JP2730940B2 - Method for producing cyclic olefin copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin copolymer in which an α-olefin and a cyclic olefin are copolymerized in the presence of a highly active polymerization catalyst. More specifically, the present invention relates to a method for producing a cyclic olefin copolymer in which an α-olefin and a cyclic olefin are copolymerized in the presence of a catalyst comprising a specific transition metal compound and an organoaluminum oxy compound.

BACKGROUND OF THE INVENTION Conventionally, as a method for producing a cyclic olefin-based copolymer by copolymerizing an α-olefin such as ethylene and a cyclic olefin, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound or vanadium has been used. A method using a vanadium catalyst comprising a compound and an organoaluminum compound is known.

Among these methods, in copolymerization using a titanium-based catalyst, cyclic olefins are less reactive than α-olefins such as ethylene and have low copolymerization efficiency. Production requires the presence of large amounts of cyclic olefins in the polymerization system. However, when a large amount of cyclic olefin is present in the polymerization system, the catalytic activity is impaired, and further, the molecular weight of the copolymer is reduced, so that it is difficult to obtain a high molecular weight copolymer. Furthermore, side reactions such as a ring-opening polymerization reaction of a cyclic olefin easily occur, and the molecular weight distribution of the obtained polymer is wide. On the other hand, in the copolymerization using a vanadium-based catalyst, the copolymerization efficiency of the cyclic olefin is higher and the molecular weight distribution of the produced copolymer is narrower than that of the titanium-based catalyst, but the polymerization activity is generally small.

As a new highly active polymerization catalyst used in the olefin polymerization method, a catalyst comprising a transition metal compound and an aluminoxane is disclosed in JP-A-58-19309 and JP-A-59-19309.
-95292, JP-A-60-35005, JP-A-60-35
No. 006, JP-A-60-35007, JP-A-60-35008
And Japanese Patent Application Laid-Open No. Sho 61-130314. Among these prior arts, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006,
JP-A-60-35007, JP-A-60-35008 and JP-A-61-130314 disclose that the catalyst system comprises ethylene and α-
It is described that the method is applicable to copolymerization of olefins. Further, with respect to a method for producing a cyclic olefin-based copolymer, JP-A-61-221206 discloses that when a catalyst comprising a transition metal compound and an aluminoxane is used, α-
It is described that a copolymer of an olefin and a cyclic olefin can be obtained, but the polymerization activity is low, and it has been difficult to obtain the copolymer in an excellent yield.

Furthermore, Japanese Patent Application No. 62-45152 of the present applicant discloses that a catalyst comprising a polydentate compound such as ethylenebis (indenyl) zirconium dichloride and an aluminoxane comprises an α-olefin and a cyclic olefin. It is described that it is suitable for a method for producing a copolymer, and the polymerization activity and the copolymerization efficiency of a cyclic olefin have been considerably improved.However, it is desired to further improve the polymerization activity and the copolymerization efficiency of a cyclic olefin. ing.

In J. Am. Chem. Soc., 110, 6255 (1988), it is described that syndiotactic polypropylene can be obtained by combining a specific zirconium or hafnium compound with an aluminoxane. However, α-
There is no description about copolymerization of olefins.

As described above, when producing a cyclic olefin copolymer, a method for efficiently producing a cyclic olefin copolymer having a high copolymerization efficiency of a cyclic olefin, excellent polymerization activity, and a narrow molecular weight distribution is proposed. The emergence is strongly desired.

Object of the Invention The present invention has been made in view of the above points, and is excellent in polymerization activity, and has a high cyclic olefin copolymerization efficiency, and furthermore, a cyclic olefin copolymer having a narrow molecular weight distribution. It is an object of the present invention to provide a method for producing a cyclic olefin-based copolymer that can be obtained.

SUMMARY OF THE INVENTION The method for producing a cyclic olefin-based copolymer according to the present invention comprises: (A) a transition metal compound of Group IVB in the periodic table IV represented by the following general formula (I): [Where Me is a transition metal of Group IVB of the periodic table and R ⁰
Represents a hydrocarbon group, a silylene group or a substituted silylene group, R ¹ and R ² are different and each represents a cycloalkadienyl group or a substituted product thereof (provided that ^one of R ¹ and R ² is cyclopentane) Excluding a dienyl group and the other being a substituted cyclopentadienyl group, and a case where both R ¹ and R ² are substituted cyclopentadienyl groups), R ³ and R ⁴ are cycloalkadienyl groups , Aryl group, alkyl group, aralkyl group, cycloalkyl group,
A halogen atom, hydrogen, OR ^a , SR ^b , NR ^c or PR ^d ,
R ^a , R ^b , R ^c and R ^d are an alkyl group, a cycloalkyl group,
An aryl group, an aralkyl group or a silyl group, and two R ^c and R ^d may be linked to form a ring. And (B) an α-olefin and a cyclic olefin in the presence of a catalyst formed from an organoaluminum oxy compound.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a cyclic olefin-based copolymer according to the present invention will be specifically described.

The catalyst used in the present invention is formed from a transition metal compound (A) belonging to Group IVB of the periodic table having a specific ligand (A) and an organoaluminum oxy compound (B).

Transition metal compound (A) of group B of the periodic table IV as described above
Is a periodic table IV having at least two different cycloalkadienyl groups or substituted products thereof as a ligand with a polydentate compound having a hydrocarbon group, a silylene group, or a substituted silylene group bonded thereto as a ligand. It is a transition metal compound of Group B. Periodic Table IV for such a catalyst component (A)
The Group B transition metal compound is selected from the group consisting of titanium, zirconium and hafnium. Of these, hafnium and zirconium are preferred.

Such a transition metal compound of Group IVB of the periodic table (A)
Is, for example, the general formula (I) [Where Me is a transition metal of Group IVB of the periodic table and R ⁰
Represents a hydrocarbon group or a silylene group or a substituted silylene group, R ¹ and R ² are different and each represents a cycloalkadienyl group or a substituted product thereof (provided that R ¹ and R ²
Excluding the case where one of them is a cyclopentadienyl group and the other is a substituted cyclopentadienyl group, and the case where both R ¹ and R ² are substituted cyclopentadienyl groups. ), R ³ and R ⁴ are cycloalkadienyl, aryl, alkyl, aralkyl, cycloalkyl, halogen, hydrogen, OR ^a , SR ^b , NR ^c or PR ^d , R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a silyl group, and two R ^c and R ^d can also form a ring continuously . ] It is a compound represented by these. Here, specific examples of the hydrocarbon group include an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, and a diphenylmethylene group; an alkylidene group such as an isopropylidene group and a cyclohexylidene group; and a phenylene group. And other hydrocarbon groups such as a hydrocarbon group having 1 to 10 carbon atoms. Examples of the substituted silylene group include a dimethylsilylene group. Specific examples of the cycloalkadienyl group include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group,
Examples thereof include a tetrahydroindenyl group and a fluorenyl group. As the alkyl group, specifically,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a decyl group. Specific examples of the aryl group include a phenyl group and a tolyl group. And the like. Specific examples of the aralkyl group include:
Benzyl group, neophyl group and the like can be exemplified,
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, a bicyclononyl group, and an alkyl substituent of these groups. As a halogen atom,
Examples include fluorine, chlorine, and bromine.

When the transition metal is zirconium, examples of the transition metal compound include the following compounds.

Isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-octahydrofluorenyl) ) Zirconium dichloride, isopropylidene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-)
Fluorenyl) zirconium dichloride, isopropylidene (ethylcyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (diethylcyclopentadienyl-
Fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl-2,
7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (ethylcyclopentadienyl-2,
7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (diethylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-)
Octahydrofluorenyl) zirconium dichloride, isopropylidene (ethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, isopropylidene (diethylcyclopentadienyl-
Octahydrofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-2,7-
Di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, cyclohexylidene (methylcyclopentadienyl-
Fluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (ethylcyclopentadienyl-
Fluorenyl) zirconium dichloride, cyclohexylidene (diethylcyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (methylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (ethylcyclopentadiene) Enil-
2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (diethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (methylcyclopentadiene) Enil-
Octahydrofluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, cyclohexylidene (ethylcyclopentadienyl-
Octahydrofluorenyl) zirconium dichloride, cyclohexylidene (diethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2) , 7−
Di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl-
Fluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (ethylcyclopentadienyl-
Fluorenyl) zirconium dichloride, diphenylmethylene (diethylcyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (ethylcyclopentadienyl-)
2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (diethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl-)
Octahydrofluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (ethylcyclopentadienyl-
Octahydrofluorenyl) zirconium dichloride, diphenylmethylene (diethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-2, 7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclo) Pentadienyl-
Fluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl-
Fluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl-2,
7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl-2,
7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl-
Octahydrofluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl-
Octahydrofluorenyl) zirconium dichloride.

Further, as the hafnium compound used in the present invention,
Compounds in which the center metal of the zirconium compound described above is changed from zirconium to hafnium can be exemplified.

Further, as the titanium compound used in the present invention, a compound in which the central metal of the zirconium compound as described above is changed from zirconium to titanium can be exemplified.

As the organoaluminum oxy compound used as the catalyst component (B), general formula (II) and general formula (II)
I) Aluminoxysan soluble in benzene represented by the following formula: In such an aluminoxane, R and R ₂ may be the same or different and include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
A hydrocarbon group such as -butyl group and isobutyl group, preferably a methyl group, an ethyl group, an isobutyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 or more.

As a method for producing aluminoxane as described above, for example, the following method can be exemplified.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, primary chloride
A method in which a trialkylaluminum is added to a suspension of a hydrocarbon medium such as cerium hydrate to cause a reaction.

(2) A method in which water is allowed to directly act on trialkylaluminum in a medium such as benzene, toluene, ethyl ether, and tetrahydrofuran.

Among these methods, it is preferable to adopt the method (1). The aluminoxane may contain a small amount of an organic metal component.

Further, as the organoaluminum oxy compound used in the present invention, a benzene-insoluble organoaluminum oxy compound can be exemplified. The benzene-insoluble organic aluminum oxy compound will be described below.

The benzene-insoluble organoaluminum oxy compound used in the present invention can be obtained by reacting (i) a reaction between an organoaluminum compound and water, or a reaction of an aluminoxane solution, for example, a hydrocarbon solution with water or (ii) an active hydrogen-containing compound. Obtained by

This benzene-insoluble organoaluminum oxy compound is [Wherein, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms], and the Al component soluble in benzene at 60 ° C. is 10% or less in terms of Al atoms. , Preferably 5% or less, particularly preferably 2% or less, and are insoluble or soluble in benzene.

The solubility of the organoaluminum oxy compound according to the present invention was determined by suspending the organoaluminum oxy compound corresponding to 100 milligram atoms of Al in 100 ml of benzene, mixing the mixture at 60 ° C. for 6 hours with stirring, and attaching a jacket. G-
5 Using a glass filter, perform hot filtration at 60 ° C, and separate 50 parts of benzene 50
After washing four times with ml, the amount is determined by measuring the abundance (x mmol) of Al atoms present in the total filtrate (x%).

In the above alkyloxyaluminum unit, R ¹
Is specifically exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl, cyclooctyl, etc. it can. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound according to the present invention, In addition to the alkyloxyaluminum unit represented by [Wherein R ¹ is the same as above, and R ² has 1 to 12 carbon atoms.]
A hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms and 6 carbon atoms
-20 aryloxy groups, hydroxyl groups, halogens or hydrogen, and R ¹ and R ² represent different groups from each other]. In that case, the alkyloxyaluminum unit Is preferably 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more.

(I) The organoaluminum compound used for producing such a benzene-insoluble organoaluminum oxy compound is R ¹ _n AlX _3-n (wherein R ¹ has 1 to 12 carbon atoms)
X is a halogen, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or hydrogen, and n is 2 to 3).

Such (i) organoaluminum compounds include:
Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, trise
c-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, trialkylaluminum such as tricyclooctylaluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide, diethyl Dialkylaluminum aryloxides such as aluminum phenoxide are used. Among these organoaluminum compounds, in the above general formula, an organoaluminum compound in which R is an alkyl group and X is a base atom is preferred, and a trialkylaluminum is particularly preferred.

Also, (i) an organoaluminum compound represented by the general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (x, y, and z are positive numbers and z ≧ 2x) Isoprenyl aluminum can also be used.

The (a) organoaluminum compound as described above is used alone or in combination.

In addition, as the (ii) active hydrogen-containing compound used in producing the benzene-insoluble organic aluminum oxy compound according to the present invention, alcohols such as methyl alcohol and ethyl alcohol, and diols such as ethylene glycol and hydroquinone are used. .

In the present invention, when water is used in preparing the benzene-insoluble organic aluminum oxy compound, the water is dissolved in a hydrocarbon solvent such as benzene, toluene, and hexane, an ether solvent such as tetrahydrofuran, and an amine solvent such as triethylamine. Alternatively, they can be used as dispersed or in the state of steam or ice. In addition, as water, crystallization water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, cerous chloride, etc., or inorganic compounds or polymers such as silica, alumina, aluminum hydroxide and the like are adsorbed. Adsorbed water or the like can also be used.

As described above, the benzene-insoluble organoaluminum oxy compound according to the present invention includes (i) a reaction between an organoaluminum compound and water, or an aluminoxane solution,
For example, it is obtained by a reaction between a carbonized aqueous solution and water or (ii) an active hydrogen-containing compound. In order to produce a benzene-insoluble organoaluminum oxy compound from (i) an organoaluminum compound and water, (i) contacting the (a) organoaluminum compound with water in a solvent, for example, a hydrocarbon solvent, Water may be added to the reaction system such that the amount of dissolved organic aluminum atoms in the solution is 20% or less of the total organic aluminum atoms. In order to obtain a benzene-insoluble organoaluminum oxy compound in this manner, it is desirable to contact water in an amount of 1 to 5 mol, preferably 1.5 to 3 mol, per 1 mol of the (a) organoaluminum compound.

The reaction for producing the benzene-insoluble organoaluminum oxy compound as described above is performed in a solvent, for example, a hydrocarbon solvent. Examples of the solvent include benzene, toluene, xylene, cumene, and aromatic hydrocarbons such as cumene.
Butane, isobutane, pentane, hexane, octane,
Aliphatic hydrocarbons such as decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclooctane, cyclodecane and cyclododecane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and light oil, or the above It is also possible to use halides of aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran.
Among these hydrocarbon media, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is preferably in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. The concentration of water such as water of crystallization in the reaction system is usually 1 ×
It is desirably in the range of 10 ^{−3 to} 20 mol / l, preferably 1 × 10 ⁻² to 10 mol / l. At this time, the amount of organic aluminum atoms dissolved in the reaction system is 20% or less, preferably 10% or less, more preferably 0% or less based on all the organic aluminum atoms.
It is desirable to be in the range of ５5%.

(I) The contact between the organoaluminum compound and water may be specifically performed as follows.

(1) (i) A method in which a hydrocarbon solution of organoaluminum is brought into contact with a hydrocarbon solvent containing water.

(2) A method in which (i) the organic aluminum is brought into contact with the water vapor by, for example, blowing water vapor into a hydrocarbon solution of the organic aluminum.

(3) (i) mixing a hydrocarbon solution of an organoaluminum with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and bringing (i) the organoaluminum into contact with the adsorbed water or the water of crystallization. Method.

(4) (i) A method of bringing a hydrocarbon solution of an organoaluminum into contact with ice.

The contact reaction between (i) the organoaluminum compound and water as described above is usually performed at -100 to 150C, preferably -50 to 100C.
More preferably, the reaction is performed at a temperature of -30 to 80C. The reaction time varies greatly depending on the reaction temperature, but is usually about 1 to 200 hours, preferably about 2 to 100 hours.

The benzene-insoluble organoaluminum oxy compound according to the present invention is prepared by mixing a solution of aluminoxane with water or (i
i) To prepare from an active hydrogen-containing compound, aluminoxane in a solution of aluminoxane and water or (i
i) The active hydrogen-containing compound may be brought into contact.

The solution of aluminoxane is dissolved in a solvent such as that used for producing the benzene-insoluble organic aluminum oxy compound as described above, preferably in an aromatic hydrocarbon such as benzene or toluene. Although the solution is prepared, it may contain other components as long as the reaction between the aluminoxane and water or the active hydrogen-containing compound is not adversely affected.

Water or (ii) an active hydrogen-containing compound used in the catalytic reaction is aluminum 1 in a solution of aluminoxane.
It is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, per gram atom. The concentration in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. The concentration of water inside is usually 2 × 10 ^{-4 to} 5 mol
/ l, preferably 2 × 10 ^{-3 to} 3 mol / l.

In order to contact the aluminoxane solution with water or (ii) an active hydrogen-containing compound as described above, the contact reaction between the aluminoxane solution and water will be described as an example. What should I do?

(1) A method of contacting a solution of aluminoxane with a hydrocarbon solvent containing water.

(2) A method of contacting the aluminoxane in the aluminoxane solution with the steam by, for example, blowing steam into the aluminoxane solution.

(3) mixing a solution of aluminoxane with a hydrocarbon suspension of a compound containing absorbed water or a compound containing water of crystallization,
A method in which aluminoxane in an aluminoxane solution is brought into contact with adsorbed water or crystal water.

(4) A method of bringing a solution of aluminoxane into direct contact with water or ice.

(Ii) When an active hydrogen-containing compound is used, the same can be applied as described above.

The contact reaction between the aluminoxane solution as described above and water or (ii) an active hydrogen-containing compound is usually carried out in the range of -50 to
150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C
At a temperature of The reaction time varies greatly depending on the reaction temperature, but is usually 0.5 to 300 hours, preferably 1 to 300 hours.
It is about 150 hours.

As the α-olefin supplied to the polymerization reaction in the method of the present invention, specifically, ethylene, propylene,
-Butene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include α-olefins having 2 to 20 carbon atoms, such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Specific examples of the cyclic olefin supplied to the polymerization reaction in the method of the present invention include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, and octacene. Monocycloalkenes such as cyclodecene and cycloeicosene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5, 5,6-trimethyl-2-norbornene, 2-
Tricycloalkenes such as bicycloalkenes such as bornene, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene , 1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-
In addition to octahydronaphthalene, 2-methyl-1,4,5,
8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano 1,2,3,4,4a, 5,8 ,
8a-octahydronaphthalene, 2-propyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-stearyl-1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-
3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene,
2-bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5, 8-dimethano-1,2,3,4,4a,
5,8,8a- tetra cycloalkenes such octahydronaphthalene, hexacyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0
^9.14] heptadecene -4 pentacyclo [8,8,1 ^2.9, 1
^4.7, 1 ^11.18, 0,0 ^3.8, 0 ^12.17] henicosenoic -5, octacyclo [8,8,1 ^2.9, 1 ^4.7, 1 ^11.18, 1 ^13.16, 0,0 ^3.8, 0
^12.17 ] Cyclic monoenes such as polycycloalkenes such as dococene-5, dicyclopentadiene, 5-methylene-
2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene, 1,5-cyclooctadiene, 5,8
And cyclic polyenes such as endmethylene hexahydronaphthalene and alkylidenetetrahydroindene.

In the method of the present invention, the starting olefin supplied to the polymerization reaction system is a mixture of the above-mentioned α-olefin and cyclic olefin. The content of the α-olefin in the polymerization olefin is usually 1 to 90 mol%,
It is preferably in the range of 2 to 80 mol%, and the content of the cyclic olefin is usually in the range of 10 to 99 mol%, preferably 20 to 98 mol%.

In the method of the present invention, the polymerization reaction of the olefin is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; alicyclics such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, petroleum fractions such as gasoline, kerosene, and light oil, olefins as raw materials also serve as hydrocarbon media.

In the method of the present invention, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is usually employed. The temperature during the polymerization reaction is usually in the range of -50 to 150C, preferably -30 to 120C.

The rate of use of the transition metal compound when the method of the present invention is carried out by a liquid phase polymerization method, as the concentration of the transition metal atom in the polymerization reaction system, is usually 10 ^-8 to 10 ^-2 g atom / l, preferably. Is
It is in the range of 10 ^-7 to 10 ^-3 gram atom / l. Further, the use ratio of the organic aluminum oxy compound is usually 10 ⁻⁴ to 10 ⁻¹ g atom / l, preferably 10 ^{−3 to} 5 × 10 ⁻² g atom / l as the concentration of aluminum atoms in the polymerization reaction system. And the ratio of aluminum atom to transition metal atom in the polymerization reaction system is usually 4 to 10 ⁷ , preferably 10 to 1
0 ⁶ is in the range of. The molecular weight of the copolymer can be adjusted by hydrogen and / or polymerization temperature.

In the method of the present invention, a cyclic olefin-based copolymer is obtained by treating the polymerization reaction mixture after the polymerization reaction in a conventional manner. The composition of the cyclic olefin copolymer is such that the α-olefin component is usually 20 to 99.9 mol%, preferably 30 to 99.5 mol%, more preferably 50 to 99 mol%.
Mol%, and the cyclic olefin component is usually 0.1 to 80.
Mol%, preferably 0.5-70 mol%, more preferably 1 mol%
In the range of ~ 50 mol%. The intrinsic viscosity [η] of the cyclic olefin-based copolymer measured in a decalin solvent at 135 ° C. is usually 0.005 to 10 dl / g, preferably 0.01 to 6 dl / g.
The molecular weight distribution measured by gel permeation chromatography (GPC) is usually 4 or less, preferably 3 or less.

Effect of the Invention According to the method of the present invention, a cyclic olefin-based copolymer having excellent polymerization activity and a narrow molecular weight distribution can be efficiently produced.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these examples.

Example 1 [Preparation of aluminoxane] Al ₂ (SO ₄ ) ₃ · 14 was placed in a 400 ml flask which was sufficiently purged with nitrogen.
After charging 37 g of H ₂ O and 125 ml of toluene and cooling to 0 ° C., trimethylaluminum 5 diluted with 125 ml of toluene was added.
00 mmol was added dropwise. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours.

After completion of the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the filtrate to obtain 13 g of aluminoxane as a white solid. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in the catalyst component [B] was 14. In the polymerization, the aluminoxane obtained as described above was redissolved in toluene and used.

[Preparation of zirconium catalyst] Fluorene 8.3 was placed in a 400 ml flask which was sufficiently purged with nitrogen.
g and 150 ml of tetrahydrofuran (THF).
After cooling to ℃, n-butyl lithium hexane solution (1.
6M) was added dropwise. After reacting for 5 hours, 5.0 g of 6,6-dimethylfulvene was added dropwise, and after the temperature was raised to room temperature, the reaction was continued overnight.

After the completion of the reaction, toluene was extracted from the reaction mixture,
Next, purification by silica gel column chromatography was performed to obtain 4 g of 2-cyclopentadienyl-2-fluorenylpropane.

Next, 4 g of 2-cyclopentadienyl-2-fluorenylpropane and TH were placed in a 400 ml flask sufficiently purged with nitrogen.
After charging 150 ml of F and cooling to −78 ° C., 40 ml of an n-butyllithium hexane solution (1.6 M) was added dropwise. Zirconium tetrachloride was added to the resulting dianion and allowed to react overnight. Filtration yielded 2 g of the desired catalyst, i.e., isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride.

[Polymerization] After 250 ml of toluene and 7.5 g of tetracyclododecene were charged into a 500 ml glass autoclave sufficiently purged with nitrogen, ethylene gas was flowed at a rate of 60 l / hour and kept at 20 ° C for 10 minutes. Subsequently, 2.5 mg of aluminoxane in terms of aluminum atom and 2.5 × 10 ⁻² mmol of the zirconium catalyst synthesized above were charged to initiate polymerization. After polymerization at 20 ° C. for 30 minutes under normal pressure, the polymerization was stopped with isopropanol. The resulting polymer solution was added to a large amount of methanol / acetone mixture, to precipitate a polymer, and vacuum dried overnight at 120 ℃, ¹³ C-NM
18.3 g of a polymer having an ethylene content of 88 mol% by R measurement, an [η] of 2.40 dl / g measured in decalin at 135 ° C., and a w / n of 2.06 by GPC measurement were obtained.

Example 2 A polymerization was carried out in the same manner as in Example 1 except that 7.5 g of norbornene was used instead of tetracyclododecene. As a result, the ethylene content was 72.0 mol%, and [η] was obtained. Was 2.33 dl / g, and 9.2 g of a polymer having a w / n of 2.20 was obtained.

Example 3 750 ml of toluene and 37.5 g of 5-methyl-2-norbornene were charged into 1 glass autoclave sufficiently purged with nitrogen, and propylene gas was passed at 100 l / hour.
Hold at 0 ° C. for 10 minutes. Subsequently, the aluminoxane was replaced with Al
7.5 × 10 ⁻² mg atoms of the zirconium catalyst synthesized in Example 1 and 7.5 mg atoms in terms of atoms were charged, and polymerization was started. Polymerization was carried out at 20 ° C. for 2 hours under normal pressure. Subsequent operations were performed in the same manner as in Example 1. As a result, the propylene content was 67 mol%, and [η] was 0.24 dl.
/ g, and 7.4 g of a polymer having a w / n of 2.09 was obtained.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for producing the cyclic olefin copolymer according to the present invention.

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Claims (2)

(57) [Claims] (A) a transition metal compound of Group IVB of the Periodic Table IV represented by the following general formula (I): [Where Me is a transition metal of Group IVB of the periodic table and R ⁰
Represents a hydrocarbon group, a silylene group or a substituted silylene group, R ¹ and R ² are different and each represents a cycloalkadienyl group or a substituted product thereof (provided that ^one of R ¹ and R ² is cyclopentane) Excluding a dienyl group and the other being a substituted cyclopentadienyl group, and a case where both R ¹ and R ² are substituted cyclopentadienyl groups), R ³ and R ⁴ are cycloalkadienyl groups , Aryl group, alkyl group, aralkyl group, cycloalkyl group,
A halogen atom, hydrogen, OR ^a , SR ^b , NR ^c or PR ^d ,
R ^a , R ^b , R ^c and R ^d are an alkyl group, a cycloalkyl group,
An aryl group, an aralkyl group or a silyl group, and two R ^c and R ^d may be linked to form a ring. And (B) a method for producing a cyclic olefin copolymer, which comprises copolymerizing an α-olefin and a cyclic olefin in the presence of a catalyst formed from an organoaluminum oxy compound. 2. The cycloalkadienyl group or a substituent thereof in the general formula (I) is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, The method for producing a cyclic olefin-based copolymer according to claim 1, which is an indenyl group, a tetrahydroindenyl group, or a fluorenyl group.