JP2603059B2 - Catalyst component for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst obtained by homopolymerizing olefins having 2 or more carbon atoms or copolymerizing two or more olefins. More specifically, the present invention relates to a catalyst component obtained by reacting a transition metal compound having a specific structure with an organic compound having two or more hydroxyl groups.

[0002]

2. Description of the Related Art Conventionally, in the production of olefin polymers, a catalyst system comprising a solid titanium compound containing titanium trichloride as a main component and an organoaluminum compound, or a solid obtained by supporting titanium tetrachloride on magnesium chloride and an organoaluminum compound And a catalyst system comprising an electron-donating compound. Further, a method using a polymerization catalyst comprising a cyclopentadienyl compound of titanium, zirconium, and hafnium and an aluminoxane has been proposed (for example, JP-A-58-19309 (US Pat.
542,199) and JP-A-60-217209.
However, the method using these polymerization catalysts has a drawback that the obtained olefin polymer, particularly the propylene polymer, has a small molecular weight.

On the other hand, there has been proposed a method for producing an olefin polymer using an aromatic hydrocarbon compound having Ti (OR) _n X _4-n and at least one hydroxyl group as a part of a catalyst component (US Pat. No. 4). , 525, 556). However, in this catalyst system, MgR ₂ and an inorganic or organic halogen compound are essential as other catalyst components, and as an organoaluminum compound, AlR _n X _{n ′} (R is a hydrocarbon group, X is a halogen, n, n 'Is a value from 0 to 3 and n +
n '= 3).

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to develop a novel catalyst system to solve such a problem and to produce a high-molecular-weight olefin polymer with high efficiency by using the same. It is the aim.

[0005]

Means for Solving the Problems The catalyst component of the present invention, which has been developed as a result of the intense efforts of the present inventors, is represented by the following general formula: Component (1): General formula M (R) _l (OR ') _m X _{n- (l + m)} (where M is a transition metal atom selected from titanium, zirconium, hafnium and vanadium, and R and R 'are carbon atoms of 1)
And X represents a halogen atom. l,
m and n represent numbers that satisfy l ≧ 0, m ≧ 0, and n− (l + m) ≧ 0. n corresponds to the valence of the transition metal. And a component (2) represented by the general formulas I, II, III, IV, V and VI.
An olefin polymerization catalyst component obtained by a reaction with at least one compound selected from the group consisting of organic compounds having at least two hydroxyl groups,

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(Wherein R ″ and R ′ ″ have 1 to 20 carbon atoms.
A hydrocarbon group, Y is a hydrocarbon group having 1 to 20 carbon atoms,

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(R_FiveIs hydrogen or a hydrocarbon having 1 to 6 carbon atoms
Use the group. ). Where R¹, R^Two, R^ThreeAnd
And R^FourRepresents a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, nitro
Group, nitrile group, hydrocarboxy group or halogen atom
Represents a child. In this case R¹, R ^Two, R^ThreeAnd R^FourIs the same
They may be one or different. n 'is 0 or 1 or more
And represents the number of repetitions of the unit Y. Or
y, y ', y ", y"', z, z ', z ", and
z "" represents the number of substituents bonded to the aromatic ring.
You. y, y ', z and z' are 0 or integers from 1 to 4
Numbers, y ″ and z ″ are 0 or integers from 1 to 2,
y "" and z "" represent 0 or an integer from 1 to 3;
You. ).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be described below in detail. General formula M used as component (1) in the present invention
In the transition metal compound represented by (R) _l (OR ') _m X _{n- (l + m)} , M is titanium, zirconium,
Examples include hafnium and vanadium, especially titanium,
Zirconium gives favorable results. R or R 'is a hydrocarbon group having 1 to 20 carbon atoms.
To 18 alkyl groups and 6 to 18 carbon atom aryl groups can be suitably used.

Specific examples of R or R 'include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl and n-octyl. , N-decyl, n
-Alkyl groups such as dotesyl, aryl groups such as phenyl and naphthyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, allyl groups such as propenyl, and aralkyl groups such as benzyl. Among them, R is preferably a methyl, ethyl, phenyl, benzyl group and the like, and R 'is preferably an alkyl group such as n-propyl, isopropyl, n-butyl and t-butyl and an aryl group such as phenyl. .

The halogen atom represented by X includes chlorine, bromine and iodine. Particularly, chlorine is preferably used. l, m, and n are, for this catalyst, l ≧
0, m ≧ 0, and n− (l + m) ≧ 0. That is, in the catalyst component obtained from the component (1) that is a transition metal compound and the component (2) that is an organic compound having at least two hydroxyl groups, for example, titanium tetrachloride and zirconium tetrachloride having m = 0 can be used. Become.

Specific examples of the component (1) include titanium tetrachloride, zirconium tetrachloride, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, diphenoxy titanium dichloride, and dinaphthoxy. Titanium dichloride, tetraisopropoxy zirconium, tetra-n-butoxy zirconium, tetra-t-butoxy zirconium and the like can be mentioned.

General formula used as component (2) in the present invention

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Embedded image In the compound represented by the formula, R ″ and R ′ ″ are a hydrocarbon group having 1 to 20 carbon atoms, Y is a hydrocarbon group having 1 to 20 carbon atoms,

Embedded image (Where R ⁵ represents a hydrocarbon group having 1 to 6 carbon atoms).

The hydrocarbon group having 1 to 20 carbon atoms represented by R ", R""and Y includes methylene, ethylene,
Examples include trimethylene, propylene, diphenylmethylene, ethylidene, n-propylidene, isopropylidene, n-butylidene, and isobutylidene groups. Among them, methylene, ethylene, ethylidene, isopropylidene and isobutylidene groups are preferably used. Where n '
Is an integer of 0 or 1 or more, represents the number of repetitions of the unit Y, and 0 or 1 gives particularly preferable results.

R ¹ , R ² , R ³ and R ^{4 each} have 1 carbon atom.
~ 20 hydrocarbon groups, hydroxyl groups, nitro groups, nitrile groups,
Represents a hydrocarboxy group or a halogen atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
t-butyl, n-amyl, isoamyl, n-hexyl,
alkyl groups such as n-heptyl, n-octyl, n-decyl and n-dodecyl; aryl groups such as phenylnaphthyl;
Examples thereof include cycloalkyl groups such as cyclohexyl and cyclopentyl, allyl groups such as propenyl, and aralkyl groups such as benzyl. Among them, an alkyl group having 1 to 10 carbon atoms is preferably used. y, y ', y ", y"',
z, z ', z ", z"' represent the number of substituents attached to the aromatic ring, y, y ', z, z' are 0 or an integer from 1 to 4, y ", z ″ represents 0 or an integer from 1 to 2, and y ″ ′ and z ′ ″ represent 0 or an integer from 1 to 3.

As a specific example of the component (2), for example,
2,4-dihydroxypentane, 2- (2-hydroxypropyl) phenol, catechol, resorcinol,
4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 2,2'-biphenyldiol,
1,1′-bi-2-naphthol, 2,2′-dihydroxy-6,6′-dimethylbiphenyl, 4,4 ′, 6,
6'-tetra-t-butyl-2,2'-methylenediphenol, 4,4'-dimethyl-6,6'-di-t-butyl-2,2'-methylenediphenol, 4,4 ', 6,
6'-tetramethyl-2,2'-isobutylidene diphenol, 2,2'-dihydroxy-3,3'-di-t-
Butyl-5,5'-dimethyldiphenyl sulfide and the like can be exemplified. Among them, 2,4-dihydroxypentane, catechol, 2,2'-biphenyldiol, 1,
1'-bi-2-naphthol, 4,4 ', 6,6'-tetra-t-butyl-2,2'-methylenediphenol,
4,4'-dimethyl-6,6'-di-t-butyl-2,
2'-methylene diphenol, 4,4 ', 6,6'-tetramethyl-2,2'-isobutylidene diphenol,
2,2'-dihydroxy-3,3'-di-t-butyl-
5,5'-Dimethyldiphenyl sulfide gives good results.

When this catalyst system is applied to olefin polymerization, for example, in the case of propylene polymerization, in the polymerization using components (1) and (2), depending on the type of component (2), an isotactic steric compound is used. A regular (crystalline) polymer is formed. For example, in the case of solvent polymerization, component (1) is added in an amount of 10 ⁻¹⁰ to 10 ⁻¹⁰ as a transition metal atom.
10 ³ mmol / l, preferably used in the range of 10 ^-7 to 10 ² mmol / l.

Component (2) can be used in an amount of 0.01 to 4 (molar ratio) based on the transition metal atom of component (1). The component (2) needs to be reacted with the component (1) in advance before being used for polymerization. Reaction is -20 to 20
The reaction can be carried out at a temperature of 0 ° C. in a hydrocarbon solvent or a halogenated hydrocarbon solvent. Component (2) may be used directly in the reaction, but when component (1) is a halogen-containing transition metal compound, ammonia, pyridine, or pyridine is added to the reaction system in order to capture hydrogen halide generated during the reaction. It is also possible to add an alkylamine or the like. In this case, it is preferable to subject the compound after removing the precipitated hydrogen halide-containing compound to polymerization. In addition, component (2)
May be reacted with an alkali metal such as sodium metal or a hydride of an alkali metal such as lithium hydride to synthesize a metal alcoholate, a metal phenolate, a metal naphtholate or the like, and then subject the reaction to this reaction. In this case, it is preferable to remove the precipitated alkali metal salt and then conduct the polymerization.

Further, when the component (1) contains a hydrocarboxy group, the component (2) can be reacted with a carboxylic acid such as acetic acid in advance, and then subjected to this reaction as an ester compound. In the reaction between the transition metal compound and the organic compound having at least two hydroxyl groups, it is considered that a compound having a form in which at least two hydroxyl groups of the organic compound are bonded to the same transition metal is generated.

The olefin applicable to the present invention includes:
It has 2 to 10 carbon atoms, and specific examples include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and vinylcyclohexane. . These compounds can be used alone or in copolymerization of two or more types, but the present invention should not be limited to the above compounds. The catalyst component of the present invention is used together with other co-catalyst components at the time of olefin polymerization.

The polymerization method is not particularly limited either. For example, aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbon solvents such as benzene and toluene, and methylene chloride Solvent polymerization using a halogenated hydrocarbon solvent such as solvent polymerization, solution polymerization, or bulk polymerization or gas-phase polymerization in a gaseous monomer is possible, and continuous polymerization,
Either batch polymerization is possible.

The polymerization temperature can range from -50.degree. C. to 200.degree. C., particularly preferably -20.degree. C. and 100.degree.
The polymerization pressure is from normal pressure to 60 kg / cm ² G. Is preferred. The polymerization time is generally determined appropriately depending on the kind of the target polymer and the reaction apparatus, but can range from 5 minutes to 40 hours. For example, in the case of ethylene polymerization, 5 minutes to 10 minutes
Time, and preferably 30 minutes to 20 hours in the case of propylene polymerization.

[0022]

EXAMPLES The effects of the present invention will be specifically described with reference to the following examples of the present invention and comparative examples, but the present invention is not limited to these examples. The molecular weight in the examples is
Intrinsic viscosity [η] or weight average molecular weight calculated using gel permeation chromatography (GPC). [Η] was measured at 135 ° C. with a tetralin solution. GPC used Waters 150C type | mold. The measurement was performed at 140 ° C. using o-dichlorobenzene as a solvent. Three Shodex 80M / S columns were used. As polystyrene for preparing a calibration curve, 14 kinds of monodispersed standard polystyrene having a molecular weight range of 500 to 6.8 × 10 ⁶ were used. The molecular weight was represented by a weight average molecular weight determined by a universal method from an average molecular weight in terms of polystyrene.

The isotactic stereoregularity of the polymer obtained in the propylene polymerization can be determined by the presence or absence of an isotactic crystal band of 997 cm ^{-1 in} the IR spectrum or the isotactic triad mole fraction determined from the ¹³ C NMR spectrum. Rate (hereinafter [m
m] fraction. ) Value was evaluated. The measurement was made by JEOL F
Performed at 135 ° C. using an X-100 spectrometer. The polymer was dissolved in o-dichlorobenzene.
The [mm] fraction was determined from an enlarged spectrum in the methyl carbon region.

Embodiment 1 1. Reaction of components (1) and (2) After a flask having an inner volume of 500 ml equipped with a stirrer, a dropping funnel and a reflux condenser was replaced with argon, 100 ml of methylene chloride and 0.015 mol of titanium tetrachloride were replaced.
Was charged into a flask and heated until methylene chloride was refluxed. Next, methylene chloride 20 was added from the dropping funnel.
0ml and 1,1'-bi-2-naphthol 0.015mo
1 was gradually added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour under reflux. After standing overnight, the precipitate was removed by filtration to obtain a uniform black solution. 1 ml of this solution contained 0.04 mmol of Ti.

2. Synthesis of cocatalyst components Inner volume with stirrer, dropping funnel, reflux condenser
After replacing the 0.5 liter flask with argon, 3
8.2 g (0.15 mol) of CuSO_Four・ 5H _TwoO
Suspend in 200 ml of toluene and keep the internal temperature at 25 ° C
While stirring, 0.58 of trimethylaluminum
mol and 100ml of toluene over 5 hours
And dropped. After completion of the dropwise addition, stirring was continued at room temperature for 20 hours.
After removing the precipitate, the solvent was removed under reduced pressure, and 12.0 g
Of methylaluminoxane was obtained. Use toluene for polymerization
It was used after dilution (0.1 g / ml). The following implementation
The polymerization of Examples 3 to 8 and Comparative Example 1
Solution was used.

3. Polymerization of Propylene After replacing the stainless steel autoclave of a stirring method with a magnetic stirrer with an inner volume of 130 ml with argon, 0.1 ml of the reaction solution of the components (1) and (2), 3 ml of the cocatalyst component, and 80 ml of liquefied propylene were added. Charged in autoclave. 2 while stirring the autoclave
Hold at 0 ° C. for 1 hour. After releasing the excess propylene, the polymer was recovered. The polymer was washed with a 1N HCl / methanol solution and then washed with methanol and dried. The obtained polymer is 0.25 g, which is 1 mmol.
This corresponds to an activity of 62.5 grams per Ti. The molecular weight of this polymer is 314,000, [mm] fraction 0.55
Met.

Example 2 A toluene solution of ethylaluminoxane (0.1 g) synthesized using triethylaluminum instead of trimethylaluminum in the synthesis of the promoter component of Example 1
/ Ml) and propylene polymerization in Example 6 using 0.5 ml of a reaction solution of the components (1) and (2) reacted in Example 1.
Was performed in the same manner as described above. The obtained polymer was 146 mg,
The molecular weight of this polymer was 274,000 [mm] and the fraction was 0.49.

Embodiment 3 1. Reaction of components (1) and (2) In the reaction of components (1) and (2) in Example 1, 1,
A uniform black solution was obtained in the same manner except that 0.015 mol of 2,2'-biphenyldiol was used instead of 1'-bi-2-naphthol. 1 ml of this solution contains T
0.027 mmol of i was contained. 2. Polymerization of Propylene The procedure of Example 1 was repeated except that 10 ml of the reaction solution of the components (1) and (2) and 9 ml of the cocatalyst component were used.
The catalytic activity was 15.0 g polymer / mmol Ti. The molecular weight of this polymer is 191,000, [mm]
The fraction was 0.50.

[0029]Example 4 200 ml volumetric flask with stirrer and thermometer
After replacing コ with argon, methylene chloride 60m
1. Reaction solution of components (1) and (2) synthesized in Example 1.
20 ml and 1.5 m of the promoter component synthesized in Example 1.
l was charged. Keep the internal temperature at 25 ° C and
Replace with pyrene and set pressure to 0.1kg / cm ^TwoKeep G 2
Polymerization was carried out for hours. The inside of the system was replaced with argon again
Then, 1N-HCl / methanol solution is added, and 0.5 hour
Stirring was continued. By evaporating the toluene layer to dryness
1.9 g of polymer were recovered. The molecular weight of this polymer is
258,000, [mm] fraction was 0.55.

Embodiment 5 1. Reaction of Components (1) and (2) After a 500-ml flask equipped with a stirrer, a dropping funnel, and a reflux condenser was purged with argon, 100 ml of methylene chloride and 0.01 m of zirconium tetrachloride were added.
was charged into the flask and heated until the methylene chloride refluxed. Next, from the dropping funnel, toluene 100m
l and 4,4 ', 6,6'-tetra-t-butyl-2,
A solution consisting of 0.01 mol of 2'-methylenediphenol was gradually added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued under reflux for 50 hours. After standing overnight, the precipitate was removed by filtration to obtain a uniform brown solution. 1 ml of this solution
It contained 0.009 mmol of Zr. 2. Polymerization of propylene The same procedure as in Example 1 was carried out except that 1 ml of a reaction solution of the components (1) and (2) was charged. The resulting polymer was 0.1
5 g, molecular weight 309,000, [mm] fraction 0.7
It was 3.

Embodiment 6 1. Reaction of components (1) and (2) After a 100-ml flask equipped with a stirrer, dropping funnel and reflux condenser was purged with argon, 20 ml of methylene chloride and 4,4 ', 6,6'-tetramethyl- 2,2'-isobutylidene diphenol 0.002
8 mol was charged into the flask and heated until the methylene chloride was refluxed. Next, a methylene chloride solution of 0.0028 mol of tetraisopropoxytitanium was added dropwise from the dropping funnel, followed by stirring under reflux for 1 hour.
The reaction product was obtained by removing the solvent from the solution under reduced pressure and drying. The obtained reaction product was dissolved in a toluene solution (4.3 × 10 ⁻⁵ m).
ol / ml). 2. Polymerization of Propylene The same procedure as in Example 1 was carried out except that 1 ml of a reaction solution of the components (1) and (2) was charged. The resulting polymer was 0.4
1 g, the molecular weight is 850,000, and the [mm] fraction is 0.1.
53.

Embodiment 7 1. Reaction of components (1) and (2) As catalyst component (1), tetraisoproxyl zirconium (0.0028) was used instead of tetraisopropoxytitanium.
3. Performed in the same manner as in Example 6 except that mmol was used.
A toluene solution of 0 × 10 ⁻⁵ mol / ml was obtained. 2. Polymerization of propylene Example 1 was repeated except that 1 ml of the reaction solution of the components (1) and (2) was used and polymerization was performed at 60 ° C. for 4 hours.
Polymerization was carried out in the same manner as described above. The resulting polymer was 0.07
g, molecular weight 730,000, [mm] fraction 0.7
It was 0.

Embodiment 8 1. Reaction of components (1) and (2) As component (1), instead of tetraisopropoxytitanium, tetra-t-butoxyzirconium 0.0028 m
The same procedure as in Example 6 was carried out except that mol was used, and 6.0 was used.
A toluene solution of × 10 ^-5 mol / ml was obtained. 2. Polymerization of propylene As a result of performing polymerization in the same manner as in Example 1 except that 1 ml of the reaction solution of the components (1) and (2) was used and polymerization was performed at 80 ° C. for 2 hours, 0.5 g of a polymer was obtained. I got The molecular weight of this polymer is 500,000, [mm]
The fraction was 0.83.

Comparative Example 1 Biscyclopentadienyl titanium dichloride in toluene solution (1.2 × 10 ⁻⁵ mol / ml) as component (1)
Polymerization was carried out in the same manner as in Example 1 except that 3 ml was used. The obtained polymer weighed 3.6 g, had a low molecular weight of 2,800, and had a [mm] fraction of 0.25, and was amorphous polypropylene.

Embodiment 9 1. Reaction of components (1) and (2) After a flask having an inner volume of 100 ml equipped with a stirrer and a reflux condenser was purged with argon, 2,2'-dihydroxy-3,3'-di-t-butyl-5,5 was added. 0.84 mmol of '-dimethyldiphenyl sulfide was charged into a flask, and 50 ml of dried n-butyl ether was added thereto, followed by stirring and dissolving. To this solution, 0.84 mmol of titanium tetrachloride, which was previously made into an n-butyl ether solution, was gradually added by a syringe, and then stirring was continued at 25 ° C. for about 6 hours. After standing, the supernatant was removed, and the precipitate was recovered. Part of the precipitate was dissolved in toluene, and Ti was added in an amount of 0.001 mmol /
A solution containing ml was prepared.

2. Synthesis of cocatalyst components Inner volume with stirrer, dropping funnel, reflux condenser
After purging the 500 ml flask with argon, 38.
2gr (0.15mol) CuSO_Four・ 5H _TwoO to 2
Suspended in 00 ml of toluene, keeping the internal temperature at 5 ° C and stirring
While performing trimethylaluminum 0.58mo
and a solution consisting of 100 ml of toluene over 5 hours
I dropped it. After completion of the dropwise addition, stirring was continued at room temperature for 20 hours. Settling
After removing the substance, the solvent was removed under reduced pressure, and 10.0 g of methyl chloride was removed.
Lualuminoxane was obtained. Diluted with toluene for polymerization
(0.05 g / ml). The following example
For the polymerizations of 10 to 14 and Comparative Example 2,
A xane solution was used.

3. Polymerization of ethylene To a 100 ml flask, 50 ml of toluene, 3 ml (150 mg) of a cocatalyst component, and 1 ml (0.001 mmol) of a reaction solution of the components (1) and (2) are sequentially added.
The temperature was raised to 0 ° C. Next, ethylene was continuously introduced into the flask, and a polymerization reaction was performed at 0.2 kg / cm ² G for 10 minutes. After completion of the reaction, methanol was added to decompose the catalyst, followed by drying to obtain 0.35 g of polyethylene. The catalytic activity of this catalyst was 2,100 g / mmol Ti · hr per hour. The molecular weight of the obtained polymer was 530,000.

Example 10 After replacing a stainless steel autoclave of a stirring type with a magnetic stirrer having an internal volume of 130 ml with argon, 0.001 mmol of a reaction solution of the components (1) and (2) synthesized in Example 9 and a cocatalyst were prepared. 3 ml of the components were sequentially added, 40 g of propylene was introduced, and polymerization was carried out at 30 ° C. for 1 hour. After completion of the reaction, propylene was purged, methanol was added to decompose the catalyst, and then dried to obtain polymer 3.9.
g was obtained. The molecular weight of the obtained polypropylene is 1,80.
It was 0000.

Embodiment 11 1. Reaction of components (A) and (C) 2,2 'is placed in a 100 ml-volume flask equipped with a stirrer.
-Dihydroxy-3,3'-di-tert-butyl-5,5 '
-0.9 mmol of dimethyldiphenyl sulfide was taken, replaced with argon and dried with n-butyl ether 5;
0 ml was added and dissolved by stirring. 0.9 mmol of tetraisopropoxytitanium was added to this solution. By stirring at 25 ° C., a precipitate formed after a few minutes. After continuing stirring for about 2 hours, the mixture was allowed to stand, the supernatant was removed, and the precipitate was recovered.
Washed. Part of the precipitate was dissolved in toluene to obtain 9.1 Ti.
A solution containing × 10 ⁻⁴ mmol / ml was prepared. 2. Polymerization of propylene 1 ml of a reaction solution of components (1) and (2) obtained in 1 above
Polymerization was performed in the same manner as in Example 10 except that
0.86 g of polymer was obtained. The molecular weight of this polymer was 1,600,000.

Comparative Example 2 1. Polymerization of propylene The same procedure as in Example 10 was carried out except that 0.0009 mmol of biscyclopentadienylhafnium dichloride was used as the component (1), and that the cocatalyst component synthesized in Example 9 was used. Obtained. The molecular weight of the obtained polymer was as low as 19,000.

Embodiment 12 1. Reaction of components (1) and (2) After a flask having an inner volume of 100 ml equipped with a stirrer and a reflux condenser was replaced with argon, 0.0053 mol of 2,4-dihydroxypentane was charged into the flask, and 30 ml of dried n-butyl ether was added. Was added and stirred to dissolve. To this solution, 0.0053 mol of titanium tetrachloride, which was previously made into an n-butyl ether solution, was gradually added by a syringe. Stirring was continued at 25 ° C. for about 10 hours. After standing, the supernatant was removed, and the precipitate was recovered. A part of the precipitate was dissolved in toluene to prepare a solution containing 0.0023 mmol / ml Ti.

2. Polymerization of Propylene After replacing the stainless steel autoclave of a stirring type with a magnetic stirrer with an inner volume of 130 ml with argon, 0.0023 mmol of a reaction solution of the components (1) and (2) was replaced.
1 and 3 ml of the cocatalyst component synthesized in Example 9 were sequentially added, 40 g of propylene was introduced, and polymerization was carried out at 30 ° C. for 1 hour. After completion of the reaction, propylene was purged, methanol was added to decompose the catalyst, and then dried to obtain 0.15 g of a polymer. The molecular weight of the obtained polypropylene was 960,000, and the IR spectrum showed that it was an amorphous polypropylene.

Embodiment 13 1. Reaction of components (1) and (2) After replacing a 100 ml flask equipped with a stirrer and reflux condenser with argon, catechol 0.00
53 mol was put into a flask, 30 ml of dried n-butyl ether was added, and the mixture was stirred and dissolved. To this solution, 0.0053 mol of titanium tetrachloride, which was previously made into an n-butyl ether solution, was gradually added by a syringe.
Stirring was continued at a temperature of about 6 hours. The reaction solution was dried and a part was dissolved in toluene to prepare a solution containing 0.18 mmol / ml of Ti.

2. Polymerization of Propylene After replacing the stainless autoclave of a stirring type with a magnetic stirrer with an inner volume of 130 ml with argon, 0.18 mmol of the reaction solution obtained in the above (1) and 3 ml of the cocatalyst component synthesized in Example 14 were successively added. In addition, 40 g of propylene was introduced, and polymerization was performed at 30 ° C. for 1 hour. After completion of the reaction, propylene was purged, methanol was added to decompose the catalyst, and then dried to obtain polymer 0.0
2 g were obtained. The molecular weight of the obtained polypropylene is 51.
It was 000 and the IR spectrum indicated that it was amorphous polypropylene.

Embodiment 14 1. Reaction of components (1) and (2) After a 0.5-liter flask equipped with a stirrer, a dropping funnel, and a reflux condenser was purged with nitrogen, 100 ml of methylene chloride and 0.015 mol of titanium tetrachloride were replaced.
Was charged into a flask and heated until methylene chloride was refluxed. Next, methylene chloride 20 was added from the dropping funnel.
0ml and 1,1'-bi-2-naphthol 0.015mo
1 was slowly added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued for 5 hours under reflux. After standing overnight, the precipitate was removed by filtration to obtain a uniform black solution. 1 ml of this solution contained 0.04 mmol of Ti.

2. Synthesis of Cocatalyst Component After replacing a 1-liter flask equipped with a stirrer, a dropping funnel and a reflux condenser with nitrogen, 43.4 g of the flask was replaced with nitrogen.
_{(0.17mol) CuSO 4 · 5H 2} O the 400m of
1 ml of toluene, a solution consisting of 0.58 mol of trimethylaluminum and 140 ml of toluene was added dropwise over 4 hours while stirring while maintaining the internal temperature at 5 ° C.
After further reacting at this temperature for 1 hour,
The reaction was continued for hours. After standing overnight, the precipitate was removed by filtration, and then the solvent was removed under reduced pressure to obtain 11.3 g of methylaluminoxane. For polymerization, dilute with toluene (0.
1 g / ml).

3. Ethylene-propylene copolymerization After substituting a 0.5-liter flask equipped with a reflux condenser with nitrogen, 200 ml of dried methylene chloride and 1 ml of a cocatalyst component were added, and a thermometer and a stirrer were attached to bring the internal temperature of the flask to 30 ° C. Kept. A mixed gas of 50 mol% of ethylene and 50 mol% of propylene was passed through the mixture at a flow rate of 3 liter (standard state) / min for 10 minutes to dissolve the mixed gas. Next, 1 ml of a reaction solution of the components (1) and (2) was added to start copolymerization. Polymerization was carried out at 30 ° C. by flowing the above mixed gas under stirring for 1 hour, and the polymer liquid was poured into a large amount of methanol to collect the entire amount of the copolymer. The obtained copolymer was 1.55 g. This copolymer has 23w
It contained t% of propylene and [η] was 8.4.

Embodiment 15 1. Polymerization of Ethylene-Propylene A 0.5-liter flask equipped with a reflux condenser was purged with nitrogen.
1 ml of the promoter component synthesized in 4-2 was added, and the inside temperature of the flask was kept at 50 ° C. by attaching a thermometer and a stirrer. A mixed gas of 40 mol% of ethylene and 60 mol% of propylene was flowed at a flow rate of 3 liter (standard state) / min for 10 minutes to dissolve the mixed gas. Next, a toluene solution of tetraisopropoxytitanium (0.017 mmol) was added as component (1) to start copolymerization. The above mixed gas was flowed under stirring for 1 hour to carry out polymerization at 50 ° C., and the polymer liquid was poured into a large amount of methanol to collect the entire amount of the copolymer.
The obtained copolymer was 0.34 g. This copolymer contained 25 wt% of propylene, and [η] was 8.8.

[0049]

The catalyst of the present invention can produce a high-efficiency, high-molecular-weight olefin polymer by adding other co-catalyst components as shown in the above examples. In particular, the industrial significance of facilitating the production of a high molecular weight amorphous olefin polymer, which has been extremely difficult to produce, is extremely large.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (20)

(57) [Claims] 1. Component (1): General formula M (R)_l(OR ')_mX_{n- (l + m)} (Where M is titanium, zirconium, hafnium and banana
A transition metal atom selected from the group consisting of R and R 'has 1 carbon atom.
And X represents a halogen atom. l,
m and n are l ≧ 0, m ≧ 0, n− (l + m) ≧ 0
Represents n corresponds to the valence of the transition metal. )
And a transition metal compound represented by the following formula (2):
Has two or more hydroxyl groups shown in III, IV, V and VI
At least one compound selected from the group consisting of organic compounds
Catalyst for Olefin Polymerization Obtained by Reaction with Compounds
Min,Embedded imageEmbedded imageEmbedded imageEmbedded imageEmbedded image(Wherein R ″ and R ′ ″ are hydrocarbons having 1 to 20 carbon atoms)
A group, Y is a hydrocarbon group having 1 to 20 carbon atoms,(R^FiveRepresents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.
You. ). Where R¹, R^Two, R^ThreeAnd R^FourIs
C1-C20 hydrocarbon group, hydroxyl group, nitro group, nitro
Represents a lyl group, hydrocarboxy group or halogen atom
You. In this case R¹, R ^Two, R^ThreeAnd R^FourAre the same
Or different. n 'is 0 or an integer of 1 or more
And represents the number of repetitions of the unit Y. And y, y ',
y ", y" ", z, z", z "and z" "are aromatic
Indicates the number of substituents bonded to the group ring. y, y ', z
And z 'are 0 or an integer from 1 to 4, and y ", z" are
0 or an integer from 1 to 2; y "", z "" is 0 or
Represents an integer of 1 to 3. ). 2. Component (1) having the general formula M (R)
_{l (OR ') m X n-} (l + m) is an olefin polymerization catalyst component according to claim 1, wherein the titanium tetrachloride or zirconium tetrachloride. 3. Component (1) having the general formula M (R)
_{l (OR ') m X n-} (l + m) of R and R' is an alkyl or aryl group, an olefin polymerization catalyst component according to claim 1 X is chlorine. 4. The composition according to claim 1, wherein in the component (1), R is a methyl, ethyl, phenyl or benzyl group and R ′ is an n-propyl, isopropyl, n-butyl, t-butyl or phenyl group. Catalyst component for olefin polymerization. 5. A compound of the general formula M (R) in component (1)
_l (OR ') _m X _{n- (l + m)} is tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, diphenoxytitanium dichloride, dinaphthoxytitanium dichloride, tetraisopropoxyzirconium , Tetra-n-butoxyzirconium or tetra-
The olefin polymerization catalyst component according to claim 1, which is t-butoxyzirconium. 6. The olefin polymerization catalyst component according to claim 1, wherein the component (2) is a compound represented by the general formula I or II. 7. The olefin polymerization catalyst component according to claim 1, wherein the component (2) is a compound represented by the general formula V or VI. 8. Component (2) is represented by the general formula: The catalyst component for olefin polymerization according to claim 7, wherein a compound represented by the following formula is used. 9. In the component (2), y, y ′ ″, z
9. The olefin polymerization catalyst component according to claim 8, wherein a compound wherein z '''is 1 is used. 10. In the component (2), n ′ is 1 and Y is
The catalyst component for olefin polymerization according to any one of claims 7 to 9, wherein a compound is a hydrocarbon group having 1 to 20 carbon atoms. 11. The olefin polymerization catalyst component according to claim 7, wherein a biphenyldiol or a binaphthol compound in which n ′ is 0 is used in the component (2). 12. Component (2) wherein n ′ is 1 and Y is The olefin polymerization catalyst component according to any one of claims 7 to 9, wherein the compound is: 13. Component (2) wherein n 'is 1 and Y is -S
The catalyst component for olefin polymerization according to claim 12, wherein the compound is-. 14. In the component (2), R ″, R ″ ″
Is a methylene, ethylene, ethylidene or isobutylidene group. 15. In the component (2), R ¹ , R ² , R
The olefin polymerization catalyst component according to claim 6 or 7, wherein ³ or R ⁴ is an alkyl group or an aryl group having 1 to 10 carbon atoms. 16. In the component (2), R ¹ , R ² , R ³
Or R ⁴ is methyl, ethyl, n- propyl, isopropyl, n-butyl, olefin polymerization catalyst component according to claim 15 is isobutyl or t- butyl group. 17. The olefin polymerization catalyst component according to claim 6, wherein 2,4-dihydroxypentane or catechol is used as the component (2). 18. The olefin polymerization catalyst component according to claim 11, wherein 2,2′-biphenyldiol or 1,1′-bi-2-naphthol is used as the component (2). 19. Component (2) comprising 4,4 ', 6',
6'-tetra-t-butyl-2,2'-methylenediphenol, 4,4 ', 6,6'-di-t-butyl-2,
The catalyst component for olefin polymerization according to claim 10, wherein 2'-methylenediphenol or 4,4 ', 6,6'-tetramethyl-2,2'-isobutylidenediphenol is used. 20. The catalyst component for olefin polymerization according to claim 13, wherein 2,2'-dihydroxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylsulfide is used as component (2).