JPH1160622A - Metallic compound for polymerization and preparation of aromatic vinyl compound/olefin copolymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an arom. vinyl compd.-contg. copolymer which has high activity and practicality by copolymerizing an arom. vinyl compd. with an olefin in the presence of a specified transition metal compd. and a co-catalyst. SOLUTION: An arom. vinyl compd. is copolymerized with an olefin in the presence of a transition metal compd. represented by formula I or II [wherein Ind1 to Ind4 represent each a (un) substd. indenyl; R<1> and R<2> represent each H, a 1-12C alkyl, a 6-10C aryl, or a 7-20C alkylaryl; Z is 2 to 10; (x) and (y) are each 0 to 10, provided that x+y is 2 or more; X1 to X4 represent each H, a halogen, an alkyl, an amide represented by formula III (wherein A1 and A2 represent each R<1> ) or the like; R<3> to R<3> ' represent each H, a 1-20C alkyl, a 6-10C aryl, a 7-20C alkylaryl, a halogen or the like; M represents Zr, Hf, or Ti] and a co-catalyst represented by formula IV or V (wherein R<5> and R<6> represent each a 1-5C alkyl, a 6-10C aryl, or H; (m) and (n) are each 2 to 100) at -78 to 200 deg.C, pref. 0 to 160 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound for the polymerization of an aromatic vinyl compound-containing copolymer such as an aromatic vinyl compound-olefin copolymer, and an aromatic vinyl compound-olefin copolymer using the same. The present invention relates to a method for manufacturing a united product.

[0002]

2. Description of the Prior Art Copolymers of olefins and aromatic vinyl compounds, for example, ethylene and styrene, have been studied using so-called heterogeneous Ziegler-Natta catalysts. For example, Polymer Bulletin, 20 , 23
7-241 (1988), Macromolecule
s, 24 , 5476 (1991). However, conventional heterogeneous Ziegler-Natta catalyst systems have low activity and the resulting copolymers have low styrene content, do not have a uniform, regular copolymerized structure, and It is not practical because it contains many homopolymers such as polyethylene, isotactic, and atactic polystyrene.

There are also known several styrene-ethylene copolymers obtained by using a so-called homogeneous Ziegler-Natta catalyst system comprising a transition metal compound and an organoaluminum compound, and a method for producing the same. JP-A-3-1630
No. 88 and JP-A-7-53618 describe a styrene-ethylene copolymer having no normal styrene chain, which is obtained using a complex having a so-called constrained geometric structure, a so-called pseudo-random copolymer. I have.
Note that a normal St chain refers to a chain of head-tail bonds. In addition, styrene may be described as St below.
However, the phenyl group having a styrene-ethylene alternating structure present in the pseudorandom copolymer has no stereoregularity. Further, the activity is not practically sufficient.

JP-A-6-49132, and Pol
ymer Preprints, Japan, 42 , 2
No. 292 (1993) discloses a styrene-ethylene copolymer having no normal St chain using a catalyst comprising a cross-linked Cp-based Zr complex (where Cp represents cyclopentadienyl) and a co-catalyst, a so-called styrene-ethylene copolymer. A method for producing a pseudo-random copolymer is described. The phenyl group of the alternating styrene-ethylene structure present in the pseudorandom copolymer has no substantial stereoregularity. Further, the activity of this catalyst system is insufficient for practical use.

On the other hand, T having a substituted phenolic ligand
Styrene-ethylene alternating copolymers obtained using i-complexes are known (JP-A-3-250007,
And Stud. Surf. Sci. Catal. , 51
7 (1990)). This copolymer is characterized in that it has a substantially alternating structure of ethylene and styrene. Since the obtained copolymer is a copolymer containing substantially only an alternating structure, 50 mol of ethylene in the copolymer is used.
% And styrene 50 mol% are substantially difficult to change. Although the stereoregularity of the phenyl group is isotactic, the isotactic dyad fraction m is about 0.92, the weight average molecular weight is as low as about 20,000, and it gives practical properties as a crystalline polymer. It is not enough. In addition, since the catalyst activity is extremely low and it is obtained as a mixture with syndiotactic polystyrene or the like, it is not practical.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a transition metal compound for the polymerization of an aromatic vinyl compound-containing copolymer, for example, for the copolymerization of an aromatic vinyl compound and an olefin, and a highly active and practical polymer using the same. An object of the present invention is to provide a method for producing an aromatic vinyl compound-containing copolymer.

[0007]

The present invention provides an aromatic vinyl compound-containing copolymer represented by the following general formulas (1) and (2), preferably a copolymer of an aromatic vinyl compound and an olefin. It is a transition metal compound for joint use.

[0008]

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In the formula, Ind1 and Ind2 are unsubstituted or substituted indenyl groups represented by the following general formula (6), and Ind1 and Ind2 may be the same or different.

[0010]

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Here, R7, R7 ', R7 ", R7"'
Is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 10 carbon atoms.
An aryl group, an alkylaryl group having 7 to 20 carbon atoms,
Halogen atom, OSiR8 ₃ group, SiR8 ₃ group or P
R8 ₂ group (R8 are all represent a hydrocarbon group having 1 to 10 carbon atoms), and may be the same or different.
Adjacent R7, R7 ′, R7 ″, R7 ″ ″ groups may be combined to form a 5- to 8-membered aromatic or aliphatic ring.

As Ind1 or Ind2, 1-indenyl is used as an unsubstituted indenyl group, and 4-alkyl-1-indenyl, 4-aryl-1-indenyl and 4,5-dialkyl-1-indenyl are used as substituted indenyl groups. , 4,6-dialkyl-1-indenyl, 5,6
-Dialkyl-1-indenyl, 4,5,6-trialkyl-1-indenyl, 5-aryl-1-indenyl, 5,6-diaryl-1-indenyl, 4,5-diaryl-1-indenyl, 4, 6-diaryl-1-
And indenyl.

R1 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, which may be the same or different. Further, adjacent R1 groups may be combined to form a 5- to 8-membered aliphatic ring. z represents an integer of 2 to 10.

Examples of the substituent for bridging Ind1 and Ind2 include cyclopentylidene, cyclohexylidene, cycloheptylidene, 3-methylcyclopentylidene, 4-phenylcyclohexylidene, and 3,4-dimethylcyclohexane. Butylidene, 3-phenylcyclohexylidene group and the like.

X1 and X2 are hydrogen, a halogen atom, an alkyl group, an aryl group, a silyl group, an alkoxy group or an amide group represented by the following general formula (3). Chlorine, bromine and the like as a halogen atom, methyl and ethyl as an alkyl group, phenyl and the like as an aryl group, trimethylsilyl and the like as a silyl group, methoxy and ethoxy as an alkoxyl group, Isopropoxy group and the like. X1 and X2 may be the same or different.

[0016]

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In the formula, A1 and A2 are hydrogen, having 1 to 20 carbon atoms.
, An aryl group having 6 to 10 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms, which may be the same or different. Further, the A1 and A2 groups may be combined to form a 5- to 8-membered aromatic or aliphatic ring.

Examples of such an amide group include a dimethylamide group, a diethylamide group, a diisopropylamide group,
Examples include a diphenylamide group, a methylethylamide group, a pyrrolidinyl group, a piperidinyl group, and a pyridinyl group.

Preferred examples of X1 and X2 include a dimethylamide group and a diethylamide group. As an advantage when the substituent is selected, a conventionally known process of reacting a lithium salt of a ligand with zirconium tetrachloride or the like at a low temperature of −78 ° C. when synthesizing a transition metal compound is eliminated, and the complex The manufacturing process is greatly simplified, and as a result, a transition metal compound can be synthesized at low cost. M is Zr, Hf or Ti.

[0020]

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In the formula, Ind3 and Ind4 represent the same structure as Ind1 and Ind2 in the general formula (1).

R2 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, which may be the same or different. Further, adjacent R2 groups may be combined to form a 5- to 8-membered aliphatic ring.

X and y each represent an integer from 0 to 10;
And y is 2 or more. R3, R3 ', R3 ", R
3 ″ ′ is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms.
10 aryl group, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, OSiR4 ₃ group, a sir4 ₃ group or PR4 ₂ group (R4 represents either a hydrocarbon group having 1 to 10 carbon atoms), They may be the same or different. In addition, adjacent R3, R3 ′, R3 ″, R3 ′ ″
The groups may together form a 5- to 8-membered aromatic or aliphatic ring.

X3 and X4 represent X in the general formula (1)
1, showing the same structure as X2. M is Zr, Hf or T
i.

Examples of such transition metal compounds include the following compounds. For example, as the transition metal compound represented by the general formula (1), cyclopentylidenebis (1
-Indenyl) zirconium dichloride, cyclohexylidenebis (1-indenyl) zirconium dichloride, cycloheptylidenebis (1-indenyl) zirconium dichloride, 3-methylcyclopentylidenebis (1-indenyl) zirconium dichloride, cyclopentylidene ( 1-indenyl) (4-phenyl-1-indenyl) zirconium dichloride, cyclopentylidenebis (1-indenyl) bisdimethylamidozirconium, cyclohexylidenebis (1-indenyl) bisdimethylamidozirconium, cycloheptylidenebis ( 1-indenyl) bisdimethylamidozirconium,
3-methylcyclopentylidenebis (1-indenyl)
Bisdimethylamidozirconium, cyclopentylidene (1-indenyl) (4-phenyl-1-indenyl)
Bisdimethylamidozirconium, cyclopentylidenebis (1-indenyl) bisdiisopropylamidozirconium, cyclopentylidenebis (1-indenyl)
Bisdiisopropylamidozirconium, cyclopentylidenebis (1-indenyl) bisdiphenylamidozirconium, cyclopentylidenebis (1-indenyl) bispyrrolidinyl zirconium, cyclopentylidenebis (1-indenyl) bisdipiperidinyl zirconium, Cyclopentylidenebis (1-indenyl) bisdipyridinyl zirconium, cyclopentylidenebis (1-indenyl) dimethylamidozirconium chloride and the like can be mentioned.

Examples of the transition metal complex represented by the general formula (2) include 2-indanilidenebis (1-indenyl) zirconium dichloride and 2-indanilidenebis (1-indenyl) bisdimethylamide. Zirconium, 2-indanilidenebis (1-indenyl) bisdiethylamidozirconium, 1-indanilidenebis (1-indenyl) zirconium dichloride, 1-indanilidenebis (1-indenyl) bisdimethylamidozirconium, 1-in Danilidenebis (1-indenyl) bisdiethylamidozirconium and the like.

A particularly preferred transition metal is cyclopentylidenebis (1-indenyl) bisdimethylamidozirconium.

Although the Zr complex has been exemplified above, Ti, Hf
As the complex, a compound similar to the above is preferably used. Also,
Although the above-mentioned complex uses a racemic form, even if a D-form is used, L
A body may be used.

The present invention is also a method for producing an aromatic vinyl compound-olefin copolymer which is polymerized using a polymerization catalyst comprising these transition metal compounds and a cocatalyst.
As the cocatalyst used in the present invention, a cocatalyst conventionally used in combination with a transition metal compound can be used. As such a cocatalyst, aluminoxane (or alumoxane) or a boron compound is preferable. Used for Further, the present invention is a method for producing an aromatic vinyl compound-olefin copolymer in which the cocatalyst used in this case is an aluminoxane represented by the following general formulas (4) and (5).

[0030]

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In the formula, R5 is an alkyl group having 1 to 5 carbon atoms;
An aryl group having 6 to 10 carbon atoms or hydrogen, m is 2 to 1
It is an integer of 00. Each R5 may be the same or different.

[0032]

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In the formula, R6 is an alkyl group having 1 to 5 carbon atoms,
An aryl group having 6 to 10 carbon atoms or hydrogen, and n is 2 to 1
It is an integer of 00. Each R6 may be the same or different.

As the aluminoxane, methylalumoxane, ethylalumoxane and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferably used. If necessary, a mixture of these different alumoxanes may be used. These alumoxanes may be used in combination with alkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, and alkylaluminums containing halogen, for example, dimethylaluminum chloride.

The boron compound used as a promoter is
Triphenylcarbenium tetrakis (pentafluorophenyl) borate, {trityltetrakis (pentafluorophenyl) borate}, lithium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) borane, trimethylammonium tetraphenylborate, triethylammonium tetraphenyl Borate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (n-butyl) ammoniumtetra (p
-Tolyl) phenyl borate, tri (n-butyl) ammonium tetra (p-ethylphenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, trimethylammonium tetra (p
-Tolyl) borate, trimethylammonium tetrakis-3,5-dimethylphenylborate, triethylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis-2,4-dimethyl Phenyl borate, anilinium tetrakis pentafluorophenyl borate, N,
N′-dimethylanilinium tetraphenyl borate,
N, N'-dimethylanilinium tetrakis (p-tolyl) borate, N, N'-dimethylanilinium tetrakis (m-tolyl) borate, N, N'-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate N, N'-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, N, N'-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N'-diethylanilinium tetrakis (pentafluorophenyl) Borate, N, N'-
2,4,5-pentamethylanilinium tetraphenyl borate, N, N'-2,4,5-pentaethylanilinium tetraphenyl borate, di- (isopropyl)
Ammonium tetrakis pentafluorophenyl borate, di-cyclohexylammonium tetraphenyl borate, triphenylphosphonium tetraphenyl borate, tri (methylphenyl) phosphonium tetraphenyl borate, tri (dimethylphenyl) phosphonium tetraphenyl borate, triphenylcarbenium tetrakis (p- Tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) borate, tropylium tetrakispenta Fluorophenyl borate, tropylium tetrakis (p-tolyl) borate, tropylium tetrakis (m-tri ) Borate, tropylium tetrakis (2,4-dimethylphenyl) borate, tropylium tetrakis (3,5-dimethylphenyl) borate. These boron compounds and the above-mentioned organoaluminum compounds may be used simultaneously. In particular, when a boron compound is used as a co-catalyst, the addition of an alkyl aluminum compound such as triisobutyl aluminum is effective for removing impurities such as water contained in the polymerization system that adversely affect the polymerization.

The aromatic vinyl compound used in the present invention includes styrene and various substituted styrenes such as p
-Methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene,
Examples thereof include o-chlorostyrene, α-methylstyrene, and the like, and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. Industrially, styrene, p-methylstyrene and p-chlorostyrene are preferably used, and styrene is particularly preferably used. Further, as the olefin used in the present invention, an α-olefin having 2 to 20 carbon atoms, that is, ethylene, propylene, 1-
Butene, 1-hexene, 4-methyl-1-pentene, 1
Octene and cyclic olefins, such as norbornene and norbornadiene, are suitable. Among them, ethylene,
Propylene is preferred, and ethylene is particularly preferred. In the following description, ethylene will be described as an example of olefin.

In producing the copolymer of the present invention, an olefin, an aromatic vinyl compound exemplified above,
A transition metal compound which is a metal complex is brought into contact with a co-catalyst, but polymerized in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chloro-substituted benzene, chloro-substituted toluene , Methylene chloride, chloroform and the like, using a single or mixed solvent of a saturated aliphatic or aromatic hydrocarbon or a halogenated hydrocarbon. If necessary, a method such as batch polymerization, continuous polymerization, batch polymerization, or preliminary polymerization can be used.

[0038] The polymerization temperature is suitably from -78 ° C to 200 ° C, preferably from 0 ° C to 160 ° C. A polymerization temperature lower than -78 ° C is industrially disadvantageous, and a temperature higher than 200 ° C is not suitable because decomposition of the metal complex occurs.

When an organoaluminum compound is used as a cocatalyst, an aluminum atom /
The complex metal atom ratio is 0.1 to 100,000, preferably 1
It is used in a ratio of 0-10000. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as a cocatalyst, a boron atom / complex metal atom ratio of 0.01
To 100, preferably 0.1 to 1
0, particularly preferably 1, is used. If it is less than 0.01, the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization. To the copolymer of the present invention, additives, auxiliaries and the like usually used for polymers can be added as long as the effects of the present invention are not impaired. Suitable additives and auxiliaries include antioxidants, lubricants, plasticizers, ultraviolet absorbers, stabilizers, pigments, colorants, fillers, foaming agents, and the like.

When the aromatic vinyl compound-ethylene copolymer obtained by the present invention has an aromatic vinyl compound content of from 1 to less than 99.9% by mole fraction, the following general formula (7) ) Wherein the stereoregularity of the phenyl group in the alternating structure of ethylene and the aromatic vinyl compound is greater than 0.75 in the isotactic dyad fraction m (meso dyad fraction) given by the following formula (I): And an aromatic vinyl compound-ethylene copolymer, wherein the alternating structure index λ given by the following formula (II) is smaller than 70 and larger than 1. m = Am / (Ar + Am) Formula (I) Here, Ar is 25 pp obtained by 13 C-NMR.
The peak area derived from the r (racemic diad) structure derived from methylene carbon observed in the vicinity of m may slightly shift depending on the measurement conditions and the solvent. For example, deuterated chloroform is used as a solvent and tetramethylsilane is used as a reference. , Appears around 25.4 to 25.5 ppm, and 25.3 to 25.4 ppm based on the center of the triplet of heavy tetrachloroethane (73.89 ppm) using heavy tetrachloroethane as a solvent. Appears nearby. Similarly,
Am is a peak derived from the m (meso dyad) structure. For example, when heavy chloroform is used as a solvent and tetramethylsilane is used as a reference, 25.2 to 25.3 ppm is used.
And appears around 25.1 to 25.2 ppm when heavy tetrachloroethane is used as a solvent and the center peak of the triplet of heavy tetrachloroethane is used as a reference. λ = A3 / A2 × 100 Formula (II) Here, A3 is three kinds of peaks derived from an aromatic vinyl compound-ethylene alternate structure represented by the following general formula (7 ′) and obtained by 13 C-NMR measurement. This is the sum of the areas a, b, and c. A2 is 1 based on TMS.
It is the total area of peaks derived from main chain methylene and methine carbon observed in the range of 0 to 50 ppm by 3C-NMR.

[0041]

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In the formula, Ph is an aromatic group such as a phenyl group, w
Represents the number of repeating units and represents an integer of 2 or more.

[0043]

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In the formula, Ph is an aromatic group such as a phenyl group, w
Represents the number of repeating units and represents an integer of 2 or more.

The aromatic vinyl compound-ethylene copolymer obtained according to the present invention has an alternating structure having high stereoregularity of ethylene and an aromatic vinyl compound, and simultaneously an ethylene chain of various lengths and an aromatic vinyl compound. Heterogeneous binding,
It is characterized by having various structures such as a chain of aromatic vinyl compounds. In the present invention, the ratio of the alternating structure can be variously changed in the range of 1 to less than 70 by the λ value obtained by the above formula depending on the content of the aromatic vinyl compound in the copolymer. Since this stereoregular alternating structure is a crystallizable structure, the copolymer of the present invention can be made crystalline or non-crystalline by controlling the degree of crystallinity by the content of the aromatic vinyl compound or by controlling the crystallinity by an appropriate method. It is possible to provide various properties such as a polymer having a crystalline property and a partially crystalline structure. When the λ value is less than 70, it is necessary to provide significant toughness and transparency while being a crystalline polymer.
It is important to become a partially crystalline polymer or a non-crystalline polymer.

The copolymer of the present invention has an initial tensile strength in various regions of the content of the aromatic vinyl compound and various crystallinities as compared with the conventional aromatic vinyl compound-ethylene copolymer having no stereoregularity. It has improved properties such as elastic modulus, hardness, breaking strength, elongation, and solvent resistance, and exhibits physical properties characteristic of a thermoplastic elastomer, a transparent soft resin, or a novel crystalline resin. Further, by changing the content of the aromatic vinyl compound, the glass transition point can be changed in a wide range. That is, the copolymer obtained by the present invention exhibits different characteristic physical properties in the aromatic vinyl compound content region.

[0047]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. In the following description, Me represents a methyl group, Ph represents a phenyl group, Flu represents a fluorenyl group, and Cp represents a cyclopentadienyl group.

The copolymers obtained in each of the examples and comparative examples were analyzed by the following means. The 13C-NMR spectrum was measured using a heavy chloroform solvent or a heavy 1,1,2,2-tetrachloroethane solvent with α-500 manufactured by JEOL Ltd. based on TMS. The 13C-NMR spectrum measurement for quantifying the peak area is performed by NOE
Is eliminated by the proton gate decoupling method
The pulse width was a 45 ° pulse, and the repetition time was 5 seconds as a standard. By the way, the measurement was performed under the same conditions except that the repetition time was changed to 1.5 seconds, and the quantitative value of the peak area of the copolymer coincided with the case of the repetition time of 5 seconds within the measurement error range.

The determination of the styrene content in the copolymer was determined by 1H
-Performed by NMR, using α-500 manufactured by JEOL Ltd. Using a heavy chloroform solvent or heavy 1,1,2,2-tetrachloroethane, based on TMS, a peak derived from a phenyl group proton (6.5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 7.5 ppm). 3 ppm). For the molecular weight in the examples, a weight average molecular weight and a number average molecular weight in terms of standard polystyrene were determined using GPC (gel permeation chromatography). The copolymer soluble in THF at room temperature was measured using HLC-8020 manufactured by Tosoh Corporation using THF as a solvent. The glass transition temperature and the melting point were measured by DSC, and the DSC measurement was performed using a DSC200 manufactured by Seiko Denshi Co., Ltd. at a heating rate of 10 ° C./min under a stream of N ₂ . The measuring device of GC-MS used QP-1000 made by Shimadzu Corporation.

Experimental Example <Synthesis of transition metal compound> Rac- (1,1-cyclopentylidene) bis (1-indenyl) bisdimethylamidozirconium of the following formula was synthesized by the following synthesis method.

1,1-cyclopentylidenebis (1-
Synthesis of indene) Pulverized potassium hydroxide 0.285mo under Ar atmosphere
1 is 1,2-dimethoxyethane (hereinafter abbreviated as DME) 1
The suspension was suspended in 50 ml, 0.215 mol of indene was added dropwise, and the mixture was refluxed for 1 hour. Thereafter, 0.107 mol of cyclopentanone was added dropwise and refluxed for 4 days. The reaction product was poured into water and diethyl ether, the organic layer was separated, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane-dichloromethane) to give 1,1-cyclopentylidenebis (1-indene).
Was obtained as yellow-white crystals (3.2 g, yield 10%). GC
-It was confirmed by MS measurement that the substance was the target substance.

Synthesis of rac-1,1-cyclopentylidenebis (1-indenyl) bisdimethylamidozirconium Under an Ar atmosphere, 4.3 mmol of 1,1-cyclopentylidenebis (1-indene) and 3.7 mmol of Zirconium tetrakisdimethylamide, ΔZr (NMe ₂ )
₄と と も に were charged together with 25 ml of toluene.
Stirred for days. The toluene was distilled off under reduced pressure to obtain a brown solid. An aliquot was taken, washed several times with hexane, and dried to obtain 0.1 g of orange powder rac-1,1-cyclopentylidenebis (1-indenyl) bisdimethylamidozirconium. 7.83 ppm (d, 2H), 7.48 ppm by 1H-NMR spectrum measurement
(D, 2H), 7.03 ppm (t, 2H), 6.72
ppm (t, 2H), 6.52 ppm (d, 2H),
6.37 ppm (d, 2H), 6.26 ppm (d, 2H)
H) 3.03 ppm (m, 2H), 2.85 ppm
(M, 2H), 2.37 ppm (s, 12H), 1.9
It has a peak at the position of 7 ppm (m, 2H), 1.90 ppm (m, 2H). Measurement is based on TMS, CD
Performed with Cl ₃ as solvent.

<Synthesis of Copolymer> Example 1 Polymerization was carried out using an autoclave having a capacity of 1 L, a stirrer and a heating jacket. 400m of dehydrated toluene
l, 80 ml of dehydrated styrene was charged and heated and stirred at an internal temperature of 50 ° C. The system was purged by bubbling about 40 L of nitrogen, and triisobutylaluminum 0.84 mmol
l, Methyl alumoxane (Tosoh Akzo Co., Ltd., MMAO
-3 mmol) was added in an amount of 8.4 mmol based on Al. Immediately after ethylene was introduced and the pressure was stabilized at 10 kg / cm ² G, the catalyst rac-1,1-cyclopentylidenebis (1-indenyl) bisdimethylamidozirconium was placed in a catalyst tank placed on an autoclave at 4.2 μm.
ol and about 50 ml of a toluene solution of 0.84 mmol of triisobutylaluminum were added to the autoclave. About 30 minutes after the introduction of the catalyst, the internal temperature rose to a maximum of 90 ° C. due to heat of polymerization. The polymerization was carried out for 2 hours while maintaining the pressure at 10 kg / cm ² G. After the completion of the polymerization, the resulting polymerization solution was poured little by little into excessively vigorously stirred excess methanol to precipitate the produced polymer. 60 ° C under reduced pressure
And dried until no change in weight was observed.
74 g of polymer were obtained.

Example 2 Polymerization was carried out using an autoclave having a capacity of 1 L, a stirrer and a heating jacket. 80m of dehydrated toluene
l, 400 ml of dehydrated styrene is charged, and the internal temperature is 50 ° C.
And heated and stirred. The system was purged by bubbling about 40 L of nitrogen, and triisobutylaluminum 0.84 mmol
l, Methyl alumoxane (Tosoh Akzo Co., Ltd., MMAO
-3A) was added in an amount of 21.0 mmol based on Al. Immediately after ethylene was introduced and the pressure was stabilized at 1 kg / cm ² G, the catalyst rac-1,1-cyclopentylidenebis (1-indenyl) bisdimethylamidozirconium was added from the catalyst tank installed on the autoclave to 21.0 μm.
mol, triisobutylaluminum 0.84 mmol
About 50 ml of a toluene solution in which was dissolved was added to the autoclave. About 10 minutes after the introduction of the catalyst, the internal temperature rose to a maximum of 57 ° C. due to heat of polymerization. The polymerization was carried out for 3.5 hours while maintaining the pressure at 1 kg / cm ² G. After the completion of the polymerization, the resulting polymerization solution was poured little by little into excessively vigorously stirred excess methanol to precipitate the produced polymer. Under reduced pressure, 6
When dried at 0 ° C. until no change in weight was observed, 96.3 g of a polymer was obtained.

Example 3 Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. Dehydrated toluene 4
000 ml and 800 ml of dehydrated styrene were charged and heated and stirred at an internal temperature of 50 ° C. 7. About 100 L of nitrogen was bubbled through to purge the system, and triisobutylaluminum was added.
4 mmol, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.
MMAO-3A) was added in an amount of 84 mmol based on Al. Immediately after ethylene was introduced and the pressure was stabilized at 10 kg / cm ² G, the catalyst rac-1,1-cyclopentylidenebis (1) was removed from the catalyst tank installed on the autoclave.
7.-indenyl) bisdimethylamidozirconium.
4 μmol, 0.84 mm triisobutylaluminum
Approximately 50 ml of a toluene solution of ol was added to the autoclave. Internal temperature 50 ° C, ethylene pressure 10Kg / c
The polymerization was carried out for 2.5 hours while maintaining the pressure at m ² G (ethylene pressure 11 atm). During the polymerization, the temperature of the reaction solution and the consumption rate of ethylene were monitored by a flow integrator, and the polymerization was carried out until the polymerization reaction was substantially completed. After the completion of the polymerization, the resulting polymerization solution was poured little by little into excessively vigorously stirred excess methanol to precipitate the produced polymer. Under reduced pressure,
After drying at 60 ° C. until no change in weight was observed, 686 g of a polymer was obtained.

Example 4 The catalyst amount was changed to 21 μmol, styrene to 2400 ml,
Polymerization and post-treatment were carried out in the same manner as in Example 3, except that the amount of toluene was changed to 2400 ml and the polymerization time was changed to 2 hours.
As a result, 1354 g of a polymer was obtained.

Comparative Example 1 Am. Chem. Soc. , 110 , 6255
(1988), diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride (@ Flu-CP), which is an Ewen-type Zr complex,
h ₂ -Cp} ZrCl ₂₎ was synthesized.

[0058]

Embedded image

The catalyst was added to diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride, the amount of the catalyst was 164 μmol, and the ethylene pressure was 3 kg / g.
cm ² G, toluene to 800 ml, and styrene to 40 ml.
The polymerization and post-treatment were carried out in the same manner as in Example 3, except that the polymerization time was changed to 00 ml and the polymerization time was changed to 4 hours. As a result 286
g of polymer were obtained.

Comparative Example 2 With reference to JP-A-7-053618, a CGCT (constrained geometric structure) type Ti complex (tertiary butylamide) dimethyl (tetramethyl-η5-cyclopentadienyl) silane titanium dichloride, (｛ CpMe ₄ -SiMe _2-
NtBu @ TiCl ₂ ) was synthesized.

The catalyst is a CGCT (constrained geometric structure) type Ti complex (tertiary butylamide) dimethyl (tetramethyl-η)
Polymerization and post-treatment were carried out in the same manner as in Example 3, except that 21 μmol of 5-cyclopentadienyl) silanetitanium dichloride, toluene was changed to 1500 ml, and styrene was changed to 3300 ml. As a result, 550 g of a polymer was obtained.

Table 1 shows the polymerization conditions and the polymerization results of the respective examples and comparative examples. Table 2 shows the styrene content, molecular weight, molecular weight distribution, melting point, and glass transition temperature of the copolymers obtained in each of the examples and comparative examples. Further, Table 3 shows the λ value and the m value.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

When the transition metal compound component of the present invention is used, the activity and productivity per unit catalyst are significantly higher than those of the conventional method at any styrene content.

As an example of the copolymer obtained in the present invention,
FIG. 1 shows the NMR spectrum of the copolymer obtained in Example 4.
3 to 3 and the GPC chart is shown in FIG.

[0068]

By using the transition metal compound of the present invention, a copolymer containing an aromatic vinyl compound, for example, a copolymer of an aromatic vinyl compound and an olefin, can be produced by a very active and practical method. Can be done.

[Brief description of the drawings]

FIG. 1 shows 1H-NMR of a copolymer obtained in Example 4.
Spectrum

FIG. 2 shows C13-NM of the copolymer obtained in Example 4.
R spectrum, overall view

FIG. 3 shows C13-NM of the copolymer obtained in Example 4.
R spectrum, methine, methylene region

FIG. 4 is a GPC chart of the copolymer obtained in Example 4.

Claims (5)

[Claims] 1. A transition metal compound for polymerization of an aromatic vinyl compound-containing copolymer, which is represented by the following general formula (1) or (2). Embedded image In the formula, Ind1 and Ind2 are unsubstituted or substituted indenyl groups, and Ind1 and Ind2 may be the same or different. R1 is hydrogen, carbon number 1-2
A zero alkyl group, an aryl group having 6 to 10 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms, which may be the same or different. Further, the R1 group bonded to the same carbon atom or the R1 group bonded to the adjacent carbon may be combined to form a 5- to 8-membered aliphatic ring. z represents an integer of 2 to 10. X1 and X2 are hydrogen, a halogen atom, an alkyl group, an aryl group, a silyl group, an alkoxy group or an amide group represented by the following general formula (3). May be. Embedded image In the formula, A1 and A2 are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 20 carbon atoms.
And may be the same or different from each other. Further, the A1 and A2 groups are integrated into 5 to 8
It may form a membered aromatic or aliphatic ring. M is Z
r, Hf or Ti. Embedded image In the formula, Ind3 and Ind4 are unsubstituted or substituted indenyl groups, and Ind3 and Ind4 may be the same or different. R2 is hydrogen, carbon number 1-2
A zero alkyl group, an aryl group having 6 to 10 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms, which may be the same or different. Further, adjacent R2 groups may be combined to form a 5- to 8-membered aliphatic ring. x and y are 0
To 10 and the sum of x and y is 2 or more. R3, R3 ′, R3 ″, R3 ′ ″ are hydrogen, carbon number 1
-20 alkyl group, C6-C10 aryl group, C7-C20 alkylaryl group, halogen atom, O
Sir4 ₃ group, a sir4 ₃ group or PR4 ₂ group (R4 represents either a hydrocarbon group having 1 to 10 carbon atoms),
They may be the same or different. In addition, adjacent R
3, R3 ′, R3 ″ and R3 ′ ″ groups are 5 to 8
It may form a membered aromatic or aliphatic ring. X3, X
4 is hydrogen, a halogen atom, an alkyl group, an aryl group,
It is a silyl group, an alkoxy group or an amide group represented by the following general formula (3), and X3 and X4 may be the same or different. Embedded image In the formula, A1 and A2 are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 20 carbon atoms.
And may be the same or different from each other. Further, the A1 and A2 groups are integrated into 5 to 8
It may form a membered aromatic or aliphatic ring. M is Z
r, Hf or Ti. 2. The transition metal compound according to claim 1, wherein M is Zr and used for polymerization of an aromatic vinyl compound-olefin copolymer. 3. A method for producing an aromatic vinyl compound-olefin copolymer, comprising polymerizing using the transition metal compound according to claim 2 and a promoter. 4. The aromatic vinyl compound-olefin copolymer according to claim 3, wherein the cocatalyst is an aluminoxane (or alumoxane) represented by the following general formula (4) or (5). Manufacturing method. Embedded image In the formula, R5 is an alkyl group having 1 to 5 carbon atoms, and 6 to 1 carbon atoms.
0 is an aryl group or hydrogen, and m is an integer of 2 to 100. Each R5 may be the same or different. Embedded image In the formula, R6 is an alkyl group having 1 to 5 carbon atoms, and 6 to 1 carbon atoms.
0 is an aryl group or hydrogen, and n is an integer of 2 to 100. Each R6 may be the same or different. 5. The method for producing an aromatic vinyl compound-olefin copolymer according to claim 3, wherein the olefin is ethylene.