JP2002069117A - Catalyst composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst composition for the polymerization of conjugated diene or the copolymerization of the diene and an aromatic vinyl compound. SOLUTION: The composition contains the components (A) a neodymium complex and (B) an ionic compound comprising a non-coordinated anion and cation and/or aluminoxane. Therefore, a polymer having a significant high content of cis 1,4-structure in a microstructure and a narrow molecular weight distribution can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst composition for conjugated diene polymerization, a cocatalyst contained in the catalyst composition, a method for producing a conjugated diene polymer using the catalyst composition, and a method for producing the same. New conjugated diene polymers to be obtained. Further, the present invention provides a catalyst composition for copolymerizing a conjugated diene and an aromatic vinyl compound, a cocatalyst contained in the catalyst composition, and a copolymer of the conjugated diene and the aromatic vinyl compound using the catalyst composition. The present invention relates to a method for producing a polymer and a novel copolymer obtained by the production method.

[0002]

2. Description of the Related Art Numerous proposals have been made for polymerization catalysts for conjugated dienes, and they play an extremely important role industrially. In particular, in order to obtain conjugated diene polymers with improved thermal and mechanical properties, a number of polymerization catalysts that provide a high cis 1,4 bond content have been studied.
Has been developed. For example, composite catalyst systems based on transition metal compounds such as nickel, cobalt and titanium are known, some of which are already butadiene,
It is widely used industrially as a polymerization catalyst for isoprene and the like (End. Ing. Chem., 48, 784, 1956; JP-B-37-819).
No. 8).

In order to achieve higher cis 1,4 bond content and excellent polymerization activity, a composite catalyst system comprising a rare earth metal compound and a group I-III organometallic compound has been studied and developed, and has a high stereospecificity. Research on polymerization has been actively conducted (Makromol. Chem. Suppl, 4, 61, 1981; J. Poly
m.Sci., Polym.Chem.Ed., 18, 3345, 1980; German Patent Application 2,848,964; Sci.Sinica., 2/3, 734, 1980; Rub
ber Chem. Technol., 58, 117, 1985, etc.). Among these catalyst systems, it has been confirmed that a composite catalyst containing a neodymium compound and an organoaluminum compound as main components has a high cis-1,4 bond content and excellent polymerization activity, and has already been industrialized as a polymerization catalyst for butadiene and the like. (Macrom
olecules, 15, 230, 1982; Makromol. Chem., 94, 119,
1981).

[0004] With the recent advancement of industrial technology, the market demand for polymer materials has become more and more advanced,
There has been a strong demand for the development of polymer materials having even higher thermal properties (such as thermal stability) and mechanical properties (such as tensile modulus and flexural modulus). One of the powerful means to solve this problem is to use a catalyst with high polymerization activity for conjugated dienes, and to use
Attempts have been made to produce polymers having a high 1,4-structure content and a narrow molecular weight distribution. However,
Heretofore, a method for producing a polymer having such characteristics has not been known. On the other hand, catalysts for copolymerizing conjugated dienes and aromatic vinyl compounds have been proposed many times, and play an extremely important role industrially. In particular, to obtain copolymers of conjugated dienes and aromatic vinyl compounds with improved thermal and mechanical properties, research was conducted on copolymerization catalysts that are controlled to have a high cis 1,4 bond content. -Has been developed.

[0005] For example, a composite catalyst system containing a transition metal compound such as nickel, cobalt, titanium or the like as a main component (Industrial Chemistry Magazine, 72, 2081, 1969; Plast. Kautsch., 40, 356, 19)
93; Makromol. Chem. Phys., 195, 2623, 199), and a composite catalyst system containing a rare earth metal compound such as neodymium or gadolinium (Macromol. Rapid Commun. 1).
6, 563, 1992; J. Polym. Sci., Par A; Polym. Chem.,
32, 1195, 1994; Polymer, 37, 349, 1996). In these catalyst systems, some high cis 1,
4 Although controllability was exhibited, it was not possible to produce a polymer having a high molecular weight, a narrow molecular weight distribution, and a random monomer composition in the copolymer.

[0006]

An object of the present invention is to provide a catalyst for polymerizing conjugated dienes. More specifically, an object of the present invention is to provide a polymerization catalyst for producing a polymer having a high content of a cis 1,4-structure in a microstructure and a narrow molecular weight distribution. Another object of the present invention is to provide a polymer having the above characteristics and a method for producing the same. Another object of the present invention is to provide a catalyst for copolymerizing a conjugated diene and an aromatic vinyl compound. More specifically, cis 1,
An object of the present invention is to provide a polymerization catalyst for producing a copolymer having a high content of 4-structure and having a high molecular weight and a narrow molecular weight distribution, preferably a random copolymer having the above characteristics. Still another object of the present invention is to provide a copolymer having the above characteristics and a method for producing the same.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a rare earth metallocene type polymerization catalyst such as a samarium complex, a non-coordinating anion and a cation are used. By using a catalyst composition in combination with an ionic compound comprising and / or a co-catalyst containing an aluminoxane, it is possible to efficiently polymerize conjugated dienes, and by using the above-described polymerization catalyst composition, It has been found that a conjugated diene polymer having a very high cis 1,4-structure content in the microstructure and a narrow molecular weight distribution can be produced. They also found that this method can be used for the production of copolymers and filed patent applications for these inventions (PCT / JP00 / 1188).

The present inventors have further studied and found that
Among the rare earth metallocene-type polymerization catalysts, neodymium complexes have been found to provide particularly excellent polymerization activity, and the present invention has been completed. That is, the present invention provides a catalyst composition for polymerization of a conjugated diene or copolymerization of a conjugated diene and an aromatic vinyl compound, comprising the following components: (A) a neodymium complex, and (B) a non-coordinating anion. It is intended to provide a composition comprising an ionic compound comprising a cation and a cation and / or an aluminoxane. According to a preferred embodiment of the present invention, the ionic compound is triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) The above catalyst composition which is borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate; and furthermore, the periodic table I-III
The above catalyst composition comprising an organometallic compound of a group III element is provided.

From another viewpoint, a catalyst for polymerization of a conjugated diene containing a neodymium complex or a cocatalyst for use together with a polymerization catalyst for copolymerization of a conjugated diene containing a neodymium complex with an aromatic vinyl compound is provided. Accordingly, a co-catalyst comprising an ionic compound comprising a non-coordinating anion and a cation and / or an aluminoxane is provided by the present invention.
From still another viewpoint, a method of polymerizing a conjugated diene in the presence of the above-described polymerization catalyst composition; and a method of copolymerizing a conjugated diene and an aromatic vinyl compound in the presence of the above-described polymerization catalyst composition are described. Provided by the present invention.

[0010]

The DETAILED DESCRIPTION OF THE INVENTION The neodymium complex, for example, the general formula _{(I): R a MX b} · L c or the general formula (II): in R _a MX _b QX _b (wherein, M represents a neodymium; R is a pentadienyl group,
A substituted pentadienyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group; X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, or an amide group Or a hydrocarbon group having 1 to 20 carbon atoms; L represents a Lewis basic compound; Q represents a Group III element of the periodic table; a represents an integer of 1, 2, or 3; Represents an integer of 0, 1, or 2; c represents an integer of 0, 1, or 2). When a is 2, two Rs may be the same or different. Similarly, when b or c is 2,
Two Xs or Ls may be the same or different.

The type, number, and substitution position of the substituents in the substituted pentadienyl group, the substituted cyclopentadienyl group, the substituted indenyl group, and the substituted fluorenyl group are not particularly limited. Examples thereof include a methyl group, an ethyl group, and an n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, se
In addition to a c-butyl group, a tert-butyl group, a hexyl group, a phenyl group, a benzyl group and the like, a hydrocarbon group containing a silicon atom such as a trimethylsilyl group can be exemplified. R may be bonded to a part of X by a cross-linking group such as a dimethylsilyl group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, or a substituted ethylene group. They may be bonded by a cross-linking group such as a silyl group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, and a substituted ethylene group.

Specific examples of the substituted pentadienyl group include:
For example, a 2-methylpentadienyl group, a 2-benzylpentadienyl group, a 2,4-dimethylpentadienyl group, a 2,4-dibenzylpentadienyl group and the like can be mentioned. Specific examples of the substituted cyclopentadienyl group include, for example, methylcyclopentadienyl group, benzylcyclopentadienyl group, vinylcyclopentadienyl group, 2-methoxyethylcyclopentadienyl group, trimethylsilylcyclopentadienyl Group, tert-butylcyclopentadienyl group,
Ethylcyclopentadienyl group, phenylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,
3-dimethylcyclopentadienyl group, 1,3-di (tert-butyl) cyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopenta Dienyl group, pentamethylcyclopentadienyl group,
1-ethyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-benzyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-phenyl-2,3,4, 5-tetramethylcyclopentadienyl group, 1-trimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trifluoromethyl
-2,3,4,5-tetramethylcyclopentadienyl group and the like. Specific examples of the substituted indenyl group include, for example, a 1,2,3-trimethylindenyl group, a heptamethylindenyl group, and a 1,2,4,5,6,7-hexamethylindenyl group. R is preferably a pentamethylcyclopentadienyl group.

The alkoxide group represented by X includes 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,
Aryl oxide groups such as 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, and 2-isopropyl-6-neopentylphenoxy group Or a 2,6-di-tert-butylphenoxy group.

The thiolate group represented by X includes thiomethoxy, thioethoxy, thiopropoxy, thion-
Butoxy group, thioisobutoxy group, thiosec-butoxy group, aliphatic thiolate group such as thiotert-butoxy group,
Thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, or any of arylthiolate groups such as 2,4,6-triisopropylthiophenoxy group,
A 2,4,6-triisopropylthiophenoxy group is preferred.

Examples of the amide group include an aliphatic amide group such as a dimethylamide group, a diethylamide group, and a diisopropylamide group, a phenylamide group, a 2,6-di-tert-butylphenylamide group, and a 2,6-diisopropylphenylamide group. ,
2,6-dineopentylphenylamide group, 2-tert-butyl-
Arylamide groups such as 6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, and 2,4,6-tert-butylphenylamide group Or a 2,4,6-tert-butylphenylamide group is preferred.

The halogen atom represented by X is a fluorine atom,
Any of a chlorine atom, a bromine atom and an iodine atom may be used, but a chlorine atom and an iodine atom are preferred. 1 to 20 carbon atoms
Specific examples of the hydrocarbon group of, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group, linear or branched aliphatic hydrocarbon group such as octyl, phenyl group, tolyl group, aromatic hydrocarbon group such as naphthyl group, In addition to an aralkyl group such as a benzyl group, a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group may be used. Among these, a methyl group, an ethyl group, an isobutyl group, a trimethylsilylmethyl group and the like are preferable. X is preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

The Lewis basic compound represented by L is not particularly limited as long as it is a Lewis basic compound capable of coordinating a metal with a counter electron, and may be an inorganic compound or an organic compound. As Lewis basic compounds, for example, ether compounds, ester compounds, ketone compounds,
An amine compound, a phosphine compound, a silyloxy compound, or the like can be used, but is not limited thereto. In the general formula (II), Q represents a Group III element in the periodic table, and specific examples of the element include boron, aluminum, and gallium, with aluminum being preferred.

Specific examples of the neodymium complex represented by the formula (I) include, for example, tris (2,4-dimethylpentadienyl) neodymium, chlorobis (2,4-dimethylpentadienyl) neodymium, dichloro (2 , 4-dimethylpentadienyl) neodymium, methylbispentamethylcyclopentadienyltetrahydrofuran neodymium, chlorobispentamethylcyclopentadienyltetrahydrofuran neodymium, iodobispentamethylcyclopentadienyltetrahydrofuran neodymium, and the like; Specific examples of the neodymium complex represented by II) include, for example, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) neodymium.

The ionic compound used as the co-catalyst is not particularly limited as long as it comprises a non-coordinating anion and a cation. For example, the ionic compound can be reacted with the neodymium complex to form a cationic transition metal compound. Ionic compounds and the like can be mentioned. Non-coordinating anions include, for example, tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (penta) (Fluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, trideca Hydride-
7,8-dicarboundecaborate and the like.

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 a trisubstituted carbonium cation such as a triphenylcarbonium cation and a trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, trialkylammonium cation such as tri (n-butyl) ammonium cation, N, N-diethylanilinium cation, N And N, N-dialkylanilinium cations such as N, 2,4,6-pentamethylanilinium cation, dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As the ionic compound, a non-coordinating anion and a cation which are arbitrarily selected and combined can be preferably used. For example, ionic compounds include triphenylcarbonium tetrakis (pentafluorophenyl) borate and triphenylcarbonium tetrakis (tetrafluorophenyl)
Borates, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferable. The ionic compounds may be used alone or in combination of two or more. As a Lewis acid capable of producing a cationic transition metal compound by reacting with a transition metal compound, B (C ₆ F ₅ ) ₃ , Al (C ₆ F ₅ ) ₃ or the like can be used, and these are the ionic compounds described above. May be used in combination.

As the aluminoxane used as the cocatalyst, for example, an aluminoxane obtained by contacting an organic aluminum compound with a condensing agent can be used. More specifically, an aluminoxane represented by the general formula (-Al (R ')) A chain aluminoxane or a cyclic aluminoxane represented by O-) _n can be used. In the above formula, R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom and / or an alkoxy group. n indicates the degree of polymerization, and is preferably 5 or more, more preferably 10 or more. R ′ is a methyl group, an ethyl group, a propyl group,
Examples include an isobutyl group, and a methyl group is preferred. Examples of the organoaluminum compound used as a raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. Particularly preferred is trimethylaluminum. Aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can also be suitably used. Aluminoxanes may be used in combination with ionic compounds.

The catalyst composition of the present invention comprises the above components (A) and (B), and further comprises, as component (C), Periodic Tables I to III
It may contain an organometallic compound of a group element. Examples of the organic metal compound include an organic aluminum compound, an organic lithium compound, an organic magnesium compound, an organic zinc compound, an organic boron compound, and the like. More specifically, methyllithium, butyllithium, phenyllithium, benzyllithium, neopentyllithium, trimethylsilylmethyllithium, bistrimethylsilylmethyllithium, dibutylmagnesium, dihexylmagnesium, diethylzinc, dimethylzinc, trimethylaluminum, triethylaluminum, triethylaluminum Isobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, and the like can be used. Further, organic metal halides such as ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride, ethyl aluminum dichloride, etc .; and hydrogenated organic metals such as diethyl aluminum hydride and sesquiethyl aluminum hydride. Compounds may be used. You may use these organometallic compounds in combination of 2 or more types.

The above component (A) in the catalyst composition of the present invention.
The proportion of (B) and (B) can be appropriately selected depending on the type of the monomer to be polymerized and the type and conditions of the reaction. Generally, in a composition containing a neodymium complex and an aluminoxane, the component (A): component (B) (molar ratio) is 1: 1 to
The ratio can be set to about 1: 10000, preferably about 1:10 to 1: 1000, and more preferably about 1:50 to 1: 500. In a composition containing a neodymium complex and an ionic compound, component (A):
Component (B) (molar ratio) is from 1: 0.1 to 1:10, preferably 1: 0.
The ratio may be about 2 to 1: 5, more preferably about 1: 0.5 to 1: 2. In the catalyst composition containing the component (C), the blending ratio (molar ratio) of the neodymium complex and the component (C) is, for example, 1:
It is about 0.1 to 1: 1000, preferably about 1: 0.2 to 1: 500, and more preferably about 1: 0.5 to 1:50.

The type of the conjugated diene compound monomer that can be polymerized by the polymerization method of the present invention is not particularly limited.
Examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. Of these, 1,3-
Butadiene is preferred. These monomer components may be used alone or in combination of two or more.

The type of the conjugated diene compound monomer copolymerizable by the polymerization method of the present invention is not particularly limited. For example, 1,3-butadiene, isoprene, 1,3-pentadiene,
2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene,
2-methylpentadiene, 4-methylpentadiene, or 2,
4-hexadiene and the like.
1,3-butadiene is preferred. These monomer components may be used alone or in combination of two or more.

The kind of the aromatic vinyl compound monomer copolymerizable by the polymerization method of the present invention is not particularly limited. For example, styrene, p-methylstyrene, m-methylstyrene,
p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, p-tert-butoxystyrene, dimethylaminomethylstyrene, dimethylaminoethylstyrene,
Vinyl toluene and the like are used. Of these, styrene is preferred. These monomer components may be used alone or in combination of two or more.

The polymerization method of the present invention may be carried out in the presence or absence of a solvent. When a solvent is used, its type is not particularly limited as long as the solvent is substantially inert in the polymerization reaction and has sufficient solubility in the monomer and the catalyst composition. For example, butane,
Saturated aliphatic hydrocarbons such as pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; monoolefins such as 1-butene and 2-butene; aromatic hydrocarbons such as benzene and toluene; Methylene,
Examples thereof include halogenated hydrocarbons such as chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, and chlorotoluene. Of these, toluene is preferable. Further, two or more solvents may be used in combination.

The polymerization temperature in the polymerization method of the present invention is, for example, in the range of -100 to 100 ° C, preferably in the range of -50 to 80 ° C. The polymerization time is, for example, about 1 minute to 12 hours, preferably about 5 minutes to 5 hours. However, these reaction conditions can be appropriately selected according to the type of the monomer and the type of the catalyst composition, and are not limited to the ranges exemplified above. After the polymerization reaction reaches a predetermined polymerization rate, a known polymerization terminator is added to the polymerization system to stop the polymerization, and then the produced polymer can be separated from the reaction system according to a usual method.

The content of the cis structure in the microstructure of the polymer obtained by the method for polymerizing a conjugated diene of the present invention is as follows:
It is usually at least 80 mol%, preferably at least 90 mol%,
It is more preferably at least 95 mol%, particularly preferably at least 98 mol%. Further, regarding the molecular weight distribution, Mw / Mn is 2.00
Or less, preferably 1.80 or less, more preferably 1.60 or less, still more preferably 1.40 or less, particularly preferably 1.30 or less.
It is as follows.

The content of the cis structure in the microstructure of the copolymer obtained by the copolymerization method of the present invention is usually 80.
mol% or more, preferably 90 mol% or more, particularly preferably 9 mol% or more.
5 mol% or more, the molecular weight Mn is 10,000 or more, preferably
20,000 or more, more preferably 50,000 or more, particularly preferably 100,000 or more, the molecular weight distribution Mw / Mn is 2.50 or less,
It is preferably at most 2.00, more preferably at most 1.80, particularly preferably at most 1.50. Further, the copolymer of the present invention is a random copolymer whose monomer composition shows substantially randomness.

The polymer obtained by the polymerization method of the present invention is expected to have high thermal properties (thermal stability, etc.) and mechanical properties (tensile modulus, flexural modulus, etc.). It can be used for various purposes as a material.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples. The microstructure of the polybutadiene in the examples is the peak [ ¹ HN obtained by ¹ H NMR and ¹³ C NMR.
MR: δ 4.8-5.0 (= CH ₂ of 1,2-vinyl unit), 5.2-5.8
(-CH = of 1,4-unit and -CH = of 1,2-vinyl unit),
¹³ C NMR: δ 27.4 (1,4-cis unit), 32.7 (1,4-trans unit), 127.7-131.8 (1,4-unit), 113.8
-114.8 and 143.3-144.7 (1,2-vinyl units)], and the styrene content was determined by the peak obtained by ¹ H NMR [δ 4.8-5.0 (butadiene 1,2-vinyl units). = CH ₂ ), δ 5.2-5.8 (-CH = of 1,4-vinyl unit and 1,2-vinyl unit of butadiene), and δ 6.3-7.3 (aromatic ring of styrene unit)]. . The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were determined by GPC using polystyrene as a standard substance.

Example 1 Drying well in a glove box under a nitrogen atmosphere
Dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) neodymium [(Cp ^* ) ₂ Nd (μ-Me) ₂ AlMe ₂ ] (Cp ^* : pentamethylcyclopentadienyl 0.01 mmol) and toluene
Dissolved in 6 ml. Then, MMAO (toluene-soluble aluminoxane sold by Tosoh Akzo) was converted to Al / N
The bottle was stoppered by adding so that d = 200 element ratio.
Then remove the bottle from the glove box and
1.5 g of butadiene was charged and polymerization was carried out at 50 ° C. for 5 minutes. After polymerization, 10 wt% of BHT (2,6-bis (tert-butyl) -4-
The reaction was stopped by adding 10 ml of methanol containing [methylphenol], and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and dried in vacuo at 60 ° C. The yield of the obtained polymer was 66 wt%. The polymer microstructure has a cis content of 97.5 mol%, a number average molecular weight of 362,400,
Mw / Mn was 1.89.

Example 2 Drying well in a glove box under a nitrogen atmosphere
A 30 ml pressure-resistant glass bottle was charged with 0.01 mmol of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) neodymium [(Cp ^* ) ₂ Nd (μ-Me) ₂ AlMe ₂ ] and dissolved in 6 ml of toluene. . Then, 0.03 mmol of triisobutylaluminum and triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
The bottle was stoppered with the addition of 0.01 mmol. Then remove the bottle from the glove box and add 1,3-butadiene
1.35 g was charged and polymerization was carried out at 50 ° C. for 5 minutes. After polymerization, 10w
The reaction was stopped by adding 10 ml of methanol containing t% BHT,
Further, the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and vacuum-dried at 60 ° C. The yield of the obtained polymer is 76 wt.
%Met. The microstructure of the polymer has a cis content of 96.1 mo
1%, the number average molecular weight was 400,600, and Mw / Mn was 1.66.

Example 3 Drying well in a glove box under a nitrogen atmosphere
Dimethyl aluminum (μ-
Dimethyl) bis (pentamethylcyclopentadienyl)
Neodymium _{^{[(Cp *) 2 Nd (}} μ-Me) 2 AlMe 2] a 0.01 mmol charged,
It was dissolved in 6 ml of toluene. Then, triethylaluminum 0.03 mmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
The bottle was stoppered with the addition of 0.01 mmol. Then remove the bottle from the glove box and add 1,3-butadiene
1.35 g was charged and polymerization was carried out at 50 ° C. for 5 minutes. After polymerization, 10w
The reaction was stopped by adding 10 ml of methanol containing t% BHT,
Further, the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and vacuum-dried at 60 ° C. The yield of the obtained polymer is 84 wt.
%Met. Polymer microstructure with cis content of 77.0 mol%
And the number average molecular weight was 239,500 and Mw / Mn was 1.42.

Example 4 Drying well in a glove box under a nitrogen atmosphere
Dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) neodymium [(Cp ^* ) ₂ Nd (μ-Me) ₂ AlMe ₂ ] was charged into a 30 ml pressure-resistant glass bottle in an amount of 0.01 mmol, and dissolved in 6 ml of toluene. . Then, trimethylaluminum 0.03 mmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 0.
01 mmol was added and the bottle was stoppered. Then remove the bottle from the glove box and add 1,3-butadiene to 1.
35 g was charged and polymerization was carried out at 50 ° C. for 5 minutes. After polymerization, 10 wt
The reaction was stopped by adding 10 ml of methanol containing
Further, the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and vacuum-dried at 60 ° C. The yield of the obtained polymer is 93 wt.
%Met. The microstructure in the polymer has a cis content of 6
4.8 mol%, number average molecular weight 353,400, Mw / Mn 1.56
Met.

Example 5: Fully dried in a glove box under a nitrogen atmosphere
A 30 ml pressure-resistant glass bottle was charged with 0.01 mmol of tris (2,4-dimethylpentadienyl) neodymium [(2,4-DMBD) ₃ Nd] and dissolved in 6 ml of toluene. Next, MMAO (toluene-soluble aluminoxane sold by Tosoh Akzo Co., Ltd.) was added at an Al / Nd = 200 element ratio, and the bottle was stoppered. Thereafter, the bottle was taken out of the glove box, charged with 1.35 g of 1,3-butadiene, and polymerized at 50 ° C. for 5 minutes. After the polymerization, the reaction was stopped by adding 10 ml of a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol], and the polymer was further diluted with a large amount of a methanol / hydrochloric acid mixed solvent. Separate and vacuum dry at 60 ° C. The yield of the obtained polymer was 86 wt%. The microstructure of the polymer was found to have a cis content of 81.8 mol%, a number average molecular weight of 39,700, and Mw / Mn of 2.21.

Example 6: Fully dried in a glove box under a nitrogen atmosphere
Dimethyl aluminum (μ-
Dimethyl) bis (pentamethylcyclopentadienyl)
0.03 mmol of neodymium [(Cp ^* ) ₂ Nd (μ-Me) ₂ AlMe ₂ ] was charged,
It was dissolved in 1 ml of toluene. Then, 0.09 mmol of triisobutylaluminum and triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ )
₄ ) 0.03 mmol was added and the bottle was stoppered. Thereafter, the bottle was taken out of the glove box, 0.81 g of 1,3-butadiene and 1.7 ml of styrene were charged, and polymerization was performed at 50 ° C. for 1 hour. After polymerization, 10 ml of methanol containing 10 wt% BHT
Was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and dried at 60 ° C. under vacuum. The yield of the obtained polymer was 25 wt%. The styrene content in the polymer was 8.1 mol%, the microstructure of the butadiene unit was 87.8 mol% in cis content, the number average molecular weight was 46,100, and Mw / Mn was 1.61.

[0040]

When the polymerization of a conjugated diene or the copolymerization of a conjugated diene and an aromatic vinyl compound is carried out using the catalyst composition of the present invention, the content of the cis 1,4-structure in the microstructure is extremely high and narrow. A polymer having a molecular weight distribution can be produced.

Continued on the front page F term (reference) 4J028 AA01A AB00A AC49A BA00A BA01B BB01B BC12B BC25B EA01 EB12 EB13 EB14 EB21 EC01 EC02 GA06 GA11 4J100 AB02Q AB03Q AB04Q AB07Q AB08Q AS01P AS02P AS03 FA10CA04 BA04BA

Claims (6)

[Claims] 1. A catalyst composition for polymerizing a conjugated diene or copolymerizing a conjugated diene with an aromatic vinyl compound, comprising: (A) a neodymium complex; and (B) a non-coordinating anion. A composition comprising an ionic compound composed of a cation and a cation and / or an aluminoxane. 2. The method according to claim 1, wherein the ionic compound is triphenylcarbonium tetrakis (pentafluorophenyl) borate,
2. The compound according to claim 1, which is triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, or 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate. Catalyst composition. 3. The catalyst composition according to claim 1, further comprising an organometallic compound of an element in Groups I to III of the periodic table. 4. A co-catalyst for use together with a catalyst for polymerizing a conjugated diene containing a neodymium complex or a catalyst for copolymerizing a conjugated diene containing a neodymium complex with an aromatic vinyl compound, comprising a non-coordinating anion and A cocatalyst containing an ionic compound comprising a cation and / or an aluminoxane. 5. A method for polymerizing a conjugated diene in the presence of the catalyst composition according to claim 1. Description: 6. A method for copolymerizing a conjugated diene and an aromatic vinyl compound in the presence of the catalyst composition according to claim 1. Description: