JPH05320257A - Cycloolefin copolymer composition and its production - Google Patents

Abstract

PURPOSE:To improve the resistances to impact and heat by copolymerizing an alpha-olefin with a specific cycloolefin in the presence of a hydrocarbon elastomer. CONSTITUTION:10-90mol% alpha-olefin and 90-10mol% cycloolefin of formula I (wherein n and q are each 0 or 1; m is 0 or a positive integer; and R<1> to R<18>, R<a>, and R<b> are each H, halogen, or a hydrocarbon group provided that R<15> to R<18> may combine with each other to form a mono- or polycycle optionally having a double bond) or formula II (wherein p and q are each 0 or 1 or higher; m and n are each 0-2; and R<1> to R<19> are each H, halogen, an aliph., alicyclic, or arom. hydrocarbon group, etc.) are copolymerized under 0-50kg/cm<2> pressure at -50 to 150 deg.C for 5min to 5hr in the presence of 1-50wt.% hydrocarbon elastomer having an intrinsic viscosity (in decalin at 135 deg.C) of 0,05-10dl/g, a glass transition of 10 deg.C or lower, and no polymerizable double bond.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin copolymer composition and a method for producing the same, more specifically,
The present invention relates to a cycloolefin 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 and a cyclic olefin such as tetracyclododecene is excellent in transparency, and further has heat resistance, heat aging resistance and chemical resistance. , Solvent resistance, dielectric properties,
It is known that it is a synthetic resin with well-balanced rigidity and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers. (For example, JP-A-60-168,708 and JP-A-61-9.
8,780, JP 61-115,912, JP 61-115,916, JP 61-
120,816 and JP-A-62-252407, these cyclic olefin-based random copolymers are resins having excellent heat resistance and rigidity, but further improvement in impact resistance is required. There is.

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

Such a resin composition is superior in impact resistance to the cyclic olefin random copolymer, but its impact strength is not always sufficient, and the reason is considered as follows. .. That is, the above-mentioned resin composition is generally prepared by melt-blending a cyclic olefin-based random copolymer and a soft polymer using a Brabender or an extruder. It is considered that the compatibility with the soft polymer is not always sufficient, and thus the impact strength of the resulting resin composition is not always sufficient.

The present inventors have conducted extensive studies to solve the above-mentioned problems in the prior art, and as a result, in the presence of a hydrocarbon elastomer having substantially no polymerizable double bond, ethylene, etc. The present invention has been completed by finding that the cyclic olefin-based copolymer composition obtained by copolymerizing the α-olefin having 2 or more carbon atoms with the cyclic olefin has excellent impact resistance. Came to do.

[0006]

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

[0007]

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

[0008]

[Chemical 3]

[I] (In the 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 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 monocycle or polycycle, and the monocycle or polycycle is It may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.),

[0010]

[Chemical 4]

[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 the 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, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are They may be bonded to each other to form a monocyclic or polycyclic aromatic ring).

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

[0013]

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin-based copolymer composition and the method for producing the same according to the present invention will be specifically described below.

First, a hydrocarbon-based elastomer containing substantially no polymerizable double bond will be described.

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

Hereinafter, these 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 types 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-
C2-C20 alpha-olefins, such as eicosene, can be mentioned.

Specific examples of such α-olefin copolymers include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1- Hexene copolymer, ethylene-4-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 thereof include a propylene / 1-dodecene copolymer, a propylene / 1-tetradecene copolymer, a propylene / 1-hexadecene copolymer, a propylene / 1-octadecene copolymer and a propylene / 1-eicosene copolymer.

Such an α-olefin-based copolymer is
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 it is desirable that the glass transition temperature (Tg) is lower than 10 ° C, preferably 0 ° C or lower. (Ii) α-Olefin / Cyclic Olefin Copolymer α-Olefin / Cyclic Olefin Copolymer is a random copolymer formed from at least one α-olefin 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
Mention may be made of olefins.

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

Specific examples of such α-olefin / cycloolefin copolymers include ethylene / norbornene copolymers, ethylene / 5-methyl-2-norbornene copolymers, 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 / 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 Examples thereof include -decene / 5-dodecyl-2-norbornene copolymer, ethylene / 1-decene / 5-phenyl-2-norbornene copolymer, and ethylene / 1-decene / tetracyclododecene copolymer.

13 of these α-olefin copolymers
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.
is in the range of 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 cycloolefin copolymer composition of the present invention will be described. The cyclic olefin-based copolymer composition according to the present invention contains an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) having a substantially polymerizable double bond as described above. It is obtained by copolymerization in the presence of a hydrocarbon-based elastomer [A].

Specific examples of the α-olefin (a) having 2 or more carbon atoms include 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 can be mentioned.

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

[0026]

[Chemical 5]

[I] In the formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. In addition, when q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group, and 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, the halogen atom is a fluorine atom,
Examples thereof include chlorine atom, bromine atom and iodine atom.

The hydrocarbon group is usually, independently of each other, an alkyl group having 1 to 20 carbon atoms and 3 to 1 carbon atoms.
And the cycloalkyl group of 5. More specifically,
Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and examples of the cycloalkyl group include a cyclohexyl group.

These groups may be substituted with 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 ^{15 16} and R ¹⁷ may be bonded to each other (cooperate 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 monocycle or polycycle formed here is exemplified below.

[0032]

[Chemical 6]

In the above exemplification, the carbon atom numbered 1 or 2 is represented by R ¹⁵ (R ¹⁶ ) in the formula [I].
Alternatively, it is a carbon atom forming an alicyclic structure to which R ¹⁷ (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 usually includes an alkylidene group having 2 to 20 carbon atoms, and specific examples thereof include an ethylidene group, a propylidene group and an isopropylidene group.

[0035]

[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 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 above formula [I].

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

The alicyclic hydrocarbon group has 3 carbon atoms.
The alicyclic hydrocarbon group of 15 to 15 are mentioned, and a cyclohexyl group is specifically mentioned. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specifically include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenylethyl group, and the like, and these groups are lower alkyl groups. May have.

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

[0043]

[Chemical 8]

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

Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo [2.2.1] hept-2-ene derivative 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 12,16} ] -5-Eicosene derivative, 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 can be mentioned.

The details will be described below.

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical formula 12]

[0051]

[Chemical 13]

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

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

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 the formula [II] and the α-olefin (a) having 2 or more carbon atoms. ,
It is an addition polymer obtained by polymerizing in the presence of the above-mentioned hydrocarbon elastomer [A] which does not substantially contain a polymerizable double bond.

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-based copolymer composition thus obtained is an α-olefin having 2 or more carbon atoms in the presence of a hydrocarbon-based elastomer [A] which does not substantially contain a polymerizable double bond. (A) and cyclic olefin (b)
As a result, the dispersibility of the cyclic olefin random copolymer formed from the α-olefin (a) and the cyclic olefin (b) and the hydrocarbon elastomer [A] is extremely good. .. This is 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 that does not substantially contain a polymerizable double bond. The cyclic olefin-based copolymer composition simply melts the cyclic olefin random copolymer obtained by copolymerizing the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) and the hydrocarbon-based elastomer. It is also shown to be superior in impact resistance to the cycloolefin copolymer composition obtained by mixing and blending.

In the above cyclic olefin copolymer composition according to the present invention, in addition to the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) within a range not impairing the properties of the copolymer. , Α-other than the above α-olefins
It is also possible to carry out addition polymerization of an olefin (third monomer) or a cyclic olefin (other cyclic olefin) other than the cyclic olefin represented by the above formula [I] or [II].

The α-olefin used here may be a linear α-olefin or a branched α-olefin, and examples of such α-olefin include propylene and 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 these, 3 carbon atoms
It is preferred to use .about.15, especially 3 to 10 .alpha.-olefins.

The "other cyclic olefin" used herein is 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 thereof 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 added in a liquid phase, preferably in a hydrocarbon solvent, to the copolymer composition obtained in an amount of 1 to 50 parts by weight of the component [A]. It can be prepared by copolymerization such that it is present in an amount of%.

The above 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. It can be carried out in the presence of a catalyst formed with an oxy compound.

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

These compounds can be used alone or in combination of two or more kinds. The soluble vanadium compound 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. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilane, and nitrogen-containing electron donors such as ammonia, 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, isopropylbenzyl. C1-C18 alcohols such as alcohols and C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol , C6-20 phenols which may have a lower alkyl group such as naphthol, acetone, methyl ethyl ketone Emissions, methyl isobutyl ketone,
C2-C15 ketones such as acetophenone, benzophenone and benzoquinone, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other carbon atoms 2
~ 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 benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate and other organic acid esters having 2 to 18 carbon atoms, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and the like having 2 to 1 carbon atoms
5, acid halides, methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether, acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic acid, and alkoxy such as ethyl silicate and diphenyldimethoxysilane. Acid amides such as silane, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine Examples thereof include nitriles such as acetonitrile, benzonitrile and trinitrile, and pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine.

When preparing an electron donor adduct of a soluble vanadium compound, these electron donors can be used alone or in combination of two or more kinds. In the present invention, the organoaluminum compound used together with the soluble vanadium compound in forming the catalyst (i) has at least one Al-C bond in the molecule, and for example, the following (a) and (b ) Is represented by the formula.

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² are usually 1 to 15 carbon atoms,
It is preferably 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, p is 0 ≦ p <
3 and q are numbers 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 (a) above include the following compounds. (1) General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as described above, and m is preferably a number of 1.5 ≦ m <3). (2) General formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above, X is a 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
Is the number of). (4) General formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
Is. ).

More specifically, the organoaluminum compound represented by (a) can be exemplified by the following compounds. Examples of the organoaluminum compound represented by (1) are trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Sesquiethoxide, butyl aluminum sesquibutoxide and R ¹ _2.5 Al
Partially alkoxylated alkyl aluminum having an average composition represented by (OR ² ) _{0.5 and 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 and butyl aluminum dibromide.

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

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

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

[0091]

[Chemical 31]

Examples thereof include: The compound belonging to (b) above includes LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₇ H ₁₅₎ and the like can be exemplified _4.

Of these, alkylaluminum halides, alkylaluminum dihalides and mixtures thereof are particularly preferable. It is then used in the present invention (ii)
A catalyst formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminumoxy compound will be described.

A metallocene compound of a transition metal 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 that coordinates to a transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and has this cyclopentadienyl skeleton. The ligand may have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton include 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, 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.
Hydrocarbon group, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (-SO ₃ R ^a), wherein a halogen atom or a hydrogen atom (, R ^a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or It is 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. More specifically, a methyl group, an ethyl group, and n-propyl are exemplified. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, etc. Examples thereof 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 neofil group.

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

Examples of the aryloxy group include phenoxy group and the like. Examples of the sulfonic acid-containing group (—SO ₃ ^Ra ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The metallocene compound represented by the above formula (a) has a transition metal 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 formula (b), M is the above transition metal, and R ² is a group (ligand) having a cyclopentadienyl skeleton. 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
It is the above integer, and k + l + m + n = 4.

Examples of the metallocene compound in which M is zirconium and at least two ligands having a cyclopentadienyl skeleton are shown below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopenta 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 methoxy chloride, bis (cyclopentadienyl) di Ruconium ethoxy chloride, 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 (trifluoromethane sulfonate),
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 1,3-position-substituted cyclopentadienyl group is replaced with a 1,2-position-substituted cyclopentadienyl group can also be used.

In the above formula (b), R ² , R ³ and R
^At least two of ⁴ and R ⁵ , ie R ² and R ³
Is a group (ligand) having a cyclopentadienyl skeleton, and these groups having two cyclopentadienyl skeletons are bonded to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. It is also possible to exemplify a bridge-type metallocene compound. At this time, R ⁴ and R ⁵ are independently the same as L other than the ligand having the cyclopentadienyl skeleton described in the formula (a).

Examples of such bridge-type metallocene compounds include the following compounds. Ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (indenyl) zirconium bis (P-toluenesulfonato), ethylenebis (indenyl) zirconium bis (p-chlorobenzenesulfonato), etc.

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

These compounds may be used alone or
You may use it in combination of 2 or more type. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.
In the present invention, the metallocene compound is preferably diluted with a hydrocarbon solvent before use.

The metallocene compound as described above can also be used together with the carrier compound by bringing it into contact with the particulate carrier compound. Carrier compounds include 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 and ThO, polyethylene, polypropylene, poly-1-butene, poly 4-
Resins such as methyl-1-pentene and styrene-divinylbenzene copolymer can be used. These carrier compounds may be used as a mixture of two or more kinds.

In the present invention, as the metallocene compound, a zirconocene compound having a central metal atom of zirconium and having a ligand containing 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 explained. The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound.

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

[0112]

[Chemical 32]

(In the above general formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more. , Preferably an integer of 5 to 40.) where the aluminoxane has the formula (OA
1 (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OA1 (R ² )) [wherein R ¹ and R ² are the same hydrocarbon groups as R. And R ¹ and R ²
Represent different groups].

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 adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice, or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent.

Among these methods, it is preferable to adopt the method (1). The organoaluminum compound used in producing the solution of aluminoxane specifically includes trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum, tri
tert-Butylaluminium, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, trialkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminium chloride, diethylaluminium chloride, diethylaluminum bromide, diisobutylaluminum chloride. Dialkyl aluminum hydrides such as dialkyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride, etc., dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, etc.
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers, and z ≧ 2x) The above-mentioned organic aluminum The compounds may be used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or the above-mentioned organoaluminum compound and water. It can be obtained by a method of contacting.

[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 preferably in the range of to 0.07.

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

[0121]

[Chemical 33]

In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group.
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 preferable, and a methyl group is particularly preferable.

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]

[Chemical 34]

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. Further, R ⁸ and R ⁷ in the above formula represent different groups.

When containing an oxyaluminum unit, an organoaluminum oxy having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion 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. The organoaluminum oxy compound can also be used by supporting it on the above-mentioned carrier compound.

In the present invention, the catalyst (i) or (ii) as described above is used, and in the presence of the hydrocarbon elastomer [A], an α-olefin having 2 or more carbon atoms and the above formula [I]. Alternatively, the cyclic olefin represented by [II] is copolymerized in a liquid phase, preferably in a hydrocarbon solvent.

Examples of such a hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof, and cycloaliphatic 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. The above-mentioned copolymerization reaction can also be carried out by using α-olefin or cyclic olefin itself as a hydrocarbon solvent. These solvents may be mixed and used.

In the present invention, the copolymerization is preferably carried out in the coexistence of the above 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 copolymerization may be carried out by either a batch method or a continuous method, but it 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 liter of the polymerization volume, and an organic solvent. The aluminum compound is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20 in terms of a ratio of aluminum atoms to vanadium atoms in the polymerization system (Al / V). 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 (when the copolymerization is carried out by a continuous method) present in the polymerization system. It is desirable to be 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 hydrocarbon solvent and supplied to the polymerization system. At this time, the soluble vanadium compound is preferably diluted to the above-mentioned concentration, but the organoaluminum compound should be prepared at 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 amount of the metallocene compound in the polymerization system is usually 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 organoaluminumoxy compound is such that the aluminum atom in the organoaluminumoxy compound is usually about 1 to 10000 mol, preferably 10 to 5000 mol, relative to 1 mol of the transition metal atom in the metallocene compound. Used in quantity.

The copolymerization reaction carried out in the presence of the catalyst (i) or (ii) as described above is usually carried out at a temperature of -50 ° C to 1 ° C.
50 ° C., preferably −30 ° C. to 100 ° C., more preferably −20 ° C. to 70 ° C., pressure exceeding 0 to −50 Kg /
It is carried out under the condition of cm ² , preferably more than 0 and -20 kg / cm ² . Further, the reaction time (average residence time when the copolymerization is carried out by a continuous method) depends on the kind of the monomer used,
The time is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours, varying depending on conditions such as catalyst concentration and polymerization temperature.

In the above copolymerization reaction, α-containing 2 or more carbon atoms is used.
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 an amount such that it is 0/50.

Further, in the case of copolymerization, a molecular weight modifier such as hydrogen can be used. As described above, in the presence of the hydrocarbon 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 added. By copolymerization, a solution containing the cyclic olefin-based copolymer composition is obtained.
In such a solution, the cyclic olefin-based copolymer composition is usually 10 to 500 g / liter and 10 to 300 g.
Included at a concentration of / liter. This solution is processed by a conventional method to obtain a cyclic olefin-based copolymer composition.

In order to produce the cyclic olefin copolymer composition according to the present invention, more specifically, the hydrocarbon elastomer [A] already produced, for example, elastomer pellets or bails is dissolved in a hydrocarbon solvent. In this solution, the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) may be copolymerized, and first, the above-mentioned hydrocarbon type elastomato [A] is produced and the polymerization thereof is carried out. The α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) may be copolymerized in the solution.

The cyclic olefin copolymer composition provided by the present invention is molded by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, practicator, mixer, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder. Machine, screwless extruder, etc., extrusion molding, injection molding, blow molding, rotational molding.

Further, the cyclic olefin copolymer composition of the present invention is compounded with a rubber component for further improving the impact strength, to the extent that the object of the present invention is not impaired. Alternatively, a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like can be appropriately added.

For example, as a stabilizer to be added 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′-oxamide bis [ethyl-3 (3,5- Di-t-butyl-4-hydroxyphenyl)] propionate and other phenolic antioxidants, zinc stearate, calcium stearate, fatty acid metal salts such as 12-hydroxy calcium stearate, glycerin monostearate, glycerin monolaurate, glycerin Examples thereof include fatty acid esters of polyhydric alcohols such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate and Examples thereof include a combination with glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a polyhydric alcohol fatty acid ester in combination, and the polyhydric alcohol fatty acid ester is one of the alcoholic hydroxyl groups of the trihydric or higher polyhydric alcohol. The part is preferably a polyhydric alcohol fatty acid ester esterified. As such fatty acid ester of polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid ester 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. The fatty acid ester 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.

In the present invention, the cyclic olefin-based random copolymer composition may contain silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, water insofar as the object of the present invention is not impaired. Aluminum oxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber Fillers such as silicon carbide fibers, α-olefin fibers having 2 or more polycarbons, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

[0143]

Industrial Applicability The cyclic olefin copolymer composition obtained by the present invention has α 2 or more carbon atoms in the presence of a hydrocarbon elastomer which does not substantially contain a polymerizable double bond.
-Since the olefin (a) and the cyclic olefin (b) are copolymerized, the cyclic olefin copolymer phase and the elastomer phase are well dispersed, 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 was measured using a DSC-220C manufactured by Seiko Instruments Inc. in a nitrogen atmosphere at a temperature rising rate of 10 ° C / min. (3) Softening temperature (TMA) It was measured by 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, add a load of 49 g, and 5 ℃
The temperature rises at a rate of / min, and the quartz needles make 0.635 on the sheet.
The temperature of mm penetration was taken as TMA. (4) Preparation of test piece Using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold, molding was performed under the following molding conditions. After molding, the test piece was allowed to stand at room temperature for 48 hours and then measured. (5) Bending test The bending test was performed according to ASTM D790.

Test piece shape: 5 × 1/2 × 1/8 t inch, span distance 51 mm (6) Izod impact test Measured according to ASTM D256.

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

[0148]

Example 1 Using a 2-liter glass polymerization vessel equipped with a stirring blade, ethylene and tetracyclo [4.4.0.1 ^{2] in the} presence of a hydrocarbon-based elastomer substantially free of a polymerizable double bond. Copolymerization with ^{, 5} .1 ^7,10 ] -3-dodecene (hereinafter abbreviated as TCD) was continuously carried out by the following method.

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

Copolymerization reaction was carried out while maintaining the polymerization system at 10 ° C. by circulating a refrigerant in a jacket attached to the outside of the polymerization vessel. A solution of a cyclic olefin-based copolymer composition composed of an ethylene / propylene copolymer and an ethylene / TCD copolymer produced by the above-mentioned copolymerization reaction is constantly fed from the upper part of the polymerization vessel to 1 liter of the polymerization liquid in the polymerization vessel. (That is, the average residence time was 0.5 hours) was continuously withdrawn. To the extracted polymerization liquid,
The polymerization reaction was stopped by adding a cyclohexane / isopropyl alcohol (1: 1) mixed solution. 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 using a homomixer, and the catalyst residue was transferred to a water tank. After allowing the contact mixture to stand, the aqueous phase was separated and removed, and then distilled water was added to remove the mixture.
It was washed with water twice, and the polymerization liquid phase was purified and separated.

Then, the purified and separated polymerization liquid was contacted with 3-fold amount of acetone under strong stirring, and then the solid portion was collected by filtration and thoroughly washed with acetone. In addition, the solid portion washed to extract the TCD present in the polymer is 40
After charging into acetone so that the concentration would be g / liter, 6
The extraction operation was performed under the conditions of 0 ° C. for 2 hours. After the extraction process,
The solid part was collected by filtration, and under nitrogen flow, at 130 ° C, 3
It was dried at 50 mmHg for 24 hours.

As described above, a cyclic olefin copolymer composition comprising an ethylene / propylene copolymer and an ethylene / TCD copolymer was added at 81.4 g / hour, that is, 40.7 g / liter. Obtained. The ratio of the component [A] contained in the produced 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, the impact strength test and the TMA softening test.

[0154]

Example 2 In Example 1, the amount of ethylene / propylene copolymer supplied was changed from 1.2 g / liter to 4.0 g / liter.
A cyclic olefin-based 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 1 liter.

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

[0156]

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

A test piece was prepared from the obtained copolymer composition and its physical properties were evaluated. The results are shown in Table 2. When various elastomers were used, all systems showed a high impact improving effect.

[0158]

Example 6 In Example 1, except that 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter abbreviated as MTHF) was used in place of TCD which was the component (b) (B). The same operation as in Example 1 was performed.

A test piece was prepared from the obtained cyclic olefin copolymer composition, and its physical properties were evaluated. The results are shown in Table 2.
Shown in.

[0160]

Example 7 Ethylenebis (indenyl) zirconium dichloride [Et (Ind) ₂ ZrCl _{2 as} a catalyst, concentration in polymerization system: 0.2 mmol / liter] and methylaluminoxane [MAO, Al concentration in polymerization system: 20.0 Was used in the same manner as in Example 1 except that a part of the polymerization conditions was changed, and a cyclic olefin copolymer composed of an ethylene / propylene copolymer and an ethylene / TCD copolymer was used. A composition was produced.

A test piece was prepared from the obtained copolymer composition and its physical properties were evaluated. The results are shown in Table 2. In this case as well, the effect of improving impact resistance by copolymerization in the presence of an elastomer was clarified.

[0162]

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

A test piece was prepared from the obtained copolymer and its physical properties were evaluated. The results are shown in Table 3.

[0164]

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

Test pieces were prepared from the obtained copolymer and the physical properties thereof were evaluated. The results are shown in Table 3.

[0166]

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

Test pieces were prepared from the obtained pellets and the physical properties were evaluated. The results are shown in Table 3.

[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 in Comparative Example 2.

Test pieces were prepared from the obtained composition, and the physical properties were evaluated. The results are shown in Table 3.

[0170]

[Table 1]

[0171]

[Table 2]

[0172]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshimasa Takada 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. An intrinsic viscosity [η] measured at 135 ° C. in decalin [A] 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 having substantially no double bond capable of polymerization, (b) ) Obtained by copolymerizing with a cyclic olefin represented by the following general formula [I] or [II], and the component [A] is present in the resulting copolymer composition in an amount of 1 to 50% by weight. A cyclic olefin-based 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, and 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 monocycle or polycycle, and the monocycle or polycycle is a double bond. 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 R ¹³ (or R ¹⁰ ) is bonded to the carbon atom to which R ¹³ or R ¹¹ is 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. The intrinsic viscosity [η] measured at 135 ° C. in decalin [A] 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 having substantially no double bond capable of polymerization, (b) ) In the liquid phase, a cyclic olefin represented by the general formula [I] or [II] is copolymerized, and the resulting copolymer composition contains 1 to 50% by weight of the component [A]. And a cyclic olefin-based copolymer composition.