JPS63234005A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polymer of high molecular weight in high efficiency by polymerization of an olefin using a catalyst consisting of each specific transition metal compound having substituted cyclopentadienyl group and aluminoxane. CONSTITUTION:The objective polyolefin can be obtained by polymerization of an olefin such as ethylene or 1,4-hexadiene, using a catalyst consisting of (A) a transition metal compound of formula I (Rn<2>-C2H5-n is substituted cyclopentadienyl; n is 2-4; R<2> is 1-5C alkyl; M is Ti, Zr, V or Hf; X is halogen) [e.g., bis(1,3-dimethyl cyclopentadienyl)zirconium dichloride] and (B) an aluminoxane of formula II or III (m is 4-20; R<1> is hydrocarbon).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing polyolefins.

More specifically, the present invention relates to a method for efficiently producing polyolefins using a catalyst comprising a novel transition metal compound and a specific aluminoxane.

[Conventional technology and its problems]

Kasinsky's catalyst, that is, a catalyst consisting of bis(cyclopentadienyl)zirconium dichloride or the like and aluminoxane, polymerizes olefins with high activity, as disclosed in #I Publication No. 1989-19309', Makram et al.
ol, CheIl, Rapid Commun,,
Volume 4, 41? Page (1983).

In addition, recently, techniques using various transition metal compounds have been known to adjust molecular weight, molecular weight distribution, and copolymerizability (Japanese Patent Laid-Open No. 80-35008, Japanese Patent Laid-Open No. 80-3
5007, JP-A-80-35008), these patents describe the use of a transition metal compound having a substituted cyclopentadienyl group as a catalyst component; There are no examples using transition metal compounds with cyclopentadienyl groups.

Although this conventional Ka1nsky catalyst has high activity, it can only yield polymers with low molecular weights, and when producing high molecular weight polymers, there is a problem in that the activity is significantly reduced.

As a result of repeated research to solve the above-mentioned problems, the present inventors found that a new transition metal compound consisting of a transition metal compound having 2, 3 and 4fi-substituted cyclopentadienyl groups and aluminoxane as a supporting metal. The inventors have discovered that a catalyst can produce highly active and high molecular weight polymers, leading to the present invention.

[Means for solving problems]

That is, the present invention.

(1) (A) Transition metal compound, and (B) general formula [I] or general formula [■] R2A1y0A
Polymerize an olefin using a catalyst containing an aluminoxane represented by 1h-OAIR2[I] (the number of layers is 4 to 20, and R1 represents a hydrocarbon group) to produce a polyolefin. In the method.

(A)! As a transfer metal compound, the general formula [ml(Rn
-CsHs-n)zMX2[m] (However, Rn -C
5Hs-n represents a substituted cyclopentadienyl group, n is an integer of 2 to 4, R2 is an alkyl group having 1 to 5 carbon atoms,
represents titanium, zirconium, vanadium or hafnium, and X represents a halogen atom.

The transition metal compound (A) as a catalyst component used in the method of the present invention is a transition metal compound having two 2.3- and 4-substituted cyclopentadienyl groups and two /\ rogene atoms. It is a compound.

These compounds are new compounds, and the manufacturing method is
- Obtained by reacting a 2- to 4-substituted alkylcyclopentadiene with a transition metal compound as illustrated in the Examples below. Examples of the transition metal atom include titanium, zirconium, vanadium, and hafnium, with zirconium being preferred. The 2Wi-substituted cyclopentadienyl group includes 1.2- and 1.3-R2-C3H
There are two types, No. 5, but both are included. Also, for the 3-substituted cyclopentazinyl group, 1,2.3
There are two types, 2.4-R3-as and 2.4-R3-as R2, both of which are included. R2 is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5e
c-butyl group.

Hydrocarbon groups such as tert-butyl group and pentyl group, preferably methyl group and ethyl group. X is fluorine,
A halogen atom such as chlorine, bromine, or iodine, preferably chlorine.

Furthermore, specifically, the transition metal compound is bis(1,
2-dimethylcyclopentagenyl) titanium dichloride, bis(l,2-diethylcyclopentagenyl)titanium dichloride, bis(l,2-dimethylcyclopentagenyl)titanium dichloride, bis(1,3-dimethylcyclopentadienyl) titanium dichloride, bis(1,2
, 3-trimethylcyclopentagenyl) titanium dichloride, bis(1,2,4-trimethylcyclopentagenyl) titanium dichloride, bis(1,2,3,4-tetramethylsifpentagenyl) titanium dichloride, etc. Titanium compound, bis(1,2-dimethylcyclopentadienyl)zirconium dichloride, bis(1,2-diethylcyclopentagenyl)zirconium dichloride,
Bis(1,3-dimethylcyclopentagenyl)zirconium dichloride, bis(l,3-diethylshifpentagenyl)zirconium dichloride, bis(1,3-dimethylcyclopentagenyl)zirconium dibromide, bis(1, 2,3-)limethylcyclopentadienyl)zirconium dichloride, bis(1,2゜3-trimethylcyclopentadienyl)zirconium dibromide, bis(1,2,4-)diethylcyclopentadienyl)zirconium dichloride , bis(1,2,4-trimethylcyclopentadienyl)zirconium dibromide,
bis(1,2,4-)diethylcyclopentadienyl)
Zirconium diiodate, his(1,2,4-)dimethylcyclopentagenyl)zirconium dichloride,
Bis(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride, bis(1,2,3,4
zirconium compounds such as -tetramethylcyclopentagenyl) zirconium dibromide, bis(l,2-dimethylcyclopentagenyl) hafnium dichloride,
Bis(1,3-dimethylcyclopentagenyl)hafnium dichloride, bis(1,2,3-)dimethylcyclopentagenyl)hafnium dichloride, bis(1゜2
．． Hafnium compounds such as 4-)diethylcyclopentagenyl)hafnium dichloride, bis(1,2,3,4-tetramethylcyclopentagenyl)hafnium dichloride, bis(1,2-dimethylcyclopentagenyl)vanadium dichloride , bis(1°3-dimethylcyclopentadienyl) vanadium dichloride, bis(1
,2,3-)diethylcyclopentagenyl)vanadium dichloride, bis(1,2,4-trimethylcyclopentagenyl)vanadium dichloride, bis(1,2,
Examples include vanadium compounds such as 3,4-tetramethylcyclopentagenyl)vanadium dichloride.

Among these compounds, bis, (1,3-
dimethylcyclopentagenyl) zirconium dichloride, bis(1,2,4-trimethylcyclopentagenyl)zirconium dichloride, bis(1,2,3,4-
Tetramethylcyclopentadienyl) zirconium dichloride and the like are used.

Aluminoxane (B), another catalyst component used in the method of the present invention, is an organoaluminum compound represented by the above-mentioned general formula [II] or general formula [II]. R+ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and preferably a methyl group,
It is an ethyl group. Maro is an integer from 4 to 20, preferably 6 or more, especially 10 or more. Methods for producing compounds of this type are known. An example of a method is to add trialkylaluminum to a suspension of copper aluminum sulfate (copper aluminum sulfate hydrate, etc.) in a hydrocarbon medium and cause the reaction to occur.

The olefins used in the monopolymerization reaction in the method of the present invention include ethylene, propylene, 1-butene, 4-methyl-1-pentene, l-hexene, l-octene, l-decene, l-dodecene, l-tetradecene, These are α-olefins such as 1-hexadecene, 1-octadecene, and 1-eicosene, and a mixture of two or more of these components can also be subjected to polymerization. Furthermore, butadiene, 1. Dienes such as tohexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, etc., or cyclopropane, cyclobutene,
It is also effective for copolymerization of cyclic olefins such as cyclohexene, norbornene, dicyclopentadiene, and α-olefins.

As the polymerization method, any of suspension polymerization, solution polymerization, and gas phase polymerization is possible. Polymerization solvents for liquid phase polymerization include aliphatic hydrocarbons such as butane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane, and alicyclic carbonates such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. Hydrogen, aromatic hydrocarbons such as benzene, toluene, and xylene, and petroleum fractions such as gasoline, kerosene, and light oil are used. Among these, aromatic hydrocarbons are preferred.The olefin pressure in the reaction system is normal pressure to 50 kg/am2G, and the degree of polymerization is from -50°C to 230°C, preferably from -20°C to 20°C.
Molecular weight adjustment during zero polymerization in the range of 0° C. can be carried out by known means, such as temperature selection or hydrogen introduction.

In the method of the present invention, (A) a transition metal compound.

(B) A premixed blue component of aluminoxane may be supplied to the reaction system, or (A) and (B) blue components may be supplied to the reaction system individually. In either case, the blue component There is no particular restriction on the concentration per molar ratio of the components in the polymerization system, but preferably the transition metal concentration is 10-4.
~10-9 sol/1, and the Al/metal atom molar ratio is preferably 100 or more, particularly 1000 or more.

〔Effect of the invention〕

As a novel transition metal compound in combination with aluminoxane, 2.3- and 4B-substituted cyclopentadienyl groups can be combined with 2.
As is clear from the Examples and Comparative Examples described below, the method of the present invention using a transition metal compound having 1. A highly active and high molecular weight polymer can be obtained. Moreover, if two or more of these novel transition metal compounds are used simultaneously, the molecular weight distribution can be easily controlled.

〔Example〕

Next, the present invention will be specifically explained using examples.

Catalyst Production Example 1 [Bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride] All reactions were performed under an inert gas atmosphere. In addition, one reaction solvent used was one that had been dried in advance. In a 500 μm glass reaction vessel, 5.5 g (51 mmol) of 1.2.4-)limethylcyclopentadiene was diluted with 150 μg of tetrahydrofuran to prepare a 15% solution of n-butyllithium/hexane in a 3B solution. was dripped. 1 at room temperature
After stirring for an hour, the white suspension of 1,2.4-)limethylcyclopentadienyllithium was cooled to 0°C and 5.9 g (25 mmol) of zirconium tetrachloride was added in five portions. The reaction solution was slowly raised to room temperature and heated to 48
Stir for hours. The solvent was distilled off under reduced pressure from the yellow solution containing the white precipitate (LiC1), and then extracted with methylene chloride 300 ml.
It was filtered. Concentrate the yellow filtrate, add pentane,
It was cooled to -30°C to obtain 4.0 g of white crystals. Sublimation (
130~bl mmHg) After purification, 3.5g (yield 3
B%) of the target product was obtained. The melting point of this compound is 172-1
The temperature was 73°C.

Example 1 [11 combination] In a SUS autoclave with an internal volume of 1.51 that was sufficiently purged with nitrogen, 450 mJL of purified toluene and methylaluminoxane (molecule 1909) manufactured by Toyo Stouffer Chemical ■ were added.
13.3 mmol and the bis(
0.02 mmol of 1,2,4-trimethylcyclopentadienyl)zirconium dichloride is sequentially added, and 5
The temperature was raised to 0°C, then propylene was added to it at a total pressure of 8°C.
Continuously introduced so as to maintain Kg/crn'G, 1
．． After 5 hours of polymerization, the catalyst component was decomposed with methanol, and the resulting polypropylene was dried. As a result, 280 g of atactic polypropylene was obtained. The catalyst activity was 95 kg/g Zr-by, and the molecular weight was 13,000 te.

Catalyst Production Example 2 [Bis(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride] All reactions were performed under an inert gas atmosphere. In addition, the reaction solvent used was one that had been dried in advance.
1. In a glass reaction vessel, 2.5 g (20 mmol) of 1.2,3.4-tetramethylcyclopentadiene was added in 1.
It was diluted with 1,501 parts of 2-dimethoxyethane, and 151 parts of a 15% solution of n-butyllithium/hexane was added dropwise. After stirring for 1 hour at room temperature, the white suspension of 1,2,3,4-tetramethylcyclopentadienyllithium was heated to 0°C.
The reaction solution to which 2.3 g (10 mmol) of zirconium tetrachloride was added in five portions was heated and stirred under reflux for 72 hours. The solvent was distilled off under reduced pressure from the yellow solution containing the white precipitate (LiC1), followed by extraction with methylene chloride 3001 and filtration. Concentrate the yellow filtrate and add pentane to -3
It was cooled to 0°C to obtain 0.18 g of white crystals. Sublimation (1
After the preparation of 30-b, 0.13 g (yield 3%) of the target product was obtained.

The melting point of this compound was 270-271°C.

Example 2 [Polymerization] Purified toluene 4,501.1.ml. Methylaluminoxane manufactured by Toyo Stouffer Φ Chemical ■ (molecular weight 909) 8
．． 3 mmol and bis(1
, 0.02 mmol i of 2,3,4-tetramethylcyclopentadienyl)zirconium dichloride,
The temperature was raised to 50°C, and then propylene was continuously introduced into it so as to maintain a total pressure of 8 kg/cm''G.
After 2 hours of polymerization, the catalyst component was decomposed with methanol, and the resulting polypropylene was dried. As a result, 280 g of atactic polypropylene was obtained.

What is the catalyst activity? There was 1Kg/g Zr-byte, and the molecular weight was 85G (lte).

Catalyst Production Example 3 [Bis(1,3,-dimethylcyclopentadienyl)zirconium dichloride] All reactions were performed under an inert gas atmosphere. Moreover, the reaction solvent used was one that had been dried in advance. 500s
1.3 in a jL glass reaction vessel. 3.4 g (38 mmol) of -dimethylcyclopentadiene was diluted with 150 l of tetrahydrofuran, and 241 l of a 15% solution of n-butyllithium/helical chloride was added dropwise at 0°C. 1 at room temperature
After stirring for an hour, 1.3. A solution of -dimethylcyclopentadienyllithium was cooled to 0°C, and 3.5 g (15 mmol) of zirconium tetrachloride was added in 5 portions to the 0 reaction solution, which was slowly warmed to room temperature and stirred for 48 hours.

The solvent was distilled off under reduced pressure from the yellow solution containing the white precipitate (LiC1), followed by extraction with methylene chloride 3001 and filtration. Concentrate the yellow filtrate, add pentane, cool to -30°C,
1.7 g of white crystals were obtained. Sublimation (130-140℃7
After purification (1 smHg), 1.1 g (yield 22%) of the target product was obtained. The melting point of this compound is 175-17B'0
Met.

Example 3 [Polymerization] In a SUA autoclave with an internal volume of 1.51 which was sufficiently purged with nitrogen, 450 ml of purified toluene and methylaluminoxane (molecular weight 1110, manufactured by Toyo Stouffer Chemical) were added.
1) 8.3 mmol Catalyst Preparation Example 3 and bis(1,3
, -dimethylcyclopentadienyl)dyl, and 0.02 mmol of conium dichloride were added sequentially.

The temperature was raised to 50°C, and then propylene was continuously introduced into it so that the total pressure was maintained at 8 kg/crn''G.
After 4 hours of polymerization, the catalyst component was decomposed with methanol, and the resulting polypropylene was dried. As a result, 450 g of active polypropylene was obtained. The catalyst activity was 81 Kg/gZr-hr and the molecular weight was 5 ooo.

Comparative Example 1 450g+1 of purified toluene was placed in a jus autoclave with an internal volume of 1.51 which was sufficiently purged with nitrogen, and methylaluminoxane (molecular weight 90) manufactured by Toyo Stouffer Φ Chemical
9) 8.3 mmol and 0.02 mmol of bis(cyclopentadienyl) di,ruconium dichloride were sequentially added, and the temperature was raised to 50°C. Next, propylene was added to the mixture at a total pressure of 8 Kg/crrI″G. After 4 hours of polymerization, the catalyst component was decomposed with methanol and the resulting polypropylene was dried.As a result, atactic polypropylene 150
g was obtained. The catalyst activity was 20 Kg/g Zr-hr, and the molecular weight was 1300 Te.

Comparative Example 2 Contents of sufficient nitrogen replacement! 450ml of purified toluene, Toyo Stouffer Chemical Paving Methylaluminoxane (molecular weight 909
) 8.3 mmol and 0.02 mmol of bis(pentamethylcyclopentadienyl)zirconium dichloride were sequentially added, and the temperature was raised to 50°C.

Next, propylene was added to this at a total pressure of 8 Kg/am''
After 0 reaction in which G was continuously introduced so as to maintain it and polymerization was carried out for 4 hours, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 210 g of atactic polypropylene was obtained. Catalyst activity is 28K
g/gZr-hr, and the molecular weight was 300.

Comparative Example 3 450 ml of purified toluene was placed in a SUS autoclave with an internal volume of 1.51 that was sufficiently purged with nitrogen, and methylaluminoxane (molecular weight 909) manufactured by Toyo Stouffer Chemical ■ was added.
8.3 mmol and 0.02 mmol of bis(methylcyclopentagenyl)zirconium dichloride were added sequentially, and the temperature was raised to 50°C. Next, propylene was added continuously to this so that the total pressure was maintained at 8 Kg/cnfG. After 0 reaction in which polymerization was carried out for 4 hours, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 220 g of atactic polypropylene was obtained.

Catalytic activity is 30Kg/gZr-hr, molecular weight is 8
There was 00 te.

Comparative Example 4 450 ml of purified toluene was placed in a SUS autoclave with an internal volume of 1.51 that was sufficiently purged with nitrogen, and methylaluminoxane (molecular weight 90θ) manufactured by Toyo Stouffer Chemical ■ was added.
8.3 mmol and 0.02 mmol of bis(t-butylcyclopentagenyl)zirconium dichloride were sequentially added, and the temperature was raised to 50°C. Next, propylene was added to this while maintaining the total pressure of 8 Kg/crn"G. After 0 reaction in which polymerization was carried out for 4 hours, the catalyst component was decomposed with methanol and the obtained polypropylene was dried.As a result, atactic polypropylene 1110
g was obtained.

The catalyst activity was 22Kg/gZr-hr, and the molecular weight was 500T.

Catalyst Production Example 4 [Bis(1,2,-dimethylcyclopentadienyl)zirconium dichloride] All reactions were performed under an inert gas atmosphere. Moreover, the reaction solvent used was one that had been dried in advance. 2.0 g (21 mmol) of 1,2I-dimethylcyclopentadiene was diluted with 150 ml of tetrahydrofuran in a reaction vessel made of 500 mm glass, and 181 15% n-butyllithium/hexane solution was added dropwise at 0°C. After stirring at room temperature for 1 hour, 1,2. - A white suspension solution of dimethylcyclopentadienyllithium was cooled to 0°C, and 0 reaction solution to which 2.4 g (10 mmol) of zirconium tetrachloride was added in 5 portions was slowly raised to room temperature. Stirred for 12 hours. After the solvent was distilled off under reduced pressure from the yellow solution containing the white precipitate (LiC1), the product was sublimed (taO ~ 140 ° C. 7
1■-1g) Purified white crystal target product 0.25g
(yield 7%). The melting point of this compound is 252-25
The temperature was 4°C.

Example 4 [Tongue^] 450 ml of purified toluene was placed in a SUS autoclave with an internal volume of 1.51 that was sufficiently purged with nitrogen, and methylaluminoxane (Molecular I 909 manufactured by Toyo Stouffer Chemical ■) was added.
) 8.3 mmol Bis(1
,2,-dimethylcyclopentagenyl) zirconium dichloride was added in sequence, and the temperature was raised to 50°C.Next, propylene was added to this at a total pressure of 8 kg/a.
After the zero reaction in which polymerization was carried out for 4 hours by continuously introducing m''G so as to maintain it, the catalyst was decomposed with methanol and the obtained polypropylene was dried. As a result, 300 g of atactic polypropylene was obtained. Catalytic activity is 41K
g/gZr-hr, and the molecular weight was 300G.

Catalyst Production Example 5 [Bis(1,2,3-)dimethylcyclopentadienyl)zirconium dichloride] All reactions were performed under an inert gas atmosphere. Moreover, the reaction solvent used was one that had been dried in advance. 5001
In a 1 fL glass reaction vessel, 3.5 g (32 mmol) of L 1,2.3- )dimethylcyclopentadiene was diluted with 150 ml of tetrahydrofuran, and 251 ml of a 15% n-butyllithium/hexane solution was added dropwise. After stirring for 1 hour at room temperature, the white suspension of 1,2,3-trimethylcyclopentadienyllithium was cooled to 0 °C and 3.7 g (16 mmol) of zirconium tetrachloride was added in 5 portions. 0 reaction solution was slowly raised to room temperature,
Stirred for 3 hours. After distilling the solvent off under reduced pressure from the yellow solution containing the white precipitate (LiC1), the product was sublimed (0.88 g (yield 11%) of the target product as crystal 130-b was obtained. The melting point of this compound was 252- The temperature was 253°C.

Example 5 [Polymerization] 450 ml of purified toluene was placed in a SUS autoclave with an internal volume of 1.51 which was sufficiently purged with nitrogen. Toyo Stouffer
・Methylaluminoxane manufactured by Chemical■ (molecular weight 909)
lli, 3 mmol and bis(1,2,3-trimethylcyclopentagenyl) obtained in Catalyst Production Example 5
0.02 mmol of zirconium dichloride was sequentially added and the temperature was raised to 50°C.Next, propylene was continuously introduced into the mixture so as to maintain a total pressure of 8 Kg/cm''G, and polymerization was carried out for 4 hours. After the reaction, the catalyst component was decomposed with methanol and the obtained polypropylene was dried.As a result, atactic polypropylene 180.

Example 6 [Polymerization] In a SUS autoclave with an internal volume of 1.51 which was sufficiently purged with nitrogen, 450 ml of purified toluene and methylaluminoxane (molecular weight 909, manufactured by Toyo Stouffer Chemical) were added.
) 1.5 mmol and 0.002 mmol of bis(1,2,3-)limethylcyclopentadienyl)zirconium dichloride obtained in Catalyst Production Example 5 were sequentially added, and the temperature was raised to 50°C. Ethylene was continuously introduced into this so that the total pressure was maintained at 4 Kg/am''G,
After 2 hours of polymerization, the catalyst component was decomposed with methanol and the resulting polyethylene was dried. As a result, 30 g of polyethylene was obtained. Catalytic activity is 82K
g/gZr-hr, and the molecular weight was 177,000.

Comparative Example 5 [Polymerization] 450 ml of purified toluene was placed in a SUA autoclave with an internal volume of 1.51 that was sufficiently purged with nitrogen, and methylaluminoxane (molecular weight 909) manufactured by Toyo Stouffer Chemical ■ was added.
2.0 mmol and 0.003 mmol of bis(pentamethylcyclopentagenyl)zirconium dichloride were sequentially added, and the temperature was raised to 50°C.Next, ethylene was added to this so as to maintain a total pressure of 4 kg/cm"G. After 0 reaction, the catalyst components were decomposed with methanol and the resulting polyethylene was dried. As a result, 18 g of polyethylene was obtained. The catalyst activity was 32 Kg/g Zr-hr. With Te, molecular weight is 70
It was 000.

that's all

Claims (4)

[Claims] (1) (A) Transition metal compound, and (B) General formula [I] or general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ] (where m is a number from 4 to 20 and R^1 represents a hydrocarbon group) In a method for producing a polyolefin by polymerizing an olefin using a catalyst containing aluminoxane as a component, (A) As a transition metal compound, the general formula [III] (R^2
_n-C_5H_5_-_n)_2MX_2[III](
However, R^2_n-C_5H_5_-_n represents a substituted cyclopentadienyl group, n is an integer of 2 to 4, R^2 is an alkyl group having 1 to 5 carbon atoms, and M is titanium, zirconium, vanadium or hafnium. shows. Moreover, X represents a halogen atom) A method for producing a polyolefin, characterized by using a compound represented by: (2) The method according to claim (1), wherein the transition metal compound (A) is a compound having two disubstituted cyclopentadienyl groups. (3) The method according to claim (1), wherein the transition metal compound (A) is a compound having two trisubstituted cyclopentadienyl groups. (4) The method according to claim (1), wherein the transition metal compound (A) is a compound having two 4-substituted cyclopentadienyl groups.