JP2001106730A - Production of cyclic olefin-based copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cyclic olefin-based copolymer for improving its hue and light transmittance without harming its transparency, heat resistance, heat-aging resistance, chemical resistance, solvent resistance, dielectric characteristics and mechanical properties. SOLUTION: This method for producing a cyclic olefin-based copolymer by copolymerizing an α-olefin having >=2 number of carbon atoms with a cyclic olefin having a specific structure in the presence of a polymerization catalyst and a hydrocarbon-based solvent in a polymerization reactor, and separating un-reacted monomers, the catalyst and the solvent from the polymerization reaction liquid is provided by re-using the solvent treated with the removal of impurities containing unsaturated bond in the above separated solvent and returned into the polymerization reactor. The method for the removal treatment of the impurities containing unsaturated bond is preferably selected from a hydrogenation method, rectification method and adsorption treatment method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a cyclic olefin-based copolymer. More specifically, a cyclic olefin copolymer having excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and particularly excellent hue and light transmittance. The present invention relates to a method for manufacturing a united product.

[0002]

2. Description of the Related Art An α-olefin / cyclic olefin copolymer (referred to as a cyclic olefin copolymer in the present invention) obtained by copolymerizing an α-olefin and a cyclic olefin has transparency, heat resistance and weather resistance. It is a synthetic resin having excellent properties, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and is widely used in various fields.

[0003] The cyclic olefin copolymer is generally produced by copolymerizing an α-olefin and a cyclic olefin in a hydrocarbon solvent in the presence of a polymerization catalyst. That is, the production process of the cyclic olefin-based copolymer is a polymerization process in which the α-olefin of the reaction monomer and the cyclic olefin, a solvent, and a catalyst are supplied to the reactor to carry out copolymerization, and the unreacted α-olefin It consists of a monomer removal step for removing olefins, a deashing step for removing catalyst, a separation and recovery step for separating and recovering the solvent, and a commercialization step for obtaining products. Here, since the unreacted cyclic olefin has a boiling point close to that of the solvent, it is recovered in the separation and recovery step.

In the production process of this cyclic olefin-based copolymer, the recovered unreacted monomer and solvent are usually returned to the polymerization reactor and reused. Therefore, impurities gradually accumulate in unreacted monomers and solvents, and when polymerization is carried out using the monomers and solvents in which these impurities are accumulated, the polymerization reactivity changes and the resulting cyclic olefin copolymers change. There is a problem that physical properties such as transparency, hue, light transmittance and the like of the coalescence are deteriorated.

[0005] Many proposals have been made on a method for purifying a solvent for olefin polymerization. For example, Japanese Patent Publication No. 49-38243 discloses a method for purifying a solvent for ethylene polymerization, which comprises subjecting a catalyst carrying a Group VIII metal to a hydrogenation treatment, followed by treatment with an ion exchange resin. JP-A-3-31304 describes a method of purifying a polymerization solvent through a washing step, a distillation step, an adsorption step, and a hydrogenation step. All of these studies were conducted on a purification method for a solvent for ethylene polymerization, mainly from the viewpoint of catalytic activity. However, for the cyclic olefin-based copolymer according to the present invention, purification was performed with particular emphasis on its hue and light transmittance. No method is disclosed.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, 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 properties. To provide a method for producing a cyclic olefin copolymer in order to improve the hue and light transmittance without impairing the mechanical properties of the above.

[0007]

According to the present invention, an α-olefin having 2 or more carbon atoms and a cyclic olefin represented by the following general formula (I) or (II) are prepared by polymerizing a polymerization catalyst with a hydrocarbon-based compound. In the method of producing a cyclic olefin-based copolymer by separating an unreacted monomer, a catalyst and a solvent from the polymerization reaction solution in the presence of a solvent and copolymerizing in a polymerization reactor, A method for producing a cyclic olefin-based copolymer is provided, wherein the solvent from which the unsaturated bond-containing impurities have been removed is returned to the polymerization reactor and reused.

[0008]

Embedded image (In the formula, n is 0 or 1, m is 0 or an integer of 1 or more, 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 ^{1 5} to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, and also monocyclic or polycyclic have a double bond good, and R ¹ is ⁵ and the R ^{1 6,} or R ^{1 7} and R ^{1 8} and in may form an alkylidene group.)

[0009]

Embedded image (Where p and q are 0 or an integer of 1 or more;
And n is 0, 1 or 2, each R ¹ to R ^{1 9} independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group,
Alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ^{1 0} are attached,
The carbon atom to which R ^{1 3} or R ^{1 1} is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when the ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form a monocyclic or polycyclic aromatic ring bonded to each other. ).

According to the present invention, α having 2 or more carbon atoms is used.
An olefin and a cyclic olefin represented by the above general formula (I) or (II) are copolymerized in a polymerization reactor in the presence of a polymerization catalyst and a hydrocarbon-based solvent; In the method for producing a cyclic olefin-based copolymer by separating the α-olefin and the cyclic olefin of the reaction monomer, the catalyst and the solvent, the cyclic olefin in which the unsaturated bond-containing impurities in the separated cyclic olefin have been removed, The present invention provides a method for producing a cyclic olefin copolymer, which is returned to a polymerization reactor and reused.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a cyclic olefin copolymer according to the present invention will be described in detail below. The cyclic olefin-based copolymer according to the present invention comprises: an α-olefin having 2 or more carbon atoms and a cyclic olefin represented by the following general formula (I) or (II), in the presence of a polymerization catalyst and a hydrocarbon-based solvent. Below is a copolymer obtained by copolymerization in a polymerization reactor.

Specific examples of the α-olefin having 2 or more carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
-Carbon number 2 such as heptene, 1-octene and 1-decene
To 20 α-olefins. Of these, ethylene and propylene are preferred from the viewpoint of polymerization activity and the molecular weight of the resulting polymer, and ethylene is particularly preferred. These may be used alone or in combination of two or more.

The cyclic olefin used in the present invention is represented by the following general formula (I) or (II).

Embedded image

In the above formula (I), n is 0 or 1,
m is 0 or an integer of 1 or more, and q is 0 or 1. When q is 1, R ^a and R ^b are each independently an atom or a hydrocarbon group shown below, and q
Is 0, the respective bonds are combined to form a 5-membered ring.

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,
It is a bromine atom or an iodine atom.

The hydrocarbon groups each independently 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. And the aromatic hydrocarbon group includes a phenyl group and a naphthyl group.
These hydrocarbon groups may be substituted with a halogen atom. In addition the above formula (I), the attached R ^{1 5} to R ¹⁸ are each (jointly with each other) may form a monocyclic or polycyclic, moreover, monocyclic or formed in this manner The polycyclic ring may have a double bond.

[0017]

Embedded image In the above formula (II), p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2. Also R ¹ ~
R ^{1 9} are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

The halogen atom has the same meaning as the halogen atom in the formula (I). As the hydrocarbon group, each independently represents an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms,
15 cycloalkyl groups or aromatic hydrocarbon groups. 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. A cyclohexyl group is mentioned, and an aromatic hydrocarbon group is 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. These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0020] Here, the carbon atom to which R ⁹ and R ^{1 0} is attached, the carbon atom to which R ^{1 3} carbon atoms or R ^{1 1} are bonded is bonded, directly or number of carbon atoms 1 to
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are linked via an alkylene group, a group represented by R ⁹ and R ^{1 3} is, or a group represented by R ^{1 0} and R ^{1 1,} together jointly, a methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or propylene group _{(-CH 2 CH 2 CH 2 -} ) to form one alkylene group of the.

Furthermore, when ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form an aromatic ring bonded to a monocyclic or polycyclic one another . As monocyclic or polycyclic aromatic ring in this case, for example, R ¹ as described below ⁵ and R ^{1 2}
Is a group further forming an aromatic ring.

[0022]

Embedded image Here, q has the same meaning as q in the formula (II).

The cyclic olefin represented by the above formula (I) or (II) will be more specifically illustrated below.
As an example,

Embedded image (In the above general formula, the numbers 1 to 7 indicate the position numbers of carbon atoms) and a derivative obtained by substituting a hydrocarbon group for the compound. No.

As the substituted hydrocarbon group, 5-methyl, 5,
6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5-phenyl, 5-benzyl, 5-tolyl, 5- (ethyl Phenyl), 5-
(Isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), and 5,6-diphenyl.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a -
Bicyclo [2.2.1] -2-heptene derivatives such as hexahydroanthracene can be exemplified.

In addition, tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and other tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives, tricyclo [4.4.0.1
^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1 ^2,5 ]
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as -3-undecene,

Embedded image In tetracyclo shown [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, and this hydrocarbon group include derivatives substituted.

As the hydrocarbon group, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10 -Dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl
-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,1
2-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8
-Ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-
n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8 -Isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-
Isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-
Fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl),
8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), 5,6-diphenyl and the like are exemplified. be able to.

[0028] Furthermore, - tetracyclo such (cyclopentadiene acenaphthylene adduct) and adduct of cyclopentadiene [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5 .1
^9,12 .0 ^8,13] -3-pentadecene and its derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3 , 6.0} 2,7.0 ^9,14 ]-
4-hexadecene and its derivatives, hexacyclo [6.6.
1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene and its derivatives, heptacyclo ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3, ⁸ .0
^12,16 ] -5-Eicosene and its derivatives, heptacyclo
^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- eicosene and its derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7. 1
^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene and its derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0
^3,8 .0 ^{12, 17} ] -5-docosene and its derivatives, nonacyclo
^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 2, 10 .0 3,8 .0 12,21 .0
^14,19] -5-pentacosene and derivatives thereof.

Specific examples of the above formula (I) or formula (II) which can be used in the present invention are as described above. More specific structures of these compounds are described in the applicant's application. And paragraphs [0032] to [0054] of JP-A No. 7-145213, and in the present invention, those exemplified in the above specification may be used as the cyclic olefin of the present invention. it can.

As a method for producing the cyclic olefin represented by the general formula (I) or (II) as described above, for example,
A Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure can be mentioned. These cyclic olefins can be used alone or in combination of two or more.

Next, a method for producing the cyclic olefin copolymer according to the present invention will be described. In the present invention, the above α-olefin having 2 or more carbon atoms and a cyclic olefin,
A catalyst formed from (i) a soluble vanadium compound and an organoaluminum compound in a hydrocarbon solvent, or (ii)
The copolymerization is carried out in the presence of a catalyst formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminum oxy compound.

The soluble vanadium compound forming such a catalyst (i) is specifically represented by the following general formula. VO (OR) aXb or V (OR) cXd In the above formula, R is a hydrocarbon group, and a, b, c, and d are respectively 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, and 2 ≦ a + b ≦ 3. , 0
≤ c ≤ 4, 0 ≤ d ≤ 4, and 3 ≤ c + d ≤ 4.

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-C 4 H 9) 3, VOCl 3 ·
A vanadium compound such as 2OC ₈ H ₁₇ OH is used.
These compounds can be used alone or in combination of two or more.

The above-mentioned soluble vanadium compound can also be used as an electron donor adduct obtained by contacting the following electron donor. Examples of the electron donor used include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides,
Organic acid or inorganic acid esters, ethers, diethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, nitriles, pyridines, isocyanates, etc. Examples include a nitrogen-containing electron donor.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as cumyl alcohol, isopropyl alcohol, and isopropylbenzyl alcohol; C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol; phenol, cresol, xylenol, and ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; and C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone. , Acetaldehyde, propionaldehyde, octylaldehyde,
C2-15 aldehydes such as benzaldehyde, tolaldehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, etc.
18 organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, acid halides having 2 to 15 carbon atoms such as anisic acid chloride, methyl ether,
C2-C20 ethers such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride; ethyl silicate; diphenyldimethoxysilane Acid amides such as alkoxysilane, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, etc. Amines, acetonitrile, benzonitrile, nitriles such as trinitrile,
Examples thereof include pyridines such as pyridine, methylpyridine, ethylpyridine, and dimethylpyridine. When preparing an electron donor adduct of a soluble vanadium compound, these electron donors can be used alone or in combination of two or more.

In the present invention, the organoaluminum compound used together with the soluble vanadium compound in forming the catalyst (i) has at least one Al-C bond in the molecule. And (b). (a) Formula R ¹ mAl (OR ² ) nHpXq (where R ¹ and R ² are usually hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X is a halogen atom,
m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number satisfying 0 ≦ q <3, and m + n + p + q = 3
Is).

[0037] (b) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, K, R ¹ is as defined above) alkylated complex of Group 1 metal and aluminum represented by.

The following compounds can be specifically exemplified as the organoaluminum compound represented by the formula (a). (1) General formula R ¹ mA1 (OR ² ) 3-m (where R ¹ and R ² are the same as above, m is preferably a number of 1.5 ≦ m <3). (2) Formula R ¹ mAX 3 -m (where R ¹ is the same as above; X is a halogen, and m is preferably a number of 0 <m <3). (3) Formula R ¹ mAH 3 -m (where R ¹ is the same as above. M is preferably 2 ≦ m <
3). (4) Formula R ¹ mAl (OR ² ) n Xq (where R ¹ and R ² are the same as above; X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
Is).

As the organoaluminum compound represented by the formula (a), more specifically, the following compounds can be exemplified. Examples of the organoaluminum compound represented by (1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum Sesquietoxide,
Butyl sesquichloride butoxide, and R ¹ _2.5 A
Examples thereof include partially alkoxylated alkyl aluminum having an average composition represented by l (OR ² ) _{0.5 and the} like.

Examples of the organoaluminum compound represented by (2) include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkyls such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Aluminum sesquihalide; alkyl aluminum partially halogenated such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide;

Examples of the organoaluminum compound represented by (3) include dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and partially hydrogenated alkylaluminums such as ethylaluminum dihydride and propylaluminum dihydride. Can be mentioned.

As the organoaluminum compound represented by (4), there can be mentioned partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Further, a compound similar to the compound represented by the formula (a), for example, an oxygen atom or a nitrogen atom,
An organic aluminum compound in which the above aluminum is bonded may be used. As such compounds, specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl
(C ₄ H ₉ ) ₂ and (C ₂ H ₅ ) ₂ AlN (C ₆ H ₆ ) OAl (C ₂ H ₅ ) ₂ .

The compounds belonging to the above formula (b) include:
LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. Of these, alkyl aluminum halides, alkyl aluminum dihalides, and mixtures thereof are particularly preferred.

Next, (ii) Periodic Table IV used in the present invention
A catalyst formed from a metallocene compound of a transition metal selected from Group B and an organoaluminum oxy compound will be described. The metallocene compound of a transition metal selected from Group IVB of the periodic table is specifically represented by the following formula (c). MLx… (c)

In the formula (c), M is a transition metal selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, and x is the valence of the transition metal.
L is a ligand coordinating to the transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and a ligand having this cyclopentadienyl skeleton May have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, n-,
i-, sec-, t-butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group , Pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethyl Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as butylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and further indenyl group, 4,5,6,7-tetrahydroindenyl group , Fluoreni And the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ Ra
), A halogen atom or a hydrogen atom (where Ra
Is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like, and more specifically, a methyl group, an ethyl group, and an n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, cycloalkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group and the like Examples include an aryl group such as an alkyl group, a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neophyl group.

As the alkoxy group, a methoxy group,
Examples include ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, pentoxy, hexoxy, octoxy and the like.

Examples of the aryloxy group include a phenoxy group. Examples of the sulfonic acid-containing group (—SO ₃ Ra) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

The metallocene compound represented by the above formula (c) is, for example, when the valence of the transition metal is 4,
Specifically, it is represented by the following equation (d). R ² kR ³ lR ⁴ mR ⁵ nM (d) In the formula (d), M is the above-mentioned transition metal, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ and R ^{3 4} and R ⁵ are independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the above formula (c). k is an integer of 1 or more, and k + 1 + m + n = 4.

The following are examples of metallocene compounds in which M is zirconium and which contains at least two ligands having a cyclopentadienyl skeleton. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentane Dienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) )
Zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (sec-butylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) Zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (Indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) di Ruconium ethoxycyclolide, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) ) Zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadiene) Enyl) zirconium bis (trifluoromethanesulfonato), bis (butylcyclopentadienyl)
Zirconium bis (trifluoromethanesulfonate),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-ethylcyclopentadi (Enyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (Trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride, bis (1-
Methyl-3-hexylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-octylcyclopentadienyl) zirconium dichloride, bis (1-ethyl
-3-butylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methyl Examples thereof include benzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, and bis (methylcyclohexylcyclopentadienyl) zirconium dichloride. A compound in which the above 1,3-position substituted cyclopentadienyl group is substituted by a 1,2-position substituted cyclopentadienyl group can also be used.

In the above formula (d), at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton;
A bridge-type metallocene compound in which the two groups having a cyclopentadienyl skeleton are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like can also be illustrated. At this time,
R ⁴ and R ⁵ are each independently the same as L except for the ligand having a cyclopentadienyl skeleton described in the formula (c).

Examples of such bridge-type metallocene compounds include the following compounds. Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene bis (indenyl) zirconium bis (methanesulfonato), ethylene bis (indenyl) zirconium bis (P-toluenesulfonato), ethylenebis (indenyl) zirconiumbis (p-chlorobenzenesulfonato) and the like.

Although a zirconocene compound has been described above as an example of a metallocene compound, a compound in which zirconium is replaced with titanium or hafnium can also be used.

These compounds may be used alone,
Two or more kinds may be used in combination. It may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.
In the present invention, the metallocene compound is preferably used after being diluted with a hydrocarbon solvent.

The above-mentioned metallocene compound can be used together with a carrier compound by bringing it into contact with a particulate carrier compound. As carrier compounds, SiO ₂ , Al ₂ O
_{3, B 2 O 3, MgO} , ZrO 2, CaO, TiO 2, ZnO,
Inorganic carrier compounds such as ZnO ₂ , SnO ₂ , BaO, and ThO;
Polyethylene, polypropylene, poly-1-butene, poly-4
Resins such as -methyl-1-pentene and styrene-divinylbenzene copolymer can be used. These carrier compounds can be used as a mixture of two or more kinds.

In the present invention, as the metallocene compound, a zirconocene compound in which the central metal atom is zirconium and which has a ligand having at least two cyclopentadienyl skeletons is preferably used.

Next, the organoaluminum oxy compound used for forming the catalyst (ii) in the present invention will be described. The organic aluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organic aluminum oxy compound.

Such a conventionally known aluminoxane is specifically represented by the following general formula.

Embedded image (In the above formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group,
Is an integer of 2 or more, preferably 5 to 40. )

Here, this aluminoxane has the formula (OA)
l (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) wherein R ¹ and R ² are the same hydrocarbon groups as R And R ¹ and R ² represent different groups.].

The conventionally known aluminoxane is produced, for example, by the following method, and is usually recovered as a solution of an aromatic hydrocarbon solvent. (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 trialkylaluminum to an aromatic hydrocarbon solvent in which is suspended and reacting the resulting mixture to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice or steam) is allowed to directly act on an organoaluminum compound such as a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover the solution as an aromatic hydrocarbon solvent solution. Among these methods, it is preferable to adopt the method (1).

As the organoaluminum compound used for producing the aluminoxane solution, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, Tri sec-butyl aluminum, tri tert
-Butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum,
Trialkyl aluminum such as tridecyl aluminum, tricyclohexyl aluminum and tricyclooctyl aluminum, dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride, dialkyl aluminum halide such as diethyl aluminum hydride and diisobutyl aluminum hydride Examples thereof include hydride, dimethylaluminum methoxide, dialkylaluminum alkoxide such as diethylaluminum ethoxide, and dialkylaluminum aryloxide such as diethylaluminum phenoxide. Of these, trialkylaluminum is particularly preferred.

As the organoaluminum compound, isoprenylaluminum represented by the following general formula can also be used. _{(i-C 4 H 9)} xAly (C 5 H 11) z ( wherein, x, y, z are each a positive number, and z ≧ 2x). The above-mentioned organoaluminum compounds are used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention can be prepared, for example, 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. It can be obtained by a method of contact.

[0067] In benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D1220), the absorbance at around 1260 cm ^-1 ( D1260) and the ratio (D1260 / D1220) is 0.09.
Or less, preferably 0.08 or less, particularly preferably 0.08 or less.
It is desirable to be in the range of 4-0.07.

The benzene-insoluble organoaluminum oxy compound as described above is presumed to have an alkyloxyaluminum unit represented by the following formula.

Embedded image In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. As such a hydrocarbon group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, Examples thereof include a cyclooctyl group. Of these, a methyl group and an ethyl group are preferred, and a methyl group is particularly preferred.

The benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

Embedded image In the formula, R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms,
A 12 alkoxy group, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. The R
⁸ and R ⁷ in the above formula represent different groups.

When an aluminum oxyaluminum unit is contained, the organic aluminum oxy group having an alkyloxyaluminum unit containing the alkyloxyaluminum unit in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more. Compounds are desirable.

The organoaluminum oxy compound used as a catalyst in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. Further, the organic aluminum oxy compound can be used by being supported on the above-mentioned carrier compound.

In the present invention, the above-mentioned catalyst (i) or
In the presence of (ii), an α-olefin having 2 or more carbon atoms and a cyclic olefin are copolymerized in a hydrocarbon solvent. Examples of such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof, cyclohexane, methylcyclopentane, and alicyclic hydrocarbons such as methylcyclohexane and the like. Halogen derivatives, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used.
These solvents may be used as a mixture.

In the present invention, the copolymerization is preferably carried out in the co-presence of the above-mentioned hydrocarbon solvent. Among them, cyclohexane-hexane, cyclohexane-heptane, cyclohexane-pentane, toluene-hexane, toluene-heptane, It is preferable to carry out the reaction in the presence of a mixed solvent such as toluene-pentane.

The copolymerization is carried out by a batch method or a continuous method, but is preferably carried out by a continuous method. The concentration of the catalyst used at this time is as follows. When the catalyst (i) is used, the amount of the soluble vanadium compound in the polymerization system is usually 0.01 to 5 mmol, preferably 0.05 to 3 mmol, and The aluminum compound is supplied in an amount of 2 or more, preferably 2 to 50, and more preferably 3 to 20 in a ratio of aluminum atom to vanadium atom (Al / V) in the polymerization system. The soluble vanadium compound is 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system (when the copolymerization is carried out by a continuous method). Is desirably supplied at a concentration of

The soluble vanadium compound and the organoaluminum compound are usually each a liquid monomer and / or a liquid monomer.
Alternatively, it is diluted with the above-mentioned hydrocarbon solvent and supplied to the polymerization system. At this time, it is desirable that the soluble vanadium compound is diluted to the above-described concentration, but the organoaluminum compound is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization system and supplied to the polymerization system. Is desirable.

When the catalyst (ii) is used, the metallocene compound in the polymerization system is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, per liter of the polymerization volume. The amount of the organic aluminum oxy compound is such that the aluminum atom in the organic aluminum oxy compound is usually about 1 to 10000 mol, preferably 10 to 5000 mol, per 1 mol of the transition metal atom in the metallocene compound. Used in quantity.

The copolymerization reaction carried out in the presence of the above-mentioned catalyst (i) or (ii) usually has a temperature of -50 ° C to 1 ° C.
50 ° C., preferably -30 ° C. to 100 ° C., more preferably -20 ° C. to 70 ° C., and the pressure exceeds 0 to 50 kg /
The reaction is carried out under the conditions of cm ² , preferably more than 0 and ２０20 kg / cm ² . The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on the type of monomer used, catalyst concentration, polymerization temperature and the like, but is usually 5 minutes to 5 hours. , Preferably 10 minutes to 3 hours.

In the above copolymerization, the α-olefin having 2 or more carbon atoms and the cyclic olefin are supplied to the polymerization system in such a ratio that a cyclic olefin copolymer having desired physical properties can be obtained. Usually, the α-olefin and the cyclic olefin are present in a molar ratio of 1/10 to 10/1, preferably 1/5.
５5/1. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

When the α-olefin and the cyclic olefin are copolymerized as described above, a solution containing the cyclic olefin copolymer is obtained. In such a solution, the cyclic olefin-based copolymer is usually contained at a concentration of 10 to 500 g / liter and 10 to 300 g / liter.

The cyclic olefin-based copolymer obtained as described above is taken out of the reactor together with the polymerization reaction solution, and an active hydrogen-containing compound is added to inactivate the polymerization catalyst and stop the reaction. Examples of the active hydrogen-containing compound include water, alcohols and the like, and specific examples include methanol, ethanol, 1-propanol and 2-propanol. The amount of these additives is usually 1 to 50 mol per 1 mol of the catalyst.

Next, unreacted α-olefin is distilled off and removed by distilling the reaction solution under reduced pressure. The distillation temperature and pressure are determined in consideration of the α-olefin removal efficiency.

The demineralization is performed by adding water for catalyst extraction. The added water is usually adjusted to a pH to increase the extraction efficiency of the catalyst. The catalyst is removed as wastewater by phase separation.

The oil layer is then separated into a produced polymer and a solvent by flash distillation, and the produced polymer is subjected to a commercialization step to obtain a product of a cyclic olefin copolymer.
The solvent and the like that have been flash distilled are separated into a low-boiling component, a solvent, an unreacted cyclic olefin, and a high-boiling component through a distillation step. In the prior art, the separated solvent and the unreacted cyclic olefin are separated into a polymerization reactor. Was returned and reused. In the continuous production method, a fresh solvent and an unreacted cyclic olefin are added to the polymerization reactor in addition to the recycled solvent and the unreacted cyclic olefin.

The production method of the present invention is characterized in that the separated solvent and / or unreacted cyclic olefin is subjected to a treatment for removing unsaturated bond-containing impurities and recycled to a reactor. In particular, it is preferable that the unsaturated bond-containing impurity to be removed contains a diene compound. This is because, when impurities such as olefins and dienes containing unsaturated bonds, which are presumed to be decomposition products of cyclic olefins, are returned to the polymerization system along with the solvent and unreacted cyclic olefins, the catalyst in the polymerization system Modification occurs to change copolymerizability, or due to copolymerization of dienes, unsaturated bonds remain in the copolymer and the transparency, hue, light transmittance, etc. of the cyclic olefin copolymer It is considered that the characteristics are deteriorated.

The treatment for removing unsaturated bond-containing impurities in the present invention is preferably at least one selected from a hydrogenation reaction method, a precision distillation method, and an adsorption treatment method.
Each processing method is described below.

The hydrogenation treatment can be carried out by contacting a solvent or unreacted cyclic olefin with hydrogen together with a hydrogenation catalyst. As the hydrogenation catalyst, a metal or a compound of nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, and rhenium is used alone or in combination of two or more. Particularly, a metal of rhodium, palladium, platinum, ruthenium, and rhenium is used. Alternatively, it is preferable because the compound can be hydrogenated under mild reaction conditions.

The heterogeneous catalyst can be used as it is as a metal or a metal compound, or supported on a suitable carrier.
As the carrier, activated carbon, silica, alumina, silica-alumina, diatomaceous earth, barium carbonate, calcium carbonate,
Common carriers such as titania, magnesia, zirconia, and silicon carbide are used. In this case, the amount of the metal supported on the carrier is usually in the range of 0.01 to 50% by weight,
Preferably it is 0.05 to 20% by weight. The heterogeneous reaction may be a commonly used method such as a fixed bed, a suspension bed, or a circulation system.

The reaction conditions vary depending on the catalyst to be used, but the temperature and pressure range necessary for hydrogenation of the unsaturated bond in the compound is sufficient, and usually 20 to 200.
° C, within the range of 0.1 to 5 MPa. Even in that range,
In particular, conditions under which the diene compound is selectively hydrogenated are selected. The solvent to be hydrogenated or the unreacted cyclic olefin is usually continuously and continuously supplied downward to a reaction tower filled with a hydrogenation catalyst. The amount of hydrogen to be added is determined according to the amount of the unsaturated group, and is usually used in a molar ratio of 0.1 to 10 times the molar amount of the amount. Unreacted hydrogen is easily separated and removed by gas-liquid separation.

The treatment by the precision distillation method is a method of separating and removing by utilizing a slight difference in volatility between a solvent or an unreacted cyclic olefin and an impurity having an unsaturated bond. Precision distillation is distillation in which the number of theoretical plates is much larger than that of ordinary distillation, and a tray column or packed column having a theoretical plate number of, for example, several tens to several hundreds is used. In the present invention, the component to be separated preferably has a theoretical plate number of 50 or more.

As an adsorption treatment method, an adsorbent capable of selectively adsorbing unsaturated compounds in a liquid phase is used. Specific examples of the adsorbent include bentonite, acid clay, activated clay,
Activated carbon, diatomaceous earth, silica gel, alumina, silica alumina, zeolite, titanium oxide, ion-exchange resin and the like are mentioned. Among these, activated alumina, silica gel and zeolite are preferable. Depending on the physical properties of the adsorbing substance, the type, size, presence or absence of polarity, etc. of the adsorbent can be properly used.

As the adsorption conditions, a temperature and a processing flow rate necessary for adsorbing and removing unsaturated bonds in the compound are selected, and among them, conditions for selectively hydrogenating a diene compound are preferable. The adsorption temperature is usually in the range of 0 to 150 ° C., and the fixed bed space velocity is 0.1 to 10 hr ⁻¹ .
The solvent or unreacted cyclic olefin is usually treated by flowing down an adsorption tower filled with an adsorbent.

In the production method of the present invention, a hydrogenation reaction method,
Any one of a precision distillation method and an adsorption treatment method may be used, or a combination of these treatments may be used. When they are used in combination, a method such as precision distillation method → hydrogenation reaction method, precision distillation method → adsorption treatment method, precision distillation method → hydrogenation reaction method → adsorption treatment method and the like are exemplified. In view of simplification of equipment and simplicity of operation, a hydrogenation reaction method is particularly preferred.

In the present invention, the unsaturated bond-containing impurities include impurities such as olefins and dienes containing an unsaturated bond, which are present in a solvent or an unreacted cyclic olefin, and particularly include diene-based impurities such as cyclopentadiene. The compounds are listed as being excluded. It is desirable that diene such as cyclopentadiene does not remain by the above removal treatment.

[0094]

According to the production method of the present invention, it has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and in particular, hue and light. Cyclic olefin copolymers with excellent transmittance
Since the solvent and the unreacted cyclic olefin can be continuously manufactured while being reused, it is excellent in economy.

[0095]

EXAMPLES (Example 1) [Preparation of catalyst] VO (OC ₂ H ₅ ) Cl ₂ was used as a polymerization catalyst. This was diluted with hexane to prepare a vanadium concentration of 2.5 mol / l-hexane. Ethyl aluminum sesquichloride Al (C ₂ H ₅ ) _1.5 Cl _1.5 as an organic aluminum compound catalyst was diluted with hexane to prepare an aluminum concentration of 1 mol / l-hexane.

[Polymerization] Using a stirrer having a total reaction volume of 36 liters and a polymerization reactor equipped with an external heat exchanger, tetracyclo [4.4.0.1 ^2,5 .
^7,10 ] -3-dodecene (abbreviated as tetracyclododecene)
Was carried out. Using a mixed solution of cyclohexane and hexane as a reaction solvent, the vanadium catalyst prepared by the above method was supplied at a rate such that the concentration of the vanadium catalyst with respect to the solvent in the reactor became 1 mmol / l, and the organoaluminum compound had an atomic ratio Al / V = 10 was supplied to the reactor. Polymerization solvent cyclohexane /
The amount of the hexane mixture supplied was such that the residence time in the reactor was 1 hour, and 1.5 kg / each of ethylene, tetracyclododecene, and hydrogen as a molecular weight regulator were used.
h, 8 kg / h, 3 Nl / h were fed simultaneously to the reactor. As a reaction condition, a continuous solution polymerization reaction was performed at a temperature of 23 ° C. and a pressure of 0.3 MPa (polymerization pressure was maintained with nitrogen gas).

[Deashing] To the polymerization solution continuously withdrawn from the lower portion of the reactor, methanol was added to stop the polymerization reaction, unreacted ethylene was separated, and water and an aqueous sodium hydroxide solution as a pH regulator were added. After addition, the catalyst residue remaining in the polymer was separated into oil and water and removed as waste water. [Desolvation] After the deashed solution was heated and pressurized, it was flashed to separate into a cyclic olefin-based copolymer and a solvent.

[Granulation] The copolymer separated in the desolvation step was melted by an extruder and granulated to obtain a product. [Distillation] The solvent and the like separated in the desolvation step are distilled in a tray column to obtain a high-boiling component containing unreacted tetracyclododecene from the bottom of the column. And the other high-boiling components were separated and the recovered tetracyclododecene was added to the required starting material tetracyclododecene, returned to the reactor, and reused.

[Hydrogenation] The solvent from which the high-boiling components were separated by distillation was charged in a hydrogenation reactor (temperature: 40 ° C.) packed with 1 kg of 0.5% Pd / alumina in a hydrogenation (hydrogenation) catalyst.
/ H. Hydrogen used for hydrogenation was added at 3 g / h to the solvent before being supplied to the hydrogenation reactor. After removing unreacted hydrogen, the solvent after hydrogenation was supplied again to the reactor as a polymerization solvent and reused. By the above method, 10 continuous
Table 1 shows the quality measurement results of the produced cyclic olefin-based copolymer after polymerization for 0 hours.

Comparative Example 1 A cyclic olefin copolymer was produced in the same manner as in Example 1 except that hydrogenation was not performed. Table 1 shows the quality measurement results of the obtained copolymer.

Example 2 The supply amounts of ethylene, tetracyclododecene, and hydrogen to the polymerization reactor were each 1.4.
A cyclic olefin-based copolymer was produced in the same manner as in Example 1 except that the polymerization temperature was 20 kg / h, 8 kg / h, 4 Nl / h, and the polymerization temperature was 20 ° C. Table 1 shows the quality measurement results of the obtained copolymer. Comparative Example 2 A cyclic olefin copolymer was produced in the same manner as in Example 2 except that hydrogenation was not performed. Table 1 shows the quality measurement results of the obtained copolymer.

[0102]

[Table 1]

The method of measuring the quality is as follows. [Measurement method] (1) Amount of unsaturated hydrocarbon (cyclopentane / norfourene) Gas chromatography (HP5890G) manufactured by HEWLETT PACKARD
C). The column used was HP-1 (30 m × 0.
25mm inside diameter). (2) Haze A test piece (45 mm x 45 mm x 2 mm thick) conforming to ASTM D523 molded by an injection molding machine is stored in a desiccator in a thermostatic chamber for 48 hours or more, and then a haze meter (HGM-2DP) manufactured by Suga Corporation. Was measured by

(3) b value The b value was measured with a color difference meter (SQ-300H type) manufactured by Nippon Denshoku Co., Ltd. (4) The Particle sample was dissolved in cyclohexane (3.0 g / l), and the insoluble content was measured by an automatic particle counter in liquid (KL-01) manufactured by RION. Sensor: KS-60 (measurement range 1-40 μm),
Sensor light source: emitting diode, wavelength: 730 nm. (5) Light transmittance Measured based on ASTM D1003. IS55FP manufactured by Toshiba Machine Co., Ltd.
Physical property test piece (130mm × 12mm) molded by A type injection molding machine
0mm x 3mm thickness) with Shimadzu self-recording spectrophotometer (MPS-2000
(Type).

[Brief description of the drawings]

FIG. 1 is a process chart of an example showing a method for producing a cyclic olefin-based copolymer according to the present invention.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Noboru Koga 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture F-term in Mitsui Chemicals, Inc. (reference) 4J011 AA01 AA04 AC01 4J100 AA02P AA03P AA04P AA07P AA15P AA16P AA17P AA19P AA21P AR05Q AR11Q CA04 FA10 FA21 GA22 GB12

Claims (4)

[Claims] 1. A polymerization reactor comprising an α-olefin having 2 or more carbon atoms and a cyclic olefin represented by the following general formula (I) or (II) in a polymerization reactor in the presence of a polymerization catalyst and a hydrocarbon solvent. , And from the polymerization reaction solution, an unreacted monomer,
A method for producing a cyclic olefin-based copolymer by separating a catalyst and a solvent, wherein the solvent in which the unsaturated bond-containing impurities in the separated solvent have been removed is returned to a polymerization reactor and reused. A method for producing a cyclic olefin-based copolymer as follows: (In the formula, n is 0 or 1, m is 0 or an integer of 1 or more, 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 ^{1 5} to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, and also monocyclic or polycyclic have a double bond good, and R ¹ is ⁵ and the R ^{1 6,} or R ^{1 7} and R ^{1 8} and in may form an alkylidene group.) [Chemical Formula 2] (Where p and q are 0 or an integer of 1 or more;
And n is 0, 1 or 2, each R ¹ to R ^{1 9} independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group,
Alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ^{1 0} are attached,
The carbon atom to which R ^{1 3} or R ^{1 1} is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when the ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form a monocyclic or polycyclic aromatic ring bonded to each other. ). 2. A polymerization reactor comprising an α-olefin having 2 or more carbon atoms and a cyclic olefin represented by the above general formula (I) or (II) in a polymerization reactor in the presence of a polymerization catalyst and a hydrocarbon solvent. Wherein the unreacted monomer α-olefin and cyclic olefin, a catalyst and a solvent are separated from the polymerization reaction solution to produce a cyclic olefin copolymer, wherein the unsaturated olefin in the separated cyclic olefin is A method for producing a cyclic olefin copolymer, wherein the cyclic olefin from which the bond-containing impurities have been removed is returned to the polymerization reactor and reused. 3. The cyclic olefin system according to claim 1, wherein the method of removing the unsaturated bond-containing impurities is at least one selected from a hydrogenation reaction method, a precision distillation method, and an adsorption treatment method. A method for producing a copolymer. 4. The method for producing a cyclic olefin copolymer according to claim 1, wherein the unsaturated bond-containing impurity comprises a diene compound.