JP3237073B2 - Cyclic olefin copolymer composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclic olefin copolymer composition and a method for producing the same.
The present invention relates to a cyclic olefin-based copolymer composition having excellent impact resistance and heat resistance and a method for producing the same.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION A cyclic olefin random copolymer obtained by copolymerizing ethylene with a cyclic olefin such as tetracyclododecene has excellent transparency, heat resistance, heat aging resistance, and chemical resistance. , Solvent resistance, dielectric properties,
It is a synthetic resin with a well-balanced rigidity, and is known to exhibit excellent performance in the field of optical materials such as optical memory disks and optical fibers. (For example, JP-A-60-168,708, JP-A-61-9)
8,780, JP-A-61-115,912, JP-A-61-115,916, and JP-A-61-1.
120,816, JP-A-62-252,407) These cyclic olefin-based random copolymers are resins having particularly excellent heat resistance and rigidity, but further improvement in impact resistance is required. I have.

The applicant of the present application has filed Japanese Patent Application No. 2-52,
No. 971 proposes a resin composition comprising a cyclic olefin-based random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene, and a soft polymer (rubber). I have.

[0004] Such a resin composition is superior in impact resistance to the cyclic olefin-based random copolymer, but the impact strength is not always sufficient. The reason is considered to be as follows. . That is, the above resin composition is generally prepared by melt-blending a cyclic olefin-based random copolymer and a soft polymer with a Brabender or an extruder or the like. It is considered that the compatibility with the soft polymer is not always sufficient, and therefore the impact strength of the obtained resin composition is not always sufficient.

The present inventors have conducted intensive studies to solve the above-mentioned problems in the prior art, and found that ethylene and the like are present in the presence of a hydrocarbon-based elastomer having substantially no polymerizable double bond. It has been found that a cyclic olefin-based copolymer composition obtained by copolymerizing an α-olefin having 2 or more carbon atoms with a cyclic olefin has excellent impact resistance and completed the present invention. I came to.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems in the prior art, and has the excellent characteristics of a cyclic olefin-based random copolymer, and the impact resistance is particularly high. It is an object of the present invention to provide an improved cyclic olefin copolymer composition and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION The cyclic olefin copolymer composition according to the present invention has an intrinsic viscosity [η] in decalin measured at 135 ° C. in the range of 0.05 to 10 dl / g and a glass transition temperature. (B) (a) an α-olefin having 2 or more carbon atoms in the presence of a hydrocarbon-based elastomer having a temperature (Tg) of less than 10 ° C. and containing substantially no polymerizable double bond; It is obtained by copolymerizing a cyclic olefin represented by the general formula [I] or [II], and the component [A] is present in the copolymer composition obtained in an amount of 1 to 50% by weight. It is characterized by having.

[0008]

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

[0010]

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[II] (In the formula [II], p and q are 0 or an integer of 1 or more, 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, an aromatic hydrocarbon group or an alkoxy group, wherein R ⁹ (or R ¹⁰ ) is bonded to a carbon atom, and R ¹³ or R ¹¹ is The bonded carbon atom may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are And may combine with each other to form a monocyclic or polycyclic aromatic ring.)

Further, the method for producing a cyclic olefin-based random copolymer composition according to the present invention comprises the step of:
Intrinsic viscosity [η] measured at 135 ° C is 0.05 to 10 d
1 / g, and a glass transition temperature (Tg) of 10 ° C.
[B] (a) having 2 carbon atoms in the presence of a hydrocarbon-based elastomer substantially containing no polymerizable double bond
The above-mentioned α-olefin and (b) a cyclic olefin represented by the above general formula [I] or [II] are copolymerized in a liquid phase, and the obtained copolymer composition has [ A] The component is characterized by being present in an amount of 1 to 50% by weight.

[0013]

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

First, a hydrocarbon-based elastomer which does not substantially contain a polymerizable double bond will be described.

Hydrocarbon elastomer [A] The hydrocarbon elastomer [A] used in the present invention comprises:
An elastomer which does not substantially contain a polymerizable double bond in the elastomer, and specifically includes (i) an α-olefin-based copolymer and (ii) an α-olefin-cyclic olefin-based copolymer. be able to.

The following hydrocarbon elastomers [A]
Will be described more specifically. (I) α-olefin-based copolymer The α-olefin-based copolymer is a random copolymer formed from at least two kinds of α-olefins. Here, as the α-olefin, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-
Examples thereof include α-olefins having 2 to 20 carbon atoms such as eicosene.

Specific examples of such α-olefin copolymers include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1- Hexene copolymer, ethylene / 1-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, ethylene / 1-decene copolymer, ethylene / 1-dodecene copolymer, ethylene / 1-tetradecene Copolymer, ethylene / 1-hexadecene copolymer, ethylene / 1-octadecene copolymer, ethylene / 1-eicosene copolymer, propylene / 1-butene copolymer, propylene / 1-pentene copolymer, propylene・ 1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene ・ 1
-Octene copolymer, propylene / 1-decene copolymer,
Examples include propylene / 1-dodecene copolymer, propylene / 1-tetradecene copolymer, propylene / 1-hexadecene copolymer, propylene / 1-octadecene copolymer, and propylene / 1-eicosene copolymer.

Such an α-olefin copolymer is as follows:
When the intrinsic viscosity [η] measured at 135 ° C. in decalin is 0.0
It is in the range of 5 to 10 dl / g, preferably 0.1 to 5 dl / g, and the glass transition temperature (Tg) is desirably less than 10C, preferably 0C or less. (Ii) α-olefin / cyclic olefin-based copolymer The α-olefin / cyclic olefin-based copolymer is a random copolymer formed from one or more α-olefins and a cyclic olefin.

Here, as the α-olefin, for example,
Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1
Α having 3 to 20 carbon atoms such as -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene
-Olefins.

As the cyclic olefin, specifically,
A cyclic olefin represented by the following general formula [I] or [II] is used.

Specific examples of such α-olefin / cyclic olefin copolymers include ethylene / norbornene copolymer, ethylene / 5-methyl-2-norbornene copolymer, ethylene / 5-ethyl- 2-norbornene copolymer, ethylene / 5-propyl-2-norbornene copolymer,
Ethylene / 5-butyl-2-norbornene copolymer, ethylene / 5-pentyl-2-norbornene copolymer, ethylene / 5
-Hexyl-2-norbornene copolymer, ethylene / 5-heptyl-2-norbornene copolymer, ethylene / 5-octyl-
2-norbornene copolymer, ethylene / 5-nonyl-2-norbornene copolymer, ethylene / 5-decyl-2-norbornene copolymer, ethylene / 5-undecyl-2-norbornene copolymer, ethylene / 5- Dodecyl-2-norbornene copolymer, ethylene / 5-phenyl-2-norbornene copolymer, ethylene / tetracyclododecene copolymer, ethylene / propylene / norbornene copolymer, ethylene / propylene / 5-ethylidene-2 -Norbornene copolymer, ethylene / propylene / 5-methyl-2-norbornene copolymer, ethylene / propylene / 5-ethyl-2-norbornene copolymer, ethylene / propylene / 5-propyl-2-norbornene copolymer , Ethylene, propylene, 5-butyl-2
-Norbornene copolymer, ethylene / propylene / 5-pentyl-2-norbornene copolymer, ethylene / propylene / 5-hexyl-2-norbornene copolymer, ethylene / propylene
Propylene-5-heptyl-2-norbornene copolymer, ethylene propylene / 5-octyl-2-norbornene copolymer, ethylene propylene / 5-nonyl-2-norbornene copolymer, ethylene propylene / 5-decyl 2-norbornene copolymer, ethylene / propylene / 5-undecyl-2-norbornene copolymer, ethylene / propylene / 5
-Dodecyl-2-norbornene copolymer, ethylene / propylene / 5-phenyl-2-norbornene copolymer, ethylene / propylene / tetracyclododecene copolymer, ethylene / 1-butene / norbornene copolymer, ethylene 1-butene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / 5-methyl-2-norbornene copolymer, ethylene / 1-butene / 5-ethyl-2-norbornene copolymer, ethylene 1-butene / 5-propyl-2-norbornene copolymer, ethylene / 1-butene / 5-butyl-2-norbornene copolymer, ethylene / 1-butene / 5-pentyl-2-norbornene copolymer, Ethylene / 1-butene / 5-hexyl
2-norbornene copolymer, ethylene / 1-butene / 5-heptyl-2-norbornene copolymer, ethylene / 1-butene / 5-octyl-2-norbornene copolymer, ethylene / 1-
Butene-5-nonyl-2-norbornene copolymer, ethylene / 1-butene / 5-decyl-2-norbornene copolymer, ethylene / 1-butene / 5-undecyl-2-norbornene copolymer, ethylene / 1 -Butene / 5-dodecyl-2-norbornene copolymer, ethylene / 1-butene / 5-phenyl-2-norbornene copolymer, ethylene / 1-butene / tetracyclododecene copolymer, ethylene / 1-hexene -Norbornene copolymer, ethylene / 1-hexene / 5-methyl-2-norbornene copolymer, ethylene / 1-hexene / 5-ethyl-2-
Norbornene copolymer, ethylene / 1-hexene / 5-propyl-2-norbornene copolymer, ethylene / 1-hexene / 5-butyl-2-norbornene copolymer, ethylene / 1-hexene / 5-pentyl-2 -Norbornene copolymer, ethylene / 1-hexene / 5-hexyl-2-norbornene copolymer, ethylene / 1-hexene / 5-heptyl-2-norbornene copolymer, ethylene / 1-hexene / 5-octyl- 2-norbornene copolymer, ethylene / 1-hexene / 5-nonyl
2-norbornene copolymer, ethylene / 1-hexene / 5-
Decyl-2-norbornene copolymer, ethylene / 1-hexene / 5-undecyl-2-norbornene copolymer, ethylene / 1-hexene / 5-dodecyl-2-norbornene copolymer,
Ethylene / 1-hexene / 5-phenyl-2-norbornene copolymer, ethylene / 1-hexene / tetracyclododecene copolymer, ethylene / 1-octene / norbornene copolymer, ethylene / 1-octene / 5- Methyl-2-norbornene copolymer, ethylene / 1-octene / 5-ethyl-2-norbornene copolymer, ethylene / 1-octene / 5-propyl-2
-Norbornene copolymer, ethylene / 1-octene / 5-butyl-2-norbornene copolymer, ethylene / 1-octene / 5-pentyl-2-norbornene copolymer, ethylene / 1-
Octene-5-hexyl-2-norbornene copolymer, ethylene / 1-octene / 5-heptyl-2-norbornene copolymer, ethylene / 1-octene-5-octyl-2-norbornene copolymer, ethylene / 1 -Octene-5-nonyl-2-norbornene copolymer, ethylene-1-octene-5-decyl-2
-Norbornene copolymer, ethylene / 1-octene / 5-undecyl-2-norbornene copolymer, ethylene / 1-octene / 5-dodecyl-2-norbornene copolymer, ethylene / 1-octene / 5-phenyl- 2-norbornene copolymer,
Ethylene / 1-octene / tetracyclododecene copolymer, ethylene / 1-decene / norbornene copolymer, ethylene / 1-decene / 5-methyl-2-norbornene copolymer,
Ethylene / 1-decene / 5-ethyl-2-norbornene copolymer, ethylene / 1-decene / 5-propyl-2-norbornene copolymer, ethylene / 1-decene / 5-butyl-2-norbornene copolymer , Ethylene / 1-decene / 5-pentyl-2-norbornene copolymer, ethylene / 1-decene / 5-hexyl
2-norbornene copolymer, ethylene / 1-decene / 5-heptyl-2-norbornene copolymer, ethylene / 1-decene / 5-octyl-2-norbornene copolymer, ethylene / 1-
Decene / 5-nonyl-2-norbornene copolymer, ethylene / 1-decene / 5-decyl-2-norbornene copolymer, ethylene / 1-decene / 5-undecyl-2-norbornene copolymer, ethylene / 1 -Decene / 5-dodecyl-2-norbornene copolymer, ethylene / 1-decene / 5-phenyl-2-norbornene copolymer and ethylene / 1-decene / tetracyclododecene copolymer.

The α-olefin-based copolymer 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is usually 0.05 to 10 dl / g, preferably 0.5 to 5 dl / g.
g, and the glass transition temperature (Tg) is usually 1
It is desirable that the temperature is lower than 0 ° C, preferably lower than 0 ° C.

Next, the cyclic olefin copolymer composition of the present invention will be described. The cyclic olefin-based copolymer composition according to the present invention contains a double bond capable of substantially polymerizing an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) as described above. Obtained in the presence of a hydrocarbon elastomer [A] which is not used.

As the α-olefin having 2 or more carbon atoms (a), specifically, ethylene, 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,
3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

Of these, ethylene or propylene is preferred. As the cyclic olefin (b), a cyclic olefin represented by the following formula [I] and / or [II] is used.

[0026]

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[I] In the formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group. When q is 0, each bond is bonded to form a 5-membered ring. Form.

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, as the halogen atom, a fluorine atom,
Examples include a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon groups are each independently usually an alkyl group having 1 to 20 carbon atoms, and a hydrocarbon group having 3 to 1 carbon atoms.
And 5 cycloalkyl groups. More specifically,
The alkyl group includes 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 cycloalkyl group includes a cyclohexyl group.

These groups may be substituted by a halogen atom. Further, in the above formula [I], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ may be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. May be.

The monocyclic or polycyclic ring formed here is exemplified below.

[0032]

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In the above examples, the carbon atom numbered 1 or 2 corresponds to R ¹⁵ (R ¹⁶ ) in the formula [I].
Or a carbon atom forming an alicyclic structure to which R ¹⁷ (R ¹⁸ ) is bonded.

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

[0035]

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... [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 a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group. In the formula [II], the halogen atom is the same as the halogen atom in the formula [I].

Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group and an octyl group. , Decyl, dodecyl and octadecyl groups.

The alicyclic hydrocarbon group may have 3 carbon atoms.
To 15 alicyclic hydrocarbon groups, specifically, a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and the like. Specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. May be provided.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. These groups may be substituted with a halogen atom.

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 a carbon atom having 1 to 3 carbon atoms.
May be bonded via an alkylene group of That is, when the two carbon atoms are bonded via an alkylene group, R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ together form a methylene group (—CH ₂ —) , An ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —) to form an alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include R ¹⁵ and R ¹⁵ when n = m = 0.
^The groups described below in which ¹² further forms an aromatic ring can be exemplified.

[0043]

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In the above examples, q has the same meaning as q in formula [II].

Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo [2.2.1] hept-2-ene derivatives and tricyclo [4.3.0.1
^2,5 ] -3-decene derivative, tricyclo [4.4.0.1 ^2,5 ] -3-
Undecene derivative, tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene derivative, pentacyclo [6.6.1.1
^3,6 .0 ^2,7 .0 ^9,14] -4-hexadecene derivative, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^{9, 13]} -4-pentadecene derivatives, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] -3-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [8.4.0.1 ^2,5 .0 ^9,12 .0 ^8,13] -3-hexadecene derivatives, hexacyclo [6.6.1.1 ^3,6 .1 ^10,13 .0
^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- eicosene derivatives, heptacyclo [8.7.0.1 ^2,9 .1 ^4,7 .1 ^11,17 .0
^3,8 .0 ^12,16] -5-eicosene derivatives, heptacyclo [8.
8.0.1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^{11, 18} .0
^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0 12,17] - Five-
Docosenoic 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, 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]} -6-hexacosenoic derivatives,
1.4-methano-1.4.4a.9a-tetrahydrofluorene derivative, 1.4-methano-1.4.4a.5.10.10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct and the like.

The details will be described below.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0067]

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[0068]

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The cyclic olefin (b) represented by the above general formula [I] or [II] is produced by subjecting cyclopentadiene to an olefin having a corresponding structure by a Diels-Alder reaction. Can be.

These cyclic olefins (b) can be used alone or in combination of two or more. The cyclic olefin-based copolymer composition according to the present invention comprises the cyclic olefin (b) represented by the above formula [I] or [II] and an α-olefin having 2 or more carbon atoms (a). ,
It is an addition polymer obtained by polymerizing in the presence of a hydrocarbon-based elastomer [A] containing substantially no polymerizable double bond as described above.

In this cyclic olefin copolymer composition, the hydrocarbon elastomer is present in an amount of 1 to 50% by weight, preferably 3 to 40% by weight.

The cyclic olefin copolymer composition thus obtained can be used in the presence of an α-olefin having 2 or more carbon atoms in the presence of a hydrocarbon-based elastomer [A] containing substantially no polymerizable double bond. (A) and cyclic olefin (b)
Is very good in dispersibility between the cyclic olefin random copolymer formed from the α-olefin (a) and the cyclic olefin (b) and the hydrocarbon elastomer [A]. . This can be obtained by copolymerizing an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) in the presence of a hydrocarbon-based elastomer containing substantially no polymerizable double bond. The cyclic olefin copolymer composition simply melts a cyclic olefin random copolymer obtained by copolymerizing an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) with a hydrocarbon elastomer. This is also shown by the fact that it has better impact resistance than the cyclic olefin copolymer composition obtained by mixing and blending.

In the cyclic olefin copolymer composition according to the present invention, in addition to the α-olefin having 2 or more carbon atoms (a) and the cyclic olefin (b) as long as the properties of the copolymer are not impaired. , Α-olefins other than the above-mentioned α-olefins
An olefin (third monomer) or a cyclic olefin (other cyclic olefin) other than the cyclic olefin represented by the above formula [I] or [II] can be addition-polymerized.

The α-olefin used here may be a linear α-olefin or a branched α-olefin. Examples of such α-olefin include propylene, 1-butene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-
Examples thereof include α-olefins having 3 to 20 carbon atoms such as eicosene. Among them, three carbon atoms
It is preferred to use from 15 to 15, especially from 3 to 10, α-olefins.

The “other cyclic olefin” used herein is represented by a broad concept including unsaturated polycyclic hydrocarbon compounds excluding the cyclic olefins represented by the formulas [I] and [II]. .

More specifically, examples of other cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, styrene, Examples include α-methylstyrene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene.

The cyclic olefin copolymer composition according to the present invention comprises (a) an α-olefin having 2 or more carbon atoms in the presence of the above-mentioned hydrocarbon elastomer [A];
(B) The cyclic olefin represented by the above general formula [I] or [II] is mixed with the cyclic copolymer in a liquid phase, preferably in a hydrocarbon solvent, so that the copolymer composition obtained contains 1 to 50% by weight of the component [A]. % Can be prepared by copolymerization to be present in% amounts.

The above-mentioned copolymerization reaction is carried out by (i) a catalyst formed from a soluble vanadium compound and an organoaluminum compound, or (ii) a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminum compound. The reaction can be carried out in the presence of a catalyst formed from the oxy compound.

The soluble vanadium compound forming such a catalyst (i) is specifically represented by the following general formula. VO (OR) _{a Xb} or V (OR) _c X _d wherein R is a hydrocarbon group, and a, b, c, and d are respectively 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 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 , VOCl ₃
(OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , V
_{O (O-n-C 4} H 9) Cl 2, VO (OC 2 H 5) 3, VOB
Vanadium compounds such as r ₂ , VCl ₄ , VOCl ₂ VO (On-C ₄ H ₉ ) ₃ , and VOCl ₃ .2OC ₈ H ₁₇ OH are used.

These compounds can be used alone or in combination of two or more. The soluble vanadium compound can also be used as an electron donor adduct obtained by contacting an electron donor as described below.

Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, diethers, and acid amides. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, and ammonia-containing, nitrogen-containing electron donors such as amines, nitriles, pyridines, and isocyanates. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl Alcohols having 1 to 18 carbon atoms such as alcohols and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol And phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as naphthol, acetone and methyl ethyl ketone. Emissions, methyl isobutyl ketone,
C2-C15 ketones such as acetophenone, benzophenone and benzoquinone; and C2-carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.
~ 15 aldehydes, 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, benzoate Phenyl acid,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
Organic acid esters having 2 to 18 carbon atoms such as γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate; and carbon atoms having 2 to 1 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride.
5, acid halides, methyl ether, ethyl ether,
C2-C20 ethers such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; ethyl silicate and alkoxy such as diphenyldimethoxysilane Acid amides such as silane, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, and toluic acid N, N-dimethylamide; amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, and tetramethylethylenediamine And nitriles such as acetonitrile, benzonitrile and trinitrile, and pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine.

In 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 when forming the catalyst (i) has at least one Al-C bond in the molecule, for example, the following (a) and (b) ) Expression.

[0083] (a) the general formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein R ¹ and R ^2, typically 1 to 15 carbon atoms,
Preferred are 1 to 4 hydrocarbon groups, which may be the same or different. X is a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ p <
3, q is a number satisfying 0 ≦ q <3, and m + n + p +
q = 3. ).

[0084] (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.

Specific examples of the organoaluminum compound represented by the above (a) include the following compounds. (1) General formula R ¹ _m Al (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) General formula R ¹ _m AlX _3-m (where R ¹ is the same as above; X is halogen, and m is preferably a number of 0 <m <3). (3) General formula R ¹ _m AlH _3-m (where R ¹ is the same as above. M is preferably 2 ≦ m <3)
Number). (4) General formula R ¹ _m Al (OR ² ) _n X _q (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
It is. ).

As the organoaluminum compound represented by (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 sesqui ethoxide, and butyl sesquichloride butoxide, R ¹ _2.5 Al
(OR ² ) Partially alkoxylated alkyl aluminum having an average composition represented by _0.5 or the like can be mentioned.

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

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.

Examples of the organoaluminum compound represented by (4) include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Further, a compound similar to the compound represented by the general formula (a), for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such a compound, specifically,

[0091]

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And the like. Compounds belonging to the above (b) include LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₇ H ₁₅ ) _{4 and the} like can be exemplified.

Of these, alkyl aluminum halides, alkyl aluminum dihalides and mixtures thereof are particularly preferred. Next, (ii) used in the present invention
A catalyst formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminum oxy compound will be described.

Such a transition metal metallocene compound selected from Group IVB of the periodic table is specifically represented by the following formula (a). ML _x (a) In the formula (a), 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 having this cyclopentadienyl skeleton. The ligand may have a substituent.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, 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 has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ R ^a ), 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.

The alkoxy group includes 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 R ^a ) 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 formula (a) as described above has, for example, a transition metal having a valence of 4
Is more specifically represented by the following formula (b).

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (b) In the formula (b), M is the above transition metal, and R ² is a group having a cyclopentadienyl skeleton (ligand) And R ³ , R
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 (a). k is 1
The above integer, 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-ethylcyclopentadiene) (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 (b), R ² , R ³ , R
^At least two of R ⁴ and R ⁵ , ie, R ² and R ³
Is a group (ligand) having a cyclopentadienyl skeleton, and 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. Some bridge-type metallocene compounds can also be exemplified. 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 (a).

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 the zirconocene compound has been exemplified above as the 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 metallocene compound as described above 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 , Z
Inorganic carrier compounds such as nO, SnO ₂ , BaO, 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.

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.

[0112]

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(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, and m is 2 or more. , Preferably an integer of 5 to 40.) wherein the aluminoxane has the formula (OA)
l (R ¹⁾⁾ alkyloxy aluminum units [where represented by alkyloxy aluminum units and formula represented by ^{(OAl (R 2)),} R 1 and R ² to illustrate the same hydrocarbon group as R And R ¹ and R ²
Represents a different group]].

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 water vapor) is directly applied to an organoaluminum compound such as 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 employ the method (1). As the organoaluminum compound used when producing the solution of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum, tri
tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum, trialkyl aluminum such as tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride Dialkylaluminum halides, such as dialkylaluminum hydride, diisobutylaluminum hydride, dialkylaluminum hydride, dimethylaluminum methoxide, and dialkylaluminum alkoxide such as diethylaluminum ethoxide.
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

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

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y, and z are positive numbers and z ≧ 2x). The 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.

[0119] 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 (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D _{12 60} / D ₁₂₂₀₎ is 0.09
Or less, preferably 0.08 or less, particularly preferably 0.04.
It is desirably within the range of 0.07.

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

[0121]

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-
Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a cyclohexyl group, and 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.

[0124]

Embedded image

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

In the case of containing an aluminum oxyaluminum unit, an 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 [B] used 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, using the catalyst (i) or (ii) as described above, in the presence of a hydrocarbon-based elastomer [A], an α-olefin having 2 or more carbon atoms and the above-mentioned formula [I] Alternatively, the cyclic olefin represented by [II] is copolymerized in a liquid phase, preferably 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, and alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and halogen derivatives thereof, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used. The above copolymerization reaction can also be performed using an α-olefin or a cyclic olefin itself as a hydrocarbon solvent. 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 soluble vanadium compound in the polymerization system is usually used in an amount of 0.01 to 5 mmol, preferably 0.05 to 3 mmol, per 1 liter of the polymerization volume. 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 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 liquid monomers and / or
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 usually 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 the copolymerization is carried out by a continuous method) depends on the type of monomer used,
Although it varies depending on conditions such as the catalyst concentration and the polymerization temperature, it is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours.

In the above-mentioned copolymerization reaction, α-
The olefin (a) and the cyclic olefin (b) represented by the above formula [I] or [II] have a (a) / (b) molar ratio of 10/90 to 90/10, preferably 10/90. ~ 5
It is fed to the polymerization system in such an amount as to be 0/50.

In the copolymerization, a molecular weight regulator such as hydrogen may be used. As described above, in the presence of the hydrocarbon-based elastomer [A], the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin formula (b) represented by the general formula [I] or [II] are used. Upon copolymerization, a solution containing the cyclic olefin-based copolymer composition is obtained.
In such a solution, the cyclic olefin-based copolymer composition usually contains 10 to 500 g / liter and 10 to 300 g.
Per liter. This solution is treated by a conventional method to obtain a cyclic olefin copolymer composition.

To produce the cyclic olefin copolymer composition according to the present invention, more specifically, a hydrocarbon elastomer [A], for example, an elastomer pellet or veil, which has already been produced, is dissolved in a hydrocarbon solvent. In this solution, an α-olefin having 2 or more carbon atoms (a) and a cyclic olefin (b) may be copolymerized. First, the above-mentioned hydrocarbon-based elastomat [A] is produced, and the polymerization is carried out. The α-olefin having 2 or more carbon atoms (a) and the cyclic olefin (b) may be copolymerized in the solution.

The cyclic olefin copolymer composition provided by the present invention is formed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixtruder, twin-screw conical screw extruder, planetary screw extruder, gear-type extrusion Molding, injection molding, blow molding, and rotational molding by an extruder, screwless extruder, or the like.

The cyclic olefin-based copolymer composition of the present invention is blended with a rubber component for further improving impact strength to the above-mentioned cyclic olefin-based copolymer composition as long as the object of the present invention is not impaired. In addition, heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be appropriately compounded.

For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidebis [ethyl-3 (3,5- Phenolic antioxidants such as di-t-butyl-4-hydroxyphenyl)] propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, and glycerin Examples include fatty acid esters of polyhydric alcohols such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be used alone or in combination. For example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate may be used. Examples thereof include a combination with glycerin monostearate.

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol, wherein the fatty acid ester of the polyhydric alcohol is one of alcoholic hydroxyl groups of a trihydric or higher polyhydric alcohol. It is preferable that the polyhydric alcohol fatty acid ester is partly esterified. As the fatty acid ester of such a polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid esters such as glycerin dilaurate, Pentaerythritol monostearate, pentaerythritol monolaurate,
Fatty acid esters of pentaerythritol such as pentaerythritol dilaurate, pentaerythritol distearate and pentaerythritol tristearate are used. Such a phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin resin, and a polyhydric alcohol. Is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the cyclic olefin resin.

Further, in the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, water Aluminum oxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber And fillers such as silicon carbide fibers, α-olefin fibers having 2 or more carbon atoms, polypropylene fibers, polyester fibers, and polyamide fibers.

[0143]

According to the present invention, the cyclic olefin copolymer composition obtained in the present invention can be used in the presence of a hydrocarbon-based elastomer containing substantially no polymerizable double bond and having an α of 2 or more carbon atoms.
-Since the olefin (a) and the cyclic olefin (b) are copolymerized, the dispersion of the cyclic olefin copolymer phase and the elastomer phase is improved, and the impact resistance is improved.

[0144]

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

The measuring methods and evaluation results of various physical properties in the present invention are shown below. (1) Intrinsic viscosity [η] It was measured at 135 ° C. in a decalin solution (1 g / l) using an Ubbelohde viscometer. (2) Glass transition point (Tg) The glass transition point (Tg) was measured at a rate of 10 ° C./min in a nitrogen atmosphere using DSC-220C manufactured by Seiko Electronics. (3) Softening temperature (TMA) The softening temperature was measured by the thermal deformation behavior of a sheet having a thickness of 1 mm using a Thermo Mechanical Analyzer manufactured by DuPont. That is,
Place a quartz needle on the sheet, apply a load of 49 g,
/ Minute, the quartz needle is placed on the sheet at 0.635
The temperature at which mm infiltration was defined as TMA. (4) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold. The test piece was measured after being left at room temperature for 48 hours after molding. (5) Bending test The bending test was performed according to ASTM D790.

Test specimen shape: 5 × ５ × 1/8 t inch, distance between spans 51 mm (6) Izod impact test Measured according to ASTM D256.

Test piece shape: 5/2 × 1/8 × 1/2 t inch (with notch) Test temperature: 23 ° C.

[0148]

EXAMPLE 1 with 2-liter glass polymerization vessel equipped with a stirring blade, in the presence of hydrocarbon-based elastomer which is substantially free of polymerizable double bonds, ethylene and tetracyclo [4.4.0.1 ^{2 , 5.1.7,10} ] -3-dodecene (hereinafter abbreviated as TCD) was continuously copolymerized by the following method.

A cyclohexane solution of an ethylene / propylene copolymer ([η]: 2.1 dl / g, Tg: −31 ° C.) was charged from the top of the polymerization vessel with an ethylene / propylene copolymer concentration of 1. It was fed continuously at a rate of 0.5 liter / hour to 2 grams / liter. Also T
A cyclohexane solution of CD was continuously supplied at a rate of 0.4 liter / hour so that the TCD concentration in the polymerization vessel became 65.7 g / liter. Further, as a catalyst, a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ was added from the upper part of the polymerization vessel to 0.7 liter / hour (at this time) such that the vanadium concentration in the polymerization vessel was 0.5 mmol / liter. The supply vanadium concentration is 2.86 times the vanadium concentration in the polymerization reactor, and a solution of ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 in cyclohexane is adjusted to an aluminum concentration of 4 in the polymerization reactor. The solution was continuously fed into the polymerization vessel at a rate of 0.4 liter / hour so as to be 0.0 mmol / liter, and 30.0 liter / hour of ethylene was added to the polymerization system by using a bubbling tube.
7.0 liters / hour of nitrogen and 3.0 liters / hour of hydrogen
Supplied in hours.

A copolymerization reaction was carried out while maintaining the polymerization system at 10 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. A solution of a cyclic olefin copolymer composition composed of an ethylene / propylene copolymer and an ethylene / TCD copolymer produced by the above-mentioned copolymerization reaction was supplied from the upper part of the polymerization vessel to a volume of 1 liter of the polymerization solution in the polymerization vessel. (Ie, so that the average residence time is 0.5 hours). To the extracted polymerization solution,
The polymerization reaction was stopped by adding a mixed solution of cyclohexane / isopropyl alcohol (1: 1). Thereafter, an aqueous solution containing 5 ml of concentrated hydrochloric acid and the polymerization solution were brought into contact with 1 liter of water at a ratio of 1: 1 using a homomixer under vigorous stirring to transfer the catalyst residue to a water tank. After the contact mixture was allowed to stand, the aqueous phase was separated and removed, and further distilled water was added.
The polymer was washed with water and the polymerization liquid phase was purified and separated.

Then, the polymer solution purified and separated was brought into contact with a three-fold amount of acetone under vigorous stirring, and then the solid portion was collected by filtration and sufficiently washed with acetone. Further, the solid portion washed to extract the TCD present in the polymer was added to 40 parts.
g / liter into acetone, then 6
The extraction operation was performed at 0 ° C. for 2 hours. After the extraction process,
The solid portion was collected by filtration, and at 130 ° C., 3
It was dried at 50 mmHg for 24 hours.

As described above, the cyclic olefin copolymer composition comprising the ethylene / propylene copolymer and the ethylene / TCD copolymer was obtained in an amount of 81.4 g / hour, that is, 40.7 g / liter. Obtained. The ratio of the component [A] contained in the resulting copolymer composition was 2.9% by weight.

Table 1 shows the polymerization conditions, and Table 2 shows the obtained results including the evaluation results of the bending test, impact strength test, and TMA softening test.

[0154]

Example 2 In Example 1, the supply amount of the ethylene / propylene copolymer was changed from 1.2 g / L to 4.0 g / L.
A cyclic olefin copolymer composition comprising an ethylene / propylene copolymer and an ethylene / TCD copolymer was produced in the same manner as in Example 1 except that the amount was changed to liter.

A test piece was prepared from the obtained copolymer composition and its physical properties were evaluated. Table 2 shows the results.

[0156]

Examples 3 to 5 The same procedure as in Example 2 was carried out except that the ethylene / propylene copolymer used as the component [A] was replaced with another hydrocarbon elastomer as shown in Table 1. The operation was performed to produce a cyclic olefin copolymer composition comprising a hydrocarbon elastomer and an ethylene / TCD copolymer.

Test pieces were prepared from the obtained copolymer composition, and the physical properties were evaluated. Table 2 shows the results. When various elastomers were used, all the systems showed a high effect of improving impact resistance.

[0158]

Example 6 Example 1 was repeated except that 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter abbreviated as MTHF) was used in place of TCD as the component (b) [B]. Performed the same operation as in Example 1.

Test pieces were prepared from the obtained cyclic olefin copolymer composition, and the physical properties were evaluated. Table 2 shows the results
Shown in

[0160]

Example 7 Ethylene bis (indenyl) zirconium dichloride [Et (Ind) ₂ ZrCl ₂ , concentration in the polymerization system: 0.2 mmol / l] and methylaluminoxane [MAO, Al concentration in the polymerization system: 20.0] And the cyclic olefin copolymer composed of an ethylene / propylene copolymer and an ethylene / TCD copolymer, except that some polymerization conditions were changed. A composition was prepared.

Test pieces were prepared from the obtained copolymer composition, and the physical properties were evaluated. Table 2 shows the results. Here also, the effect of improving the impact resistance by performing the copolymerization in the presence of the elastomer became clear.

[0162]

Comparative Example 1 The same operation as in Example 1 was performed except that only cyclohexane was added instead of the cyclohexane solution of the ethylene / propylene copolymer.
An ethylene / TCD copolymer was produced.

A test piece was prepared from the obtained copolymer, and its physical properties were evaluated. Table 3 shows the results.

[0164]

Comparative Example 2 The same operation as in Example 6 was performed, except that only cyclohexane was added instead of the cyclohexane solution of the ethylene / propylene copolymer.
An ethylene / MTHF copolymer was produced.

A test piece was prepared from the obtained copolymer, and its physical properties were evaluated. Table 3 shows the results.

[0166]

Comparative Example 3 An ethylene / TCD binary copolymer (TCD content: 30.1 mol%, 450 g) and an ethylene / propylene copolymer (50 g) were twin-screw extruder (BT- manufactured by Plastics Engineering Laboratory Co., Ltd.). 30, l / d = 42) at a cylinder temperature of 270 ° C. and pelletized with a pelletizer.

Test pieces were prepared from the obtained pellets, and the physical properties were evaluated. Table 3 shows the results.

[0168]

Comparative Examples 4 to 6 The same operation as in Comparative Example 2 was performed except that an elastomer other than the ethylene / propylene copolymer was used.

A test piece was prepared from the obtained composition, and the physical properties were evaluated. Table 3 shows the results.

[0170]

[Table 1]

[0171]

[Table 2]

[0172]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 45/00 C08L 45/00 (72) Inventor Toshimasa Takada 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui (56) References JP-A-3-255145 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 210/00-210/18 C08F 2/44 C08F 232/00-232/08 C08L 23/00-23/36 C08L 45/00-45/02 C08F 255/00-255/10

Claims (2)

(57) [Claims] [1] An intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.05 to 10 dl / g,
(B) (a) an α-olefin having 2 or more carbon atoms in the presence of a hydrocarbon-based elastomer having a glass transition temperature (Tg) of less than 10 ° C. and containing substantially no polymerizable double bond; ) It is obtained by copolymerizing a cyclic olefin represented by the following general formula [I] or [II], and the component [A] is present in an amount of 1 to 50% by weight in the obtained copolymer composition. A cyclic olefin copolymer composition characterized by the following: ... [I] (In the formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are Each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group; R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring; And R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.); ... [II] (In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ (or R ¹⁰ ) is bonded and R ¹³ or R ¹¹ are bonded May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other. May form a monocyclic or polycyclic aromatic ring.). 2. [A] the intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.05 to 10 dl / g,
(B) (a) an α-olefin having 2 or more carbon atoms in the presence of a hydrocarbon-based elastomer having a glass transition temperature (Tg) of less than 10 ° C. and containing substantially no polymerizable double bond; ) It is obtained by copolymerizing a cyclic olefin represented by the above general formula [I] or [II] in a liquid phase, and the obtained copolymer composition contains 1 to 50% by weight of the component [A]. A process for producing a cyclic olefin-based copolymer composition, characterized in that it is present in an amount of: