JP3280444B2 - Method for producing cyclic olefin random copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a random cyclic olefin copolymer, and more particularly, to transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties. The present invention relates to a method for producing a cyclic olefin-based random copolymer having excellent mechanical properties and substantially containing no catalyst residue.

[0002]

BACKGROUND OF THE INVENTION Cyclic olefin random copolymers composed of ethylene and a specific noble cyclic olefin are synthetic resins having a good balance of optical properties, mechanical properties, and thermal properties. JP-A-60-168708 and JP-A-61-1208 show that they can be used for applications in the field of optical materials such as memory disks and optical fibers.
No. 16 and the like.

[0003] The cyclic olefin-based random copolymers proposed in these publications are prepared in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound.
It is produced by copolymerizing ethylene with a specific cyclic olefin in a hydrocarbon solvent such as toluene, cyclohexane, hexane, heptane or using the cyclic olefin itself as a solvent. In these cyclic olefin-based random copolymer production steps, it is necessary to remove catalyst residues such as vanadium, aluminum, and chlorine.After stopping the polymerization reaction by adding alcohol to the polymerization solution, the catalyst residues are removed with methanol. Are disclosed.

[0004] In addition to the above-described method for removing catalyst residues, a method for removing a catalyst using concentrated hydrochloric acid-containing water is disclosed in Japanese Unexamined Patent Publication No. Hei.
No. 258815 and JP-A-4-45103.

Although these methods remove catalyst residues to some extent, there is a demand for an effective method of removing the catalyst remaining in the polymer.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above points, and has been made in consideration of the above problems, and includes transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties. It is an object of the present invention to provide a method for producing a cyclic olefin-based random copolymer which is excellent in water resistance and substantially does not contain a catalyst residue.

[0007]

SUMMARY OF THE INVENTION The process for producing a cyclic olefin random copolymer according to the present invention comprises (a) ethylene and (b) a compound represented by the following formula [I] or [II].

[0008]

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(However, in the above formula [I], n is 0
Or 1, m is 0 or a positive integer, and q is 0
Or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b
Are each independently a hydrogen atom, a halogen atom or a hydrocarbon group; R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group),

[0010]

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(However, in the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1
Or a 2, R ¹ to R ¹⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ or R ¹⁰ is attached, R ¹³
May be directly bonded to the carbon atom to which R ¹¹ is bonded or the carbon atom to which R ¹¹ is bonded, or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be combined with each other to form a monocyclic or polycyclic aromatic ring). And (c) 3 carbon atoms as required.
A catalyst comprising (a) a soluble vanadium compound and an organoaluminum compound, or (ii) a group IV or lanthanide transition metal compound containing a ligand having a cyclopentadienyl skeleton And a cyclic olefin random copolymer in a hydrocarbon solvent and / or a liquid phase composed of the cyclic olefin in the presence of a catalyst composed of an organic aluminum oxy compound and, if necessary, an organic aluminum compound. After the production of the union, the polymerization reaction solution contains 5 to 9 alcohols.
Alcohol-containing water contained in an amount of 0% by volume is added and stirred in an amount of 1 to 33 parts by volume with respect to 100 parts by volume of the polymerization reaction solution. It is characterized in that it is added and stirred in an amount of 500 parts by volume.

[0012]

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

The cyclic olefin random copolymer of the present invention comprises ethylene and the following general formula [I] or [II]
The copolymer is produced by copolymerizing at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the formula and, if necessary, at least one α-olefin having 3 or more carbon atoms.

Here, the cyclic olefin used for producing the above-mentioned cyclic olefin-based random copolymer is represented by the following formula [I] or [II].

[0015]

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In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group;
Is 0, the respective bonds are combined to form a 5-membered ring.

In the above formula [I], R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group usually includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

The cycloalkyl group includes a cyclohexyl group, and the aromatic hydrocarbon group includes a phenyl group and a naphthyl group. Further, the above formula [I]
In the formula, R ¹⁵ and R ¹⁶ are R ¹⁷ and R ^18, and R ¹⁵ and R ¹⁸ are
¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R
¹⁶ and R ¹⁷ may be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. May be.

Specific examples of the monocyclic or polycyclic ring formed here include the following.

[0021]

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In the above examples, the carbon atoms numbered 1 and 2 correspond to R in formula [I], respectively.
Represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded.

Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0024]

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In the above formula [II], p and q are 0
Or a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the above formula [I]. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, And a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Where R ⁹
Or a carbon atom to which R ¹⁰ is bonded and a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded,
It may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. That is, when the two carbon atoms are bonded via an alkylene group, R ⁹ and R ^9
13 or R ¹⁰ and R ¹¹ cooperate with each other to form a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —). Forms an alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Specifically, n = m = 0
In this case, the following aromatic rings formed by R ¹⁵ and R ¹² can be mentioned.

[0030]

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Here, q is the same as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo-2
-Heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-
4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-3-hexadecene derivative, pentacyclo-4-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo
-4- eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4 , 4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative.

In the following, formula [I] or [I
Specific examples of the cyclic olefin represented by I] are shown below.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The above general formula [I] or [II]
Can be produced by subjecting cyclopentadiene and an olefin having a structure corresponding to cyclopentadiene to a Diels-Alder reaction.

These cyclic olefins can be used alone or in combination of two or more. In the present invention, when producing a cyclic olefin-based random copolymer, in addition to ethylene and the cyclic olefin as described above, if necessary, an α-olefin having 3 or more carbon atoms may be copolymerized. Good.

Specific examples of such α-olefins having 3 or more carbon atoms include propylene, 1-butene, and 4-olefin.
Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Octacene, 1-eicosene, etc. with 3 to 2 carbon atoms
And α-olefins of 0.

If necessary, other copolymerizable unsaturated monomer components can be copolymerized within the range not to impair the object of the present invention. Specific examples of such a copolymerizable unsaturated monomer component include cyclopentene, cyclohexene, 3-methylcyclohexene, and cyclooctene having an equimolar amount to the cyclic olefin component unit in the produced random copolymer. Cycloolefin such as 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-
Hexadiene, 1,7-octadiene, 1,9-decadiene, 5-
Non-conjugated dienes such as vinyl-2-norbornene and the like can be exemplified.

In the present invention, ethylene and at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the above general formula [I] or [II],
If necessary, an α-olefin having 3 or more carbon atoms is
In a hydrocarbon solvent or a cyclic olefin liquid phase, copolymerized in the presence of a catalyst (a) or a metallocene catalyst (b) comprising a vanadium compound and an organoaluminum compound soluble in the solvent or the cyclic olefin, Manufactures cyclic olefin-based random copolymers.

As the above-mentioned vanadium compound, specifically, the general formula VO (OR) _{a Xb} or V (OR) _c X _d (where R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3,
2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d
Vanadium compounds represented by ≦ 4) or their electron donor adducts are used.

More specifically, VOCl ₃ , VO (OC _{2
H 5) Cl 2, VO (} OC 2 H 5) 2 Cl, VO (O-iso-C
_{3 H 7) Cl 2, VO} (O-n-C 4 H 9) Cl 2, VO (OC 2
_{H 5) 3, VOBr 2,} VCl 4, VOCl 2, VO (O-n-
Vanadium compounds such as C ₄ H ₉ ) ₃ and VOCl ₃ .20 C ₈ H ₁₇ OH are used.

The electron donors that may be used in preparing the above-mentioned soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, and the like.
Examples thereof include oxygen-containing electron donors such as carboxylic acid, organic acid or inorganic acid ester, ether, acid amide, acid anhydride and alkoxysilane, and nitrogen-containing electron donor such as ammonia, amine, nitrile and isocyanate.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, phenylethyl alcohol, isopropyl alcohol, isopropylbenzyl Alcohols having 1 to 18 carbon atoms such as alcohols;
Phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; 3 carbon atoms such as acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone and benzoquinone To 15 ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, vinyl acetate, propyl acetate, octyl acetate , Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methacrylate Methyl Le acid, ethyl crotonate, cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-cyclohexenecarboxylate
Hexyl, diethyl nadic acid, diisosopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. 2 to 3 carbon atoms
Organic esters having a carbon number of 0; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole; Ethers having 2 to 20 carbon atoms such as diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline And amines such as tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; and alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. That.

[0063] Two or more of these electron donors can be used. As the organoaluminum compound catalyst component, a compound having at least one Al-C bond in the molecule is used. For example, (a) a general formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² usually have 1 to 15 carbon atoms)
, Preferably 1 to 4 hydrocarbon groups, which may be the same or different. X is halogen, m is 0
≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ n <3q, q is 0
≦ q <3, and m + n + p + q = 3, (b) general formula M ¹ AlR ¹ (where M ¹ is Li, Na, K, and R ¹ is the same as R ¹ in the above (a)) and a complex alkylated product of a Group I metal and aluminum.

As the organoaluminum compound belonging to the above (a), the following compounds can be exemplified. (1) General formula _{^{R 1 m Al (OR 2)}} 3-m ( wherein R ¹ and R ^2, R ¹ in the (a),
The same as the R ^2. m is preferably a number satisfying 1.5 ≦ m <3). (2) A compound represented by the general formula: R ¹ _m AlX _3-m (where R ¹ is the same as R ¹ in (a) above, X is a halogen, and m is preferably 0 <m <3). (3) A compound represented by the general formula R ¹ _m AlH _3-m (where R ¹ is the same as R ¹ in the above (a); m preferably satisfies 2 ≦ m <3). (4) The general formula R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² are R ¹ ,
The same as the R ^2. X is halogen, 0 <m ≦ 3, 0 ≦ n <3,
0 ≦ q <3, and m + n + q = 3).

As the aluminum compound belonging to the above (a), more specifically, (1) trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisopropenylaluminum; diethylaluminum ethoxide;
Dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide; R ¹ _2.5 Al (OR
²⁾ _0.5 (wherein R ¹ and R ² are the (a) partially alkoxylated alkyl aluminum having an average composition represented by the same.) Or the like and R ^1, R ² in,
(2) Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, isobutylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as propylaluminum dichloride and butylaluminum dibromide; (3) dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; ethylaluminum dihydride, propylaluminumdichloride Alkyl aluminum such as hydride Partially hydrogenated alkylaluminums such as dihydride, and (4) partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide can be exemplified. .

In the present invention, a compound similar to the above (a) can also be used. As such a compound, for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom Can be mentioned. As such a compound, specifically,
(C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al
N (C ₆ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

The compound belonging to the above (b) is Li
Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified.

Among these, it is particularly preferable to use an alkyl aluminum halide, an alkyl aluminum dihalide or a mixture thereof. [A] Group IVb or lanthanide transition metal compound containing a ligand having a cyclopentadienyl skeleton (hereinafter referred to as “component [A]”) used for forming catalyst (b) in the present invention The compound represented by the following general formula [IV] can be exemplified.

ML _x ... [IV] In the above general formula [IV], M is a transition metal selected from the group IVb of the periodic table and lanthanides. Specifically, zirconium, titanium, hafnium, neodymium,
L is a ligand coordinating to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and a ligand having a cyclopentadienyl skeleton is samarium or ytterbium. L other than has 1 carbon atom
To 12 hydrocarbon groups, alkoxy groups, aryloxy groups,
A halogen atom, a trialkylsilyl group, SO ₃ R (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom; The valence of the metal.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula [IV] contains two or more groups having a cyclopentadienyl skeleton, two of the groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene. It may be bonded via a substituted alkylene group such as isopropylidene or diphenylmethylene, or a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

The ligands other than those having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyl group. Is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. Examples of the aryloxy group include a phenoxy group.

As the halogen, fluorine, chlorine, bromine,
Examples include iodine. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

When the valence of the transition metal is 4, for example, the compound represented by the general formula [IV] is more specifically represented by the following general formula [IV ']. R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [IV '] (In the general formula [IV'], M is zirconium, titanium, hafnium, neodymium, samarium or ytterbium, and R ¹ is cyclopentane A group having a dienyl skeleton; R ² , R ³ and R ⁴ represent a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, Alkylsilyl group,
SO ₃ R or a hydrogen atom, a is an integer of 1 or more, and a + b + c + d = 4. In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the general formula [IV ′] is a group having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopentadienyl A transition metal compound which is a group having a skeleton is preferably used.
These groups having a cyclopentadienyl skeleton are substituted with alkylene groups such as ethylene and propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or substituted dimethylsilylene, diphenylsilylene, and methylphenylsilylene groups. They may be bonded via a silylene group or the like. R ³ and R ⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R, or a hydrogen atom. It is. Hereinafter, specific examples of the transition metal compound in which M is zirconium will be described.

Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (Fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene Bis (indenyl) zirconium bis (methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonate),
Ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methyl (Cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium Bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydro (Indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclo) (Pentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) ) Phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclope (Antadenyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium , Bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonate),
Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadiene) (Enyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) dimethyl zirconium, bis (ethylcyclopenta Dienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride,
Bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride,
Bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium Dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples of the transition metal compound, the disubstituted cyclopentadienyl ring has 1,2- and 1,2-
Including 3-substituted, tri-substituted includes 1,2,3- and 1,2,4-substituted. Alkyl groups such as propyl and butyl are
It includes isomers such as n-, i-, sec- and tert-.

In the present invention, a transition metal compound in which the zirconium metal is replaced with a titanium metal, a hafnium metal, a neodymium metal, a samarium metal or a ytterbium metal in the above-mentioned zirconium compound may be used.

The organoaluminum oxy compound used for forming the catalyst (b) in the present invention may be a conventionally known aluminoxane.
A benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-87-87 may be used.

The conventionally known aluminoxane can be prepared, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as trialkylaluminum is directly reacted with water, ice or water vapor in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover as a hydrocarbon solution.

(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for preparing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trialkyl aluminum such as trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum Chloride, diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum is particularly preferred. Further, isoprenyl aluminum represented by the following formula [XI] can be used as the organic aluminum compound.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [XI] (where x, y and z are positive numbers and z ≧ 2x) Such organic aluminum compounds are used alone or in combination.

Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons,
A hydrocarbon solvent such as an alicyclic hydrocarbon halide, especially a chlorinated product or a brominated product, may be used. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound that can be used in the present invention can be prepared by a method of contacting an aluminoxane solution with water or an active hydrogen-containing compound, or by using the above-mentioned organoaluminum compound and water. Can be obtained by, for example, a method of bringing them into contact. Such a benzene-insoluble organic aluminum oxy compound has an Al component soluble in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble in benzene. Or it is hardly soluble.

The above-mentioned organoaluminum oxy compound (B) is usually commercially available or handled as a toluene solution. In addition, such an organic aluminum oxy compound (B) may contain a small amount of an organic compound component of a metal other than aluminum.

As the organoaluminum compound used as necessary to form the catalyst (b) in the present invention, the same compounds as the above-mentioned organoaluminum compounds are used.

In the present invention, the copolymerization reaction of ethylene, a cyclic olefin represented by the above formula [I] or [II] and, if necessary, an α-olefin having 3 or more carbon atoms is carried out by a hydrocarbon solvent and And / or in a cyclic olefin as described above.

Such hydrocarbon solvents include, for example, aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. And the like.

These solvents can be used alone or as a mixture. The above copolymerization reaction is preferably performed by a continuous method. At that time, the soluble vanadium compound (or transition metal compound) supplied to the polymerization reaction system
Is usually 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound (or transition metal compound) in the polymerization reaction system.

Further, the ratio of the aluminum atom to the vanadium atom (or the transition metal atom) in the polymerization reaction system (A
1 / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20.

The above-mentioned catalyst components are usually
It is supplied to the polymerization reaction system after being diluted with the above hydrocarbon solvent or cyclic olefin. Here, the soluble vanadium compound (transition metal compound) is desirably diluted to the above concentration range, but the organoaluminum compound is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system, and the polymerization reaction A method of supplying the system is adopted.

When producing a cyclic olefin random copolymer, the concentration of the soluble vanadium compound (transition metal compound) in the copolymerization reaction system is usually 0.01% as vanadium atom (transition metal atom). -5 mmol / l, preferably 0.05-3 mmol / l.

When the metallocene catalyst (b) is used, a transition metal compound of group IVB or lanthanide [A] containing a ligand having a cyclopentadienyl skeleton
And the organoaluminum oxy compound and the organoaluminum compound may be separately fed into the polymerization vessel or may be brought into contact outside the polymerization vessel in advance.

The concentration of the group IVB or lanthanide transition metal compound [A] is 10 ^-8 to 10 ^-2 mol / l, preferably 10 ^-6 to 10 ^-3 mol / l.
The amount of the organoaluminum oxy compound is 1 to 10 ⁴ equivalents of the transition metal compound, and the amount of the organoaluminum compound used as necessary is preferably 0.01 to 100 equivalents of the amount of the organoaluminum oxy compound. .

Such a copolymerization reaction of ethylene and a cyclic olefin is carried out at -50 to 100 ° C, preferably at -30 ° C.
-80 ° C, more preferably at a temperature of -20-60 ° C.

The reaction time (in the case of a continuous polymerization reaction, the average residence time of the polymerization reaction mixture) for carrying out the above-mentioned copolymerization reaction varies depending on the type of the polymerization raw material, the concentration of the catalyst component and the temperature. , Usually 5 minutes to 5 hours,
Preferably, it is in the range of 10 minutes to 3 hours.

The pressure at the time of carrying out the above copolymerization reaction is as follows:
Usually more than 0 and 50 kg / cm ² , preferably more than 0 and 2
It is 0 kg / cm ² . Further, in performing the above copolymerization reaction, a molecular weight regulator such as hydrogen can be used in order to adjust the molecular weight of the obtained copolymer.

In producing the cyclic olefin random copolymer, the molar ratio of ethylene / [(cyclic olefin) + (α-olefin)] supplied to the reaction system is usually 90/10 to 10/90, Preferably 20 / 80-
85/15 and the molar ratio of cyclic olefin / α-olefin is from 98/2 to 50/50, preferably 95/50.
/ 5 to 70/30.

When the copolymerization reaction of ethylene, a cyclic olefin, and an α-olefin having 3 or more carbon atoms is performed as described above, a solution of a cyclic olefin random copolymer is obtained. The concentration of the cyclic olefin-based random copolymer contained in the obtained copolymer solution is usually 2.0 to 300 g / L, preferably 1 to 300 g / L.
It is in the range of 0-100 g / l.

In the present invention, the polymerization reaction solution thus obtained is mixed with an alcohol-containing water containing an alcohol in an amount of 5 to 90% by volume in an amount of 1 to 33 parts by volume with respect to 100 parts by volume of the polymerization reaction solution. Parts, preferably 1 to 20 parts by volume,
More preferably, it is added in an amount of 2 to 5 parts by volume and stirred. This stirring is preferably performed using a strong stirrer such as an emulsifier having a large shearing force. This stirrer may be an internal circulation type or an external circulation type. The stirring time varies depending on the stirring device,
Industrially, it is about 0.5 to 10 minutes. The temperature of the polymerization reaction solution at the time of stirring is 20 to 200 ° C., preferably 4 to 200 ° C.
It is desirable that the temperature is about 0 to 100 ° C.

As the alcohols constituting the alcohol-containing water, specifically, methanol, ethanol, isopropyl alcohol, isobutyl alcohol,
2-ethylhexyl alcohol, ethylene glycol and the like are used.

Next, the polymerization reaction solution 100 containing the alcohol-containing water was added to the polymerization reaction solution 100.
50 to 500 parts by volume, preferably 100 parts by volume
Add ~ 200 parts by volume of water and stir.

The stirring may be performed using a strong stirrer as described above, or may be performed using a stirrer having a smaller shearing force than the above-described stirrer. The temperature of the polymerization reaction solution during this stirring is from 20 to 200 ° C, preferably from 40 to 10 ° C.
The temperature is preferably about 0 ° C. The stirring time is 0.5
About 20 minutes.

When the polymerization reaction solution to which water has been added and agitated in this way is centrifuged or separated by gravity (to stand still) to separate it into an oil layer and an aqueous layer, the catalyst residue is efficiently transferred to the aqueous layer. From the cyclic olefin polymer solution.

In the present invention, the above-described demineralization treatment for removing the catalyst residue, particularly the treatment of adding water to the polymerization reaction solution and stirring may be carried out once or more as necessary. Furthermore, in the present invention, an alkali such as sodium hydroxide can be added to the polymerization reaction solution as needed when performing the above-described demineralization treatment.

In the present invention, the catalyst component is removed from the polymer solution by the above-described catalyst removal operation. Although a cyclic olefin random copolymer can be obtained from the cyclic olefin random copolymer solution to which the catalyst removal operation as described above has been added in accordance with a conventional method, in the present invention, a copolymer is obtained from the above copolymer solution. The method is not particularly limited.

For example, a copolymer is obtained from the above copolymer solution by the following method. A method of precipitating and recovering the copolymer by a method such as distillation of the solvent in the above copolymer solution, or a method in which the copolymer solution is heated to high pressure and high pressure and then flashed under normal pressure. A method in which the polymer solution is poured into a polar solvent such as acetone to precipitate and separate the copolymer is used.

The cyclic olefin-based random copolymer thus obtained contains substantially no residual catalyst.
This cyclic olefin random copolymer is amorphous or crystalline, but if the cyclic olefin random copolymer is amorphous, the cyclic olefin random copolymer has excellent transparency. I have.

The cyclic olefin random copolymer obtained by the method for producing a cyclic olefin random copolymer according to the present invention usually has a glass transition point (Tg) of 1 or more.
The temperature ranges from 0 to 260 ° C, preferably from 20 to 200 ° C.

[0114]

According to the present invention, ethylene, a cyclic olefin and, if necessary, an α-olefin having 3 or more carbon atoms are converted into a hydrocarbon solvent in the presence of a catalyst comprising a soluble vanadium compound and an organoaluminum compound. and/
Or after producing a cyclic olefin-based random copolymer by copolymerization in a liquid phase composed of this cyclic olefin,
Since the alcohol-containing water is added to the polymerization reaction solution and stirred, and then the water is added and stirred, a cyclic olefin-based random copolymer substantially containing no catalyst residue can be obtained.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. The chlorine content (Cl content) in the polymer was determined by burning the polymer by an oxygen flask method and quantifying the generated HCl by an ion chromatography method. The vanadium (transition metal) and aluminum contents in the polymer were determined by burning the polymer in a platinum container and removing ash from KHSO.
After melting with _4, it was dissolved in dilute sulfuric acid and quantified by plasma emission spectrometry.

[0116]

Example 1 [Catalyst preparation] VO (OC ₂ H ₅ ) Cl ₂ was diluted with cyclohexane to prepare a vanadium catalyst having a vanadium concentration of 6.7 mmol / L-cyclohexane.

Ethyl aluminum sesquichloride (Al
(C ₂ H ₅₎ the _1.5 Cl _1.5) was diluted with cyclohexane, the aluminum concentration is 107 mmol / l - was prepared organoaluminum compound catalyst is hexane. [Polymer] Cyclic olefin random copolymer [B]
A stirring type polymerization apparatus (inner diameter 500 mm, reaction volume 100 l) with, successively, tetracyclic as ethylene and cyclic olefin [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter simply It may be called tetracyclododecene.)
By carrying out a copolymerization reaction with When performing this copolymerization reaction, the vanadium catalyst prepared by the above method is used in an amount such that the concentration of the vanadium catalyst with respect to cyclohexane in the polymerization vessel used as the polymerization solvent is 0.6 mmol / liter. Supplied within. In addition, the vanadium catalyst was diluted with cyclohexane as a polymerization solvent in advance so that the concentration of the vanadium catalyst immediately before being supplied to the polymerization vessel was less than twice the dilution factor of the catalyst concentration in the polymerization vessel. It was supplied inside the vessel.

Ethyl aluminum sesquichloride, an organoaluminum compound, was supplied into the polymerization vessel in such an amount that Al / V = 8.0. The polymerization temperature is 11 ° C.
The copolymerization reaction was carried out continuously at a polymerization pressure of 1.8 kg / cm ² G. [Deashing] The cyclic olefin random copolymer [B] solution extracted from the polymerization vessel is put into a strong stirrer (Homomix Line Flow ^™ manufactured by Tokushu Kika Co., Ltd., actual volume: 12 liters).
Liters / hour and at the same time boiler water at 60 ° C. is fed into the powerful stirrer at a rate of 0.7 liters / hour.
Pure methanol was supplied at a rate of 2.6 liter / hour, and the mixture was vigorously stirred.

Next, the polymerization reaction solution, which was vigorously stirred,
℃ boiler water in an amount as shown in Table 1 and a strong mixer (Mitsui Miike Kakoki Konactor ^TM actual volume 30 liters)
And stirred and mixed, and then separated into an oil phase and an aqueous phase by a stationary separator.

The separated oil phase (polymerization reaction solution), boiler water and 4% sodium hydroxide solution were mixed in an amount as shown in Table 1 in a strong mixer (Mitsui Miike Kakoki Konitata ^™, actual volume 50 liters). ), And the mixture was stirred and mixed, and then separated into an oil phase and an aqueous phase by a stationary separator.

The separated oil phase was supplied to a strong mixer in the same manner as described above, and the mixture was stirred and mixed, and then separated into an oil phase and an aqueous phase by a stationary separator. The amount of residual vanadium, the amount of residual aluminum and the amount of residual chlorine contained in the obtained cyclic olefin random copolymer were measured.

Table 1 shows the results.

[0123]

Example 2 The procedure of Example 1 was repeated except that the amount of the polymerization solution supplied to the high intensity stirrer was changed as shown in Table 1.

Table 1 shows the results.

[0125]

Comparative Example 1 In Example 2, boiler water was not supplied to the high intensity stirrer, and the residence time in the high intensity stirrer was shown in Table 1.
Example 1 was carried out in the same manner as in Example 1 except for changing as shown in FIG.

Table 1 shows the results.

[0127]

[Table 1]

Continuation of the front page (56) References JP-A-4-45103 (JP, A) JP-A-4-45101 (JP, A) JP-A-3-258816 (JP, A) JP-A-62-215611 (JP) , A) JP-A-62-241912 (JP, A) JP-A-6-228236 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/69 C08F 210/00-210/18 C08F 232/00-232/08 C08F 6/08

Claims (1)

(57) [Claims] (1) ethylene (a) and (b) a compound represented by the following formula [I] or [II]: (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each Independently
A hydrogen atom, a halogen atom or a hydrocarbon group; R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond; And R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom , A hydrocarbon group or an alkoxy group, and the carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or the number of carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic group. (Which may form a ring) and at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the formula (c), and if necessary, at least one of α-olefins having 3 or more carbon atoms. And (a) a soluble vanadium compound and an organic A catalyst comprising a minium compound or a transition metal compound of a group IV or lanthanide containing a ligand having a (ii) cyclopentadienyl skeleton, an organoaluminum oxy compound and, if necessary, an organoaluminum compound In the presence of, a cyclic olefin-based random copolymer is produced by copolymerization in a liquid phase composed of a hydrocarbon solvent and / or the cyclic olefin, and then the polymerization reaction solution contains 5 to 5 alcohols.
Alcohol-containing water contained in an amount of 90% by volume is added and stirred in an amount of 1 to 33 parts by volume with respect to 100 parts by volume of the polymerization reaction solution. A method for producing a cyclic olefin random copolymer, comprising adding and stirring in an amount of 500 parts by volume.