JPH05230148A - Method for producing cyclic olefin random copolymer - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a method for producing a high yield of a cyclic olefin random copolymer. [Structure] (i) ethylene, (ii) cyclic olefin, and, if necessary, (iii) α-olefin having 3 to 20 carbon atoms, [A] tertiary alkoxy group or β-diketone as a ligand Formed by the soluble vanadium compound and the organoaluminum compound represented by the formula [B] (i-Bu) _n AlCl _3-n (where n is 1.0 to 2.5) (I) ethylene-derived structural unit: 40 to 97 mol%, (ii) cyclic olefin-derived structural unit: 3 to
A method for producing a cyclic olefin-based random copolymer comprising 60 mol% and (iii) a structural unit derived from an α-olefin having 3 to 20 carbon atoms: 0 to 20 mol%. The above (ii) is, for example, Is.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin-based random copolymer, more specifically, a cyclic olefin-based random copolymer capable of producing a cyclic olefin-based random copolymer in a high yield by using a specific catalyst. The present invention relates to a method for producing a random copolymer.

[0002]

BACKGROUND OF THE INVENTION A cyclic olefin random copolymer obtained by copolymerizing ethylene with a specific cyclic olefin is excellent in well-balanced optical properties, mechanical properties, thermal properties, and the like. It is used as an optical material such as and optical fiber.

Such a cyclic olefin-based random copolymer is a cyclic olefin in a hydrocarbon solvent such as toluene, cyclohexane, hexane or heptane 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 bulky cyclic olefin using itself as a solvent.

By the way, in order to obtain the above-mentioned copolymer in a high yield, when the concentration of the copolymer in the polymerization system is increased or an attempt is made to produce a high-molecular weight copolymer, the viscosity of the polymerization system is decreased. In some cases, it became difficult to remove the heat of polymerization, it became difficult to keep the monomer composition in the system uniform, or the transportability of the polymerization solution was lowered. For this reason, it has been difficult in the prior art to produce the above-mentioned copolymer having a uniform composition in a high-concentration polymerization system, in particular, a high-molecular weight copolymer with high productivity.

As one of the measures for solving such a problem, there is a method of increasing the polymerization temperature to reduce the viscosity of the polymerization system. However, when an attempt is made to produce a cyclic olefin-based random copolymer using a catalyst formed from a conventionally used soluble vanadium compound and an organoaluminum compound, there is a problem that the polymerization activity generally decreases when the polymerization temperature rises. It was

Therefore, the copolymerization of ethylene with a specific bulky cyclic olefin is carried out with a high polymerization activity while increasing the concentration of the copolymer in the polymerization system and without the polymerization activity being significantly lowered by the polymerization temperature. Therefore, the advent of a method for producing a cyclic olefin random copolymer having a uniform composition, and particularly a high molecular weight copolymer with a high yield, has been desired. ..

As a result of researching a method for producing a cyclic olefin random copolymer in view of the above-mentioned prior art, the present inventor has found that ethylene and a specific bulky cyclic olefin are co-produced in the presence of a specific catalyst. When polymerized, a cyclic olefin-based random copolymer can be obtained in high yield,
Moreover, it was found that the temperature dependence of the polymerization activity is small,
The present invention has been completed.

[0008]

An object of the present invention is to provide a method for producing a cyclic olefin-based random copolymer capable of producing a cyclic olefin-based random copolymer, which is a copolymer of ethylene and a cyclic olefin, in a high yield. The purpose is to

[0009]

SUMMARY OF THE INVENTION The method for producing a cyclic olefin random copolymer according to the present invention comprises (i) ethylene, (ii) at least one cyclic olefin represented by the following general formula [I] or [II], And (iii) an α-olefin having 3 to 20 carbon atoms, if necessary, [A] a tertiary alkoxy group or β
-A soluble vanadium compound having a diketone as a ligand, and an organoaluminum compound represented by the formula [B] (i-Bu) _n AlCl _3-n (where n is 1.0 to 2.5) It is characterized in that it is copolymerized in a liquid phase in the presence of a catalyst formed from, and the resulting cyclic olefin random copolymer is (i) a structural unit derived from ethylene: 40 to 97 mol% (Ii) a structural unit derived from at least one cyclic olefin represented by the following general formula [I] or [II]: 3 to 60 mol%, and (iii)
It is composed of 0 to 20 mol% of a structural unit derived from an α-olefin having 3 to 20 carbon atoms.

[0010]

[Chemical 3]

[I] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^{1 a} and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are
They may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and with R ^{15 to} R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. ),

[0012]

[Chemical 4]

[II] (In the formula [II], p and q are 0 or 1)
The above integers, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. A carbon atom to which R ⁹ and R ¹⁰ are bonded, and a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded, which represent an atom or group selected from the group consisting of a group and an alkoxy group. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m
When = 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. ).

The soluble vanadium compound [A] having a tertiary alkoxy group or β-diketone as a ligand, and [B] the formula (i-Bu) _n AlCl used in the present invention.
_The catalyst formed from _3-n (wherein n is 1.0 to 2.5) exhibits high polymerization activity when copolymerizing ethylene and a cyclic olefin, but it does not copolymerize ethylene and propylene. When polymerizing, a conventionally known catalyst such as VO
Compared with the catalyst composed of (OEt) Cl ₂ and AlEt _1.5 Cl _1.5, it shows the same degree of polymerization activity.

This means that the polymerization catalyst used in the present invention shows a specific high polymerization activity for the copolymerization of ethylene and cyclic olefin.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a cyclic olefin random copolymer according to the present invention will be specifically described below.

In the present invention, a cyclic olefin-based random copolymer is produced by copolymerizing (i) ethylene, (ii) a cyclic olefin, and optionally (iii) an α-olefin. The (ii) cyclic olefin will be described.

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

[0019]

[Chemical 5]

[I] where n is 0 or 1 in the above formula [I],
m is 0 or a positive integer, and q is 0 or 1.
When q is 1, this ring becomes a 6-membered ring and q is 0.
In the case of, this ring becomes a 5-membered ring.

In the above formula [I], R¹~ R¹⁸Na
Rabini R^aAnd R^bAre each independently a hydrogen atom,
Selected from the group consisting of halogen atoms and hydrocarbon groups
Represents an atom or group. Here, as the halogen atom,
For example, fluorine atom, chlorine atom, bromine atom and iodine source
I can name a child. Further, as the hydrocarbon group,
Independently of each other, usually an alkyl having 1 to 20 carbon atoms.
Group, halogenated alkyl group having 1 to 20 carbon atoms, charcoal
Cycloalkyl groups having 3 to 15 elementary atoms and aromatic carbonization
The hydrogen group can be mentioned as a specific example of the alkyl group.
Are methyl, ethyl, propyl, isopropyl
Group, amyl group, hexyl group, octyl group, decyl group,
Can include dodecyl and octadecyl groups,
Specific examples of the alkyl halide are as described above.
At least some of the hydrogen atoms forming an alkyl group
Is a fluorine atom, chlorine atom, bromine atom or iodine atom
Mention may be made of substituted groups. Also, cycloal
A specific example of the kill group is a cyclohexyl group.
As a specific example of the aromatic hydrocarbon group,
Mention may be made of phenyl and naphthyl groups, which
These groups may have a lower alkyl group. further,
In the above formula [I], R¹⁵And R¹⁶And R ¹⁷And R¹⁸When
But R¹⁵And R¹⁷And R¹⁶And R¹⁸And R¹⁵And R¹⁸When
Or R ¹⁶And R¹⁷And are respectively combined (mutually
Together), may form a monocyclic or polycyclic group
And the mono- or polycyclic ring formed in this way
The group may have a double bond.

Here, examples of the monocyclic or polycyclic group include:
The groups described below can be mentioned.

[0023]

[Chemical 6]

In the above-exemplified groups, the carbon atoms numbered 1 and 2 are the same as R ¹⁵ in the formula [I].
Represents a carbon atom of an alicyclic structure to which the group represented by R ¹⁸ is bonded.

In addition, 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.

[0026]

[Chemical 7]

[II] In the formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2.

R ^{1 to} R ¹⁹ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, or Represents a group. Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or are alkylene groups having 1 to 3 carbon atoms. It may be bound via. That is, when the above two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ cooperate with each other. Methylene group (-CH _2- ), 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. In this case, examples of the monocyclic or polycyclic aromatic ring include R ¹⁵ and R when n = m = 0.
Mention may be made of the groups described below in which ¹² further forms an aromatic ring.

[0030]

[Chemical 8]

In the above formula, q is q in formula [II].
Is the same meaning as. In the formula [II], the halogen atom has the same meaning as the halogen atom in the above formula [I].
Further, here, the aliphatic hydrocarbon group has 1 to 20 carbon atoms.
Or an alkyl halide group having 1 to 20 carbon atoms. Specific examples of the alkyl group include:
Methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group can be mentioned, and specific examples of the halogenated alkyl group are as described above. And a group in which at least a part of hydrogen atoms forming an alkyl group are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Further, specific examples of the alicyclic hydrocarbon group include a cyclohexyl group, and specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. May have a lower alkyl group.

Examples of the cyclic olefins represented by the formulas [I] and [II] include bicyclo [2.2.1] hept-2-ene derivative, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]- 3-dodecene derivative, hexacyclo [6.6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0
^9,14] -4 Heputadensen 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 derivatives, pentacyclo [6.6.1.1 ^3,6 .0 ^2,7. 0 ^9,14 ] -4-
Hexadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-5-heneicosene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.
3.0.1 ^2,5 ] -3-Undecene derivative, pentacyclo [6.5.
1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] -4-Pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo [7.4.0.
1 ^2,5 .1 ^{9 12} .0 ^8,13] -3-pentadecene derivatives, pentacyclo [8.7.0.1.3.6.1 ^10,17 .1 ^{12,1 5.0 2,7} .0 ^11,16] -Four-
Eicosene derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1
^{15 18} .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, pentacyclo ^{[8.4.0.1 2,3 .1 9,12 .0 8,13]} - 3-hexadecene derivative, pentacyclo [8.8.0.1 ^4,7 .1 ^{11, 18.}
1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, Nonashikuro ^{[10.10.1.1 5, 8 .1 14,21 .1} 16,19 .0 2,11 .0 4,9. 0
^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives, bicyclo [2.
2.1] Hept-2-ene derivative, 1.4-methano-1.4.4a.9a-tetrahydrofluorene derivative, 1.4-methano-1.4.4a.5.1
Examples thereof include 0.10a-hexahydroanthracene derivative and cyclopentadiene-acenaphthylene adduct.

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

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

[0050]

[Chemical 25]

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

[0053]

[Chemical 28]

[0054]

[Chemical 29]

[0055]

[Chemical 30]

The above-mentioned (ii) general formula [I] or [I]
The cyclic olefin represented by the formula [I] can be produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction.

These (ii) cyclic olefins can be used alone or in combination of two or more kinds. Further, in the present invention, if necessary, (iii) α having 3 to 20 carbon atoms
-Olefins can be used. Specific examples of such α-olefins include propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,
Examples thereof include 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. These α
-The olefins may be used alone or in combination of two or more kinds.

Further, in the present invention, other copolymerizable polymerizable monomers may be copolymerized, if necessary, within a range not impairing the object of the present invention. Examples of such other polymerizable monomer include cyclic olefins other than the specific (ii) cyclic olefin represented by the general formula [I] or [II] as described above.

Specific examples of the cyclic olefin other than (ii) cyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, and 2- (2-methylbutyl) -1-.
Cyclohexene, 3a, 5,6,7a-tetrahydro-4,7-methano-
1H-indene etc. can be mentioned.

Further, olefins such as styrene and α-methylstyrene can be used. In the present invention,
(i) ethylene and the above-mentioned (ii) cyclic olefin and optionally (iii) α-olefin are copolymerized in the liquid phase in the presence of a catalyst, and the liquid phase is liquid (ii) It may be formed by the cyclic olefin and (iii) α-olefin itself, and / or by a hydrocarbon solvent as described below.

Examples of such a hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene and halogen derivatives thereof, and alicyclic hydrocarbons such as cyclohexane, methylcyclopentane, and methylcyclohexane. Hydrogen and its halogen derivatives, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used. These solvents may be mixed and used.

In the present invention, the copolymerization is preferably carried out in the coexistence of the above-mentioned hydrocarbon solvent, and among these, cyclohexane-hexane, cyclohexane-heptane, cyclohexane-pentane, toluene-hexane, toluene-heptane, It is preferably carried out in the coexistence of a mixed solvent such as toluene-pentane.

The cyclic olefin random copolymer produced according to the present invention will be described below. The copolymer comprises (i) a constitutional unit derived from ethylene and (ii)
And a structural unit derived from a cyclic olefin. In the copolymer, the structural unit derived from ethylene is usually 40 to 97 mol%, preferably 50 to 95 mol%,
More preferably, the amount of the structural unit derived from a cyclic olefin is usually 3 to 60 mol%, in an amount of 55 to 90 mol%,
Preferably 5 to 50 mol%, more preferably 10 to 4
It is present in an amount of 5 mol%. Further, (iii) the constitutional unit derived from α-olefin may be 20 mol% if necessary.
Or less, preferably 10 mol% or less, more preferably 5
It may be present in an amount up to mol%. In the copolymer, as described above, a structural unit derived from a polymerizable monomer other than these may be present within the range not impairing the object of the present invention.

The intrinsic viscosity [η] of the cyclic olefin random copolymer produced by the present invention measured in decalin at 135 ° C. is preferably 0.01 to 10 dl /
g, particularly preferably 0.05 to 5.0 dl / g.

In the present invention, when (i) ethylene, (ii) a cyclic olefin and (iii) an α-olefin are copolymerized to produce a cyclic olefin random copolymer, (i) ethylene and (ii) The cyclic olefin and, if necessary, the polymerizable monomer used are supplied to the polymerization system in such an amount that a copolymer having the above composition can be obtained.

Next, the catalyst used in the present invention will be described. FIG. 1 is an explanatory view showing a preparation process of a catalyst used in the present invention. The catalyst used in the present invention is [A]
It is formed from a soluble vanadium compound and a [B] organoaluminum compound. The term "soluble" as used herein refers to the property of being soluble in the liquid medium existing in the polymerization system.

Such a specific soluble vanadium compound [A] has a tertiary alkoxy group or β-diketone as a ligand in the molecule. Specifically, a compound having a tertiary alkoxy group as a ligand is represented by the following formula [A-1]
The compound having β-diketone as a ligand is represented by the following formula [A-2].

[0068] In ^{_{VO (OCR 1 3) a X}} b or ^{_{V (OCR 2 3) c X}} d ... [A-1] except the formula ^{[A-1], R 1} , R 2 is C1-5
Is a straight chain or branched alkyl group, and X is a chlorine atom or a bromine atom. Also, a, b, c and d are 0.
5 ≦ a ≦ 3, 0 ≦ b ≦ 2.5, 2 ≦ a + b ≦ 3, 0.5
≦ c ≦ 4, 0 ≦ d ≦ 3.5, 3 ≦ c + d ≦ 4 are satisfied.

VO (D ¹ ) _e Y _f or V (D ² ) _g Y _h ... [A-2] However, in the formula [A-2], D ¹ and D ² are acetylacetonates represented by the following formula. (Hereinafter abbreviated as acac) group or 2-methyl-1,3-butanedionate (hereinafter abbreviated as mmh) group, and Y is an alkyl group, an alkoxy group or halogen.

Further, e, f, g and h are each 1 ≦ e ≦
2, 0 ≦ f ≦ 1, 2 ≦ e + f ≦ 3, 1 ≦ g ≦ 3, 0 ≦ h
≦ 3, 3 ≦ g + h ≦ 4 are satisfied.

[0071]

[Chemical 31]

Specific examples of the soluble vanadium compound having a tertiary alkoxy group represented by the above formula [A-1] as a ligand include the following compounds. VO (tert.butyloxy) Cl ₂ , VO (tert.butyloxy) ₂ Cl, VO (tert.butyloxy) ₃ , VO
(2,3-Dimethyl-2-butyloxy) Cl ₂ , VO (2,3-Dimethyl-2-butyloxy) ₂ Cl, VO (2,3-Dimethyl-2-
Butyloxy) ₃ , VO (2-methyl-2-pentyloxy)
Cl ₂ , VO (2-methyl-2-pentyloxy) ₂ Cl, VO
(2-methyl-2-pentyloxy) ₃ , VO (3-methyl-3-
Pentyloxy) Cl ₂ , VO (3-methyl-3-pentyloxy) ₂ Cl, VO (3-methyl-3-pentyloxy) ₃ , V
O (2,3-dimethyl-3-pentyloxy) Cl ₂ , VO (2,3
-Dimethyl-3-pentyloxy) ₂ Cl, VO (2,3-methyl
-3-pentyloxy) ₃ , VO (3-ethyl-3-pentyloxy) Cl ₂ , VO (3-ethyl-3-pentyloxy) ₂ C
1, VO (3-ethyl-3-pentyloxy) ₃ , VO (2-methyl-2-hexyloxy) Cl ₂ , VO (2-methyl-2-hexyloxy) ₂ Cl, VO (2-methyl-2) -Hexyloxy) ₃ etc.

V (tert.butyloxy) Cl ₃ , V (ter
t. butyloxy) ₂ Cl ₂ , V (tert. butyloxy) ₃
Cl, V (2,3-dimethyl-2-butyloxy) Cl ₃ , V (2,
3-Dimethyl-2-butyloxy) ₂ Cl ₂ , V (2,3-dimethyl
-2-Butyloxy) ₃ Cl etc.

V (tert.butyloxy) Cl ₂ , V (ter
t. butyloxy) ₂ Cl, V (tert. butyloxy) _{3 and the} like.

Specific examples of the soluble vanadium compound having the β-diketone represented by the formula [A-2] as a ligand include the following compounds. VO (acac) ₂ , VO (mmh) ₂ , VO (acac) X ₂ , V
O (acac) X ₁ , VO (mmh) X ₂ , VO (mmh) X _1, etc.

V (acac) ₃ , V (mmh) ₃ , V (acac) ₂ X
₂ , V (acac) ₂ X, V (mmh) ₂ X ₂ , V (mmh) ₂ X
Such.

In the above compounds, X is Cl, F, B
R, I, an alkyl group, a primary alkoxy group, and a secondary alkoxy group are shown, and of these, Cl is preferable. These compounds can be used alone or in combination of two or more kinds.

Of these, VO (tertiary alkoxy group) Cl ₂ , VO (acac) ₂ , VO (mmh) ₂ , V (aca
c) ₃ and V (mmh) ₃ are preferred. The soluble vanadium compound [A] can also be used as an electron donor adduct obtained by contacting an electron donor as shown below.

Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers and acid amides. Examples thereof include oxygen-containing electron donors such as acid anhydrides and alkoxysilanes, and nitrogen-containing electron donors such as ammonias, amines, nitriles, pyridines and isocyanates. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol,
2-ethylhexanol, octanol, dodecanol,
C1-C18 alcohols such as octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, and C1-C18 alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol. Halogen-containing alcohols, phenol, cresol, xylenol,
C6-C20 phenols which may have a lower alkyl group such as ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol, carbon number such as acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone and benzoquinone 3 to 15 ketones, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms, 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, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, Organic acid esters having 2 to 18 carbon atoms such as ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate, acetyl chloride, benzoyl chloride, toluyl chloride, Acid halides having 2 to 15 carbon atoms such as nissic acid chloride, ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether, acetic anhydride, phthalic anhydride Acids, acid anhydrides such as benzoic anhydride, ethyl silicate, alkoxysilanes such as diphenyldimethoxysilane, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide and other acids Amides, trimethylamine, triethylamine, tributylamine, tribenzylamine, amines such as tetramethylethylenediamine, acetonitrile, benzonitrile, nitriles such as trinitrile, pyridine,
Pyridines such as methylpyridine, ethylpyridine and dimethylpyridine can be exemplified.

In preparing the electron donor adduct of the soluble vanadium compound, these electron donors can be used alone or in combination of two or more kinds. The organoaluminum compound [B] used in the present invention has an isobutyl group and a chlorine atom in the molecule and is specifically represented by the following formula.

Formula (i-Bu) _n AlCl _{3-n In the} formula, n is 1.0 to 2.5. Examples of such an organoaluminum compound [B] include Al (iso-but
yl) Cl ₂ , Al (iso-butyl) _1.5 Cl _1.5 , Al (iso-buty
l) _2.0 Cl etc. can be mentioned.

As the organoaluminum compound [B], an organoaluminum compound containing an alkyl group other than an isobutyl group, F, Br and I may be used together with the above compound within a range not impairing the object of the present invention.

The catalyst used in the present invention is formed from the above specific soluble vanadium compound [A] and the specific organoaluminum compound [B]. In the presence of such a specific catalyst, (i) ethylene and the above specific (ii)
By copolymerizing the cyclic olefin and optionally (iii) α-olefin, a cyclic olefin random copolymer can be produced without the polymerization activity being largely influenced by the polymerization temperature. The specific catalyst used in the present invention shows a high polymerization activity when copolymerizing ethylene and a cyclic olefin, but when copolymerizing ethylene and propylene, a conventionally known catalyst such as , VO
Compared with the catalyst composed of (OEt) Cl ₂ and AlEt _1.5 Cl _1.5, it shows only the same degree of polymerization activity. This means that the polymerization catalyst used in the present invention shows a specific high polymerization activity for the copolymerization of ethylene and cyclic olefin. As described above, in the conventional method, in the case of copolymerizing the monomer containing the bulky cyclic olefin and ethylene as described above, the polymerization activity tends to decrease when the temperature of the polymerization system is increased. Even if a monomer is copolymerized at a high temperature, a cyclic olefin-based random copolymer can be produced with high polymerization activity. Therefore, by using the catalyst, it is possible to carry out the copolymerization while raising the polymerization temperature and decreasing the viscosity of the polymerization system, so that the copolymerization can be carried out while maintaining the polymerization system at a high concentration and uniformly. ,
A copolymer having a uniform composition can be produced in high yield.
Furthermore, the heat of polymerization can be easily removed, the economy is improved, and the transportability of the polymerization solution is also improved. Further, in the case where the copolymer is produced at the same concentration as in the conventional case, a higher molecular weight copolymer can be produced.

This copolymerization is preferably carried out by a continuous method. At this time, the concentration of the soluble vanadium compound [A] in the polymerization system is usually 0.01 to 5 mmol / liter, preferably 0.05 to 3 mmol / liter. The soluble vanadium compound [A] may be supplied at a concentration of 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound [A] present in the polymerization system. desirable. The organoaluminum compound [B] is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20 in terms of the ratio of aluminum atoms to vanadium atoms in the polymerization system (Al / V).

The soluble vanadium compound [A] and the organoaluminum compound [B] are usually supplied after being diluted with the above-mentioned hydrocarbon solvent and / or liquid (ii) cyclic olefin. At this time, the soluble vanadium compound [A] is preferably diluted to the above-mentioned concentration, but the organoaluminum compound [B] is adjusted to an arbitrary concentration, for example, 50 times or less the concentration in the polymerization system, and then the polymerization system is prepared. It is desirable to be supplied within.

Such copolymerization of (i) ethylene, (ii) cyclic olefin and optionally (iii) α-olefin is usually carried out at a temperature of 0 ° C to 120 ° C, preferably 0 ° C to 8 ° C.
0 ° C., more preferably at 0 ℃ ~60 ℃, ~50Kg / cm 2 pressure above 0, is preferably carried out under the conditions of 1~20Kg / cm ^2. The reaction time (average residence time when the copolymerization is carried out by a continuous method) is usually 5 minutes to 5 hours, although it varies depending on conditions such as (ii) type of cyclic olefin, catalyst concentration and polymerization temperature. , Preferably 10 minutes to 3 hours.

Further, in the copolymerization, a molecular weight modifier such as hydrogen can be used. As above (i)
Ethylene, (ii) cyclic olefin and optionally (ii
i) A solution containing a cyclic olefin-based random copolymer is obtained by copolymerizing α-olefin. In such a solution, the cyclic olefin-based random copolymer is usually
It is contained at a concentration of 0 to 500 g / liter and 10 to 300 g / liter. When the copolymerization is carried out in the presence of the above-mentioned specific catalyst by the production method according to the present invention, the polymerization temperature can be set high, so that the upper limit of this concentration is higher than that of the conventional catalyst.

The cyclic olefin random copolymer thus obtained is amorphous or crystalline, but among these copolymers, it does not exhibit a DSC melting point and is also measured by X-ray diffraction. Amorphous copolymers are preferred.

The glass transition point (Tg) of the cyclic olefin random copolymer is usually 10 to 240 ° C, preferably 20 to 200 ° C. According to the method for producing a cyclic olefin random copolymer according to the present invention, ethylene and a specific bulky cyclic olefin can be copolymerized with high polymerization activity that does not depend on the polymerization temperature. According to such a method of the present invention, since it is possible to raise the polymerization temperature and reduce the viscosity of the polymerization system, it is possible to carry out the copolymerization while maintaining the polymerization system at a high concentration and uniformly, A copolymer having a composition can be produced in high yield. Furthermore, the heat of polymerization can be easily removed, the economy is improved, and the transportability of the polymerization solution is also improved. Further, in the case of producing a copolymer at the same concentration as in the conventional case,
Higher molecular weight copolymers can be produced.

[0090]

As described above, according to the method for producing a cyclic olefin random copolymer according to the present invention, a copolymer having a uniform composition can be produced at a high yield. further,
The heat of polymerization can be removed easily and the economy is improved.
The transportability of the polymerization liquid is also improved. Further, in the case where the copolymer is produced at the same concentration as in the conventional case, a higher molecular weight copolymer can be produced.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0092]

EXAMPLE 1 tetracyclo represented by ethylene with the following formula [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter TCD-3
And abbreviated) was continuously carried out as follows.

[0093]

[Chemical 32]

A cyclohexane solution of TCD-3 was added from the upper part of the 1-liter capacity polymerization vessel equipped with a stirring blade so that the TCD-3 concentration in the polymerization vessel was 45 g / liter.
Feed continuously at a rate of 4 liters / hour. A cyclohexane solution of VO (O.t-butyl) Cl ₂ was used as a catalyst from the upper part of the polymerization vessel, and the vanadium concentration in the polymerization vessel was 0.
0.5 liter / so that it becomes 25 mmol / liter
The amount of time (the concentration of vanadium supplied at this time is 2.86 times the concentration of vanadium in the polymerization vessel), isobutylaluminum sesquichloride (Al (i-C ₄ H ₉ ) _1.5 Cl
The cyclohexan solution of _1.5 ) was added so that the aluminum concentration in the polymerization vessel would be 2.5 mmol / liter.
4 liters / hour and cyclohexane in amounts of 0.7 liters / hour are each continuously fed into the polymerizer.
Also, ethylene was added to the polymerization system by using a bubbling tube.
7 liter / hour, 5.3 liter / hour of nitrogen and 1.0 liter / hour of hydrogen were supplied. A cooling medium was circulated in a jacket attached to the outside of the polymerization vessel to carry out a copolymerization reaction while maintaining the polymerization system at 30 ° C. The polymerization liquid containing the ethylene / TCD-3 random copolymer produced by the above-mentioned copolymerization reaction should be adjusted so that the polymerization liquid in the polymerization reactor is always 1 liter from the upper part of the polymerization reactor (that is, the average residence time is 0.5 hours). It was continuously extracted.
A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to terminate the polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were brought into contact with each other under strong stirring with a homomixer at a ratio of 1: 1 to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand still, the aqueous phase was separated and removed, and then washed twice with distilled water to purify and separate the polymerization liquid phase.

Next, the purified and separated polymerization liquid was contacted with 3 times the amount of acetone under strong stirring, and then the solid portion was collected by filtration and thoroughly washed with acetone. Further, the washed solid part for extracting TCD-3 existing in the polymer was put into acetone so as to have a concentration of 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration, and was put under nitrogen flow to remove 130
It was dried at 350 ° C. and 350 mmHg for 24 hours.

As described above, ethylene / TCD-3
65.2 g / hour of copolymer (ie 32.6 g / hour)
Liter). In the obtained copolymer, ¹³ C-
The ethylene composition measured by NMR analysis is 57.5 mol%,
The intrinsic viscosity [η] measured in decalin at 135 ° C is 0.4.
It was 5 dl / g and the iodine value was 1.0. The crystallinity by X-ray diffraction was 0%.

The glass transition temperature Tg measured by the DSC method at a heating rate of 10 ° C./min was 149 ° C. Furthermore, by DuPont 990 type DSC,
The melting point Tm was measured in the range of −120 ° C. to 400 ° C. at a heating rate of 10 ° C./mm, but no melting curve (peak) was observed.

The obtained results are shown in Table 1.

[0099]

Examples 2 to 4 Copolymerization reaction of ethylene and TCD-3 was carried out in the same manner as in Example 1 except for the conditions shown in Table 1.

The obtained results are shown in Table 1.

[0101]

Comparative Examples 1 to 4 Copolymerization reaction of ethylene and TCD-3 was carried out in the same manner as in Example 1 except for the conditions shown in Table 1.

The results obtained are shown in Table 1.

[0103]

Example 5 In Example 1, 1,4-methano- which is a Diels-Alder reaction adduct of cyclopentadiene and indene instead of TCD-3 as a cyclic olefin.
A copolymerization reaction was performed in the same manner as in Example 1 except that 1,4,4a, 9a-tetrahydrofluorene (MTHF) was used.

The obtained results are shown in Table 1.

[0105]

Example 6 A copolymerization reaction was carried out in the same manner as in Example 1 except that norbornene was used instead of TCD-3 as the cyclic olefin.

The obtained results are shown in Table 1.

[0107]

[Table 1]

[0108]

Reference Example 1 (Ethylene / Propylene Copolymerization) A well-dried 1 liter separable flask was equipped with a stirring blade, a gas blowing tube, a thermometer, and a dropping funnel and sufficiently replaced with nitrogen.
The flask was n-dehydrated and dried with a molecular sieve.
250 ml of hexane was added.

VO (Ot-Bu) was added to the flask under nitrogen flow.
Cl ₂ and Ali-Bu _1.5 were added from a dropping funnel so that the in-system concentrations were 0.2 mmol / liter and 2.0 mmol / liter, respectively. Immediately, ethylene was fed into the system at a rate of 90 liters / hr and propylene was fed into the system at a rate of 210 liters / hr through a gas blowing pipe to start a polymerization reaction. The reaction was performed for 10 minutes while controlling the temperature at 30 ° C. The reaction was stopped by adding 3.0 ml of methanol.

The polymer solution after termination of the reaction was poured into a large amount of methanol to break the copolymer, which was further washed with methanol and vacuum dried at 60 ° C. for 24 hours to obtain 3.9 g of a copolymer. The ethylene composition in the copolymer measured by ¹³ C-NMR analysis was 58 mol%, and the intrinsic viscosity [η] measured in 135 ° C. decalin was 4.0 dl / g.

The results are shown in Table 2.

[0112]

[Reference Example 2] VO (OEt) Cl ₂ / A as a polymerization catalyst
An ethylene / propylene copolymerization reaction was performed in the same manner as in Reference Example 1 except that 1Et _1.5 Cl _1.5 was used.

The obtained results are shown in Table 2.

[0114]

[Table 2] Table 2 ──────────────────────────────────── Catalyst system yield Ethylene content [η] ──────────────────────────────────── (g) (mol%) (dl / g) Reference example 1 VO (OtBu) Cl ₂ / AliBu _1.5 Cl _1.5 3.9 58 4.0 Reference example 2 VO (OEt) Cl ₂ / AlEt _1.5 Cl _1.5 4.2 59 3.8 ─────────────────── ────────────────── As shown in Table 2, in ethylene / propylene copolymerization, the catalyst system of the present invention (Reference Example 1) and the conventional catalyst system (Reference Example) were used. No significant difference in activity (yield) was observed between Example 2).

[Brief description of drawings]

FIG. 1 is an explanatory view showing a preparation process of a catalyst used in the present invention.

Claims (4)

[Claims] 1. An (i) ethylene, (ii) at least one cyclic olefin represented by the following general formula [I] or [II], and, if necessary, (iii) an α having 3 to 20 carbon atoms. An olefin, a soluble vanadium compound [A] having a tertiary alkoxy group or a β-diketone as a ligand, and [B] a formula (i-
Bu) _n AlCl _3-n (where n is 1.0 to 2.5) and a copolymer formed in a liquid phase in the presence of a catalyst formed from an organoaluminum compound represented by the formula: And (i) a structural unit derived from ethylene: 40 to 97 mol%, (ii) a structural unit derived from at least one cyclic olefin represented by the following general formula [I] or [II]: 3-
A method for producing a cyclic olefin random copolymer comprising 60 mol% and (iii) a structural unit derived from an α-olefin having 3 to 20 carbon atoms: 0 to 20 mol%; [I] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R are ^b independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are each
They may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and with R ^{15 to} R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. ), [Chemical formula 2] [II] (In the formula [II], p and q are 0 or 1
The above integers, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon. A carbon atom to which R ⁹ and R ¹⁰ are bonded, a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded, and an atom or group selected from the group consisting of a group and an alkoxy group; May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m
When = 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. ). 2. The soluble vanadium compound (A) is V
The production method according to claim 1, which is O (Ot-Bu) Cl ₂ , VO (acetylacetonate) ₂ or V (acetylacetonate) ₃ . 3. The soluble vanadium compound (A) is V
The production method according to claim 1, which is an electron donor adduct of O (Ot-Bu) Cl ₂ , VO (acetylacetonato) ₂ or V (acetylacetonate) ₃ . 4. The cyclic olefin is bicyclo [2.2.1].
Hept-2-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene or 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, characterized in that 1. The manufacturing method according to 1.