JP2012031314A - Metallocene-based composite catalyst, catalyst composition, and production method of copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallocene-based composite catalyst by which a copolymer formed of a conjugated diene compound and unconjugated olefin can be produced.SOLUTION: There is provided the metallocene-based composite catalyst which is formed of the conjugated diene compound and the unconjugated olefin, and characterized by being expressed by the following formula (A): RMXQY(in the formula, Rs each independently denote unsubstituted or substituted indenyl, the R is coordinated at M, the M denotes a lanthanoid element, scandium or yttrium, X independently denotes a hydrocarbon group whose carbon number is 1 to 20, the X is μ-coordinated at the M and Q, the Q denotes a Group-XIII element in the periodic table, Y independently denotes a hydrocarbon group whose carbon number is 1 to 20, or a hydrogen atom, the Y is coordinated at the Q, and a and b are 2.).

Description

  The present invention relates to a metallocene composite catalyst, a catalyst composition containing the metallocene composite catalyst, and a method for producing the metallocene composite catalyst or a copolymer using the catalyst composition. The present invention relates to a metallocene composite catalyst capable of producing a conjugated olefin copolymer.

  It is well known that coordinated 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. For example, Japanese Patent Publication No. 2006-503141 (Patent Document 1) and Japanese Patent Publication No. 2-61961 (Patent Document 2) have a description of copolymerization of ethylene and diene. There have been many problems such as use as a catalyst component, the resulting polymer has a limited structure, low catalytic activity, and low molecular weight of the polymer produced.

JP-T-2006-503141 Japanese Examined Patent Publication No. 2-61961

  Therefore, an object of the present invention is to provide a metallocene composite catalyst capable of producing a copolymer of a conjugated diene compound and a nonconjugated olefin, and a catalyst composition containing the metallocene composite catalyst. Another object of the present invention is to provide a method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin using the metallocene composite catalyst or the catalyst composition.

  As a result of intensive studies to achieve the above object, the present inventors can synthesize a specific metallocene catalyst and polymerize a conjugated diene compound and a nonconjugated olefin by using the metallocene catalyst. The inventors have found a method for producing a conjugated diene compound-nonconjugated olefin copolymer and have completed the present invention.

That is, the metallocene composite catalyst of the present invention 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 an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of 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。 In a preferred example of the metallocene composite catalyst of the present invention, the following formula (I):

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently have 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 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Shown]

  The catalyst composition of the present invention is characterized by containing the above metallocene composite catalyst and a boron anion.

  Furthermore, the method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin according to the present invention is characterized by polymerizing a conjugated diene compound and a non-conjugated olefin in the presence of the metallocene composite catalyst or the catalyst composition. And

  In a preferred embodiment of the method for producing a copolymer of the present invention, the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.

  In another preferred embodiment of the method for producing a copolymer of the present invention, the non-conjugated olefin is an acyclic olefin. Here, the acyclic olefin is preferably an α-olefin having 2 to 10 carbon atoms, and the α-olefin is preferably ethylene, propylene, and 1-butene.

  According to the present invention, it is possible to provide a metallocene composite catalyst capable of producing a copolymer of a conjugated diene compound and a nonconjugated olefin, and a catalyst composition containing the metallocene composite catalyst. Further, by using the metallocene composite catalyst or the catalyst composition, a copolymer of a conjugated diene compound and a nonconjugated olefin can be produced.

2 is a ¹ H-NMR spectrum chart of Compound X. FIG. 2 is a ¹ H-NMR spectrum chart of Compound Y. FIG. 2 is a ¹ H-NMR spectrum chart of Compound Z. FIG. 2 is a ¹ H-NMR spectrum chart of copolymer A. 3 is a ¹³ C-NMR spectrum chart of copolymer A. FIG. The DSC curve of the copolymer A is shown.

<Metalocene composite catalyst>
The metallocene composite catalyst of the present invention will be described in detail below. The metallocene composite catalyst of the present invention has a lanthanide 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 an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of 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 of the present invention, a copolymer of a conjugated diene compound and a non-conjugated olefin can be produced. In addition, by using the metallocene composite catalyst of the present invention, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used during the synthesis of the copolymer can be reduced or eliminated. . If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst, and if the metallocene composite catalyst of the present invention is added, about 5 equivalents of alkylaluminum is excellent. Catalysis is exerted.

  In the metallocene composite catalyst of the present invention, the metal M in the above 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 include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the above 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 a 1,2,3-trimethylindenyl group, a heptamethylindenyl group, a 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 in the periodic table, and specific examples thereof include boron, aluminum, gallium, indium, and thallium.

  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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the 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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  The metallocene composite catalyst of the present invention is preferably a metallocene composite catalyst represented by the above formula (I).

In the above formula (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 (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, 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. Note that the two Cp ^R 's in formula (I) may be the same as or different from each other.

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

In the above formula (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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, 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 of the present invention is represented by the following formula (II) in a solvent, for example:

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{e to} R ^j each independently represents a group having 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and 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 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 (II), Cp ^R is unsubstituted indenyl or substituted indenyl, and is synonymous with Cp ^R in the above formula (I). In the above formula (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 (I).

The metallocene complex represented by the above formula (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, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (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.

  Further, the metallocene complex represented by the above formula (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 for the production of the metallocene composite catalyst of the present invention is represented by AlR ^k R ^l R ^m , where R ^k and R ^l are each independently a monovalent having 1 to 20 carbon atoms. 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 the above R ^k or R ^l . 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, 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. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. 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 for the metallocene complex.

<Catalyst composition>
Next, the catalyst composition of the present invention will be described in detail. The catalyst composition of the present invention comprises the above metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the catalyst composition containing a normal metallocene catalyst. It is preferable to include. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the catalyst composition of the present invention, 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 body component in the copolymer.

  In the catalyst composition of the present invention, 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-dicarboundeborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  In addition, the said boron anion can be used as an ionic compound combined with the 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. 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. 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.

Preferred examples of the cocatalyst that can be used in the catalyst composition of the present invention include an aluminoxane in addition to the organoaluminum compound represented by the above-described AlR ^k R ¹ R ^m . 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. These aluminoxanes may be used alone or in combination of two or more.

<Method for producing conjugated diene compound-nonconjugated olefin copolymer>
Next, the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin of this invention is demonstrated in detail. The method for producing a copolymer of a conjugated diene compound and a nonconjugated olefin according to the present invention is characterized in that a conjugated diene compound and a nonconjugated olefin are polymerized in the presence of the metallocene composite catalyst or the catalyst composition. . According to the said manufacturing method, except using the said metallocene type composite catalyst or the said catalyst composition, it is the same as the manufacturing method of the polymer by a normal coordination ion polymerization catalyst, and the conjugated diene compound which is a monomer, Non-conjugated olefins can be copolymerized. 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, hexane, a cyclohexane, etc. are mentioned.

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

  On the other hand, non-conjugated olefins used as monomers increase the degree of design freedom as an elastomer by reducing the crystallinity by reducing the ratio of double bonds in the main chain of the copolymer and excellent heat resistance. It becomes possible. The non-conjugated olefin is preferably an acyclic olefin, and the acyclic olefin is preferably an α-olefin having 2 to 10 carbon atoms. Here, examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Among these, ethylene, propylene and 1-butene are exemplified. preferable. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  In the method for producing a conjugated diene compound-nonconjugated olefin copolymer of the present invention, as described above, a heavy metal by a normal coordination ion polymerization catalyst is used except that the metallocene composite catalyst or the catalyst composition is used. Polymerization can be carried out in the same manner as in the production method of the coalescence. Here, when the method for producing a copolymer of the present invention uses the above catalyst composition, for example, (1) a two-component catalyst in a polymerization reaction system containing a conjugated diene compound and a non-conjugated olefin as monomers. The components may be provided separately and used as a catalyst composition in the reaction system, or (2) a catalyst composition prepared in advance may be provided in the polymerization reaction system. 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. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. The pressure for the polymerization reaction is preferably in the range of 0.1 to 10 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.

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

  The conjugated diene compound-nonconjugated olefin copolymer preferably has a nonconjugated olefin content of 1 to 99 mol%, more preferably 10 to 60 mol%. If the content rate of a nonconjugated olefin exists in said specified range, heat resistance can be improved effectively, without raise | generating phase separation.

  The conjugated diene compound-nonconjugated olefin copolymer has no problem of lowering the molecular weight, and its weight average molecular weight (Mw) is not particularly limited. Therefore, the weight average molecular weight (Mw) of the copolymer is preferably 10,000 or more, and more preferably in the range of 30,000 to 200,000. 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 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).

  The copolymer of a conjugated diene compound and a non-conjugated olefin obtained by the method for producing a copolymer of the present invention can be suitably used for elastomer products in general, particularly for tire members.

  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.

<Preparation of metallocene composite catalyst>
(Compound X: Synthesis of Nd (N (SiMe ₃ ) ₂ ) ₃ )
Under a nitrogen atmosphere, slowly add 20 ml of an ether solution (manufactured by Aldrich) containing KN (SiMe ₃ ) ₂ (6.00 g, 30.08 mmol) to 100 mL of a THF solution of NdCl ₃ (2.60 g, 10.38 mmol) manufactured by Strem. The solution was added dropwise and stirred at room temperature for 12 hours. Then, the solvent was distilled off under reduced pressure, 150 mL of hexane was added instead, and the precipitate was filtered. Thereafter, hexane was slowly distilled off under reduced pressure to obtain Nd (N (SiMe ₃ ) ₂ ) ₃ (4.86 g, 77.5%) as blue crystals. The structure of the obtained compound X was confirmed by ¹ H-NMR. ¹ H-NMR was measured at 20 ° C. using toluene-d ₈ as a solvent. A ¹ H-NMR spectrum chart of Compound X is shown in FIG.

(Compound Y: Synthesis of (2-PhC ₉ H ₆ ) ₂ Nd [N (SiHMe ₂ ) ₂ ])
Nd (N (SiMe ₃ ) ₂ ) ₃ (3.12 g, 4.99 mmol), 2-PhC ₉ H ₇ (2-phenylindene) (1.81 g, 9.41 mmol) sold by Aldrich under a nitrogen atmosphere Then, HN (SiHMe ₂ ) ₂ (2.70 g, 20.25 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was reacted in 150 mL of hexane by stirring at 70 ° C. for 8 hours. Thereafter, hexane was distilled off under reduced pressure, and the residue was washed several times with hexane to obtain (2-PhC ₉ H ₆ ) ₂ Nd [N (SiHMe ₂ ) ₂ ] (2.50 g, 81%) as a green powder. It was. The structure of the obtained compound Y was confirmed by ¹ H-NMR. ¹ H-NMR was measured at 20 ° C. using toluene-d ₈ as a solvent. A ¹ H-NMR spectrum chart of Compound Y is shown in FIG.

(Compound Z: Synthesis of (2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe ₂ )
Under a nitrogen atmosphere, a toluene solution (Aldrich) containing AlMe ₃ (9.0 mmol) in 50 mL of a toluene solution of (2-PhC ₉ H ₆ ) ₂ Nd [N (SiHMe ₂ ) ₂ ] (2.00 g, 3.03 mmol) 4.5 ml) was slowly added dropwise and stirred at room temperature for 16 hours. Thereafter, toluene was distilled off under reduced pressure, and the residue was washed several times with hexane to obtain (2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe ₂ (1.60 g, 86%) as a green powder. It was. The structure of the obtained metallocene composite catalyst was confirmed by ¹ H-NMR. ¹ H-NMR was measured at 20 ° C. using toluene-d ₈ as a solvent. A ¹ H-NMR spectrum chart of Compound Z is shown in FIG.

Example 1
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-t-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 3.60 g. 4 shows a ¹ H-NMR spectrum chart of the copolymer A, FIG. 5 shows a ¹³ C-NMR spectrum chart of the copolymer A, and FIG. 6 shows a DSC curve of the copolymer A.

(Example 2)
After adding 300 ml of a toluene solution containing 9.25 g (0.171 mol) of 1,3-butadiene to a sufficiently dry 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 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 150 minutes. After polymerization, the reaction was stopped by adding 1 ml of 2,2'-methylene-bis (4-ethyl-6-t-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 B. The yield of the obtained copolymer B was 14.25 g.

(Example 3)
After adding 300 ml of a toluene solution containing 6.15 g (0.114 mol) of 1,3-butadiene to a sufficiently dry 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 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. 150.0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 150.0 μmol and triethylaluminum 750.0 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 180 minutes. After polymerization, the reaction was stopped by adding 1 ml of 2,2'-methylene-bis (4-ethyl-6-t-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 9.50 g.

  For the copolymers A to C of Examples 1 to 3 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 measured with ¹ H-NMR spectrum (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)] on the basis of monodisperse polystyrene The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined. The measurement temperature is 140 ° C.

Claims (8)

The following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A metallocene composite catalyst for polymerization of a conjugated diene compound and a non-conjugated olefin, characterized in that it represents a hydrogen atom, Y is coordinated to Q, and a and b are 2. Formula (I) below:

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently have 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 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. The metallocene composite catalyst according to claim 1, represented by:   A catalyst composition comprising the metallocene composite catalyst according to claim 1 or 2 and a boron anion.   A conjugated diene compound and a non-conjugated olefin, wherein the conjugated diene compound and the non-conjugated olefin are polymerized in the presence of the metallocene composite catalyst according to claim 1 or 2 or the catalyst composition according to claim 3. A method for producing a copolymer of   The method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 4, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene. .   The method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 4, wherein the non-conjugated olefin is an acyclic olefin.   The method for producing a copolymer of a conjugated diene compound and a nonconjugated olefin according to claim 6, wherein the acyclic olefin is an α-olefin having 2 to 10 carbon atoms.   The method for producing a copolymer of a conjugated diene compound and a nonconjugated olefin according to claim 7, wherein the α-olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene. .

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