JPH1180183A - Metal compound for polymerization and production of aromatic vinyl compound-olefin copolymer with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new bisindenyl group-containing transition metal compound useful as a component for polymerization catalysts greatly high in activity and enabling the production of aromatic vinyl compound-olefin copolymers by practical methods. SOLUTION: This new metal compound for polymerization catalysts is expressed by formula I [Y, Y' are each H, a 1-20C alkyl, a 6-10C aryl, a 7-20C alkylaryl; Y and Y' may together form a 5-8 membered aliphatic ring; at least one of R1 to R8 is a substituent having a stronger electron-attracting property than that of hydrogen, and the others are each H, a 1-20C alkyl, 6-10C aryl, 7-20C alkylaryl, halogen, OSiR3 (R3 is a 1-10C hydrocarbon), SiR3 or the like; X, X' are each a halogen, 1-20C alkyl, 6-10C aryl, silyl, alkoxy, amide of formula II (A1, A2 are each H, a 1-20C alkyl, 6-10C aryl or the like) or the like; M is Zr, Hf, Ti]. The compound of formula I is obtained by reacting isopropylidene bis(fluoroindene) or the like with a Zr tetrakisdimethylamide or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound for 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. And a method for producing the same.

[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, the conventional heterogeneous Ziegler-Natta catalyst system has low activity, low styrene content, does not have a uniform and regular copolymerized structure, and has a property such as polyethylene, isotactic and atactic polystyrene. It is not practical because it contains a lot of homopolymers of

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 an alternating styrene-ethylene 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
292 (1993) discloses a method for producing a similar styrene-ethylene copolymer having no normal St chain, that is, a so-called pseudo-random copolymer using a catalyst comprising a cross-linked Cp (cyclopentadiene) -based Zr complex and a promoter. 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. The stereoregularity of the phenyl group is isotactic, but the isotactic dyad fraction m is about 0.92, and the weight average molecular weight is as low as about 20,000, demonstrating practical physical properties as a crystalline polymer. It is not enough to give. 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]

SUMMARY OF THE INVENTION The present invention relates to a copolymer containing an aromatic vinyl compound, for example, a transition metal compound for copolymerizing an aromatic vinyl compound and an olefin, and a highly active and practical aromatic compound using the same. The present invention provides a method for producing an aromatic vinyl compound-olefin copolymer.

[0007]

The present invention is a transition metal compound represented by the following general formula (1) for copolymerizing an aromatic vinyl compound and an olefin.

[0008]

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In the formula, Y and Y ′ are 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, and may be the same or different. good. Further, the Y group and the Y ′ group may be combined to form a 5- to 8-membered aliphatic ring such as a cyclopentylidene group and a cyclohexylidene group. At least one of the R1 to R8 groups represents a substituent having a higher electron-withdrawing property than hydrogen, that is, a substituent having a σ value of 0 or more according to Hammett et al. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, a SiR ₃ group, or a PR ₂ group (where R represents 10 hydrocarbon groups).

Examples of the substituent having a higher electron-withdrawing property than hydrogen include -F, -Cl, -Br, -I, -NO ₂ , -C
N, -CF _3, -SO ₂ Me group, and the like (wherein Me represents a methyl group). Preferably, -Cl, -F,
—Br and —NO ₂ . That is, it means a substituent having a σ value defined by Hammett et al. (Σp or σm is given depending on the bonding position, but here both σ values are included). The value of the σ value is quoted in various documents and books, for example, as described in J. Org. Chem, 23 , 4
20 (1958) can be cited. For example, -Cl is 0.373 or 0.22
7, -F is 0.337 or 0.062, -Br is 0.3.
391 or 0.232.

X and X 'each represent a halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, a silyl group,
X is an alkoxy group or an amide group represented by the following general formula (2), and X and X ′ may be the same or different.

[0012]

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In the formula, A1 and A2 are hydrogen, and have 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 X and X 'include a dimethylamide group and a diethylamide group.

An advantage of selecting the amide group as described above is that when a transition metal compound is synthesized, a conventionally known lithium salt of a ligand is reacted with zirconium tetrachloride or the like at a low temperature of -78 ° C. This eliminates the process, greatly simplifies the complex production process, and consequently allows the transition metal compound to be synthesized at low cost.

M is a Group IV metal such as Zr, Hf and Ti.

Preferred examples of the transition metal compound include the following compounds. Isopropylidenebis (5-
Chloroindenyl) zirconium dichloride, isopropylidenebis (5-chloroindenyl) zirconium bisdimethylamide, isopropylidenebis (5-fluoroindenyl) zirconium dichloride, isopropylidenebis (5-fluoroindenyl) zirconium bisdimethylamide, Isopropylidenebis (6-fluoroindenyl) zirconium dichloride and isopropylidenebis (6-fluoroindenyl) zirconiumbisdimethylamide.

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

The present invention further provides a process for producing an aromatic vinyl compound-olefin copolymer in which the co-catalyst used is an aluminoxane (or alumoxane) represented by the following general formulas (3) and (4): It is.

[0021]

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Wherein R 9 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 R9 may be the same or different.

[0023]

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In the formula, R10 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
It is an integer of １００100. Each R10 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. In the present invention, a boron compound can be used as a promoter together with the above transition metal compound.

The boron compound used as a cocatalyst is
Triphenylcarbenium tetrakis (pentafluorophenyl) borate {trityltetrakis (pentafluorophenyl) borate}, lithium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) borane, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate , 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.

The olefin used in the present invention is 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 olefin. Olefin,
That is, norbornene and norbornadiene are suitable. Among them, ethylene and propylene are preferable, and ethylene is particularly preferable. 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.

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 in the present invention has an aromatic vinyl compound content of from 1 to less than 99.9% by mole fraction, the following general formula (5) ), The stereoregularity of the phenyl group of the alternating structure of ethylene and the aromatic vinyl compound is from 0.75 in the isotactic dyad fraction m (or also referred to as the meso dyad fraction) given by the following formula (I). And the alternating structure index λ given by the following formula (II) is 7
An aromatic vinyl compound-ethylene copolymer, which is smaller than 0 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 an m (meso dyad) structure. For example, when deuterated 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 (5 ′) 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.

[0033]

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

[0035]

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In the formula, Ph is an aromatic group such as a phenyl group, x
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 of ethylene and aromatic vinyl compound having high stereoregularity 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, the aromatic vinyl compound having no stereoregularity-each region of the aromatic vinyl compound content compared with the ethylene copolymer, in various crystallinity, initial tensile modulus, It has improved properties such as hardness, breaking strength, elongation, and solvent resistance, and exhibits physical properties characteristic of thermoplastic elastomers, transparent soft resins, or novel crystalline resins. 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.

[0038]

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, Flu represents a fluorenyl group,
p represents a sillopentadienyl group, and Ph represents a phenyl 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. Determination of the styrene content in the copolymer was performed by 1H-NMR, and the equipment was α-50 manufactured by JEOL Ltd.
0 was used. Heavy chloroform solvent or heavy 1,1,
A peak derived from a phenyl group proton (6.5 to 7.5) with reference to TMS using 2,2-tetrachloroethane.
ppm) and the proton peak derived from the alkyl group (0.8 to
3 ppm). The molecular weight in the examples is
The weight average molecular weight in terms of standard polystyrene was 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. DS
C measurements, using a Seiko Electronics Co., Ltd. DSC200, N ₂
The heating was performed at a temperature rising rate of 10 ° C./min under an air stream. GC-MS measurement was performed using Shimadzu QP-1000.

Experimental Example <Synthesis A of transition metal compound> The following rac-isopropylidene-bis (fluoroindenyl) zirconium bisdimethylamide was synthesized by the following synthesis method. here,
(Fluoroindenyl) represents a 5-fluoroindenyl group and / or a 6-fluoroindenyl group.

A-1 Synthesis of isopropylidenebis (fluoroindene) Here, isopropylidenebis (fluoroindene)
Is isopropylidenebis (5-fluoroindene),
Shown is a mixture of isopropylidenebis (6-fluoroindene) and isopropylidene (5-fluoroindene) (6'-fluoroindene). Under an Ar atmosphere, 57.4 mmol of ground potassium hydroxide was suspended in 150 ml of 1,2-dimethoxyethane (hereinafter abbreviated as DME),
4.7 mmol of 6-fluoroindene (Bull. S
oc. Chim. Fr. 11 , 3092 (1973). ) Was added dropwise and refluxed for about 10 minutes. Thereafter, 21.2 mmol of acetone was added dropwise and refluxed for 3 hours. The reaction product was poured into dilute phosphoric acid-diethyl ether, and the organic layer was separated and washed with saturated saline.
After drying over sodium sulfate, the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (eluent: hexane-dichloromethane), and 3.4 g of isopropylidenebis (fluoroindene) was obtained as yellowish white crystals.
(49% yield). It was confirmed by GC-MS measurement that the substance was the target substance.

A-2 Synthesis of rac-isopropylidenebis (fluoroindenyl) zirconium bisdimethylamide Here, rac-isopropylidenebis (fluoroindenyl) zirconium bisdimethylamide is represented by rac-
Isopropylidenebis (5-fluoroindenyl) zirconium bisdimethylamide, rac-isopropylidenebis (6-fluoroindenyl) zirconium bisdimethylamide, rac-isopropylidene (5-fluoroindenyl) (6′-fluoroindenyl 2) shows a mixture of zirconium bisdimethylamide. Under an Ar atmosphere, 1.3 mmol of isopropylidenebis (fluoroindene) and 1.3 mmol of zirconium tetrakisdimethylamide, {Zr (NMe ₂ ) ₄ }, were added to toluene 2
It was charged together with 0 ml and stirred at 100 ° C. for 24 hours.
The toluene was distilled off under reduced pressure to obtain a red solid. To this, 10 ml of hexane was added, stirred, and the precipitate was filtered off. After drying, 0.1 g of rac-isopropylidenebis (fluoroindenyl) zirconium bisdimethylamide as a dark orange powder was obtained (16% yield). 1H-N
1.7 to 2.4 ppm by MR spectrum measurement
(M, 18H), 6.4-7.9 ppm (m, 10H)
At the position. The measurement was performed using CD ₂ Cl ₂ as a solvent and the center peak of CH ₂ Cl ₂ (5.3 ppm) as a reference. From NMR, it was found that the mixture was a mixture of isomers derived from the bonding position of fluorine (that is, the fluoroindenyl group was a 5-fluoroindenyl group and / or a 6-fluoroindenyl group).

<Synthesis B of transition metal compound>
-Isopropylidenebis (5-chloroindenyl) zirconium dichloride was synthesized by the following synthesis method.

B-1 Synthesis of isopropylidenebis (5-chloroindene) 35.6 mmol of ground potassium hydroxide in an Ar atmosphere
1 is 1,2-dimethoxyethane (hereinafter abbreviated as DME) 2
0, and 33.2 mmol of 6-chloroindene (Bull. Soc. Chim. Fr. 11 , 30
96 (1973). ) Was added dropwise and refluxed for 1 hour. Then, 13.4 mmol
Was added dropwise and refluxed for 5 hours. Reactant with water,
The mixture was poured into 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 (eluent hexane-dichloromethane) to obtain 2.2 g (yield: 33%) of isopropylidenebis (5-chloroindene) as a yellow powder. GC-MS
It was confirmed by measurement that the substance was the target substance.

B-2 Synthesis of rac-isopropylidenebis (5-chloroindenyl) zirconium dichloride Under an Ar atmosphere, 0.7 g, 2.05 mmol of isopropylidenebis (5-chloroindene) was suspended in 15 ml of diethyl ether. And cooled to −20 ° C. and stirred.
The n-butyllithium hexane solution (1.59
mol / l, 3.1 ml) was slowly dropped.
The temperature was raised to room temperature over time. The solvent was distilled off, hexane was added, and the mixture was stirred, and the resulting yellow precipitate was dried to obtain a ligand Li salt. L of ligand in 20 ml of dichloromethane
i The salt-dissolved solution was cooled to -78 ° C and ZrCl
₄ 0.46 g (1.98 mmol) was added and stirred. The temperature was raised to room temperature over 5 hours, and the precipitate was filtered through celite. The obtained solution was concentrated, and the obtained black-red solid was washed with hexane and then recrystallized from toluene-hexane to obtain a pale orange powdery crystal (yield 50 m).
g, 5% yield). By 1H-NMR spectrum measurement,
2.45 ppm (d, 6H), 6.2-7.8 ppm
It has a peak at the position (m, 10H). Measurement is CD ₂
The measurement was performed using Cl ₂ as a solvent and the center of the CH ₂ Cl ₂ peak (5.3 ppm) as a reference.

<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 stabilized at a pressure of 10 kg / cm ² G, A was removed from the catalyst tank installed on the autoclave.
3. The catalyst rac-isopropylidenebis (fluoroindenyl) zirconium bisdimethylamide obtained in -2 was used.
2 μmol, 0.84 mm triisobutylaluminum
Approximately 50 ml of a toluene solution of ol was added to the autoclave. About 30 minutes after the introduction of the catalyst, the internal temperature rose to a maximum of 73 ° C. due to heat of polymerization. Pressure 10Kg / cm ² G
The polymerization was carried out for 4.5 hours while maintaining the temperature at. 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. The polymer was dried under reduced pressure at 60 ° C. until no change in weight was observed, to obtain 84 g of a polymer.

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
-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 1 kg / cm ² G, A- was removed from the catalyst tank installed on the autoclave.
12. using the catalyst rac-isopropylidenebis (fluoroindenyl) zirconium bisdimethylamide obtained in Step 2.
6 μmol, 0.84 mm triisobutylaluminum
Approximately 50 ml of a toluene solution of ol was added to the autoclave. About 2 minutes after the introduction of the catalyst, the internal temperature rose to 53 ° C. Then, the pressure was set to 1 kg / cm ² G and the temperature was set to 50 kg / cm ² G.
Polymerization was carried out for 6.6 hours while maintaining at ℃. 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. The polymer was dried under reduced pressure at 60 ° C. until no change in weight was observed, to obtain 78 g of a polymer.

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 2
400 ml, 2400 ml of dehydrated styrene were charged,
The mixture was heated and stirred at an internal temperature of 50 ° C. The system was purged by bubbling about 100 L of nitrogen, and 8.4 mmol of triisobutylaluminum and 84 mmol of methylalumoxane (MMAO-3A, manufactured by Tosoh Akzo Co., Ltd.) were added based on Al. Immediately introduce ethylene, pressure 10 kg / cm ²
After being stabilized with G, 21.0 μmol of the catalyst rac-isopropylidenebis (fluoroindenyl) zirconiumbisdimethylamide obtained in A-2 and 0.84 mmol of triisobutylaluminum were dissolved from the catalyst tank installed on the autoclave. About 50 ml of toluene solution
Was added to the autoclave. Polymerization was carried out for 6.0 hours while maintaining the internal temperature at 50 ° C. and the ethylene pressure at 10 kg / cm ² G. 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. When dried under reduced pressure at 60 ° C. until no change in weight was recognized, 41
2 g of polymer were obtained.

Example 4 The catalyst was rac-isopropylidenebis (5-chloroindenyl) zirconium dichloride, and the amount of the catalyst was 2.
Polymerization and post-treatment were carried out in the same manner as in Example 2 except that the polymerization time was changed to 1 μmol and the polymerization time was changed to 3 hours. As a result 19
g of polymer were obtained.

Comparative Example 1 Literature J. Am. Chem. Soc. , 110 , 6255
(1988), diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride of the following formula, which is an Ewen-type Zr complex, (@ Flu-C
Ph ₂ -Cp} ZrCl ₂₎ was synthesized.

[0051]

Embedded image

The catalyst was diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride, the amount of the catalyst was 164 μmol, and the Et pressure was 3 kg / cm.
To ² G, a toluene 800 ml, styrene 4000
Example 3 except that the polymerization time was changed to 4 hours and the polymerization time to 4 hours.
Polymerization and post-treatment were carried out in the same manner as described above. As a result, 286 g
Was obtained.

Table 1 shows the polymerization conditions and the polymerization results of each of the 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. Table 3 shows the styrene content, λ value, and m value of the copolymers obtained in the examples and comparative examples.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[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 1 H-NMR spectrum of the copolymer obtained in Example 3. As an example of the copolymer obtained in the present invention,
FIGS. 2 and 3 show 13C-NMR spectra of the copolymer obtained in Example 3. As an example of the copolymer obtained in the present invention, a GPC chart of the copolymer obtained in Example 3 is shown in FIG.

[0059]

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 1H-NMR of the copolymer obtained in Example 3
Spectrum

FIG. 2 shows 13C-NM of the copolymer obtained in Example 3.
R spectrum, overall view

FIG. 3 shows 13C-NM of the copolymer obtained in Example 3.
R spectrum, methine, methylene region

FIG. 4 is a GPC chart of the copolymer obtained in Example 3.

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). Embedded image In the formula, Y and Y ′ are 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, the Y group and the Y ′ group may be combined to form a 5- to 8-membered aliphatic ring. At least one of the R1 to R8 groups represents a substituent having a higher electron-withdrawing property than hydrogen, and the other substituents are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon atom having 7 carbon atoms. Represents an alkylaryl group, a halogen atom, an OSiR ₃ group, an SiR ₃ group or a PR ₃ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). X and X 'are halogen, carbon number 1
An alkyl group having from 20 to 20, an aryl group having from 6 to 10 carbon atoms, a silyl group, an alkoxy group, or an amide group represented by the following general formula (2), wherein X and X ′ are the same as each other, It may be 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 aromatic vinyl compound-containing copolymer according to claim 1, wherein in the general formula (1), at least one of R1 to R8 is a halogen atom and M is zirconium. Transition metal compound for polymerization. 3. A method for producing an aromatic vinyl compound-olefin copolymer, comprising polymerizing using a polymerization catalyst comprising the transition metal compound according to claim 1 and a cocatalyst. 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 (3) or (4). Manufacturing method. Embedded image In the formula, R9 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 R9 may be the same or different. Embedded image In the formula, R10 is an alkyl group having 1 to 5 carbon atoms, 6 to 5 carbon atoms.
10 aryl groups or hydrogen, and n is an integer of 2 to 100. Each R10 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.