JP2008280384A - Copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a copolymer of a conjugated diene compound and an olefin except the conjugated diene compound. <P>SOLUTION: The method for producing a copolymer comprises a process for polymerizing a conjugated diene compound with an olefin except the conjugated diene compound in the presence of a polymerization catalyst composition containing at least one kind of a complex selected from metallocene complexes represented by the general formula (I) (wherein M is a lanthanoide element, scandium or yttrium; Cp<SP>R</SP>s<SP></SP>are each independently nonsubstituted or substituted indenyl; R<SP>a</SP>-R<SP>f</SP>are each independently a 1-3C alkyl group; L is a neutral Lewis base; and w is an integer of 0-3) etc. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a copolymer and a method for producing the copolymer, and more particularly, to a copolymer of a conjugated diene compound and an olefin other than the conjugated diene compound having a high cis-1,4 bond amount in the conjugated diene compound portion. It relates to a manufacturing method.

  Conventionally, catalyst systems used for coordination anionic polymerization have low reactivity with olefin monomers (particularly cycloolefin), and it has been difficult to polymerize the monomers. On the other hand, since the catalyst system used for coordination anionic polymerization can control the geometric isomer structure of the polymer, including stereospecific polymerization, the formation reaction of various polymers using the catalyst system has been reported. ing. For example, in Japanese Translation of PCT International Publication No. 2006-503141 (Patent Document 1), by using a metallocene complex as a polymerization catalyst for a copolymer of ethylene and butadiene, butadiene is inserted in the form of a trans-1,2 cyclohexane bond. Is disclosed.

  By the way, with respect to the polymerization reaction of cycloolefin monomers, ring-opening metathesis polymerization has been actively studied. On the other hand, an example of vinyl addition polymerization that does not involve ring opening of cycloolefin monomers. Is rare.

JP-T-2006-503141

  Accordingly, an object of the present invention is to provide a method for producing a copolymer of a conjugated diene compound and an olefin other than the conjugated diene compound, which uses a novel metallocene complex and has a high cis-1,4 bond amount in the conjugated diene compound portion. Is to provide. Another object of the present invention is to use a conjugated diene compound and an olefin other than the conjugated diene compound, in which a cyclic olefin is used as an olefin other than the conjugated diene compound, and the cyclic olefin is polymerized by a vinyl addition type reaction mode. It is in providing the manufacturing method of the copolymer of this. Furthermore, the other object of this invention is to provide the copolymer obtained by this manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors polymerized a conjugated diene compound and an olefin other than the conjugated diene compound in the presence of a polymerization catalyst composition containing a specific metallocene complex. The inventors have found that a copolymer composed of monomers can be obtained, and have completed the present invention.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式(II)：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ^’は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式(III)：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、[Ｂ]⁻は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物の存在下、共役ジエン化合物と、該共役ジエン化合物以外のオレフィンとを重合させる工程を含むことを特徴とする。 That is, the method for producing a copolymer of the present invention comprises the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. And L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating In the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by an anion), a conjugated diene compound and an olefin other than the conjugated diene compound are polymerized. Including a process.

  Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex. The olefin is an aliphatic unsaturated hydrocarbon compound having at least one carbon-carbon double bond.

  In a preferred example of the method for producing a copolymer of the present invention, the olefin other than the conjugated diene compound is a non-conjugated olefin.

  In another preferred embodiment of the method for producing a copolymer of the present invention, the olefin other than the conjugated diene compound is a cyclic olefin. Here, as the cyclic olefin, norbornene, dicyclopentadiene, norbonadiene, cyclohexene, and ethylidene norbornene are preferable.

  In another preferred embodiment of the method for producing a copolymer of the present invention, the olefin other than the conjugated diene compound is an acyclic olefin.

  The copolymer of the present invention is selected from the group consisting of the metallocene complexes represented by the general formula (I) and the general formula (II) and the half metallocene cation complex represented by the general formula (III). It is obtained by polymerizing a conjugated diene compound and an olefin other than the conjugated diene compound in the presence of a polymerization catalyst composition containing at least one kind of complex.

  In a preferred example of the copolymer of the present invention, polymerization of the conjugated diene compound and an olefin other than the conjugated diene compound is addition polymerization.

  In another preferred embodiment of the copolymer of the present invention, the olefin other than the conjugated diene compound is a non-conjugated olefin.

  In another preferred embodiment of the copolymer of the present invention, the olefin other than the conjugated diene compound is an acyclic olefin.

  In the copolymer of the present invention, it is preferable that the conjugated diene compound and an olefin other than the conjugated diene compound are randomly polymerized.

  Furthermore, the copolymer of the present invention is a copolymer of a conjugated diene compound and a cyclic olefin other than the conjugated diene compound.

  In a preferred example of the copolymer of the present invention, the cyclic olefin repeating unit has a cyclic structure.

  In another preferred embodiment of the copolymer of the present invention, the cyclic olefin is at least one selected from the group consisting of norbornene, dicyclopentadiene, norbonadiene, cyclohexene, and ethylidene norbornene.

  In the copolymer of the present invention, it is preferable that the conjugated diene compound and a cyclic olefin other than the conjugated diene compound are randomly polymerized.

  In another preferred embodiment of the copolymer of the present invention, the cis-1,4 bond content of the conjugated diene compound moiety is 85% or more.

  According to the present invention, a copolymer comprising these monomers is produced by polymerizing a conjugated diene compound and an olefin other than the conjugated diene compound in the presence of a polymerization catalyst composition containing a specific metallocene complex. be able to. Further, by using a cyclic olefin as an olefin other than the conjugated diene compound, a copolymer obtained by polymerizing the cyclic olefin by a vinyl addition type reaction mode can be produced.

  The present invention is described in detail below. The method for producing the copolymer of the present invention is selected from the group consisting of the metallocene complexes represented by the general formula (I) and the general formula (II) and the half metallocene cation complex represented by the general formula (III). And a step of polymerizing a conjugated diene compound and an olefin other than the conjugated diene compound in the presence of a polymerization catalyst composition containing at least one kind of complex. As described above, the coordination anion polymerization catalyst has low reactivity with olefin monomers (particularly cycloolefin), and it has been difficult to polymerize the monomers. Therefore, the inventors have optimized the conjugated diene compound polymerization reaction by optimizing the central metal used for the main catalyst and the ligand of the central metal in the catalyst system used for the coordinated anion polymerization. It has been found that olefins other than diene compounds can be introduced. A copolymer of a conjugated diene compound and an olefin other than the conjugated diene compound obtained by using such a catalyst system has a high cis-1,4 bond amount in the microstructure of the conjugated diene compound portion. Therefore, the copolymer obtained by the production method of the present invention has a high elongation crystallinity of the conjugated diene compound portion and is maintained in a state where the glass transition point (Tg) is low, so that the wear resistance is improved. It can be used suitably as a rubber component in the rubber composition.

  The copolymer of the conjugated diene compound obtained by the method for producing a copolymer of the present invention and an olefin other than the conjugated diene compound is not particularly limited except that a polymerization catalyst composition described in detail later is used. It can be obtained by copolymerizing a mixture of a monomeric conjugated diene compound and an olefin other than the conjugated diene compound in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst. In the method for producing a copolymer of the present invention, the polymerization of a conjugated diene compound and an olefin other than the conjugated diene compound is preferably addition polymerization. As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. When a solvent is used for the polymerization reaction, the solvent used may be inactive in the polymerization reaction, and the amount of the solvent used is arbitrary, but the concentration of the complex contained in the polymerization catalyst composition is 0.1 to 0.0001 mol. The amount is preferably / l.

  Examples of the conjugated diene compound used as the monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene is preferable. In addition, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  On the other hand, the olefin used as the monomer is not particularly limited as long as it is an olefin excluding the conjugated diene compound, and may be a cyclic olefin or an acyclic olefin, but has excellent heat resistance and the main chain of the copolymer. Since it is possible to increase the degree of design freedom as an elastomer by reducing the proportion of double bonds in the interior and reducing the crystallinity, non-conjugated olefins are preferred, and only one carbon-carbon double bond is present. More preferred are monoolefins. Specific examples of the olefin other than the conjugated diene compound include cyclic olefins such as norbornene, dicyclopentadiene, norbonadiene, cyclohexene, and ethylidene norbornene. Among these, norbornene or dicyclopentadiene is particularly preferable. In addition, olefins other than these conjugated diene compounds may be used alone or in combination of two or more.

In the method for producing a copolymer of the present invention, when a cyclic olefin is used as an olefin other than the conjugated diene compound, the polymerization reaction does not proceed by ring-opening metathesis polymerization, but the cyclic structure of the cyclic olefin is opened. Since the process proceeds by unadditional vinyl addition polymerization, a copolymer in which the cyclic olefin repeating unit has a cyclic structure derived from the cyclic olefin is obtained. Thus, the introduction of the cyclic olefin in the form of a cyclic structure derived from the cyclic olefin into the main chain of the polymer formed in the polymerization reaction of the conjugated diene compound by a vinyl addition type reaction method has been heretofore. This is a production method that makes it possible to synthesize a copolymer of a novel conjugated diene compound and a cyclic olefin. In addition, it can confirm by the < ¹³ > C-NMR spectrum that the copolymer of a cyclic olefin and a conjugated diene compound is produced | generated and the repeating unit of the cyclic olefin in this copolymer has a cyclic structure.

  The polymerization catalyst composition used in the method for producing a copolymer of the present invention includes a metallocene complex represented by the general formula (I) and the formula (II), and a half metallocene cation complex represented by the general formula (III). It is necessary to include at least one kind of complex selected from the group consisting of, and it is preferable to further include other components such as a co-catalyst contained in a polymerization catalyst composition including a normal metallocene complex.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. In addition, two Cp ^R in the general formula (I) and the formula (II) may be the same or different from each other.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^{R ′} having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^{R ′} having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formula (I), formula (II) and formula (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a bistrialkylsilylamide ligand [—N (SiR ₃ ) ₂ ]. The alkyl groups R (R ^{a to} R ^f in the general formula (I)) contained in the bistrialkylsilylamide are each independently an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group.

The metallocene complex represented by the general formula (II) contains a silyl ligand [—SiX ^′ ₃ ]. X ^′ contained in the silyl ligand [—SiX ^′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group; phenoxy group and 2,6-di- -tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thio sec-butoxy group, a thio tert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group is preferable.

  In the general formula (III), the amide group represented by X includes aliphatic amide groups such as dimethylamide group, diethylamide group and diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate is exemplified, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may be present as a body or higher multimer.

（式中、Ｘ^’’はハライドを示す。） The metallocene complex represented by the general formula (I) is, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (I) are shown below.

(In the formula, X ^″ represents a halide.)

（式中、Ｘ^’’はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (II) are shown below.

(In the formula, X ^″ represents a halide.)

The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium 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. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Nitrotetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of a metallocene complex represented by the general formula (I) or the formula (II) and an ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable.

  On the other hand, examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, the content of the organoaluminum compound in the polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol for the metallocene complex.

  Furthermore, in the polymerization catalyst composition, each of the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) is used as an appropriate promoter. By combining them, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

  As described above, the method for producing a copolymer of the present invention is the same as the method for producing a polymer by a polymerization reaction using a conventional coordination ion polymerization catalyst, except that the polymerization catalyst composition described above is used as a polymerization catalyst. can do. Here, the method for producing a copolymer of the present invention includes, for example, (1) a component of a polymerization catalyst composition in a polymerization reaction system containing a conjugated diene compound as a monomer and an olefin other than the conjugated diene compound. The polymerization catalyst composition may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. In addition, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mole with respect to the sum total of olefins other than a conjugated diene compound and this conjugated diene compound.

  The polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas.

  The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of -100 ° C to 200 ° C, for example, and can be about room temperature. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. On the other hand, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of, for example, 1 second to 10 days, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. it can.

  In the copolymer of the conjugated diene compound obtained by the method for producing a copolymer of the present invention and an olefin other than the conjugated diene compound, the number average molecular weight (Mn) of the copolymer is not particularly limited, The problem of low molecular weight does not occur. Furthermore, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 4 or less, and more preferably 2.5 or less. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

  In the copolymer of the conjugated diene compound and the olefin other than the conjugated diene compound obtained by the method for producing a copolymer of the present invention, the conjugated diene compound and the olefin other than the conjugated diene compound are randomly polymerized. Generally, random means that the arrangement of each repeating unit in the polymer polymer chain is irregular. In the present invention, the glass transition point is determined by DSC measurement (differential scanning calorimetry) of the copolymer. When (Tg) is shown as a single peak and the glass transition point (Tg) is higher than the homopolymer of the conjugated diene compound used, the copolymer is randomly polymerized. It was judged. Here, if a copolymer of a conjugated diene compound and an olefin other than the conjugated diene compound is randomly polymerized, the phase separation can be suppressed by acting uniformly as an elastomer, thereby improving heat resistance. A monomer having the following merits can be introduced into the main chain of the copolymer.

  A copolymer of the conjugated diene compound obtained by the method for producing a copolymer of the present invention and an olefin other than the conjugated diene compound has a high cis-1,4 bond amount in the conjugated diene compound portion. Here, the amount of cis-1,4 bonds in the conjugated diene compound portion is preferably 85% or more. If the amount of cis-1,4 bonds in the conjugated diene compound portion is 85% or more, high elongation crystallinity and low glass transition point (Tg) can be maintained, thereby improving physical properties such as wear resistance. Is done. Further, when the cis-1,4 bond content of the conjugated diene compound portion is less than 85%, the elongation crystallinity is remarkably lowered and the glass transition point (Tg) is increased, so that the durability such as wear resistance is lowered. There is a case.

  The copolymer of the conjugated diene compound obtained by the method for producing a copolymer of the present invention and an olefin other than the conjugated diene compound preferably has a vinyl bond content of the conjugated diene compound portion of 20% or less, % Or less is more preferable. When the vinyl bond amount in the conjugated diene compound portion exceeds 20%, the cis-1,4 bond amount decreases, and the effect of improving the wear resistance cannot be sufficiently obtained.

  The copolymer of the conjugated diene compound obtained by the method for producing a copolymer of the present invention and an olefin other than the conjugated diene compound has an olefin content other than the conjugated diene compound in the range of 3 to 98 mol%. Is preferred. If the content of olefins other than the conjugated diene compound is within the above specified range, the merit of introducing the olefin having an effect of improving heat resistance into the main chain while acting uniformly as an elastomer is preserved. Is done. Further, when the content of olefins other than the conjugated diene compound is less than 3 mol%, the merit that the olefin is introduced into the main chain may be lost. On the other hand, when it exceeds 98 mol%, the conjugated diene compound is converted into the main chain. The merits (for example, ease of cross-linking, etc.) introduced therein may be lost.

  The copolymer of the conjugated diene compound obtained by the method for producing a copolymer of the present invention and an olefin other than the conjugated diene compound is advantageous for crosslinking while maintaining crystallinity. Can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Example 1
In a glove box under a nitrogen atmosphere, 1.88 g (20 mmol) of norbornene and 10 ml of toluene were added to a well-dried 30 ml pressure-resistant glass bottle, and the bottle was stoppered. Next, the bottle was taken out from the glove box, and 1.08 g (20 mmol) of 1,3-butadiene was charged to obtain a monomer solution. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-methylindenyl) scandium bis (trimethylsilylamide) [(2-MeC ₉ H ₆ ) ₂ ScN (SiMe ₃ ) ₂ ] 20 μmol, triphenyl Carbonium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 20 μmol and diisobutylaluminum hydride 150 μmol were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at room temperature for 5 minutes. After the polymerization, the reaction was stopped by adding 10 ml of a 10% by weight methanol solution of BHT (2,6-bis (t-butyl) -4-methylphenol), and the copolymer was added with a large amount of methanol / hydrochloric acid mixed solvent. Separation and vacuum drying at 60 ° C. gave a copolymer A. The yield of the obtained copolymer A was 1.10 g. The structure of copolymer A was confirmed by ¹ H-NMR spectrum (FIG. 1) and ¹³ C-NMR spectrum (FIG. 2 (a)) to produce copolymer A. Norbornene in copolymer A It was confirmed that the portion was introduced by a vinyl addition type reaction mode. Further, a ¹³ C-NMR spectrum (FIG. 2 (a)) of copolymer A was obtained by adding a norbornene vinyl addition homopolymer described in “JPS partA”, 2003, vol. 41, p.2095-2106. Compared with the ¹³ C-NMR spectrum of Fig. 3 (Fig. 3), the signal (30.03ppm, 47.36ppm) of norbornene vinyl addition homopolymer was not observed in the spectrum chart of Fig. 2 (a). Was not a polymer blend but a random copolymer.

(Example 2)
In a glove box under a nitrogen atmosphere, 1.32 g (10 mmol) of dicyclopentadiene and 5 ml of toluene were added to a well-dried 30 ml pressure-resistant glass bottle, and the bottle was stoppered. Next, the bottle was taken out from the glove box, and 0.54 g (10 mmol) of 1,3-butadiene was charged into a monomer solution. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-methylindenyl) scandium bis (trimethylsilylamide) [(2-MeC ₉ H ₆ ) ₂ ScN (SiMe ₃ ) ₂ ] 20 μmol, triphenyl Carbonium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 20 μmol and diisobutylaluminum hydride 150 μmol were charged and dissolved in 3 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at room temperature for 7 minutes. After the polymerization, the reaction was stopped by adding 10 ml of a 10% by weight methanol solution of BHT (2,6-bis (t-butyl) -4-methylphenol), and the copolymer was added with a large amount of methanol / hydrochloric acid mixed solvent. Separation and vacuum drying at 60 ° C. gave a copolymer B. The yield of the obtained copolymer B was 0.40 g. The structure of copolymer B is confirmed by ¹ H-NMR spectrum and ¹³ C-NMR spectrum (FIG. 2B), copolymer B is produced, and dicyclopentadiene portion in copolymer B is vinyl-added. It was confirmed that it was introduced by the reaction type of the mold.

(Reference Example 1)
In a glove box under a nitrogen atmosphere, 1.08 g (20 mmol) of 1,3-butadiene and 10 ml of toluene were added to a well-dried 30 ml pressure-resistant glass bottle, and the bottle was stoppered to obtain a monomer solution. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-methylindenyl) scandium bis (trimethylsilylamide) [(2-MeC ₉ H ₆ ) ₂ ScN (SiMe ₃ ) ₂ ] 20 μmol, triphenyl Carbonium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 20 μmol and diisobutylaluminum hydride 150 μmol were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at room temperature for 5 minutes. After the polymerization, the reaction was stopped by adding 10 ml of a 10% by weight methanol solution of BHT (2,6-bis (t-butyl) -4-methylphenol), and the copolymer was added with a large amount of methanol / hydrochloric acid mixed solvent. Separation and vacuum drying at 60 ° C. gave polybutadiene. The yield of the obtained polybutadiene was 1.01 g. The structure of polybutadiene was confirmed by ¹ H-NMR spectrum and ¹³ C-NMR spectrum.

  The microstructure and glass transition point (Tg) of the copolymer of Examples 1 and 2 and the polymer of Reference Example 1 produced as described above were measured by the following methods. The results are shown in Table 1.

(1) Microstructure The microstructure was determined by the infrared method (Morello method).

(2) Glass transition point (Tg)
After weighing 10mg ± 0.5mg of sample, putting it in an aluminum measuring pan and covering it with a DSC device (TA Instruments) from room temperature to 50 ° C and stabilizing for 10 minutes After cooling to −110 ° C. and stabilizing at −110 ° C. for 10 minutes, the glass transition point (Tg) (° C.) was measured while increasing the temperature to 50 ° C. at a temperature increase rate of 10 ° C./min.

(3) Content of olefin other than conjugated diene compound The content (mol%) of the olefin moiety other than the conjugated diene compound in the copolymer was determined from the integral ratio of the ¹ H-NMR spectrum. ¹ H-NMR was measured at room temperature using deuterated chloroform as a solvent.

  From Table 1, it can be seen that the copolymers of Examples 1 and 2 have a high proportion of cis-1,4 bonds in the conjugated diene compound portion. The ratio of the cis-1,4 bond amount is equal to or greater than the ratio of the homopolymer of the conjugated diene compound of Reference Example 1. Although not shown, the glass transition point (Tg) of the copolymers of Examples 1 and 2 shows a single peak. Further, as shown in Table 1, the glass transition point (Tg) of the polymer of Reference Example 1 is also shown. ), The copolymers of Examples 1 and 2 show that conjugated diene compounds and olefins other than the conjugated diene compounds are randomly polymerized.

¹ is a ¹ H-NMR spectrum chart of a butadiene-norbornene copolymer. (a) is a ¹³ C-NMR spectrum chart of a butadiene-norbornene copolymer, and (b) is a ¹³ C-NMR spectrum chart of a butadiene-dicyclopentadiene copolymer. It is a ¹³ C-NMR spectrum chart of a vinyl addition type homopolymer of norbornene.

Claims (15)

The following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. And L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating In the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by an anion), a conjugated diene compound and an olefin other than the conjugated diene compound are polymerized. The manufacturing method of the copolymer characterized by including a process.   The method for producing a copolymer according to claim 1, wherein the olefin other than the conjugated diene compound is a non-conjugated olefin.   The method for producing a copolymer according to claim 1 or 2, wherein the olefin other than the conjugated diene compound is a cyclic olefin.   The method for producing a copolymer according to claim 3, wherein the cyclic olefin is at least one selected from the group consisting of norbornene, dicyclopentadiene, norbonadiene, cyclohexene, and ethylidene norbornene.   The method for producing a copolymer according to claim 1 or 2, wherein the olefin other than the conjugated diene compound is an acyclic olefin.   Polymerization catalyst comprising at least one complex selected from the group consisting of metallocene complexes represented by general formula (I) and general formula (II), and half metallocene cation complexes represented by general formula (III) A copolymer obtained by polymerizing a conjugated diene compound and an olefin other than the conjugated diene compound in the presence of the composition.   The copolymer of the conjugated diene compound and an olefin other than the conjugated diene compound is an addition polymerization.   The copolymer according to claim 6 or 7, wherein the olefin other than the conjugated diene compound is a non-conjugated olefin.   The copolymer according to any one of claims 6 to 8, wherein the olefin other than the conjugated diene compound is an acyclic olefin.   The copolymer according to any one of claims 6 to 9, wherein the conjugated diene compound and an olefin other than the conjugated diene compound are randomly polymerized.   A copolymer of a conjugated diene compound and a cyclic olefin other than the conjugated diene compound.   The copolymer according to claim 11, wherein the repeating unit of the cyclic olefin has a cyclic structure.   The copolymer according to claim 11, wherein the cyclic olefin is at least one selected from the group consisting of norbornene, dicyclopentadiene, norbonadiene, cyclohexene, and ethylidene norbornene.   The copolymer according to any one of claims 11 to 13, wherein the conjugated diene compound and a cyclic olefin other than the conjugated diene compound are randomly polymerized.   The copolymer according to any one of claims 11 to 14, wherein a cis-1,4 bond content of the conjugated diene compound portion is 85% or more.

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