc. 117, 6465 (1995), and alumoxane aggregates.

In the general formulas (21) and (22), R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, and k in the general formulas (21) and (22) is an integer of 2 or more. . Examples of R ¹¹ in the general formulas (21) and (22) include groups such as ethyl, propyl, butyl, isobutyl, t-butyl, hexyl, isohexyl, octyl, and isooctyl. Of these, groups such as methyl, ethyl, isobutyl, t-butyl and the like are preferable, and a methyl group is more preferable. Moreover, it is preferable that k of the said General Formula (21) and (22) is an integer of 4-100.

  Examples of the alumoxane include methylalumoxane (MAO), ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, and isohexylalumoxane. be able to. Alumoxane can be produced by a known method. For example, trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, xylene, and water, water vapor, steam-containing nitrogen gas, or copper sulfate pentahydrate or aluminum sulfate 16-hydrate. It can be produced by adding a salt having water of crystallization to react. In addition, an alumoxane can be used individually or in mixture of 2 or more types.

  In the polymerization catalyst composition, the mixing ratio of the first complex or the second complex and the aluminoxane (the first complex or the second complex / aluminoxane) is 1/1 to 1/10000 in terms of molar ratio. Is preferably 1/10 to 1/5000, more preferably 1/50 to 1/1000.

The catalyst (γ) is an organoaluminum compound represented by the general formula (17) AlR ⁷ R ⁷ R ⁸ (however, in the general formula (17), R ⁷ is the same or different and has 1 to 10 carbon atoms. A hydrocarbon group or a hydrogen atom, and R ⁸ is the same or different hydrocarbon group having 1 to 10 carbon atoms as R ⁷ ).

  Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and trihexyl. Aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctylaluminum hydride, diisooctylaluminum hydride, ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like.

  Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. In addition, the said organoaluminum compound can be used individually or in mixture of 2 or more types.

  In the polymerization catalyst composition, the mixing ratio of the first complex or second complex and the organoaluminum compound (first complex or second complex / organoaluminum compound) is 1 / 0.1 to 0.1 in molar ratio. It is preferably 1/10000, more preferably 1 / 0.2 to 1 / 50,000, and particularly preferably 1 / 0.5 to 1/10000.

  In addition to the first complex, the second complex, and the catalysts (α) to (γ), the polymerization catalyst composition includes at least one selected from the group consisting of a conjugated diene compound and a non-conjugated diene compound. Compounds can be included. The inclusion of these compounds is preferable because the catalytic activity is further improved. As this conjugated diene compound, the same conjugated diene compound as described above can be used. Examples of non-conjugated diene compounds include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene.

  Before using the polymerization catalyst composition, each component (the first complex, the second complex, and the catalysts (α) to (γ), etc.) may be mixed and reacted in advance and aged. From the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period. The aging temperature is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. If the aging temperature is less than 0 ° C, aging may be insufficient. On the other hand, if it exceeds 100 ° C., there is a possibility that the catalytic activity is lowered and the molecular weight distribution is likely to be widened. In addition, there is no restriction | limiting in particular in aging time, 30 minutes or more is enough.

  The polymerization conditions for the conjugated diene compound are not particularly limited, but the temperature of the polymerization reaction is preferably -30 to + 200 ° C, more preferably 0 to + 150 ° C. Moreover, there is no restriction | limiting in particular also about the reaction form of a polymerization reaction, You may carry out using a batch type reactor, and you may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor.

  Further, in the polymerization reaction, a solvent (polymerization solvent) may be used or a solvent may not be used. When a polymerization solvent is used, the polymerization solvent is preferably an inert organic solvent, for example, a saturated aliphatic hydrocarbon having 4 to 10 carbon atoms such as butane, pentane, hexane, or heptane, or a carbon number such as cyclopentane or cyclohexane. 6-20 saturated alicyclic hydrocarbons, monoolefins such as 1-butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene and other halogenated hydrocarbons.

  In addition, when using a polymerization solvent, it is preferable that the mixture ratio of a conjugated diene type compound is 5-50 mass% with respect to the total amount of a reaction solution, and it is still more preferable that it is 7-35 mass%.

  Further, in order to produce a conjugated diene polymer and not to deactivate the conjugated diene polymer having an active terminal, a compound having a deactivating action such as oxygen, water, or carbon dioxide gas is contained in the polymerization system. It is preferable to consider to minimize the contamination.

  The conjugated diene polymer obtained in this step needs to have a cis-1,4-bond content of 75% or more, preferably 99% or more, and 99.5% or more. Further preferred. When a conjugated diene polymer having a cis-1,4-bond content of 99% or more is used, a modified conjugated diene polymer having improved fracture characteristics can be produced. The cis-1,4-bond content of the conjugated diene polymer can be easily adjusted by controlling the polymerization temperature. Here, the fracture characteristics are a general term for wear resistance, crack growth resistance, tensile strength, and the like.

  Further, the conjugated diene polymer obtained in this step has a ratio (Mw / Mn) of 2.0 or less of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography. Preferably, it is preferably 1.8 or less, and particularly preferably 1.5 or less. When the ratio (Mw / Mn) is more than 2.0, rubber properties such as fracture characteristics and low heat build-up properties of the vulcanized rubber obtained using the modified conjugated diene polymer produced as a material are lowered. There is a tendency. In this specification, “weight average molecular weight (Mw)” refers to a standard polystyrene equivalent value using a gel permeation chromatograph, and “number average molecular weight (Mn)” also refers to a gel permeation. It shall mean the standard polystyrene conversion value using an aation chromatograph. In addition, Mw / Mn can be easily adjusted by controlling the usage-amount of a 1st complex or a 2nd complex, and the molar ratio of a catalyst ((alpha))-((gamma)) component.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the conjugated diene polymer is preferably 5 to 50, and more preferably 10 to 40. If it is less than 5, the mechanical properties after vulcanization, wear resistance and the like may be reduced. On the other hand, if it exceeds 50, the processability during kneading of the resulting modified conjugated diene polymer may be lowered. This Mooney viscosity can be easily adjusted by controlling the amount of the first complex or the second complex used and the molar ratio of the catalyst (α) to (γ) components.

[1-2] Step (B):
Next, in the method for producing a modified conjugated diene polymer of the present embodiment, a modifier is reacted with the obtained conjugated diene polymer.

  By reacting the modifier, the active end of the conjugated diene polymer obtained in the step (A) reacts and a controlled branched structure is introduced, so that the modified conjugated diene heavy polymer having good cold flow characteristics is introduced. There is an advantage that coalescence can be obtained.

  The modifier is capable of reacting with the conjugated diene polymer, and by this reaction, it is possible to provide a vulcanized rubber that maintains low heat buildup and wear resistance, as well as cold flow characteristics. Is not particularly limited as long as it can obtain a modified conjugated diene polymer with good cold flow (suppressed cold flow), but at least selected from the group consisting of the following components (a) to (g): It is preferable that it contains a kind of compound. Hereinafter, each component will be described.

  The component (a) is an alkoxysilane compound containing in its molecular structure at least one group selected from the group consisting of an epoxy group and an isocyanate group.

  Examples of the component (a) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltriphenoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane, (3- Glycidyloxypropyl) methyldiethoxysilane, (3-glycidyloxypropyl) methyldiphenoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane condensate, (3-glycidyloxypropyl) methyldiethoxysilane condensate, Contains epoxy groups such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane condensate, and 3-glycidyloxypropyltriethoxysilane condensate That the alkoxysilane compound can be exemplified. These may be used alone or in combination of two or more.

  Among these, 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxypropyltriethoxysilane are preferable from the viewpoint that cold flow characteristics can be improved.

  Examples of the component (a) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltriphenoxysilane, (3-isocyanatopropyl) methyldimethoxysilane, ( 3-isocyanatopropyl) methyldiethoxysilane, (3-isocyanatopropyl) methyldiphenoxysilane, (3-isocyanatopropyl) methyldimethoxysilane condensate, (3-isocyanatopropyl) methyldiethoxysilane condensation , Β- (isocyanatocyclohexyl) ethyltrimethoxysilane, (3-isocyanatopropyl) trimethoxysilane condensate, and (3-isocyanatopropyl) triethoxysilane condensate It can be exemplified alkoxysilane compounds.

  Among these, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane are preferable from the viewpoint that cold flow characteristics can be improved.

  These components (a) can be used alone or in combination of two or more.

Component (b) has the general formula ^{_{(1) R 1 n M 1}} X 4-n, the general formula ⁽²⁾ M 1 _{X 4,} the general formula ⁽³⁾ from the group consisting of compounds represented by M 2 _{X 3} It can be at least one compound selected.
(However, in the general formula (1), ^{R 1} is the same or different, respectively, a hydrocarbon group having 1 to 20 carbon atoms, the general formula (1) and (2), ^{M 1} each, tin atom , Silicon atom, or germanium atom, in formula (3), M ² is a phosphorus atom, and in formulas (1) to (3), each X is a halogen atom, 1), n is an integer of 0 to 3)

  That is, the compound represented by the general formula (1) is a halogenated organometallic compound, and the compounds represented by the general formulas (2) and (3) are metal halide compounds.

When M ¹ is a tin atom, examples of the compound represented by the general formula (1) include triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, Examples thereof include dibutyltin dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride and the like. Examples of the compound represented by the general formula (2) include tin tetrachloride and tin tetrabromide.

When M ¹ is a silicon atom, examples of the compound represented by the general formula (1) include triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, Examples include dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenylchlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, and methyltrichlorosilane. Examples of the compound represented by the general formula (2) include silicon tetrachloride and silicon tetrabromide.

When M ¹ is a germanium atom, examples of the compound represented by the general formula (1) include triphenyl germanium chloride, dibutyl germanium dichloride, diphenyl germanium dichloride, butyl germanium trichloride, and the like. Examples of the compound represented by the general formula (2) include germanium tetrachloride and germanium tetrabromide.

  Examples of the compound represented by the general formula (3) include phosphorus trichloride and phosphorus tribromide.

  In addition, the compounding ratio of the compound represented by general formula (1)-(3) in (b) component can be determined suitably.

  The component (c) is a compound having a structure represented by the general formula (4) Y = C = Z in the molecular structure (provided that, in the general formula (4), Y represents a carbon atom, an oxygen atom) , A nitrogen atom, or a sulfur atom, and Z is an oxygen atom, a nitrogen atom, or a sulfur atom).

  For example, in the general formula (4), when Y is a carbon atom and Z is an oxygen atom, it is a ketene compound, and when Y is a carbon atom and Z is a sulfur atom, it is a thioketene compound, Y is a nitrogen atom, Z Is an isocyanate compound, Y is a nitrogen atom, and Z is a sulfur atom, it is a thioisocyanate compound, and when both Y and Z are nitrogen atoms, it is a carbodiimide compound, and Y and Z are When both are oxygen atoms, it is carbon dioxide, when Y is an oxygen atom and Z is a sulfur atom, it is carbonyl sulfide, and when both Y and Z are sulfur atoms, it is carbon disulfide. In addition, (c) component is not limited to these combinations, Arbitrary combinations can be selected.

  Examples of the ketene compound include ethyl ketene, butyl ketene, phenyl ketene, and toluyl ketene. Examples of the thioketene compound include ethylene thioketene, butyl thioketene, phenyl thioketene, toluyl thioketene, and the like. Examples of the isocyanate compound include phenyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like. Can be mentioned. Examples of the thioisocyanate compound include phenylthioisocyanate, 2,4-tolylene diisocyanate, hexamethylene dithioisocyanate, and the like. Examples of the carbodiimide compound include N, N′-diphenylcarbodiimide, N, N′-diethylcarbodiimide, and the like.

  Among these, isocyanate compounds are preferable, and polymer type diphenylmethane diisocyanate and hexamethylene diisocyanate are particularly preferable as the isocyanate compound.

  The component (d) is a compound having a structure represented by the following general formula (5) in its molecular structure (in the general formula (5), Z represents an oxygen atom, a nitrogen atom, or a sulfur atom) Is). That is, the component (d) is a compound containing a hetero three-membered ring.

  For example, in the general formula (5), when Z is an oxygen atom, it is an epoxy compound, when it is a nitrogen atom, it is an ethyleneimine derivative, and when it is a sulfur atom, it is a thiirane compound.

  Examples of the epoxy compound include ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, and ethylene glycol diglycidyl. Ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycidyl methacrylate, glycidyl acrylate, N, N-diglycidyl Aniline, N, N-diglycidyl tolui Emissions, N, N-glycidyl-glycidyloxy aniline, can be mentioned tetraglycidyl diaminodiphenyl methane and the like.

  Among these, epoxidized soybean oil, trimethylolpropane polyglycidyl ether, or tetraglycidylaminodiphenylmethane is preferable from the viewpoint that cold flow characteristics can be improved.

  Examples of the ethyleneimine derivative include ethyleneimine, propyleneimine, N-phenylethyleneimine, N- (β-cyanoethyl) ethyleneimine, and the like. Furthermore, examples of the thiirane compound include thiirane, methylthiirane, and phenylthiirane.

  The component (e) is a compound having a structure represented by the general formula (6) N = C—X in the molecular structure. That is, the component (e) is a halogenated isocyano compound.

  Examples of the component (e) include 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, 3,6-dichloro- 4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6-dichloropyrimidine 6-chloro-2,4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4,5,6-tetra Chloropyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6-dichloropyrazine, 2,4-bis ( Tilthio) -6-chloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 2-bromo-5-nitrothiazole, 2-chlorobenzothiazole, 2-chlorobenzo Examples include oxazole.

  Among these, 2,4,5,6-tetrachloropyrimidine is preferable from the viewpoint that cold flow characteristics can be improved.

The component (f) includes general formula (7) R ⁴ (COOH) _m , general formula (8) R ⁴ (COX) _m , general formula (9) R ⁴ (COO-R ⁴ ) _m , general formula (10) R ⁴ -OCOO-R ⁴ , General Formula (11) R ⁴ (COOCO-R ⁴ ) _m , the following General Formula (12), or a compound represented by the following General Formula (13) (however, the above General Formula In (7) to (12), R ⁴ is the same or different and is a hydrocarbon group having 1 to 50 carbon atoms. In the general formula (8), X is a halogen atom, and the general formula (7). , (8) and (11), m is an integer of 1 to 5, and R ⁵ in the general formula (13) is an alkylene group which may contain a substituent, and h is 1 to 50. Is an integer).

  Examples of the compound represented by the general formula (7) include acetic acid, stearic acid, adipic acid, maleic acid, benzoic acid, acrylic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyro Examples include merit acid, merit acid, polymethacrylic acid ester compound, hydrolyzate or partial hydrolyzate of polyacrylic acid compound, and the like.

  The compound represented by the general formula (8) is an acid halide, for example, acetic acid chloride, propionic acid chloride, butanoic acid chloride, isobutyric acid chloride, octanoic acid chloride, acrylic acid chloride, benzoic acid chloride, stearic acid chloride. Phthalic acid chloride, maleic acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, benzoyl fluoride and the like.

  The compound represented by the general formula (9) is an ester compound. For example, ethyl acetate, ethyl stearate, diethyl adipate, diethyl maleate, methyl benzoate, ethyl acrylate, ethyl methacrylate, diethyl phthalate Dimethyl terephthalate, tributyl trimellitic acid, tetraoctyl pyromellitic acid, hexaethyl meritate, phenyl acetate, polymethyl methacrylate, polyethyl acrylate, polyisobutyl acrylate and the like. Among these, diethyl adipate, diethyl maleate, and tetraoctyl pyromelliate are preferable from the viewpoint that cold flow characteristics can be improved.

  The compound represented by the general formula (10) is a carbonate compound, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dihexyl carbonate, and diphenyl carbonate.

  Examples of the compound represented by the general formula (11) include acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptanoic anhydride, benzoic anhydride, and cinnamic anhydride.

  Examples of the compound represented by the general formula (12) include succinic anhydride, methyl succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, and phthalic anhydride.

In general formula (7) ~ (12), R 4 is a hydrocarbon group having 1 to 50 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon having 1 to 8 carbon atoms More preferably, it is a group. If the carbon number is more than 50, the mixing property is not sufficient and there is a possibility that the reaction does not occur uniformly. Moreover, m in general formula (7), (8) and (11) is an integer of 1-5, It is preferable that it is an integer of 1-3, and it is still more preferable that it is an integer of 1-2. When m is more than 5, the mixing property is not sufficient and there is a possibility that the reaction does not occur uniformly.

  Examples of the compound represented by the general formula (13) include a styrene-maleic anhydride copolymer, an ethylene-maleic anhydride copolymer, and a propylene-maleic anhydride copolymer.

In general formula (13), R ⁵ is an alkylene group which may contain a substituent, and the alkylene group preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. preferable. H is an integer of 1 to 50, preferably an integer of 1 to 40, and more preferably an integer of 2 to 30. Examples of the substituent for R ⁵ include an aryl group and an alkyl group.

  The component (f) may be used alone or in combination of two or more.

(G) component is represented by the general formula _{^{(14) R 6 l M 3}} (OCOR 6) 4-l, formula _{^{(15) R 6 l M 3}} (OCOR 6 -COOR 6) 4-l or below general, a compound represented by the formula (16) (where, in the general formula (14) ~ (16), ^{R 6} are the same or each a hydrocarbon group having 1 to 20 carbon atoms, ^{M 3} is a tin An atom, a silicon atom, or a germanium atom, l is an integer of 0 to 2, and J is 0 or 1.

  Examples of the compound represented by the general formula (14) include triphenyltin laurate, triphenyltin-2-ethyl hexatate, triphenyltin naphthate, triphenyltin acetate, triphenyltin acrylate, tri-n- Butyltin laurate, tri-n-butyltin-2-ethylhexarate, tri-n-butyltin naphthate, tri-n-butyltin acetate, tri-n-butyltin acrylate, tri-t-butyltin laurate, tri-t- Butyl tin-2-ethyl hexatate, tri-t-butyl tin naphthate, tri-t-butyl tin acetate,

  Tri-t-butyltin acrylate, triisobutyltin laurate, triisobutyltin-2-ethylhexarate, triisobutyltin naphthate, triisobutyltin acetate, triisobutyltin acrylate, triisopropyltin laurate, triisopropyltin-2 -Ethyl hexatate, triisopropyl tin naphthate, triisopropyl tin acetate, triisopropyl tin acrylate, trihexyl tin laurate, trihexyl tin-2-ethyl hexatate, trihexyl tin acetate, trihexyl tin acrylate, trioctyl tin Laurate, trioctyltin-2-ethylhexarate, trioctyltin naphthate, trioctyltin acetate, trioctyltin acrylate, tri- - ethylhexyl tin dilaurate, tri-2-ethylhexyl tin 2-ethylhexanoate Tate, tri-2-ethylhexyl Suzuna off Tate, tri-2-ethylhexyl tin acetate, tri-2-ethylhexyl tin acrylate,

  Tristearyl tin laurate, Tristearyl tin-2-ethyl hexatate, Tristearyl tin naphthate, Tristearyl tin acetate, Tristearyl tin acrylate, Tribenzyl tin laurate, Tribenzyl tin-2-ethyl hexatate, Tribenge Rutin naphthate, tribenzyltin acetate, tribenzyltin acrylate, diphenyltin dilaurate, diphenyltin-di-2-ethylhexarate, diphenyltin distearate, diphenyltin dinaphthate, diphenyltin diacetate, diphenyltin diacrylate,

  Di-n-butyltin dilaurate, di-n-butyltin di-2-ethylhexarate, di-n-butyltin distearate, di-n-butyltin dinaphthate, di-n-butyltin diacetate, di-n-butyltin Diacrylate, di-t-butyltin dilaurate, di-t-butyltin di-2-ethylhexarate, di-t-butyltin distearate, di-t-butyltin dinaphthate, di-t-butyltin diacetate, di- t-butyltin diacrylate, diisobutyltin dilaurate, diisobutyltin di-2-ethylhexarate, diisobutyltin distearate, diisobutyltin dinaphthate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate,

  Diisopropyltin-di-2-ethylhexarate, diisopropyltin distearate, diisopropyltin dinaphthate, diisopropyltin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexarate, dihexyltin di Stearate, dihexyltin dinaphthate, dihexyltin diacetate, dihexyltin diacrylate, di-2-ethylhexyltin dilaurate, di-2-ethylhexyltin-di-2-ethylhexarate, di-2-ethylhexyltin distearate Rate, di-2-ethylhexyltin dinaphthate, di-2-ethylhexyltin diacetate, di-2-ethylhexyltin diacrylate, dioctyltin dilaurate, dioctylus Di-2-ethylhexanoate Tate, dioctyltin distearate, dioctyltin naphthoquinone Tate, dioctyltin diacetate, dioctyltin diacrylate,

  Distearyl tin dilaurate, distearyl tin di-2-ethyl hexatate, distearyl tin distearate, distearyl tin dinaphthate, distearyl tin diacetate, distearyl tin diacrylate, dibenzyl tin dilaurate, dibenzyl tin di-2 -Ethyl hexatate, dibenzyl tin distearate, dibenzyl tin dinaphthate, dibenzyl tin diacetate, dibenzyl tin diacrylate, phenyl tin trilaurate, phenyl tin tri-2-ethyl hexatate, phenyl tin tri Naphthate, phenyltin triacetate, phenyltin triacrylate,

  n-butyltin trilaurate, n-butyltin tri-2-ethylhexarate, n-butyltin trinaphthate, n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2- Ethyl hexatate, t-butyl tin trinaphthate, t-butyl tin triacetate, t-butyl tin triacrylate, isobutyl tin trilaurate, isobutyl tin tri-2-ethyl hexatate, isobutyl tin trinaphthate, isobutyl tin triacetate, isobutyl tin Triacrylate, isopropyl tin trilaurate, isopropyl tin tri-2-ethyl hexatate, isopropyl tin trinaphthate, isopropyl tin triacetate, isopropyl tin triacrylate Hexyl tin trilaurate, hexyl tin tri-2-ethyl hexatate, hexyl tin trinaphthate, hexyl tin triacetate, hexyl tin triacrylate, octyl tin trilaurate, octyl tin tri-2-ethyl hexatate, Octyltin trinaphthate, octyltin triacetate, octyltin triacrylate, 2-ethylhexyltin trilaurate, 2-ethylhexyltin tri-2-ethylhexarate, 2-ethylhexyltin trinaphthate, 2-ethylhexyltin triacetate, 2 -Ethylhexyl tin triacrylate, stearyl tin trilaurate, stearyl tin tri-2-ethyl hexatate, stearyl tin trinaphthate, stearyl tin triacetate, stear Dibutyltin triacrylate, benzyl tin trilaurate, benzyl tin tri-2-ethylhexanoate Tate, benzyl tin tri naphthoquinone Tate, benzyl tin triacetate, and benzyl tin triacrylate.

  Examples of the compound represented by the general formula (15) include diphenyltin bismethylmalate, diphenyltin bis-2-ethylhexylmalate, diphenyltin bisoctylmalate, diphenyltin bisbenzylmalate, and di-n-butyltin bismethylmalate. Di-n-butyltin bis-2-ethylhexyl malate, di-n-butyltin bisoctyl malate, di-n-butyltin bisbenzyl malate, di-t-butyltin bismethylmalate, di-t-butyltin Bis-2-ethylhexyl malate, di-t-butyltin bisoctylmalate, di-t-butyltin bisbenzylmalate, diisobutyltin bismethylmalate, diisobutyltin bis-2-ethylhexylmalate, diisobutyltin bisoctylmalate rate, Isobutyl tin bis benzyl maleate, diisopropyl tin bis methyl maleate, diisopropyl tin bis-2-ethylhexyl maleate, diisopropyl tin bis-octyl maleate, diisopropyl tin bis benzyl maleate,

  Dihexyltin bismethylmalate, dihexyltin bis-2-ethylhexylmalate, dihexyltin bisoctylmalate, dihexyltin bisbenzylmalate, di-2-ethylhexyltin bismethylmalate, di-2-ethylhexyltin bis- 2-ethylhexylmalate, di-2-ethylhexyltin bisoctylmalate, di-2-ethylhexyltin bisbenzylmalate, dioctyltin bismethylmalate, dioctyltin bis-2-ethylhexylmalate, dioctyltin bisoctylmer Rate, dioctyltin bisbenzyl malate,

  Distearyl tin bismethyl malate, distearyl tin bis-2-ethylhexyl malate, distearyl tin bis octyl malate, distearyl tin bis benzyl malate, dibenzyl tin bismethyl malate, dibenzyl tin bis-2- Ethylhexyl malate, dibenzyltin bisoctyl malate, dibenzyltin bisbenzyl malate, diphenyltin bismethyladipate, diphenyltin bis-2-ethylhexyl adipate, diphenyltin bisoctyl adipate, diphenyltin bisbenzyladipate,

  Di-n-butyltin bismethyl adipate, di-n-butyltin bis-2-ethylhexyl adipate, di-n-butyltin bisoctyl adipate, di-n-butyltin bisbenzyl adipate, di-t-butyltin bismethyladipate, di- t-butyltin bis-2-ethylhexyl adipate, di-t-butyltin bisoctyl adipate, di-t-butyltin bisbenzyl adipate, diisobutyltin bismethyladipate, diisobutyltin bis-2-ethylhexyl adipate, diisobutyltin bisoctyl adipate, diisobutyl Tin bisbenzyl adipate, diisopropyl tin bismethyl adipate, diisopropyl tin bis-2-ethylhexyl adipate, diisopropyl tin bisoctyl adipate, dii Propyl tin bis-benzyl adipate, dihexyl tin bis-methyl adipate,

  Dihexyltin bis-2-ethylhexyl adipate, dihexyltin bismethyladipate, dihexyltin bisbenzyladipate, di-2-ethylhexyltin bismethyladipate, di-2-ethylhexyltin bis-2-ethylhexyl adipate, di-2-ethylhexyltin Bisoctyl adipate, di-2-ethylhexyltin bisbenzyladipate, dioctyltin bismethyladipate, dioctyltin bis-2-ethylhexyladipate, dioctyltin bisoctyladipate, dioctyltin bisbenzyladipate, distearyltin bismethyladipate, distearyl Tin bis-2-ethylhexyl adipate, distearyl tin bisoctyl adipate, distearyl tin bisbenzyl adipate, Benzyl tin bis-methyl adipate, may be mentioned dibenzyl tin bis-2-ethylhexyl adipate, dibenzyl tin bis-octyl adipate, dibenzyl tin bis-benzyl adipate.

  Furthermore, as the compound represented by the general formula (15), for example, two carboxylic acid skeletons such as malonic acid, malic acid, and succinic acid may be used instead of the compound containing the maleic acid skeleton or the adipic acid skeleton. The compound to contain may be sufficient.

  Among these, from the viewpoint that cold flow characteristics can be improved, dioctyltin bis-2-ethylhexyl malate, dioctyltin bisoctyl malate, dioctyltin bisbenzyl malate, dioctyltin bis-2-ethylhexyl adipate, Dioctyltin bisoctyl adipate and dioctyltin bisbenzyl adipate are preferred.

  Examples of the compound represented by the general formula (16) include diphenyl tin maleate, di-n-butyl tin maleate, di-t-butyl tin maleate, diisobutyl tin maleate, diisopropyl tin maleate, dihexyl tin maleate, Di-2-ethylhexyl tin malate, dioctyl tin malate, distearyl tin malate, dibenzyl tin malate, diphenyl tin adipate, di-n-butyl tin adipate, di-t-butyl tin adipate, diisobutyl tin adipate, diisopropyl tin adipate , Dihexyltin adipate, di-2-ethylhexyltin adipate, dioctyltin adipate, distearyltin adipate, dibenzyltin adipate, and the like.

  Furthermore, as the compound represented by the general formula (16), for example, two carboxylic acid skeletons such as malonic acid, malic acid, and succinic acid may be used instead of the compound containing the maleic acid skeleton or the adipic acid skeleton. The compound to contain may be sufficient.

  Among these, from the viewpoint that cold flow characteristics can be improved, di-2-ethylhexyltin maleate, dioctyltin maleate, di-2-ethylhexyltin adipate, or dioctyltin adipate is preferable.

R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 8 carbon atoms. When the number of carbon atoms is more than 20, the mixing property is not sufficient and there is a possibility that they will not react uniformly. The component (g) may be used alone or in combination of two or more.

  As the modifier used in the method for producing the modified conjugated diene polymer of the present embodiment, the components (a) to (g) described above may be used alone or in combination of two or more.

  In addition, the manufacturing method of the modified conjugated diene polymer of this embodiment further uses (a) component and at least 1 type of compound selected from the group which consists of (b)-(g) component. It is particularly preferable to use the component (a) and at least one compound selected from the group consisting of the component (c) or the component (g). By such a combination, a modified conjugated diene polymer having better cold flow characteristics can be obtained.

  It is preferable that the usage-amount of the modifier used for the manufacturing method of the modified conjugated diene polymer of this embodiment is 0.02-20 mmol with respect to 1 mol of conjugated diene polymers, and is 0.1-10 mmol. Is more preferable, and it is especially preferable that it is 0.2-5 mmol. If the usage-amount of a modifier | denaturant is less than 0.02 mmol, there exists a possibility that progress of a modification | denaturation reaction may not be enough and the improvement effect of cold flow characteristics may not be expressed. On the other hand, even if it exceeds 20 mmol, the effect of improving the cold flow characteristics is saturated, and the effect obtained for the cost tends to be insufficient. Moreover, there exists a possibility that a toluene insoluble content, ie, a gel, may be generated.

  Further, the modifier contains (a) component and at least one compound selected from the group consisting of components (b) to (g) (hereinafter may be referred to as “other components”). In this case, the content ratio of the component (a) and the total amount of the other components is preferably 5 to 90 mol% of the component (a) (95 to 10 mol% of the other components), and the component (a) More preferably, it is 10-80 mol% (other components are 90-20 mol%). If the component (a) is outside the above range (less than 5 mol% or more than 90 mol%), the effect of improving cold flow characteristics may not be sufficiently obtained.

  The reaction conditions for the conjugated diene polymer and the modifying agent are not particularly limited, but it is preferably performed by a solution reaction. This solution reaction may be, for example, a solution containing unreacted monomers used when polymerizing a conjugated diene polymer. The reaction format is not particularly limited, and may be performed using a batch reactor, or may be performed continuously using an apparatus such as a multistage continuous reactor or an inline mixer. Moreover, when using 2 or more types among (a)-(g) component, there is no restriction | limiting in particular in the order which adds (a)-(g) component to a reaction solution.

  Moreover, the reaction temperature of this process can use the polymerization temperature at the time of superposing | polymerizing a conjugated diene type polymer at the said (A) process as it is. Specifically, 0 to 120 ° C is preferable, and 10 to 100 ° C is more preferable. When the polymerization temperature is less than 0 ° C, the viscosity of the resulting modified conjugated diene polymer may be increased. On the other hand, if it exceeds 120 ° C., the polymerization active terminal may be easily deactivated. The reaction time is preferably 5 minutes to 5 hours, and more preferably 15 minutes to 1 hour.

  The desired modified conjugated diene polymer can be recovered by adding a polymerization terminator or polymerization stabilizer to the reaction system, if necessary, and carrying out conventionally known solvent removal and drying operations in the production of the modified conjugated diene polymer. can do.

[2] Modified conjugated diene polymer:
One embodiment of the modified conjugated diene polymer of the present invention is produced by the method for producing a modified conjugated diene polymer described above. Such a modified conjugated diene polymer has an advantage that a vulcanized rubber having low heat build-up and excellent wear resistance can be obtained.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the modified conjugated diene polymer of the present embodiment is preferably 10 to 100, and more preferably 20 to 80. If the Mooney viscosity (ML _{1 + 4} , 100 ° C.) is less than 10, rubber properties such as fracture characteristics may be deteriorated. On the other hand, when the Mooney viscosity (ML _{1 + 4} , 100 ° C.) is more than 100, workability when kneading with the compounding agent may be deteriorated.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the modified conjugated diene polymer is preferably 3.5 or less. 3.0 or less is more preferable, and 2.5 or less is particularly preferable.

  Further, the modified conjugated diene polymer preferably has a cold flow value of 1.5 mg / min or less, more preferably 1.0 mg / min or less, and 0.5 mg / min or less. Particularly preferred. If the cold flow value exceeds 1.5 mg / min, the shape stability during storage may be deteriorated.

Here, in this specification, “cold flow value” means that the modified conjugated diene polymer is maintained at a temperature of 50 ° C. and the modified conjugated diene polymer is 1 at a pressure of 3.5 lb / in ² (24.1 kPa). / 4 inch (6.35 mm) orifice, and after 10 minutes from the point of extrusion (after the extrusion speed becomes constant), the modified conjugated diene polymer is extruded every 30 minutes for 90 minutes. ) And the average value (mg / min) obtained.

[3] Rubber composition:
One embodiment of the rubber composition of the present invention includes the above-described modified conjugated diene copolymer. With such a configuration, it is possible to obtain a rubber composition that can provide a vulcanized rubber having low heat build-up and excellent wear resistance. The details will be described below.

  The content ratio of the modified conjugated diene copolymer in the rubber composition of the present embodiment is not particularly limited, but is preferably 20% by mass or more, and 30% by mass or more with respect to the total amount of the rubber composition. More preferably, it is more preferably 40% by mass or more. If the content is less than 20% by mass, the resulting rubber composition may have insufficient mechanical properties, crack growth resistance, and wear resistance.

  In addition, the rubber composition of this embodiment may contain a kind of modified conjugated diene copolymer, or may contain two or more kinds of modified conjugated diene copolymers.

  Moreover, the rubber composition of this embodiment may contain other polymer components in addition to the modified conjugated diene copolymer. Examples of other polymer components include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-diene copolymer, and acrylonitrile-butadiene. Examples thereof include copolymers, chloroprene rubber, halogenated butyl rubber, and mixtures thereof. The other polymer component may be a polyfunctional type partly such as a polymer having a branched structure treated with a modifier such as tin tetrachloride or silicon tetrachloride. Good.

  The rubber composition preferably further contains carbon black. By containing carbon black, there is an advantage that the effect of improving the grip performance and fracture resistance of the rubber composition is increased. Examples of the carbon black include carbon blacks of various grades such as SRF, GPF, FEF, HAF, ISAF, and SAF. Among these, HAF, ISAF, SAF, and the like are preferable from the viewpoint of excellent wear resistance. In addition, the said carbon black can be used individually or in mixture of 2 or more types. Further, the carbon black preferably has an iodine adsorption amount (IA) of 60 mg / g or more and a dibutyl phthalate oil absorption (DBP) of 80 ml / 100 g or more.

  The rubber composition contains 20 parts by mass of the modified conjugated diene copolymer with respect to 100 parts by mass of the total amount of the modified conjugated diene copolymer and other polymer components (hereinafter sometimes referred to as “rubber component”). % Or more, the content of carbon black in the rubber composition is preferably 20 to 120 parts by mass with respect to 100 parts by mass of the rubber component. From a viewpoint, it is still more preferable that it is 25-100 mass parts. If the carbon black content is less than 20 parts by mass, the effect of improving the fracture resistance and the like may be insufficient. On the other hand, if the carbon black content is more than 120 parts by mass, the processability of the rubber composition may be reduced.

  Further, the rubber composition can contain silica in addition to carbon black. By containing silica, silica acts as a reinforcing filler, and the reinforcing effect can be further improved. As silica, it is preferable that a silane coupling agent is contained, for example.

  Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). Silylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane,

  3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-di Ethoxymethylsilylpropyl) tetrasulfide,

  Examples include 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, and dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide. Among these, bis (3-triethoxysilylpropyl) polysulfide, 3-trimethoxysilylpropylbenzothiazyl tetrasulfide, and the like are preferable from the viewpoint of reinforcing effect. In addition, the said silane coupling agent can be used individually or in mixture of 2 or more types.

  Although the usage-amount of a silane coupling agent changes with kinds etc. of a silane coupling agent, it is preferable that it is 1-20 mass% with respect to 100 mass% of silica, and it is still more preferable that it is 3-15 mass%. . There exists a possibility that the effect as a coupling agent may become difficult to fully exhibit that the said usage-amount is less than 1 mass%. On the other hand, if it exceeds 20% by mass, the rubber component may be easily gelled.

  In addition, the chemical | medical agent, additive, etc. which are normally used in the rubber industry can be added to the rubber composition of this embodiment as needed in the range which does not impair the objective of this invention. Examples of various chemicals and additives that can be added to the rubber composition of the present embodiment include vulcanizing agents, vulcanizing aids, processing aids, vulcanization accelerators, process oils, anti-aging agents, and scorch prevention. Agents, zinc white, stearic acid and the like.

  As the vulcanizing agent, for example, sulfur can be used. The amount of sulfur used is preferably 0.1 to 3 parts by mass and more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component. As the vulcanization aid and processing aid, for example, stearic acid can be used. The amount of stearic acid used is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. Examples of the vulcanization accelerator include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide. The amount of the vulcanization accelerator used is preferably 0.1 to 5 parts by mass and more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.

  The rubber composition of the present embodiment is a rubber component, and if necessary, carbon black or silica, using a kneader such as an open kneader such as a roll, a closed kneader such as a Banbury mixer, It can be manufactured by kneading. The rubber composition produced in this manner is molded and then vulcanized, for example, a low fuel consumption tire, a large tire, a high performance tire tread material, and a high performance tire sidewall material. It can be used as various rubber products.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Various measurements in Examples and Comparative Examples were performed by the following methods.

[Mooney viscosity (ML _{1 + 4} , 100 ° C.)]:
According to JIS K6300, an L rotor was used, and preheating was performed for 1 minute, a rotor operation time of 4 minutes, and a temperature of 100 ° C.

[Molecular weight distribution (Mw / Mn)]:
Using a gel permeation chromatograph (trade name “HLC-8120GPC” (manufactured by Tosoh Corporation)), a differential refractometer was used as a detector, and measurement was performed under the following conditions, and the standard polystyrene conversion value was calculated.
Column: 2 brand names “GMHXL” (manufactured by Tosoh Corporation) Column temperature: 40 ° C.
Mobile phase; tetrahydrofuran flow rate; 1.0 ml / min sample concentration; 10 mg / 20 ml

[Cis-1,4-bond content]:
Measurement was performed using NMR (trade name “EX-270” (manufactured by JEOL Ltd.)).

The cis-1,4-bond content of the conjugated diene polymer produced by Examples and Comparative Examples using butadiene as the conjugated diene compound was measured as follows. 1,4-bond in ¹ H-NMR analysis: signal intensity ratio of 5.30-5.50 ppm, 1,2-bond: 4.94-5.03 ppm, After calculating the ratio of 1,2-bond, from the intensity ratio of signals of cis-1,4-bond: 25.5 ppm and 1,4-trans bond: 32.8 ppm in ¹³ C-NMR analysis, cis-1 The 4-bond content was calculated as a measured value.

The cis-1,4-bond content of the conjugated diene polymer produced by Examples and Comparative Examples using isoprene as the conjugated diene compound was measured as follows. 1,4-trans bond in ¹³ C-NMR analysis: 15.5 to 16.5 ppm, 3,4-bond: 18.0 to 19.0 ppm, cis-1,4-bond: 23.0 to 24.0 ppm From the signal intensity ratio, the cis-1,4-bond content was calculated and used as the measured value.

[Cold flow value]:
The modified conjugated diene polymer was held at a temperature of 50 ° C., and the modified conjugated diene polymer was extruded from a 6.35 mm orifice at a pressure of 24.1 kPa. Ten minutes after the time of extrusion (after the extrusion speed becomes constant), the modified conjugated diene polymer is measured for extrusion amount (mg) every 30 minutes for 90 minutes, and the average value is the cold flow value. (Mg / min).

[Low exothermicity (3% tan δ)]:
A dynamic spectrometer (manufactured by Rheometrics, USA) was used, and measurement was performed under the conditions of tensile dynamic strain 3%, frequency 15 Hz, and 50 ° C. The measured value was converted into an index with the measured value of the vulcanized rubber of Comparative Example 9 as “100”, and the converted value was used as an evaluation value for low exothermic property (3% tan δ). It shows that exothermic property is so small and favorable that an index | exponent is large. In Table 4, “low heat generation” is indicated.

[Abrasion resistance]:
The measurement was performed at room temperature using a Lambourn type wear tester (manufactured by Shimada Giken Co., Ltd.) with a slip ratio of 60%. The measured value (wear amount (g)) of the vulcanized rubber of Comparative Example 9 was converted to an index with “100”, and the converted value was used as an evaluation value for wear resistance. The larger the index value, the better the wear resistance.

Example 1
[Production of Modified Conjugated Diene Polymer]:
First, a toluene solution containing a compound represented by the formula (C ₅ (CH ₃ ) ₅ ) Sm (C ₄ H ₈ O) ₂ (hereinafter sometimes referred to as “Cp · Sm”) as the first complex. (3.5 mmol / L) and a toluene solution (0.7 mol / L) containing toluene-soluble aluminoxane (trade name “MMAO3”, manufactured by Tosoh Finechem) as a promoter component were mixed at a ratio of 1: 1. The mixture was reacted at room temperature for 30 minutes and aged to obtain a catalyst solution. Next, 2.4 kg of toluene and 300 g of 1,3-butadiene (shown as “BD” in Tables 1 and 2) as a conjugated diene compound were added to an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Prepared. Thereafter, 2 L of the catalyst solution was charged, and a polymerization reaction was performed at room temperature for 60 minutes to obtain a polymerization solution. The reaction conversion rate of 1,3-butadiene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing 2,4-di-tert-butyl-p-cresol (hereinafter sometimes referred to as “BHT”). The polymerization of the polymer solution was stopped.

In addition, in order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution is desolvated by steam stripping, and then dried by a roll heated to 110 ° C. to be conjugated diene polymer. (Conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 21, a molecular weight distribution (Mw / Mn) of 2.1, and a cis-1,4-bond content of 99.3%. there were. Table 1 shows the formulation and evaluation results.

Next, the polymer solution is kept at room temperature, 0.37 mmol of 3-glycidyloxypropyltrimethoxysilane (hereinafter sometimes referred to as “GPMOS”) is added to the polymer solution as a modifier, and the reaction is performed for 15 minutes. I let you. Thereafter, 0.18 mmol of dioctyltin bisoctyl malate (hereinafter may be referred to as “DOTBOM”) was further added as a modifier, and the reaction was allowed to proceed for 15 minutes. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping and then dried by a roll heated to 110 ° C. to obtain a modified conjugated diene polymer (shown as “polymer A” in Tables 3 and 4). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 52, a molecular weight distribution (Mw / Mn) of 2.2, and a cold flow value of 0.2 mg / min.

(Example 2)
First, as a first complex, a toluene solution (1.8 mmol / L) containing Cp · Sm and a toluene solution containing triisobutylaluminum (hereinafter sometimes referred to as “TIBA”) as a promoter component ( 18 mmol / L) and a toluene solution (1.8 mmol / L) containing triphenylcarbonium tetrakis (pentafluorophenyl) borate (hereinafter sometimes referred to as “PCFB”) 1: 1 (first complex: (Promoter component) were mixed, reacted at room temperature for 30 minutes, and aged to obtain a catalyst solution. Next, 2.4 kg of toluene and 300 g of 1,3-butadiene as a conjugated diene compound were charged in an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Thereafter, 2 L of the catalyst solution was charged, and a polymerization reaction was performed at room temperature for 120 minutes to obtain a polymerization solution. The reaction conversion rate of 1,3-butadiene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing BHT, and the polymerization of the polymer solution was stopped.

In addition, in order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution is desolvated by steam stripping, and then dried by a roll heated to 110 ° C. to be conjugated diene polymer. (Conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 19, a molecular weight distribution (Mw / Mn) of 1.4, a cis-1,4-bond content of 96.9%. there were. Table 1 shows the formulation and evaluation results.

Next, the polymer solution was kept at room temperature, and 1 L of a toluene solution (0.37 mmol / L) containing GPMOS as a modifier was added to the polymer solution and allowed to react for 15 minutes. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping, and then dried by a roll heated to 110 ° C. to obtain a modified conjugated diene polymer (shown as “polymer B” in Tables 3 and 4). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 47, a molecular weight distribution (Mw / Mn) of 1.7, and a cold flow value of 0.4 mg / min.

(Example 3)
First, as the first complex, a compound represented by the formula (C ₅ (CH ₃ ) ₅ ) Gd (μ-CH ₃ ) ₂ Al (CH ₃ ) ₂ (hereinafter sometimes referred to as “Cp · Gd”) A toluene solution containing 11 mmol / L and a toluene solution containing TIBA (55 mmol / L) and a PCFB containing toluene solution as a promoter component (11 mmol / L) were mixed at a ratio of 1: 1. The mixture was reacted at room temperature for 30 minutes and aged to obtain a catalyst solution. Next, 2.4 kg of toluene and 300 g of 1,3-butadiene as a conjugated diene compound were charged in an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Thereafter, 2 L of the catalyst solution was charged, and a polymerization reaction was performed at room temperature for 30 minutes to obtain a polymerization solution. The reaction conversion rate of 1,3-butadiene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing BHT, and the polymerization of the polymer solution was stopped.

In addition, in order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution is desolvated by steam stripping, and then dried by a roll heated to 110 ° C. to be conjugated diene polymer. (Conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 23, a molecular weight distribution (Mw / Mn) of 1.9, and a cis-1,4-bond content of 98.5%. there were. Table 1 shows the formulation and evaluation results.

Next, the polymer solution was kept at room temperature, and a toluene solution (0.37 mmol / 0.37 mol / min) containing 3-isocyanatopropyltriethoxysilane (hereinafter sometimes referred to as “IPEOS”) as a modifier was added to the polymer solution. 1 L of L) was added and allowed to react for 15 minutes. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping and then dried by a roll heated to 110 ° C. to obtain a modified conjugated diene polymer (shown as “polymer C” in Tables 3 and 4). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 45, a molecular weight distribution (Mw / Mn) of 2.2, and a cold flow value of 0.4 mg / min.

Example 4
First, 2.4 kg of toluene and 300 g of 1,3-butadiene as a conjugated diene compound were charged in an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Next, a toluene solution (40 mmol / L) containing TIBA as a promoter component was added and stirred at room temperature for 10 minutes. Then, as a second complex, the formula ((2- (C ₆ H ₅ ) ₂ P) C ₆ H ₄ ) ₂ N) Y (CH ₂ Si (CH ₃ ) ₃ ) ₂ (C ₄ H ₈ O) ( Hereinafter, a toluene solution (3.8 mmol / L) containing a compound represented by “PNPY” may be added, and further a toluene solution (3.8 mmol / L) containing PCFB is added, The polymerization reaction was carried out for 20 minutes to obtain a polymerization solution. The reaction conversion rate of 1,3-butadiene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing BHT, and the polymerization of the polymer solution was stopped.

In addition, in order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution is desolvated by steam stripping, and then dried by a roll heated to 110 ° C. to be conjugated diene polymer. (Conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 24, a molecular weight distribution (Mw / Mn) of 1.1, and a cis-1,4-bond content of 99.0%. there were. Table 1 shows the formulation and evaluation results.

Next, the polymer solution is kept at room temperature, and polymethylene polyphenyl polyisocyanate (trade name “PAPI135”, manufactured by Dow Chemical Japan Co., Ltd., hereinafter referred to as “CMDI” may be used as a modifier. 1 L of a toluene solution containing 0.7) (0.72 mmol (isocyanate group equivalent) / L) was added and reacted for 15 minutes. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping and then dried by a roll heated to 110 ° C. to obtain a modified conjugated diene polymer (shown as “Polymer D” in Tables 3 and 4). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 56, a molecular weight distribution (Mw / Mn) of 1.3, and a cold flow value of 0.2 mg / min.

(Example 5)
First, a toluene solution (3.5 mmol / L) containing Cp · Sm as the first complex and a toluene solution (0.7 mol / L) containing MMAO ₃ as the promoter component were used at a ratio of 1: 1. The mixture was mixed, reacted at room temperature for 30 minutes, and aged to obtain a catalyst solution. Next, 2.4 kg of toluene and 300 g of 1,3-butadiene as a conjugated diene compound were charged in an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Thereafter, 2 L of the catalyst solution was charged, and a polymerization reaction was performed at room temperature for 60 minutes to obtain a polymerization solution. The reaction conversion rate of 1,3-butadiene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing BHT, and the polymerization of the polymer solution was stopped.

In addition, in order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution is desolvated by steam stripping, and then dried by a roll heated to 110 ° C. to be conjugated diene polymer. (Conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 21, a molecular weight distribution (Mw / Mn) of 2.1, and a cis-1,4-bond content of 99.1%. there were. Table 1 shows the formulation and evaluation results.

Next, the above polymer solution is kept at room temperature, and 0.37 mmol of trimethylolpropane polyglycidyl ether (hereinafter sometimes referred to as “TMMPGE”) as a modifier is added to the polymer solution and reacted for 15 minutes. It was. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping and then dried by a roll heated to 110 ° C. to obtain a modified conjugated diene polymer (shown as “polymer E” in Tables 3 and 4). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 44, a molecular weight distribution (Mw / Mn) of 2.2, and a cold flow value of 0.5 mg / min.

(Example 6)
A modified conjugated diene polymer (in Tables 3 and 4) was used in the same manner as in Example 5 except that 0.37 mmol of silicon tetrachloride (hereinafter sometimes referred to as “TCS”) was added instead of TMMPGE. "Polymer F") was obtained. This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 54, a molecular weight distribution (Mw / Mn) of 2.2, and a cold flow value of 0.2 mg / min.

(Example 7)
Modified conjugated diene system in the same manner as in Example 5 except that 0.37 mmol of 2,4,5,6-tetrachloropyrimidine (hereinafter sometimes referred to as “TCP”) was added instead of TMMPGE. A polymer (shown as “Polymer G” in Tables 3 and 4) was obtained. This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 42, a molecular weight distribution (Mw / Mn) of 2.3, and a cold flow value of 0.4 mg / min.

(Example 8)
A modified conjugated diene polymer (in Tables 3 and 4) was used in the same manner as in Example 5 except that 0.18 mmol of maleic anhydride (hereinafter sometimes referred to as “MAUHT”) was added instead of TMPPGE. "Polymer H") was obtained. This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 48, a molecular weight distribution (Mw / Mn) of 2.4, and a cold flow value of 0.3 mg / min.

Example 9
A modified conjugated diene polymer (Table 3) was prepared in the same manner as in Example 1 except that TCS (0.18 mmol) was added instead of GPMOS, and TCP (0.18 mmol) was added without adding DOTBOM. , 4 shows “Polymer I”). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 46, a molecular weight distribution (Mw / Mn) of 2.2, and a cold flow value of 0.4 mg / min.

(Example 10)
A modified conjugated diene polymer (Table 3) was prepared in the same manner as in Example 1 except that TMPPGE (0.18 mmol) was added in place of GPMOS, and MAUH (0.09 mmol) was added without adding DOTBOM. , 4 shows “Polymer J”). This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 45, a molecular weight distribution (Mw / Mn) of 2.3, and a cold flow value of 0.3 mg / min.

(Example 11)
First, a toluene solution (0.14 mol / L) containing Cp · Gd as the first complex, a toluene solution (0.7 mol / L) containing TIBA as a promoter component, and a toluene solution containing PCFB ( 0.14 mol / L) was mixed at a ratio of 1: 1, reacted at room temperature for 30 minutes, and aged to obtain a catalyst solution. Next, 2.4 kg of toluene and 300 g of isoprene (shown as “IP” in Tables 1 and 2) as a conjugated diene compound were charged in an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Thereafter, 2 L of the catalyst solution was charged, and a polymerization reaction was performed at room temperature for 30 minutes to obtain a polymerization solution. The reaction conversion rate of isoprene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing BHT, and the polymerization of the polymer solution was stopped.

In order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution was desolvated by steam stripping and then dried at 110 ° C. for 12 hours in a hot air dryer. A system polymer (conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 34, a molecular weight distribution (Mw / Mn) of 1.4, and a cis-1,4-bond content of 98.4%. there were. Table 1 shows the formulation and evaluation results.

Next, the polymer solution is kept at room temperature, and 1 L of a toluene solution (0.37 mmol / L) containing diethyl adipate (hereinafter sometimes referred to as “AADE”) as a modifier is added to the polymer solution. And allowed to react for 15 minutes. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping and then dried in a hot air dryer at 110 ° C. for 12 hours to obtain a modified conjugated diene polymer (shown as “Polymer K” in Tables 3 and 4). It was. This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 75, a molecular weight distribution (Mw / Mn) of 1.6, and a cold flow value of 0.2 mg / min.

Example 12
First, a chlorobenzene solution (7.5 mmol / L) containing PNPY as the second complex and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (hereinafter referred to as “PNFB”) may be used as the promoter component. ) Containing chlorobenzene solution (7.5 mmol / L) at a ratio of 1: 1 (second complex: promoter component), reacted at room temperature for 30 minutes, and aged to obtain a catalyst solution. Next, 2.4 kg of chlorobenzene and 300 g of isoprene as a conjugated diene compound were charged in an autoclave reactor with an internal volume of 5 liters purged with nitrogen under nitrogen. Thereafter, 2 L of the catalyst solution was charged, and a polymerization reaction was performed at room temperature for 30 minutes to obtain a polymerization solution. The reaction conversion rate of isoprene was almost 100%. Next, 200 g of the obtained polymer solution was added to a methanol solution (0.2 g / L) containing BHT, and the polymerization of the polymer solution was stopped.

In order to perform various evaluations of the conjugated diene polymer in the polymer solution, the polymer solution was desolvated by steam stripping and then dried at 110 ° C. for 12 hours in a hot air dryer. A system polymer (conjugated diene polymer before modification) was obtained. This conjugated diene polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 33, a molecular weight distribution (Mw / Mn) of 1.1, and a cis-1,4-bond content of 99.4%. there were. Table 1 shows the formulation and evaluation results.

Next, the polymer solution was kept at room temperature, and 1 L of a toluene solution (0.37 mmol / L) containing GPMOS as a modifier was added to the polymer solution and allowed to react for 15 minutes. After the reaction, this reaction solution was added to a methanol solution containing BHT (1.5 g / L) to stop the polymerization reaction. The reaction solution was desolvated by steam stripping and then dried in a hot air dryer at 110 ° C. for 12 hours to obtain a modified conjugated diene polymer (shown as “polymer L” in Tables 3 and 4). It was. This modified conjugated diene polymer had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 86, a molecular weight distribution (Mw / Mn) of 1.3, and a cold flow value of 0.1 mg / min.

(Comparative Example 1)
Except that the concentration of the toluene solution containing TIBA was changed to 28 mmol / L and IPEOS as a modifier was not added, a conjugated diene polymer (in Tables 3 and 4, “Polymer M” "). Table 2 shows various evaluation results of the conjugated diene polymer.

(Comparative Example 2)
The conjugated diene polymer (in Tables 3 and 4, “heavy” was used in the same manner as in Example 6 except that the concentration of the toluene solution containing TIBA was changed to 0.35 mol / L and the modifier AADE was not added. Combined N ”) was obtained. Table 2 shows various evaluation results of the conjugated diene polymer.

(Reference Example 1)
The Mooney viscosity (ML _{1 + 4} , 100 ° C.), molecular weight distribution (Mw / Mn), and cis-1,4-bond content were measured for a commercially available polybutadiene rubber (trade name “polybutadiene rubber BR01”, manufactured by JSR). As a result of the measurement, the Mooney viscosity (ML _{1 + 4} , 100 ° C.) was 45, the molecular weight distribution (Mw / Mn) was 4.0, and the cis-1,4-bond content was 95.0%. In Tables 3 and 4, “Polymer O” is shown.

(Reference Example 2)
Measurement of Mooney viscosity (ML _{1 + 4} , 100 ° C.), molecular weight distribution (Mw / Mn), and cis-1,4-bond content of commercially available polyisoprene rubber (trade name “Polyisoprene Rubber I R2200”, manufactured by JSR) did. As a result of the measurement, the Mooney viscosity (ML _{1 + 4} , 100 ° C.) was 82, the molecular weight distribution (Mw / Mn) was 3.5, and the cis-1,4-bond content was 98.0%. In Tables 3 and 4, “Polymer P” is shown.

(Example 13)
[Preparation of rubber composition]:
50 parts of the polymer A obtained in Example 1, 50 parts of natural rubber, 50 parts of carbon black (trade name: Seast KH, manufactured by Tokai Carbon Co., Ltd.), 3.5 parts of zinc oxide, 2 parts of stearic acid, anti-aging N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (trade name: Nocrack 6C, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 1.5 parts as a vulcanizing agent, N-cyclohexyl as a vulcanization accelerator A rubber composition was obtained by kneading 1.5 parts of 2-benzothiazylsulfenamide (trade name: Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1 part of sulfur.

  The resulting rubber composition was vulcanized at 145 ° C. for 33 minutes to obtain a vulcanized rubber, and the low exothermic property (3% tan δ) and wear resistance of this vulcanized rubber were evaluated by the methods described above. The evaluation results were a low exothermic property (3% tan δ) of 106 and an abrasion resistance of 126.

(Examples 14 to 24, Comparative Examples 3 to 6)
A rubber composition was prepared according to the formulation shown in Table 3 (Formulation 1 or 2), and the resulting rubber composition was vulcanized at 145 ° C. for 33 minutes to obtain a vulcanized rubber. The low exothermic property (3% tan δ) and the abrasion resistance were evaluated by the methods described above. The evaluation results are shown in Table 4.

  As is clear from Tables 1 and 2, the conjugated diene compound is polymerized in the presence of the polymerization catalyst composition to obtain a conjugated diene polymer, and the resulting conjugated diene polymer is reacted with a modifier (modification reaction). The modified conjugated diene polymers of Examples 1 to 12 obtained in Example 1 were the polymers of Comparative Examples 1 and 2 and Reference Examples 1 and 2 obtained without performing the above-described modification reaction (conjugated diene polymers). Compared to the polymer), the cold flow was low (plastic deformation hardly occurred) and good, and it was confirmed that the storage stability was excellent. That is, it can be seen that the modified conjugated diene polymer obtained by the method for producing the modified conjugated diene polymer of the present invention is excellent in stability during storage.

  Further, as is apparent from Table 4, the modified conjugated diene polymers of Examples 1 to 12 are as low as exothermic properties as Comparative Examples 1 and 2 and Reference Examples 1 and 2 (conjugated diene polymers). It was also confirmed that the wear resistance was maintained.

  Further, as is apparent from Table 4, the vulcanized rubber formed by the rubber compositions of Examples 13 to 24 has lower heat build-up and the vulcanized rubber formed by the rubber compositions of Comparative Examples 3 to 6. It was confirmed that the wear resistance was excellent.

  According to the method for producing a modified conjugated diene polymer of the present invention, a modified conjugated diene heavy polymer which can be suitably used as a vulcanized rubber material excellent in heat generation and wear resistance and has good cold flow characteristics. A coalescence can be manufactured and the modified conjugated diene-type polymer obtained can be used suitably, for example as a material of a fuel-efficient tire.

  The modified conjugated diene polymer of the present invention can be suitably used, for example, as a material for low fuel consumption tires.

  The rubber composition of the present invention can be suitably used, for example, as a material for low fuel consumption tires.

Claims (8)

The conjugated diene compound is polymerized in the presence of a polymerization catalyst composition containing a metallocene type complex containing at least one group 3 element or a bis (phosphinophenyl) amide type complex containing at least one group 3 element, A conjugated diene polymer having a cis-1,4-bond content of 75% or more is obtained;
A method for producing a modified conjugated diene polymer, wherein a modifier is reacted with the obtained conjugated diene polymer. The method for producing a modified conjugated diene polymer according to claim 1, wherein the modifier contains at least one compound selected from the group consisting of the following components (a) to (g).
(A) Component: Alkoxysilane compound containing in its molecular structure at least one group selected from the group consisting of an epoxy group and an isocyanate group (b) Component: General formula (1) R ¹ _n M ¹ At least one compound selected from the group consisting of compounds represented by X _4-n , general formula (2) M ¹ X ₄ , and general formula (3) M ² X ₃ (provided that the general formula (1) R ¹ is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms. In the general formulas (1) and (2), M ¹ is a tin atom, a silicon atom, or a germanium atom, respectively. In the general formula (3), M ² is a phosphorus atom, in the general formulas (1) to (3), each X is a halogen atom, and in the general formula (1), n is 0 to 0, respectively. (It is an integer of 3)
(C) Component: a compound having a structure represented by the general formula (4) Y = C = Z in the molecular structure (wherein Y is a carbon atom, oxygen atom, nitrogen atom in the general formula (4)) Or a sulfur atom, and Z is an oxygen atom, a nitrogen atom, or a sulfur atom)
Component (d): A compound having a structure represented by the following general formula (5) in its molecular structure (however, in the general formula (5), Z is an oxygen atom, a nitrogen atom, or a sulfur atom).

(E) Component: Compound having a structure represented by general formula (6) N = C—X in the molecular structure (f) Component: General formula (7) R ⁴ (COOH) _m , General formula (8 ₎ ^R 4 (COX) _m, the general formula ^{(9) R 4 (COO-} R 4) m, the general formula ^{(10) R 4 -OCOO-R} 4, the general formula ^{(11) R 4 (COOCO-} R 4) m , At least one compound selected from the group consisting of compounds represented by the following general formula (12) and the following general formula (13) (provided that, in the general formulas (7) to (12), R ⁴ represents It is the same or different, It is a C1-C50 hydrocarbon group, In said general formula (8), X is a halogen atom, In said general formula (7), (8) and (11), m is respectively an integer from 1 to 5, in the general formula (13), R ⁵ is optionally contain a substituent alkyl Is down based on, h is an integer of 1 to 50)

Component (g): General formula _{^{(14) R 6 l M 3}} (OCOR 6) 4-l, formula _{^{(15) R 6 l M 3}} (OCOR 6 -COOR 6) 4-l, and the following formula At least one compound selected from the group consisting of compounds represented by (16) (provided that, in the general formulas (14) to (16), each R ⁶ is the same or different and is a hydrocarbon having 1 to 20 carbon atoms) And M ³ is a tin atom, a silicon atom, or a germanium atom, l is an integer of 0 to 2, and J is 0 or 1)

The modified conjugated diene polymer according to claim 1 or 2, wherein the polymerization catalyst composition further contains at least one catalyst selected from the group consisting of the following catalysts (α) to (γ) as a promoter component. Manufacturing method.
Catalyst (α): ionic compound composed of non-coordinating anion and cation Catalyst (β): Aluminoxane Catalyst (γ): Organoaluminum compound represented by formula (17) AlR ⁷ R ⁷ R ⁸ However, in said general formula (17), R < ⁷ > is the same or different, respectively, and is a hydrogen atom or a C1-C10 hydrocarbon group, R < ⁸ > is the same or different C1-C10 hydrocarbon as R < ⁷ >. Base)   The metallocene type complex is selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), and lutetium (Lu). Containing at least one selected element, wherein the bis (phosphinophenyl) amide type complex is scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd) The modified conjugated diene system according to any one of claims 1 to 3, which contains at least one element selected from the group consisting of samarium (Sm), gadolinium (Gd), and lutetium (Lu). A method for producing a polymer.   The conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. A process for producing a modified conjugated diene polymer.   The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw) of the conjugated diene polymer having a cis-1,4-bond content of 99% or more and measured by gel permeation chromatography. / Mn) is 2.0 or less, The manufacturing method of the modified conjugated diene polymer as described in any one of Claims 1-5.   The modified conjugated diene polymer manufactured by the manufacturing method of the modified conjugated diene polymer as described in any one of Claims 1-6.   A rubber composition comprising the modified conjugated diene polymer according to claim 7.