JP5557642B2 - Copolymer of conjugated diene compound and non-conjugated olefin - Google Patents

Description

  The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin, and particularly to a conjugated diene compound-non-conjugated olefin copolymer having a non-conjugated olefin content of 11 to 50 mol%.

  It is well known that coordinating anionic polymerization using a catalyst system typified by a Ziegler-Natta catalyst can homopolymerize olefins and dienes. However, in such a polymerization reaction system, it has been difficult to efficiently copolymerize olefin and diene. In particular, by applying a copolymer of conjugated diene and non-conjugated olefin as a compound rubber, the double bond of the conjugated diene moiety in the copolymer is less than that of the conjugated diene polymer, improving ozone resistance. To do. However, if the non-conjugated olefin content is increased, the ozone resistance is improved, but the processability is reduced. Conversely, if the non-conjugated olefin content is decreased to improve the processability, Since ozone resistance will fall, it is calculated | required to make both compatible.

  For example, JP 2000-154210 A (Patent Document 1) discloses a conjugated diene polymerization catalyst containing a Group IV transition metal compound such as a titanium compound having a cyclopentadiene ring structure. Examples of monomers copolymerizable with conjugated dienes include α-olefins such as ethylene. However, the copolymerization of a conjugated diene compound and a non-conjugated olefin is not specifically described. Naturally, Patent Document 1 does not describe the polystyrene-reduced weight average molecular weight of the copolymer of the conjugated diene compound and the nonconjugated olefin or the content of the nonconjugated olefin. In particular, there is no description or suggestion that by making the content of the non-conjugated olefin 11 mol% to 50 mol%, both ozone resistance and workability can be achieved.

  For example, Japanese Patent Laid-Open No. 2006-249442 (Patent Document 2) discloses an olefin polymerization catalyst comprising a transition metal compound such as a titanium compound and a cocatalyst, and the co-polymerization of an α-olefin and a conjugated diene compound. The union is disclosed, and in claim 1 and paragraph [0010] of Patent Document 2, it is described that “the content of the structural unit derived from α-olefin is 1 to 99.9 mol%”. However, only the examples 131 to 157 in the paragraphs [0531] to [0554] of the specification of Patent Document 2 support the production and use of the α-olefin, which is a non-conjugated olefin. Was only in the range of 66.7-99.1 mol%. That is, the specific description regarding the conjugated diene compound-nonconjugated olefin copolymer whose nonconjugated olefin content is 11 to 50 mol% is not described in Patent Document 2. In particular, there is no description or suggestion that by making the content of the non-conjugated olefin 11 mol% to 50 mol%, both ozone resistance and workability can be achieved.

  In addition, JP 2006-503141 A (Patent Document 3) discloses a copolymer of ethylene and butadiene synthesized using ethylene and butadiene as starting materials using a special organometallic complex as a catalyst component. The butadiene monomer is inserted into the copolymer in the form of trans-1,2-cyclohexane, and is different in structure from the copolymer of the present invention. Further, in claims 1, 5, 6 and 7 of Patent Document 3, “a copolymer of ethylene and butadiene, the molar content of units derived from butadiene being 8% or more”, “15% or more”, “20 % Or more "and" 30% or more ". However, its production and use are specifically supported by No. 1 of Example 1 in paragraphs [0012] to [0016] of the specification of Patent Document 3. Only 1 to 9, and the ethylene content as a non-conjugated olefin was only in the range of 69.6 to 89.0 mol%. Here, the ethylene content was determined by subtracting the molar content of units derived from butadiene whose numerical values are disclosed from 100 mol%. That is, the specific description regarding the conjugated diene compound-nonconjugated olefin copolymer whose nonconjugated olefin content is 11 to 50 mol% is not described in Patent Document 3. In particular, there is no description or suggestion that by making the content of the non-conjugated olefin 11 mol% to 50 mol%, both ozone resistance and workability can be achieved.

JP 2000-154210 A JP 2006-249442 A JP-T-2006-503141

  Accordingly, an object of the present invention is to provide a copolymer of a conjugated diene compound and a non-conjugated olefin having a non-conjugated olefin content of 11 to 50 mol%. That is, it is to provide a copolymer of a conjugated diene compound and a non-conjugated olefin that can achieve both ozone resistance and processability by setting the content of the non-conjugated olefin to 11 to 50 mol%.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a conjugated diene compound-nonconjugated olefin copolymer obtained by polymerizing a conjugated diene compound and a nonconjugated olefin in the presence of a specific catalyst. The present inventors have found that the content of non-conjugated olefin is 11 to 50 mol% and have completed the present invention.

  That is, the copolymer of the conjugated diene compound and the nonconjugated olefin of the present invention is characterized in that the content of the nonconjugated olefin is 11 to 50 mol%.

  In a preferred example of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the non-conjugated olefin is an acyclic olefin.

  In another preferred example of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the non-conjugated olefin is an α-olefin having 2 to 10 carbon atoms.

  In another preferred embodiment of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene and 1-butene.

  In another preferable example of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the lower limit of the content of the non-conjugated olefin is 20 mol% or more, the upper limit is preferably 40 mol% or less, and more preferably 30 mol%. The following is more preferable.

  In another preferable example of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the conjugated diene compound has 4 to 8 carbon atoms, and in another preferable example, the conjugated diene compound is , 1,3-butadiene and isoprene.

  The copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention preferably has a conjugated diene compound content of 80 to 50 mol%.

  The copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention preferably has a polystyrene equivalent weight average molecular weight of 10,000 or more. Further, the molecular weight distribution (Mw / Mn) is preferably 10 or less, and more preferably 6 or less.

  According to the present invention, a copolymer of a conjugated diene compound and a non-conjugated olefin having a non-conjugated olefin content of 11 to 50 mol% can be provided. That is, by setting the content of the non-conjugated olefin to 11 to 50 mol%, it is possible to provide a copolymer of a conjugated diene compound and a non-conjugated olefin that can achieve both ozone resistance and processability.

  The present invention is described in detail below. The copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention is characterized in that the content of the non-conjugated olefin is 11 to 50 mol%.

  The copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention has a non-conjugated olefin content of 11 to 50 mol%. If the content of the non-conjugated olefin is within the specified range, the heat resistance can be effectively improved without causing phase separation.

  On the other hand, non-conjugated olefins used as monomers are non-conjugated olefins other than conjugated diene compounds, and control crystallinity by reducing the heat resistance and the proportion of double bonds in the main chain of the copolymer. By doing so, it becomes possible to raise the design freedom as an elastomer. The non-conjugated olefin is preferably an acyclic olefin, and the non-conjugated olefin is preferably an α-olefin having 2 to 10 carbon atoms. If it is an α-olefin, since it has a double bond at the α-position of the olefin, copolymerization with a conjugated diene can be carried out efficiently. Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred. These non-conjugated olefins may be used alone or in combination of two or more. Olefin refers to a compound that is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  In addition, it is preferable that the conjugated diene compound used as a monomer has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used alone or in combination of two or more.

  On the other hand, in the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the content of the conjugated diene compound is in the range of 89 mol% to 50 mol%, and preferably in the range of 80 to 50 mol%. If the content of the conjugated diene compound is within the specified range, the copolymer of the present invention can behave uniformly as an elastomer.

  The weight average molecular weight (Mw) of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention does not cause a problem of lowering the molecular weight. From the viewpoint of application to a polymer structure material, the copolymer Mw is preferably 10,000 or more, more preferably 1,000,000 or less. This is because if Mw is 10,000 or less, the mechanical strength as a structural material is insufficient, and if Mw exceeds 1,000,000, the moldability is deteriorated. Further, 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 10 or less, and more preferably 6 or less. This is because it becomes easy to generate uniform physical properties. Here, the average molecular weight and the molecular weight distribution can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  In the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the amount of cis-1,4 bonds in the conjugated diene compound portion is preferably 50% or more, and more preferably 70% or more. If the amount of cis-1,4 bonds in the conjugated diene compound portion is 50% or more, high elongation crystallinity and low glass transition point (Tg) can be maintained, thereby improving physical properties such as wear resistance. Is done.

  In the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the non-conjugated olefin portion may not be continuous.

<Manufacturing method>
Next, the method for producing the copolymer of the present invention will be described in detail. In the method for producing a copolymer of the present invention, a conjugated diene compound and a non-conjugated olefin are polymerized in the presence of a polymerization catalyst or a polymerization catalyst composition shown below. 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. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane etc. are mentioned.

  According to the above production method, a conjugated diene compound as a monomer and a non-conjugated compound are produced in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst except that the polymerization catalyst or the polymerization catalyst composition is used. Olefin can be copolymerized.

（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のアルキル基又は水素原子を示し，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（以下，第一重合触媒組成物ともいう）が挙げられ，該重合触媒組成物は，更に，通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分，例えば助触媒等を含んでいてもよい。ここで，メタロセン錯体は，一つ又は二つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり，特に，中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を，ハーフメタロセン錯体と称することがある。なお，重合反応系において，第一重合触媒組成物に含まれる錯体の濃度は0.1〜0.0001mol/lの範囲であることが好ましい。 <Production Method (1): First Polymerization Catalyst Composition>
The polymerization catalyst composition includes 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. A metallocene complex represented by the following formula (II): and a group or a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3.

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R 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 an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or 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 [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) containing at least one complex selected from the group consisting of a half metallocene cation complex represented by The product may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. 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 referred to as a half metallocene complex. In the polymerization reaction system, the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

In the metallocene complexes represented by the 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. The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group 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. Note that the two Cp ^R 's in the general formulas (I) and (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. 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. The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group 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 above 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. 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. The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group 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 formulas (I), (II) and (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 silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of Ra to Rc is a hydrogen atom and at least one of Rd to Rf is a hydrogen atom. The alkyl group 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, tert-butoxy group; phenoxy group, 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 is a thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thiosec-butoxy group, thio tert-butoxy group, or 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 , 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; bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

  In the general formula (III), the silyl group represented by X includes 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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 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: Hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group, and the like. 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 tetraphenyl borate, 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.

  The metallocene complexes represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) may exist as monomers, It may exist 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) 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 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 it 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 it 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. As the tri (substituted phenyl) carbonyl cation, specifically, tri (methylphenyl) cation. ) 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- Examples thereof include 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. Further, the ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times mol, more preferably about 1 time mol to the metallocene complex. 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. 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 general formula (I) or formula (II) and an ionic compound represented by 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 first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst of 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 the aluminoxane in the first 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 to make it.

    On the other hand, the organoaluminum compound includes a general formula AlRR′R ″ (wherein R and R ′ are each independently a C1 to C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1 to C10). An organoaluminum compound represented by (a hydrocarbon group) is preferable. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Furthermore, 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, and more preferably about 10 times mol to the metallocene complex.

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

<Production Method (2) Second Polymerization Catalyst Composition>
In addition, as the polymerization catalyst composition,
Component (A): a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon;
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen A polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds (hereinafter also referred to as a second polymerization catalyst composition) can be suitably exemplified.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
Component (C): the following general formula (X):
YR ¹ _a R ² _b R ³ _c ... (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is characterized by including.

The second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (A) and the component (B), and the polymerization catalyst composition contains the ionic compound (B -1) and at least one of the above halogen compounds (B-3),
Component (C): the following general formula (X):
YR ¹ _a R ² _b R ³ _c ... (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is necessary to include. Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. Even when the polymerization catalyst composition contains the aluminoxane (B-2), the polymerization catalyst composition can contain the component (C). The second polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth compound polymerization catalyst composition.

  The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed. The object does not have a bond between rare earth elements and carbon. When the rare earth compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the rare earth element compound or a reaction product of the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII):
M ¹¹ X ¹¹ ₂・ L ¹¹ w (XI)
M ¹¹ X ¹¹ ₃・ L ¹¹ w (XII)
[Wherein M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. Represents a group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3].

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include hydrogen atom; methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert- Aliphatic alkoxy group such as butoxy group; phenoxy group, 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, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio Aliphatic thiolate groups such as sec-butoxy group and thiotert-butoxy group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiol Ofenoxy group, 2,6-Dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentyl group Arylthiolate groups such as phenoxy group and 2,4,6-triisopropylthiophenoxy group; aliphatic amide groups such as dimethylamide group, diethylamide group and diisopropylamide group; phenylamide group and 2,6-di-tert-butyl Phenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group Arylamide groups such as 1,2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; Bistrialkylsilylamide groups such as tilsilylamide groups; silyl groups such as trimethylsilyl groups, tris (trimethylsilyl) silyl groups, bis (trimethylsilyl) methylsilyl groups, trimethylsilyl (dimethyl) silyl groups, triisopropylsilyl (bistrimethylsilyl) silyl groups; Examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Furthermore, aldehyde residues such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [from Shell Chemical Co., Ltd., a mixture of isomers of C10 monocarboxylic acid Composed Residues of carboxylic acids such as synthetic acid], phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; thiocarboxylic acids such as hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Residue, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate, dioleyl phosphate , Diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphate (1-methylheptyl) (2- Residues of phosphoric acid esters such as ethylhexyl) and phosphoric acid (2-ethylhexyl) (p-nonylphenyl); 2-ethylhexylphosphonic acid monobutyl, 2-ethylhexyl Mono-2-ethylhexyl phosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl phosphonate, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate, mono-phosphonate residues of phosphonates such as p-nonylphenyl, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, Bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid , 2-Ethylhexylphosphinic acid, 1-methylheptylphos Fins acid, oleyl phosphinic acid, lauryl phosphinic acid, phenyl phosphinic acid, can also be mentioned residues of the phosphinic acids such as p- nonylphenyl phosphinic acid. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A) used in the second polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), w is 2 or 3), the Lewis base L ¹¹ is the same or different. It may be.

  The component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of an ionic compound (B-1), an aluminoxane (B-2), and a halogen compound (B-3). is there. In addition, it is preferable that the total content of the component (B) in the second polymerization catalyst composition is 0.1 to 50 times the mol of the component (A).

  The ionic compound represented by (B-1) is composed of a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound (A) or a Lewis base thereof to become cationic. Examples thereof include ionic compounds capable of generating a transition metal compound. Here, as the non-coordinating anion, for example, tetraphenyl borate, 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-dicarbaound decaborate and the like. On the other hand, 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. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Therefore, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Nitrotetrakis (pentafluorophenyl) borate and the like are preferable. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the content of the ionic compound in the second polymerization catalyst composition is preferably 0.1 to 10 times mole, more preferably about 1 time mole relative to the component (A).

  The aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, a repeat represented by the general formula: (-Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as the raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used. The content of the aluminoxane in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

    The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a halogenated transition metal compound or a compound having a transition metal center with insufficient charge can be generated. In addition, it is preferable that the total content of halogen compounds in the second polymerization catalyst composition is 1 to 5 times moles relative to the component (A).

As the Lewis acid, a boron-containing halogen compound such as B (C ₆ F ₅ ) _{3 and} an aluminum-containing halogen compound such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. As the halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc. Among these, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are particularly preferred. preferable.

  Examples of the metal halide constituting the complex compound of the above metal halide and Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol, oleyl Examples include alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2- Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c ... (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. Yes, the following general formula (Xa):
AlR ¹ R ² R ³ ... (Xa)
[In the formula, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound of the formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, 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 hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum dihydride, Butyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organometallic compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that content of the organoaluminum compound in the said 2nd polymerization catalyst composition is 1-50 times mole with respect to (A) component.

<Production Method (3): Polymerization Catalyst and Third Polymerization Catalyst Composition>
The polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element in the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q and a and b are 2].

［式中，Ｍ¹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及びＲ^Bは，それぞれ独立して炭素数１〜２０の炭化水素基を示し，該Ｒ^A及びＲ^Bは，Ｍ¹及びＡｌにμ配位しており，Ｒ^C及びＲ^Dは，それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す］で表されるメタロセン系複合触媒が挙げられる。 In a preferred example of the polymerization catalyst, the following formula (3-I):

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^A and R ^B each independently represents a group having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene composite catalysts represented by

  The third polymerization catalyst composition includes the metallocene composite catalyst and a boron anion.

<Metalocene composite catalyst>
Below, the said polymerization catalyst is demonstrated in detail. The polymerization catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element in the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2.] By using the metallocene polymerization catalyst, a copolymer of a conjugated diene compound and a non-conjugated olefin can be produced. In addition, by using the above polymerization catalyst, for example, a catalyst previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used at the time of copolymer synthesis. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum during copolymer synthesis. For example, in conventional catalyst systems, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. However, in the case of the above metallocene composite catalyst, adding about 5 equivalents of alkylaluminum provides excellent catalytic action. Is demonstrated.

In the metallocene composite catalyst, the metal M in the formula (A) 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 metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. 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. It is done.

  In the above formula (A), Q represents a group 13 element of the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (3-I), the metal M ¹ 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 metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (3-I), Cp ^R 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. The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group 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. Note that the two Cp ^R 's in formula (3-I) may be the same or different from each other.

In the above formula (3-I), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R are μ-coordinated to M ¹ and Al. . Here, as a C1-C20 hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (3-I), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

（式中，Ｍ²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^E〜Ｒ^Jは，それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し，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を，ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお，反応温度は室温程度にすればよいので，温和な条件で製造することができる。また，反応時間は任意であるが，数時間〜数十時間程度である。反応溶媒は特に限定されないが，原料及び生成物を溶解する溶媒であることが好ましく，例えばトルエンやヘキサンを用いればよい。なお，上記メタロセン系複合触媒の構造は，¹Ｈ-ＮＭＲにより決定することが好ましい。 The metallocene composite catalyst is, for example, in a solvent, represented by the following formula (3-II):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{E to} R ^J each independently represents 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but it 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 or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR.

In the metallocene complex represented by the above formula (3-II), Cp ^R is unsubstituted indenyl or substituted indenyl, and is synonymous with Cp ^R in the above formula (3-I). In the above formula (3-II), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (3-I).

The metallocene complex represented by the above formula (3-II) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the catalyst can be easily synthesized. Furthermore, the alkyl group is preferably a methyl group.

  The metallocene complex represented by the above formula (3-II) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases 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.

  Moreover, the metallocene complex represented by the above formula (3-II) may exist as a monomer, or may exist as a dimer or a multimer higher than that.

On the other hand, the organoaluminum compound used to produce the metallocene composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. R ^M is a hydrogen group or a hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl 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 , Dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum dihydride , It includes isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. These organoaluminum compounds can be used alone or in combination of two or more. The amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 2 to 50 times mol, more preferably about 3 to 5 times mol, relative to the metallocene complex.

<Third polymerization catalyst composition>
The polymerization catalyst composition (hereinafter also referred to as a third polymerization catalyst composition) includes the metallocene composite catalyst and a boron anion, and further includes a normal metallocene catalyst. It is preferable to include other components contained in the composition, such as a promoter. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, it is possible to produce a conjugated diene compound-nonconjugated olefin copolymer as in the case of the metallocene composite catalyst. It becomes possible to arbitrarily control the content of the monomer component in the copolymer.

  In the third polymerization catalyst composition, specific examples of the boron anion constituting the two-component catalyst include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  The boron anion can be used as an ionic compound combined with a cation. Examples of the cation 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. As the tri (substituted phenyl) carbonyl cation, specifically, tri (methylphenyl) cation. ) 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- Examples thereof include 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. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. The ionic compound composed of a boron anion and a cation is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene composite catalyst.

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. 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. In addition, these aluminoxanes may be used individually by 1 type, and may be used in combination of 2 or more types.

  In the first production method of the conjugated diene compound-nonconjugated olefin copolymer of the present invention, as described above, except for using the metallocene composite catalyst or the third polymerization catalyst composition, Polymerization can be carried out in the same manner as in the method for producing a polymer using a coordination ion polymerization catalyst. Here, when the method for producing a copolymer of the present invention uses the third polymerization catalyst composition, for example, (1) in a polymerization reaction system containing a conjugated diene compound and a non-conjugated olefin as a monomer, A component component of the two-component catalyst may be provided separately, and the third polymerization catalyst composition may be provided in the polymerization reaction system. (2) A third polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. May be provided. In addition, the usage-amount of the said metallocene type composite catalyst has the preferable range of 0.0001-0.01 times mole with respect to the sum total of a conjugated diene compound and a nonconjugated olefin.

  Moreover, in the manufacturing method of the conjugated diene compound-nonconjugated olefin copolymer of this invention, you may stop superposition | polymerization using polymerization terminators, such as ethanol and isopropanol.

  In the method for producing a conjugated diene compound-nonconjugated olefin copolymer of the present invention, the polymerization reaction of the conjugated diene compound and the nonconjugated olefin 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. Note that when the polymerization temperature is increased, the cis-1,4 selectivity of the polymerization reaction may decrease. The pressure for the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the conjugated diene compound and the non-conjugated olefin into the polymerization reaction system. Further, the reaction time of the above polymerization reaction is not particularly limited, and is preferably in the range of, for example, 1 second to 10 days. it can.

  In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa. When the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. In addition, even if the pressure of the non-conjugated olefin is increased too much, the effect of efficiently introducing the non-conjugated olefin reaches its peak, so the pressure of the non-conjugated olefin is preferably 10 MPa or less.

In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) means the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the non-conjugated olefin concentration / conjugated diene compound concentration to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

  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
After adding 325 ml of toluene solution containing 13.58 g (0.25 mol) of 1,3-butadiene to a well-dried 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.4 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 18.0 μmol, Dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 36.0 μmol and 0.90 mmol of diisobutylaluminum hydride were charged and dissolved in 10 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, and an amount of catalyst solution of 17.5 μmol in terms of gadolinium was added to the monomer solution, followed by polymerization at room temperature for 180 minutes. After polymerization, the reaction was stopped by adding 1 ml of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass isopropanol solution, and a copolymer with a large amount of methanol. Was separated and vacuum dried at 70 ° C. to obtain a copolymer A. The yield of the obtained copolymer A was 12.00 g.

(Example 2)
Polymerization was carried out in the same manner as in Example 1 except that the amount of diisobutylaluminum hydride charged was 1.35 mmol. Copolymer B was obtained in a yield of 13.65 g.

(Example 3)
After adding 20 ml of a toluene solution containing 3.38 g (0.063 mol) of 1,3-butadiene to a sufficiently dry 200 ml pressure glass reactor, 2.45 g (0.088 mol) of ethylene was introduced. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 5.5 μmol, Dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 11.0 μmol and triisobutylaluminum 0.41 mmol were charged and dissolved in 10 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, and a catalyst solution in an amount of 17.5 μmol in terms of gadolinium was added to the monomer solution, followed by polymerization at room temperature for 240 minutes. After polymerization, the reaction was stopped by adding 1 ml of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass isopropanol solution, and a copolymer with a large amount of methanol. Was separated and vacuum dried at 70 ° C. to obtain a copolymer C. The yield of the obtained copolymer C was 4.15 g.

(Example 4)
After adding 300 ml of a toluene solution containing 18.20 g (0.34 mol) of 1,3-butadiene to a sufficiently dry 400 ml pressure glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, trisbistrimethylsilylamide gadolinium [Gd (N (SiMe ₃ ) ₂ ) ₃ ] 34.0 μmol, dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 41.0 μmol and 1.19 mmol of triisobutylaluminum were charged and dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of catalyst solution of 33.7 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 180 minutes. After polymerization, the reaction was stopped by adding 1 ml of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass isopropanol solution, and a copolymer with a large amount of methanol. Was separated and vacuum dried at 70 ° C. to obtain a copolymer D. The yield of the obtained copolymer D was 29.50 g.

(Example 5)
After adding 320 ml of a toluene solution containing 3.95 g (0.073 mol) of 1,3-butadiene to a sufficiently dry 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.6 MPa. On the other hand, dimethylaluminum (μ-dimethyl) bis (2-phenylindenyl) neodymium [(2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe _{2 is} placed in a glass container in a glove box under a nitrogen atmosphere. 204.0 μmol and triphenylcarbonium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 195.0 μmol were charged and dissolved in 20 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 90 minutes. After polymerization, the reaction was stopped by adding 1 ml of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass isopropanol solution, and a copolymer with a large amount of methanol. Was separated and vacuum-dried at 70 ° C. to obtain a copolymer E. The yield of the obtained copolymer E was 3.60 g.

(Comparative Example 1)
Polymerization was carried out in the same manner as in Example 2 except that ethylene was introduced at 0.1 MPa, and copolymer F was obtained in a yield of 23.50 g.

(Comparative Example 2)
Polymerization was carried out in the same manner as in Example 4 except that the amount of 1,3-butadiene charged was 13.50 g (0.25 mol), whereby Copolymer G was obtained in a yield of 23.50 g.

  For the copolymers A to E of Examples 1 to 5 produced as described above, the microstructure, ethylene content, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured by the following methods: evaluated.

(1) Microstructure The microstructure of the butadiene moiety in the copolymer was determined by ¹ H-NMR spectrum (bonding amount of 1,2-vinyl bond) and ¹³ C-NMR spectrum (cis-1,4 bond and trans-1). , 4-bond content ratio). The calculated values of cis-1,4 bond amount (%) are shown in Table 1.
(2) Content of ethylene The content (mol%) of the ethylene moiety in the copolymer was determined from the integral ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum.
(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI), GPC measurement temperature: 140 ° C.] The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined on the basis of monodispersed polystyrene.

  A rubber compound having a compounding formulation shown in Table 2 was prepared, and roll processability and ozone resistance were measured according to the following methods for a vulcanized rubber obtained by vulcanization at 160 ° C. for 20 minutes.

* 1: N- (1,3-dimethylbutyl) -N'-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., Knock Rack 6C
* 2: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ-G
* 3: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DM-P

Physical property evaluation test method << roll workability >> An unvulcanized rubber compound was wound around an 8-inch open roll at 60 ° C, and the winding condition was visually observed to evaluate the roll workability in the following three stages.
A: Adheres to the roll and roll processability is good.
○: Some bagging occurs, but it can be wound around a roll.
×: Not sticky, does not wind around the roll, and cannot be rolled (powder, granular).
The results are shown in Table 3.

<< Ozone Resistance >> Ozone resistance was measured according to JIS K 6259. The strip-shaped test piece was exposed to 40 ° C. and ozone concentration of 50 ppm while giving 30% dynamic elongation, and the state of the sample (presence of cracks) after 24 hours was judged visually. The results are shown in Table 3.

Claims (9)

A copolymer of a conjugated diene compound and an acyclic nonconjugated olefin,
The content of the non-conjugated olefin is 11 to 50 mol% ,
A copolymer of a conjugated diene compound and a non-conjugated olefin, wherein the cis-1,4 bond content of the conjugated diene compound portion is 50% or more . The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 1 , wherein the non-conjugated olefin is an α-olefin having 2 to 10 carbon atoms. The copolymer of a conjugated diene compound and a nonconjugated olefin according to claim 1 or 2, wherein the nonconjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene. Content of the said nonconjugated olefin is 11-40 mol%, The copolymer of the conjugated diene compound and nonconjugated olefin in any one of Claims 1-3 characterized by the above-mentioned. The copolymer of a conjugated diene compound and a non-conjugated olefin according to any one of claims 1 to 4 , wherein the conjugated diene compound has 4 to 8 carbon atoms. The conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene, and the conjugated diene compound and the non-conjugated olefin according to any one of claims 1 to 5 are characterized in that Polymer. The copolymer of a conjugated diene compound and a non-conjugated olefin according to any one of claims 1 to 6 , having a polystyrene-reduced weight average molecular weight of 10,000 or more. Molecular weight distribution (Mw / Mn) is 10 or less, The copolymer of the conjugated diene compound and nonconjugated olefin in any one of Claims 1-7 characterized by the above-mentioned. The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 8 , wherein the molecular weight distribution (Mw / Mn) is 6 or less.