JPH05320267A - Cycloolefin copolymer composition and its production - Google Patents

Abstract

PURPOSE:To obtain a copolymer excellent in impact strength, toughness, etc., by copolymerizing at least two monomers selected from the group consisting of an alpha-olefin, a cycloolefin, and a diene compd. in the presence of a specific cycloolefin random copolymer. CONSTITUTION:A 2C or higher alpha-olefin and a cycloolefin of formula I or II (wherein R<1> to R<19> R<a>, and R<b> are each H, halogen, a hydrocarbon group, etc.) are copolymerized to give a cycloolefin random copolymer having a glass transition temperature by DSC of 50 deg.C or higher and an intrinsic viscosity in decalin at 135 deg.C of 0.1-5dl/g. At least two monomers selected from the group consisting of the 2C or higher alpha-olefin, the cycloolefin of formula I or II, and a diene compd. are copolymerized in the presence of the random copolymer to give a hydrocarbon elastomer having a glass transition temperature of 10 deg.C or lower and a content of the random copolymer of 50-99wt.%.

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 inventors of the present invention have made extensive studies to solve the above problems in the prior art. As a result, they can be obtained by copolymerizing an α-olefin having 2 or more carbon atoms such as ethylene with a cyclic olefin. In the presence of the cyclic olefin copolymer, at least two kinds of monomers selected from (i) α-olefin, (ii) cyclic olefin, and (iii) diene compound are copolymerized to obtain a hydrocarbon elastomer. The inventors have found that the cyclic olefin-based copolymer composition obtained by production has a good balance of mechanical properties such as impact resistance, heat resistance, etc., and completed the present invention.

[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 copolymer composition according to the present invention is represented by [A] (a) an α-olefin having 2 or more carbon atoms and (b) represented by the following general formula [I] or [II]. Obtained by copolymerizing at least one cyclic olefin
The glass transition point measured by SC is 50 ° C or higher, 13
Intrinsic viscosity [η] measured in decalin at 5 ° C is 0.10
To 5.0 dl / g in the presence of a cyclic olefin-based random copolymer, [B] i) an α-olefin having 2 or more carbon atoms ii) represented by the following general formula [I] or [II] Cyclic olefin iii) Diene compound, which is obtained by copolymerizing at least two kinds of monomers selected from the following to produce a hydrocarbon elastomer, and the glass transition point of the component [B] is less than 10 ° C, and the composition is [A] in things
The components are characterized in that they are present in an amount of 50 to 99% by weight.

[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).

The method for producing a cyclic olefin random copolymer composition according to the present invention comprises [A] (a) an α-olefin having 2 or more carbon atoms and (b) the above general formula [I] or [II]. ] The glass transition point (Tg) measured by DSC is 50 ° C. or higher, and the intrinsic viscosity [η] measured in decalin at 135 ° C. Is 0.10 to 5.0 dl / g, in the presence of a cyclic olefin-based random copolymer, [B] i) an α-olefin having 2 or more carbon atoms ii) the above general formula [I] or [II] A hydrocarbon-based elastomer is produced by copolymerizing at least two kinds of monomers selected from cyclic olefins iii) diene compounds represented by the following formula, and the glass transition point of the component [B] is less than 10 ° C .: [A] component in the composition,
It is characterized in that it is present in an amount of 50 to 99% 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, the cyclic olefin random copolymer [A] will be specifically described.

Cyclic Olefin Random Copolymer [A] The cyclic olefin random copolymer [A] used in the present invention comprises an α-olefin (a) having 2 or more carbon atoms and the following formula [I] or [I]: II] a random copolymer with a cyclic olefin (b), having a glass transition point measured by DSC of 50 ° C. or higher, preferably 60 ° C. or higher,
More preferably, it is 70 to 220 ° C., and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.10 to 5.0.
dl / g, preferably 0.15 to 2.0 dl / g.

The cyclic olefin random copolymer [A] as described above does not substantially contain a polymerizable double bond. 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-eikosen and the like.

These α-olefins (a) can be used alone or in combination of two or more.

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.

[0019]

[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, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and a cycloalkyl group includes a cyclohexyl group, Examples thereof include a methylcyclohexyl group, a cyclopentyl group and an ethylcyclohexyl 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.

[0025]

[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.

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, an isopropylidene group, and an isobutylidene group.

[0028]

[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 an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, an amyl group and a hexyl group. , Octyl group, decyl group, dodecyl group and octadecyl group.

The alicyclic hydrocarbon group has 3 carbon atoms.
The alicyclic hydrocarbon groups of 15 to 15 are mentioned, and specific examples thereof include a cyclohexyl group, a cyclopentyl group, a methylcyclohexyl group, and an ethylcyclohexyl group.

As the aromatic hydrocarbon group, an aryl group,
Examples thereof include an aralkyl group and the like, and specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenylethyl group, etc. These groups may have a lower alkyl group.

Examples of the alkoxy group include methoxy group, ethoxy group and 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.

[0037]

[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 .1 ^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.

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical formula 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

[0056]

[Chemical formula 24]

[0057]

[Chemical 25]

[0058]

[Chemical formula 26]

[0059]

[Chemical 27]

[0060]

[Chemical 28]

[0061]

[Chemical 29]

[0062]

[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 kinds. In the above cyclic olefin random copolymer, α
-The molar ratio (a) / (b) of the olefin (a) and the cyclic olefin (b) is 30/70 to 97/3, preferably 5
It is preferably 0/50 to 95/5.

The cyclic olefin-based copolymer as described above contains, in addition to the α-olefin (a) and the cyclic olefin (b) each having 2 or more carbon atoms, the above α-olefin as long as the properties of the copolymer are not impaired. -Α-olefins other than olefins (3rd
Monomer) or a cyclic olefin (other cyclic olefin) other than the cyclic olefin represented by the above formula [I] or [II] may be addition-polymerized.

The α-olefin used here may be a linear α-olefin or a branched α-olefin. Examples of such an 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 represented by a broad concept including unsaturated polycyclic hydrocarbon compounds except 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, styrene and 3a, 5,6,7a-tetrahydro-4, 7-
Examples thereof include methano-1H-indene.

Next, the cycloolefin copolymer composition according to the present invention will be described. The cyclic olefin copolymer composition according to the present invention comprises: [B] i) an α-olefin having 2 or more carbon atoms; and ii) a cyclic olefin in the presence of the cyclic olefin random copolymer [A] as described above. iii) Obtained by copolymerizing at least two monomers selected from diene compounds to produce a hydrocarbon elastomer.

I) As the α-olefin having 2 or more carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Mention may be made of 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Ii) As the cyclic olefin, specifically, the cyclic olefin represented by the above general formula [I] or [II] is used. iii) Specific examples of the diene compound include butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene and 2-methyl.
-1,5-hexadiene, 4-methyl-1,5-hexadiene, 5-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene,
Chain dienes such as 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2
-Norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, norbornadiene, 1,2-
Examples thereof include bis [5- (2-norbornenyl)] ethane and cyclic dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene and tetracyclo-3,8-dodecadiene.

Thus, the hydrocarbon elastomer is
It is obtained by copolymerizing at least two kinds of monomers selected from i) α-olefins having 2 or more carbon atoms, ii) cyclic olefins and iii) diene compounds. 2 or more, for example, i) 2 or more olefins having 2 or more carbon atoms may be selected.

Specific examples of such a hydrocarbon elastomer include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1-hexene copolymer. 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, propylene / 1-dodecene copolymer, propylene / 1-tetradecene copolymer, propylene / 1-hexadecene copolymer, propylene / 1-octadecene copolymer, Examples thereof include propylene / 1-eicosene copolymer.

Specific examples of the hydrocarbon elastomer 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 / 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-
Examples thereof include a phenyl-2-norbornene copolymer and an ethylene / 1-decene / tetracyclododecene copolymer.

Further, as specific examples of the hydrocarbon-based elastomer, firstly, specific examples of the 1,5-hexadiene-based copolymer include ethylene / 1,5-hexadiene copolymer and propylene / 1,5- Hexadiene copolymer, 1-butene-1,5-
Hexadiene copolymer, 1-pentene / 1,5-hexadiene copolymer, 1-hexene / 1,5-hexadiene copolymer, 4-
Methyl-1-pentene ・ 1,5-hexadiene copolymer, 1-octene ・ 1,5-hexadiene copolymer, 1-decene ・ 1,5-hexadiene copolymer, 1-dodecene ・ 1,5-hexadiene Copolymer, 1-tetradecene / 1,5-hexadiene copolymer,
1-hexadecene / 1,5-hexadiene copolymer, 1-octadecene / 1,5-hexadiene copolymer, 1-eicosene / 1
5-hexadiene copolymer, ethylene / propylene / 1,5-
Hexadiene copolymer, ethylene / 1-butene / 1,5-hexadiene copolymer, ethylene / 1-pentene / 1,5-hexadiene copolymer, ethylene / 1-hexene / 1,5-hexadiene copolymer, Ethylene 4-methyl-1-pentene-1,5-
Hexadiene copolymer, ethylene / 1-octene / 1,5-hexadiene copolymer, ethylene / 1-decene / 1,5-hexadiene copolymer, ethylene / 1-dodecene / 1,5-hexadiene copolymer, Ethylene / 1-tetradecene / 1,5-hexadiene copolymer, ethylene / 1-hexadecene / 1,5-hexadiene copolymer, ethylene / 1-octadecene / 1,5-hexadiene copolymer, ethylene / 1-eicocene -1,5-hexadiene copolymer, ethylene-norbornene-1,5-hexadiene copolymer, ethylene-5-methyl-2-norbornene-1,5-hexadiene copolymer, ethylene-5-ethyl
-2-norbornene ・ 1,5-hexadiene copolymer, ethylene ・ 5-phenyl-2-norbornene ・ 1,5-hexadiene copolymer, ethylene ・ tetracyclododecene ・ 1,5-hexadiene copolymer, etc. Can be mentioned.

Specific examples of the 1,7-octadiene copolymer include ethylene / 1,7-octadiene copolymer, propylene / 1,7-octadiene copolymer, 1-butene / 1,7- Octadiene copolymer, 1-pentene / 1,7-octadiene copolymer, 1-hexene / 1,7-octadiene copolymer, 4-methyl-1-pentene / 1,7-octadiene copolymer, 1- Octene / 1,7-octadiene copolymer, 1-decene / 1,7-octadiene copolymer, 1-dodecene / 1,7-octadiene copolymer, 1-tetradecene / 1,7-octadiene copolymer, 1-
Hexadecene / 1,7-octadiene copolymer, 1-octadecene / 1,7-octadiene copolymer, 1-eicosene / 1,7-
Octadiene copolymer, ethylene / propylene / 1,7-octadiene copolymer, ethylene / 1-butene / 1,7-octadiene copolymer, ethylene / 1-pentene / 1,7-octadiene copolymer, ethylene / 1-hexene / 1,7-octadiene copolymer, ethylene / 4-methyl-1-pentene / 1,7-octadiene copolymer, ethylene / 1-octene / 1,7-octadiene copolymer, ethylene / 1 -Decene / 1,7-octadiene copolymer, ethylene / 1-dodecene / 1,7-octadiene copolymer, ethylene / 1-tetradecene / 1,7-octadiene copolymer, ethylene / 1-hexadecene / 1 7-octadiene copolymer, ethylene / 1-octadecene / 1,7-octadiene copolymer, ethylene / 1-eicosene / 1,7-octadiene copolymer, ethylene / norbornene / 1,7-octadiene copolymer, Ethylene-5-methyl-2-norbo Runne / 1,7-octadiene copolymer, ethylene / 5-ethyl-2
-Norbornene / 1,7-octadiene copolymer, ethylene / 5-phenyl-2-norbornene / 1,7-octadiene copolymer, ethylene / tetracyclododecene / 1,7-octadiene copolymer You can

Specific examples of the 1,9-decadiene copolymer include ethylene / 1,9-decadiene copolymer, propylene / 1,9-decadiene copolymer, and 1-butene / 1,9. -Decadiene copolymer, 1-pentene / 1,9-decadiene copolymer, 1-hexene / 1,9-decadiene copolymer, 4-methyl-1
-Pentene / 1,9-decadiene copolymer, 1-octene / 1,9
-Decadiene copolymer, 1-decene / 1,9-decadiene copolymer, 1-dodecene / 1,9-decadiene copolymer, 1-tetradecene / 1,9-decadiene copolymer, 1-hexadecene / 1 ,
9-decadiene copolymer, 1-octadecene / 1,9-decadiene copolymer, 1-eicosene / 1,9-decadiene copolymer,
Ethylene / propylene / 1,9-decadiene copolymer, ethylene / 1-butene / 1,9-decadiene copolymer, ethylene /
1-pentene / 1,9-decadiene copolymer, ethylene / 1-hexene / 1,9-decadiene copolymer, ethylene / 4-methyl
-1-Pentene / 1,9-decadiene copolymer, ethylene / 1-
Octene / 1,9-decadiene copolymer, ethylene / 1-decene / 1,9-decadiene copolymer, ethylene / 1-dodecene /
1,9-decadiene copolymer, ethylene / 1-tetradecene
1,9-decadiene copolymer, ethylene / 1-hexadecene /
1,9-decadiene copolymer, ethylene / 1-octadecene
1,9-decadiene copolymer, ethylene / 1-eicosene / 1
9-decadiene copolymer, ethylene / norbornene / 1,9-
Decadiene copolymer, ethylene / 5-methyl-2-norbornene / 1,9-decadiene copolymer, ethylene / 5-ethyl-2
-Norbornene / 1,9-decadiene copolymer, ethylene / 5
-Phenyl-2-norbornene-1,9-decadiene copolymer,
Examples thereof include ethylene / tetracyclododecene / 1,9-decadiene copolymer.

Specific examples of the dicyclopentadiene copolymer include ethylene / dicyclopentadiene copolymer, propylene / dicyclopentadiene copolymer, 1-butene / dicyclopentadiene copolymer, 1-pentene.・ Dicyclopentadiene copolymer, 1-hexene / dicyclopentadiene copolymer, 4-methyl-1-pentene / dicyclopentadiene copolymer, 1-octene / dicyclopentadiene copolymer, 1-decene / diene Cyclopentadiene copolymer, 1-dodecene / dicyclopentadiene copolymer, 1-tetradecene / dicyclopentadiene copolymer, 1-hexadecene / dicyclopentadiene copolymer, 1-octadecene / dicyclopentadiene copolymer, 1-eicosene / dicyclopentadiene copolymer, ethylene / propylene /
Dicyclopentadiene copolymer, ethylene / 1-butene
Dicyclopentadiene copolymer, ethylene / 1-pentene / dicyclopentadiene copolymer, ethylene / 1-hexene / dicyclopentadiene copolymer, ethylene / 4-methyl-1-pentene / dicyclopentadiene copolymer, Ethylene / 1-octene / dicyclopentadiene copolymer, ethylene / 1-decene / dicyclopentadiene copolymer, ethylene / 1-dodecene / dicyclopentadiene copolymer,
Ethylene / 1-tetradecene / dicyclopentadiene copolymer, ethylene / 1-hexadecene / dicyclopentadiene copolymer, ethylene / 1-octadecene / dicyclopentadiene copolymer, ethylene / 1-eicosene / dicyclopentadiene copolymer Copolymer, ethylene / norbornene / dicyclopentadiene copolymer, ethylene / 5-methyl-2-norbornene / dicyclopentadiene copolymer, ethylene / 5-ethyl-2-norbornene / dicyclopentadiene copolymer, ethylene / 5 -Phenyl-2-norbornene / dicyclopentadiene copolymer, ethylene / tetracyclododecene / dicyclopentadiene copolymer and the like can be mentioned.

Specific examples of the 5-vinylnorbornene-based copolymer include ethylene-5-vinylnorbornene copolymer, propylene / 5-vinylnorbornene copolymer,
1-butene / 5-vinylnorbornene copolymer, 1-pentene / 5-vinylnorbornene copolymer, 1-hexene / 5-vinylnorbornene copolymer, 4-methyl-1-pentene / 5-vinylnorbornene copolymer Coalesce, 1-octene / 5-vinylnorbornene copolymer, 1-decene / 5-vinylnorbornene copolymer, 1-dodecene / 5-vinylnorbornene copolymer,
1-tetradecene-5-vinyl norbornene copolymer, 1-hexadecene-5-vinyl norbornene copolymer, 1-octadecene-5-vinyl norbornene copolymer, 1-eicosene-5-vinyl norbornene copolymer, ethylene Propylene-5-vinylnorbornene copolymer, ethylene / 1-butene / 5-vinylnorbornene copolymer, ethylene / 1-pentene / 5-vinylnorbornene copolymer, ethylene / 1-hexene / 5-vinylnorbornene copolymer Coalescence, ethylene 4-
Methyl-1-pentene / 5-vinylnorbornene copolymer,
Ethylene / 1-octene / 5-vinylnorbornene copolymer, ethylene / 1-decene / 5-vinylnorbornene copolymer, ethylene / 1-dodecene / 5-vinylnorbornene copolymer, ethylene / 1-tetradecene-5- Vinyl norbornene copolymer, ethylene / 1-hexadecene / 5-vinyl norbornene copolymer, ethylene / 1-octadecene / 5-vinyl norbornene copolymer, ethylene / 1-eicosene-5-
Vinyl norbornene copolymer, ethylene / norbornene / 5-vinyl norbornene copolymer, ethylene / 5-methyl
-2-norbornene-5-vinylnorbornene copolymer, ethylene-5-ethyl-2-norbornene-5-vinylnorbornene copolymer, ethylene-5-phenyl-2-norbornene-5-vinylnorbornene copolymer, ethylene -Tetracyclododecene-5-vinyl norbornene copolymer and the like can be mentioned.

Such a hydrocarbon elastomer has an intrinsic viscosity [η] of 0.05 when measured in decalin at 135 ° C.
The glass transition temperature (Tg) is in the range of -10 dl / g, preferably 0.1-5 dl / g, and the glass transition temperature (Tg) is lower than 10 ° C, preferably 0 ° C or lower, and more preferably -10 ° C or lower.

In the cyclic olefin copolymer composition, the above cyclic olefin random copolymer is present in an amount of 50 to 99% by weight, preferably 80 to 98% by weight.

The thus-obtained cyclic olefin-based copolymer composition contains the α-olefin (i) having 2 or more carbon atoms, in the presence of the above-mentioned cyclic olefin-based random copolymer [A]. Since the hydrocarbon-based elastomer in which at least two kinds of monomers selected from the cyclic olefin (ii) and the diene compound (iii) are copolymerized is produced, the α-olefin (a) and the cyclic olefin ( Cyclic olefin random copolymer [A] formed from b)
The dispersibility between the phase and the hydrocarbon elastomer [B] phase is extremely good. That is, the cyclic olefin-based copolymer [A] originally having the property of a hard resin and the hydrocarbon-based elastomer [B] originally having the property of a soft resin are mixed at a micro level. This is selected from α-olefins (i) having 2 or more carbon atoms, cyclic olefins (ii) and diene compounds (iii) in the presence of the cyclic olefin random copolymer [A] as described above. A cyclic olefin-based copolymer composition obtained by copolymerizing at least two kinds of monomers is a cyclic olefin copolymer composition obtained by copolymerizing an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b). It is also shown to be superior in impact resistance to a cyclic olefin copolymer composition obtained by simply melt-blending an olefin random copolymer and a hydrocarbon elastomer and blending them.

The cyclic olefin copolymer composition according to the present invention comprises [B] i) an α-olefin having 2 or more carbon atoms in the presence of the cyclic olefin random copolymer [A] as described above ii) It is prepared by copolymerizing at least two kinds of monomers selected from cyclic olefin iii) diene compound in a liquid phase to produce a hydrocarbon elastomer.

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. It can be carried out in the presence of a catalyst formed from an oxy compound and (iii) a solid titanium catalyst, a catalyst formed from an organoaluminum compound and an electron donor.

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.

Such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers, acid amides. , Acid anhydrides, oxygen-containing electron donors such as 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. ).

[0090] (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 (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 specific examples of the organoaluminum compound represented by (a) include 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 propylaluminum 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 aluminum atoms are bound via an oxygen atom or a nitrogen atom. As such a compound, specifically,

[0097]

[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. Next, the catalyst (ii) used in the present invention, which is formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminumoxy compound, will be described.

The metallocene compound of the 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 and an aralkyl group, and more specifically, a methyl group, an ethyl group and 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, 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.

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

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The metallocene compound represented by the above formula (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 the 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 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.

[0118]

[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].

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 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.

[0123] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) The organic aluminum such as 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 a compound containing active hydrogen, or an organoaluminum compound and water as described above. It can be obtained by a method of contacting.

[0125] 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-mentioned benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0127]

[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.

[0130]

[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 organic aluminum 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.

Next, the catalyst (iii) formed from the solid titanium catalyst used in the present invention, the organoaluminum compound, and the electron donor will be described.

The solid titanium catalyst used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such a solid titanium catalyst is prepared by contacting the following magnesium compound, titanium compound and electron donor. Examples of the titanium compound used in the preparation of the solid titanium catalyst include T
A tetravalent titanium compound represented by i (OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4) can be given.

More specifically, TiCl_Four, TiB
r_Four, TiI_Four Tetrahalogenated titanium such as; Ti
(OCH₃) Cl₃, Ti (OC₂H_Five) Cl₃, Ti (O
-N-C_FourH₉) Cl ₃, Ti (OC₂H_Five) Br₃, Ti
(O-iso-C_FourH₉) Br₃Trihalogenated alco such as
Xytitanium; Ti (OCH₃)₂Cl₂, Ti (OC
₂H_Five)₂Cl₂, Ti (O-n-C_FourH₉)₂Cl₂, Ti
(OC₂H_Five)₂Br₂Such as dihalogenated dialkoxy
Tan; Ti (OCH₃)₃Cl, Ti (OC₂H_Five)₃C
l, Ti (O-n-C_FourH₉)₃Cl, Ti (OC₂H_Five)
₃Monohalogenated trialkoxy titanium such as Br; T
i (OCH₃)_Four, Ti (OC₂H_Five)_Four, Ti (O-n-
C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_Four, Ti (O-2-D
Chillhexyl)_Four Such as tetraalkoxy titanium
Can be mentioned.

Of these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred. Above all,
Titanium tetrachloride is particularly preferably used. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds are
It may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Of these titanium compounds, a tetravalent titanium compound is particularly preferable. Further, examples of the magnesium compound used for preparing the solid titanium catalyst include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl. Magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium,
Butyl magnesium halide and the like can be mentioned. These magnesium compounds may be used alone or may form a complex compound with an organic aluminum compound described later. Further, these magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, and isopropoxy magnesium chloride. Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; Alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; Ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxy magnesium such as;
Examples thereof include allyloxy magnesium such as phenoxy magnesium and dimethylphenoxy magnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reducible magnesium compound may be prepared from polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, etc. It may be brought into contact with the compound.

In the present invention, the magnesium compound may be a complex compound, a complex compound or a complex compound of the above magnesium compound with another metal, in addition to the above-mentioned reducing magnesium compound and non-reducing magnesium compound. It may be a mixture with a metal compound. Further, it may be a mixture of two or more of the above compounds.

Of these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferably used.

Examples of the electron donor used in the preparation of the solid titanium catalyst include organic carboxylic acid esters and polyvalent carboxylic acid esters described later, and specific examples thereof include compounds having a skeleton represented by the following formula. ..

[0146]

[Chemical 35]

[0147]

[Chemical 36]

[0148]

[Chemical 37]

[0149]

[Chemical 38]

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
At least one of R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a ring structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing a heteroatom such as N, O and S, and for example, -C-O-C.
-, - COOR, -COOH, -OH , -SO 3 H, -
Substituted hydrocarbon groups having a structure such as C—N—C— and —NH ₂ are mentioned.

Of these, a diester derived from a dicarboxylic acid in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms is preferable. Specific examples of the polyvalent carboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, α-
Diisobutyl methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, isopropyl diethyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl allyl malonate, diethyl diisobutylmalonate, diethyl dinormal butylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, diisobutyl butyl maleate, butyl maleate Fatty acid polycarboxylic acid ester such as diethyl acidate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconic acid, dimethyl citraconic acid; 1,2-cyclohexane Aliphatic polycarboxylic acids such as diethyl carboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Carboxylic acid ester; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate,
Monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mononormal butyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, Examples include aromatic polycarboxylic acid esters such as dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, di-2-ethylhexyl sebacate and the like. The esters derived from the long-chain dicarboxylic acids of

Among these polyvalent carboxylic acid esters,
A compound having a skeleton represented by the above-mentioned general formula is preferable, more preferably an ester derived from phthalic acid, maleic acid, substituted malonic acid and the like and an alcohol having 2 or more carbon atoms, and phthalic acid and a carbon atom. Number 2
Diesters obtained by the reaction with the above alcohols are particularly preferable.

As the polyvalent carboxylic acid ester, it is not always necessary to use the polyvalent carboxylic acid ester as described above as a starting material, and the polyvalent carboxylic acid ester is derived in the process of preparing the solid titanium catalyst. The compound capable of being used may be used to form a polyvalent carboxylic acid ester at the stage of preparing a solid titanium catalyst.

Examples of electron donors other than polyvalent carboxylic acids that can be used when preparing a solid titanium catalyst include:
Alcohols, amines, amides, as described below,
Ethers, ketones, nitriles, phosphines, stipines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes Examples thereof include organic silicon compounds such as compounds, organic acids, and amides and salts of metals belonging to Groups I to IV of the periodic table.

The solid titanium catalyst can be produced by bringing the above-mentioned magnesium compound (or magnesium metal), electron donor and titanium compound into contact with each other. In order to produce a solid titanium catalyst, a known method of preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be adopted. The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum.

The method for producing these solid titanium catalysts will be briefly described below by giving some examples. (1) A method of reacting a magnesium compound or a complex compound composed of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like. Further, when the reaction is performed as described above, the solid compound may be pulverized. Furthermore, when the reaction is carried out as described above, each component may be pretreated with an electron donor and / or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once. (2) A liquid magnesium compound having no reducing property,
A method of reacting a liquid titanium compound in the presence of an electron donor to deposit a solid titanium composite agent. (3) A method of further reacting a titanium compound with the reaction product obtained in (2). (4) In the reaction product obtained in (1) or (2),
A method of further reacting an electron donor and a titanium compound. (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be crushed in the presence of a crushing aid or the like. Alternatively, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be pulverized in the presence of the titanium compound, pretreated with a reaction aid, and then treated with halogen or the like. Examples of the reaction aid include organic aluminum compounds and halogen-containing silicon compounds. In this method, the electron donor is used at least once. (6) A method of treating the compound obtained in (1) to (4) with halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of bringing a reaction product of a metal acid compound, dihydrocarbyl magnesium and a halogen-containing alcohol into contact with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium is reacted with an electron donor, a titanium compound, and / or a halogen-containing hydrocarbon.

Among the methods for preparing a solid titanium catalyst described in (1) to (8) above, a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a method using a titanium compound is used. The method using halogenated hydrocarbons is preferable.

The amount of each of the above-mentioned components used in preparing the solid titanium catalyst varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is about 0.01 to 1 mol per mol of the magnesium compound. In an amount of 5 moles, preferably 0.05-2 moles, the titanium compound is about 0.1.
It is used in an amount of 01 to 500 mol, preferably 0.05 to 300 mol.

The solid titanium catalyst thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst, halogen / titanium (atomic ratio) is about 4-200,
It is preferably about 5-100, and the electron donor / titanium (molar ratio) is about 0.1-10, preferably about 0.2-.
About 6, and magnesium / titanium (atomic ratio) is about 1 to
Desirably 100, preferably about 2-50.

This solid titanium catalyst contains magnesium halide having a smaller crystal size than that of commercially available magnesium halide and usually has a specific surface area of about 50 m ^2.
/ G or more, preferably about 60 to 1,000 m ² / g, more preferably about 100 to 800 m ² / g. Since the solid titanium catalyst forms the catalyst component by integrating the above components, the composition thereof is not substantially changed by washing with hexane.

Such a solid titanium catalyst may be used alone or may be diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound or a polyolefin. When a diluent is used, it exhibits high catalytic activity even if it has a specific surface area smaller than that described above.

A method for preparing such a highly active titanium catalyst component is described, for example, in JP-A-50-108385.
50-126590, 51-20297, 51-28189, 51-64586, 51-92885, 51-1366
25, 52-87489, 52-100596, and
No. 52-147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-430
No. 94, No. 55-135102, No. 55-135103,
55-152710, 56-811, 56-11908, 56-18606, 58-83006, 58-1387.
05 publication, 58-138706 publication, 58-138707 publication,
58-138708, 58-138709, 58-1387
No. 10, gazette 58-138715 gazette, gazette 60-23404 gazette, the same
No. 61-21109, No. 61-37802, No. 61-37803.

As the organoaluminum compound catalyst used together with the above solid titanium catalyst, the above organoaluminum compounds are used.

The electron donor used with the above solid titanium catalyst includes alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides,
Oxygen-containing electron donor such as alkoxysilane, ammonia,
Nitrogen-containing electron donors such as amines, nitriles and isocyanates, or polyvalent carboxylic acid esters as described above can be used.

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol. Alcohols having 1 to 18 atoms; phenol, cresol, xylenol, ethylphenol, propylphenol,
6 to 20 carbon atoms which may have a lower alkyl group, such as nonylphenol, cumylphenol and naphthol
Phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, and other ketones having 3 to 15 carbon atoms;
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid. Ethyl, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, methyl malo Diisobutyl, cyclohexene carboxylic di -n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di -
Organic acid esters having 2 to 30 carbon atoms such as n-butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid 2 to 1 carbon atoms such as chloride
Acid halides of 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine , Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride Be done.

As the electron donor, an organosilicon compound represented by the following general formula can be used. R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and n is 0 <n
It is a number that satisfies <4. ) Specific examples of the organosilicon compound represented by the above general formula [1] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-ο-tolyldimethoxysilane,
Bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n
-Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane,
Vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like are used.

Of these, ethyltriethoxysilane, n-
Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis
Preferred are -p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane and diphenyldiethoxysilane.

Further, as the electron donor, an organosilicon compound represented by the following general formula can be used. SiR ¹ R ² _m (OR ³ ) _3-m (wherein R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, R ² is an alkyl group, a cyclopentyl group or a cyclopentyl group having an alkyl group; R ³ is a hydrocarbon group and m is a number satisfying 0 ≦ m ≦ 2.) R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ¹ is cyclopentyl. Other than the group, a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group and a 2,3-dimethylcyclopentyl group can be mentioned.

R ² is an alkyl group, a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a hexyl group. And the cyclopentyl group exemplified as R ¹ and the cyclopentyl group having an alkyl group can be mentioned in the same manner.

R ³ is a hydrocarbon group, and as R ³ ,
For example, alkyl group, cycloalkyl group, aryl group,
Hydrocarbon groups such as aralkyl groups may be mentioned.

Of these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane and cyclopentyltriethoxysilane; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, di Cyclopentylmethylmethoxysilane,
Examples include monoalocoxysilanes such as dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferable, and organic silicon compounds are particularly preferable.

In the present invention, the catalyst as described above is used,
In the presence of the cyclic olefin-based random copolymer [A],
Copolymerizing at least two monomers selected from α-olefins (i) having 2 or more carbon atoms, cyclic olefins (ii) and diene compounds (iii) in a liquid phase, preferably in a hydrocarbon solvent, Manufactures hydrocarbon elastomers.

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 can 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 1.0 mmol, preferably about 0.0001 to 0.5 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.

When the catalyst (iii) is used, the solid titanium catalyst is usually about 0.001 to about 1.0 mmol, preferably about 0.005 in terms of titanium atom per liter of polymerization volume. Used in an amount of ~ 0.5 mmol. The amount of the organoaluminum catalyst is such that the metal atom in the organoaluminum compound catalyst is usually about 1 to 2,000 mol, preferably about 5 to 500 mol, based on 1 mol of the titanium atom in the solid titanium catalyst. Used in. Further, the electron donor catalyst is usually about 0.001 to 10 mol, preferably 0.01 to 2 mol, and particularly preferably 0.1 to 10 mol per 1 mol of metal atom in the organoaluminum compound catalyst.
It is used in an amount such that it is from 05 to 1 mol.

The copolymerization reaction carried out in the presence of the above catalyst is usually carried out at a temperature of -50 ° C to 100 ° C, preferably -30 ° C to 80 ° C, more preferably -20 ° C to 6 ° C.
It is carried out at 0 ° C. under a pressure of more than 0 to 50 kg / cm ² , preferably more than 0 to 20 kg / cm ² . The reaction time (average residence time when the copolymerization is carried out by a continuous method) is usually 5 minutes to 5 hours, though it varies depending on conditions such as the type of monomer used, the catalyst concentration and the polymerization temperature. , Preferably 10 minutes to 3 hours.

In the above copolymerization reaction, the ratio of the monomers supplied to the polymerization system is 2 selected from the group consisting of (i) α-olefin having 2 or more carbon atoms, (ii) cyclic olefin, and (iii) diene compound. The preferred feed ratios cannot be fully described here for all combinations, since they must be changed by the reactivity of one or more monomers. However, the feed ratios can be illustrated here for some representative monomer combinations.

For example, 1) When two kinds of α-olefin having 2 or more carbon atoms are selected, 1. Ethylene / α with 3 or more carbon atoms
-For olefins the molar ratio is usually 70/30 to 1/99,
2. In the combination of α-olefins having 3 or more carbon atoms and α-olefins (a) / (a) having a larger number of primes, the molar ratio is usually 80/20 to 20/80, 2) α-olefins having 2 or more carbon atoms. In the case of a combination of olefin and cyclic olefin, 1. The ethylene / cyclic olefin combination usually has a molar ratio of 90/10 to 10/90, 2. In the combination of α-olefin / cyclic olefin having 3 or more carbon atoms, the molar ratio is usually 80/20 to 10/90, 3) In the case of combination of α-olefin having 2 or more carbon atoms and diene, 1. The ethylene / diene combination usually has a molar ratio of 70/30 to 1/99, 2. In the combination of α-olefin / diene having 3 or more carbon atoms, the molar ratio is usually 80 /
20 to 20/80 is preferable.

Further, in the copolymerization, a molecular weight modifier such as hydrogen can be used. As described above, in the presence of the cyclic olefin random copolymer [A], the α-olefin (i) having 2 or more carbon atoms and the cyclic olefin (i
i), at least 2 selected from the diene compounds (iii)
When a hydrocarbon-based elastomer is produced by copolymerizing a kind of monomer, a solution containing a cyclic olefin-based copolymer composition is obtained. In such a solution, the cyclic olefin-based copolymer composition is usually 10 to 500 g / liter, 1
It is contained at a concentration of 0 to 300 g / liter. This solution is processed by a conventional method to obtain a cyclic olefin-based copolymer composition.

To produce the cyclic olefin copolymer composition of the present invention, more specifically, the previously produced cyclic olefin random copolymer [A] is dissolved in a hydrocarbon solvent, The above hydrocarbon-based elastomer may be produced in a solution, or the above-mentioned cyclic olefin random copolymer [A] may be first produced in the first stage and then polymerized in the second stage. Α- with 2 or more carbon atoms in solution
A hydrocarbon-based elastomer may be produced by copolymerizing a monomer selected from the olefin (i), the cyclic olefin (ii) and the diene compound (iii).

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 fatty acid ester of a polyhydric alcohol in combination, and the fatty acid ester of the polyhydric alcohol 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 copolymer composition, The fatty acid ester of polyhydric alcohol is 0 per 100 parts by weight of the cyclic olefin copolymer composition.
It is used in an amount of 10 to 10 parts by weight, preferably 0 to 5 parts by weight.

In the present invention, the cyclic olefin random copolymer composition is added to silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, water in a range not impairing the object of the present invention. 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.

[0191]

The cyclic olefin-based copolymer composition obtained by the present invention comprises an α-olefin (i), a cyclic olefin (ii) and a diene having 2 or more carbon atoms in the presence of a cyclic olefin-based random copolymer. The dispersion of the cyclic olefin random copolymer phase and the elastomer phase is good because it is obtained by copolymerizing at least two kinds of monomers selected from the compound (iii) to produce a hydrocarbon elastomer. Thus, impact resistance and toughness are improved while maintaining the heat resistance and rigidity that the cyclic olefin copolymer phase originally has.

[0192]

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) Cyclic Olefin Random Copolymer and Glass Transition Point (Tg) of Composition Using a DSC-220C manufactured by Seiko Instruments Inc., the temperature was measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. (3) 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. (4) 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 (5) 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. (6) TMA softening test Using a Thermo Mechanical Analyzer manufactured by DuPont, a sheet with a thickness of 1 mm was prepared. It was measured by the thermal deformation behavior. That is, place a quartz needle on the sheet, apply a load of 49 g,
The temperature is raised at a rate of 5 ° C./min, and the quartz needle is placed on the sheet to 0.6.
The temperature at a depth of 35 mm was designated as TMA.

[0196]

Example 1 Using a 2-liter glass polymerization vessel equipped with a stirring blade, ethylene / propylene copolymerization was continuously carried out by the following method in the presence of a cyclic olefin copolymer.

From the upper part of the polymerization vessel, a cyclohexane solution of ethylene / TCD copolymer ([η] = 0.7 dl / g, Tg = 132 ° C.) was added so that the concentration of the copolymer in the polymerization vessel was 40 g / liter. Was continuously supplied at a rate of 1.1 liter / hour. In addition, as a catalyst, VO
A cyclohexane solution of (OC ₂ H ₅ ) Cl ₂ was added at 0.7 liter / hour so that the vanadium concentration in the polymerization vessel was 0.2 mmol / liter (the vanadium concentration supplied at this time was the vanadium concentration in the polymerization vessel). 2.86 times the concentration)
Of ethyl aluminum sesquichloride (Al (C ₂
H ₅₎ aluminum concentration of the cyclohexane solution in the polymerization vessel of _1.5 Cl _1.5) was continuously fed into each polymerization reactor in an amount of from 0.4 l / hr so that 1.8 mmol / l.

A bubbling tube was used for the polymerization system to supply ethylene at an amount of 25.0 liters / hour, propylene at 25.0 liters / hour, nitrogen at 145 liters / hour, and hydrogen at 5.0 liters / hour. ..

Copolymerization reaction was carried out while the polymerization system was kept at 50 ° C. by circulating a heating medium in a jacket attached to the outside of the polymerization vessel. Generated by the above copolymerization reaction,
A polymerization solution containing a cyclic olefin-based copolymer and an ethylene / propylene copolymer is constantly fed from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel becomes 1 liter (that is, an average residence time of 0.5 hours). It was continuously extracted. A cyclohexane / isopropyl alcohol (1: 1) mixture was added to the extracted polymerization solution to terminate the ethylene / propylene polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were brought into contact with each other under strong stirring using a homomixer, and the catalyst residue was transferred to a water tank. After the contact mixed solution was allowed to stand still, the aqueous phase was separated and removed, and then washed twice with distilled water to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer composition, and then a solid portion was collected by filtration and thoroughly washed with acetone. It was dried at 130 ° C. and 350 mmHg for 24 hours under nitrogen flow.

As described above, a cyclic olefin copolymer composition comprising an ethylene / propylene copolymer and an ethylene / TCD copolymer was added at an amount of 89.3 g / hour, that is, 44.7 g / liter. Obtained. The ratio of the component [A] contained in the produced copolymer composition was 89.4% by weight.

A bending test, an impact strength test and a TMA softening test were carried out on the obtained cycloolefin copolymer composition. The results obtained are shown in Table 2.

[0203]

Example 2 A cyclic olefin-based copolymer composition was produced in the same manner as in Example 1 except that the conditions shown in Table 2 were changed.

The results are shown in Table 3.

[0205]

Example 3 A cyclic olefin copolymer composition was produced in the same manner as in Example 1, except that the ethylene / norbornene copolymer was used instead of the ethylene / TCD copolymer. ..

The results are shown in Table 3.

[0207]

Example 4 As a catalyst, ethylene bis (indenyl)
Polymerization was carried out at 10 ° C. using zirconium dichloride [Et (Ind) ₂ ZrCl ₂ , polymerization system concentration: 0.002 mmol / liter] and methylaluminoxane [MAO, polymerization system concentration: 2 mmol / liter]. It was The polymerization was carried out in the same manner as in Example 1 except that the conditions shown in Table 2 were changed.

The results are shown in Table 3.

[0209]

Comparative Example 1 A cyclic olefin-based copolymer composition was produced in the same manner as in Example 1, except that the conditions shown in Table 2 were changed. It was revealed that when the ratio of [A] deviates from the range of the present invention to the lower side, the heat resistance is significantly lowered.

[0210]

Comparative Example 2 In the same manner as in Example 1, except that an ethylene / tetracyclododecene copolymer having a TMA of 60 ° C. was used as the cyclic olefin-based copolymer.
A cyclic olefin-based copolymer composition was produced. It was revealed that when the TMA of the cyclic olefin copolymer is out of the range of the present invention, the heat resistance of the obtained cyclic olefin copolymer composition is significantly reduced.

[0211]

Comparative Example 3 Ethylene / TCD Copolymer (Copolymer A)
450 g and 50 g of ethylene-propylene copolymer are twin-screw extruder (BT-3 manufactured by Plastic Engineering Laboratory Co., Ltd.)
0, 1 / d = 42) was melt-blended at a cylinder temperature of 270 ° C., and pelletized by a pelletizer. The results of evaluation using the obtained pellets are shown in Table 2.

When the cyclic olefin random copolymer and the hydrocarbon elastomer were simply melt-blended, the impact resistance was inferior to that of the copolymer composition of the present invention.

[0213]

[Table 1]

[0214]

[Table 2]

[0215]

[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. A copolymer obtained by copolymerizing [A] (a) an α-olefin having 2 or more carbon atoms and (b) at least one cyclic olefin represented by the following general formula [I] or [II]. The
The glass transition point measured by DSC is 50 ° C or higher, and 1
The intrinsic viscosity [η] measured in decalin at 35 ° C is 0.1.
0 to 5.0 dl / g, in the presence of a cyclic olefin random copolymer, [B] i) an α-olefin having 2 or more carbon atoms ii) represented by the following general formula [I] or [II] A cyclic olefin iii) a diene compound, which is obtained by copolymerizing at least two monomers selected from the following to produce a hydrocarbon elastomer, and the glass transition point of the component [B] is less than 10 ° C .: [A] in the composition
A cycloolefin copolymer composition, characterized in that the components are present in an amount of 50 to 99% by weight; [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. Obtained by copolymerizing [A] (a) an α-olefin having 2 or more carbon atoms and (b) at least one cyclic olefin represented by the above general formula [I] or [II]. The
Glass transition point (Tg) measured by DSC is 50 ° C. or higher, and intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.10 to 5.0 dl / g, in the presence of a cyclic olefin-based random copolymer, [B] i) an α-olefin having 2 or more carbon atoms ii) the above general formula [I] or [II] In the liquid phase, at least two kinds of monomers selected from cyclic olefin iii) diene compound represented by
Copolymerization to produce a hydrocarbon-based elastomer, the glass transition point of the [B] component is lower than 10 ° C, and the [A] component is present in the composition in an amount of 50 to 99% by weight. A method for producing a cyclic olefin-based copolymer composition, comprising: