KR0142817B1 - Cycloolefin copolymer composition and production thereof - Google Patents

Abstract

[A] Intrinsic viscosity measured in decatin at 135 ° C. without polymerizable double bonds [ ] Is a hydrocarbon elastomer (A-1) component of 0.05-10 dl / g and a glass transition temperature (Tg) of 10 degrees C or less, [B] alpha-olefin (a) of 2 or more carbon atoms, and following formula [I] or [II A cycloolefin copolymer composition comprising a cycloolefin random copolymer (B-1) component obtained by copolymerizing a cycloolefin (b) represented by], wherein the hydrocarbon elastomer (A-1) component is 1 to 50% by weight in the composition. A cycloolefin copolymer composition, wherein the cycloolefin random copolymer (B-1) component is present in air in the presence of a hydrocarbon elastomer (A-1) component.

Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ -R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^15- R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁸ , or R ¹⁷ and R ¹⁸ may together form an alkalidene group.

Wherein p and q are each an integer of 0 or 1 or more, m and n are each 0, 1 or 2, and R ¹ -R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic group. A hydrocarbon group or an alkoxy group, a carbon atom to which R ⁹ (or R ¹⁰ ) is bonded, and a 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 R ¹⁵ And R ¹² or R ¹⁵ and R ¹⁹ may be bonded together to form a monocyclic or polycyclic aromatic ring when n and m are zero.

Description

[Name of invention]

Cycloolefin copolymer composition and preparation method thereof

[Industrial application]

The present invention relates to a cycloolefin copolymer composition and a method for producing the same, and more particularly to a cycloolefin copolymer composition excellent in impact resistance and heat resistance and a method for producing the same.

[Technology Background]

Until now, cycloolefin random copolymers obtained by copolymerizing cycloolefins such as ethylene and tetracyclo nodecene are excellent synthetic resins with excellent transparency, heat resistance, heat resistance, chemical resistance, solvent resistance, dielectric properties and rigidity. It has been known. Cycloolefin random copolymers as described above are known to exhibit excellent performance in the field of optical materials such as optical memory disks and optical fibers. (E.g. Japanese Patent Application No. 60-168708, Japanese Patent Application No. 61-98780, Japanese Patent Application No. 61-115912, Japanese Patent Application No. 61-115916, Japanese Patent Application No. 61-120816 and Japanese Patent Application No. 62-252407)

The cycloolefin random copolymers mentioned above are synthetic resins which are particularly excellent in heat resistance, rigidity and transparency, but their impact resistance is not sufficient and further improvement is required.

The present applicant has proposed a resin composition of a cycloolefin random copolymer obtained by copolymerization of an ethylene and a cycloolefin such as tetracyclododecene and an elastomer polymer (rubber) according to Japanese Patent Application Laid-Open No. 3-255145.

However, although the impact resistance of this resin composition was improved compared to the cycloolefin random copolymer before mixing the elastomeric polymer, it was still insufficient.

The resin composition obtained by melt mixing a cycloolefin random copolymer and an elastomer polymer by a Brabender Plasticorder or an extruder is not sufficiently improved in impact resistance because of the compatibility of the cycloolefin random copolymer and the elastomer polymer. I think this is because it is not good.

The present inventors have steadily researched to solve the above-mentioned problems. As a result, the above-mentioned hydrocarbon obtained by copolymerization of a cycloolefin with an α-olefin having 2 or more carbon atoms such as ethylene in the presence of a polymerizable double bond-free hydrocarbon elastomer The present invention has been completed by discovering that the cycloolefin copolymer composition containing a certain amount of elastomer is excellent in impact resistance.

[Purpose of invention]

The present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a cycloolefin copolymer composition having excellent properties of the cycloolefin random copolymer, and in particular, improved impact resistance, and a method for preparing the composition. have.

[Summary of invention]

The cycloolefin copolymer composition of the present invention

[A] Hydrocarbon elastomer (A-1) having no polymerizable double bond and an intrinsic viscosity [η] of 0.05 to 10 dl / g and a glass transition temperature (Tg) of 10 deg. and

[B] Cycloolefin air composed of cycloolefin random copolymer (B-1) component obtained by copolymerizing α-olefin (a) having 2 or more carbon atoms and cycloolefin (b) represented by the following formula [1] or [2]: In the copolymer composition, the content of the hydrocarbon elastomer (A-1) component is 1 to 50% by weight, and the cyclooleus random copolymer (B-1) component is obtained by copolymerization in the presence of a hydrocarbon elastomer (A-1) component. It is characterized by.

(One)

Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ -R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^15- R ¹⁸ is bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁸ or R ¹⁷ and R ¹⁸ together form an alkylidene group,

(2)

Wherein p and q are each 0 or more integers, m and n are each 0, 1 or 2, and R ¹ -R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic group. The carbon atom to which R ⁹ (or R ¹⁰ ) is bonded and the carbon atom to which R ¹³ or R ¹¹ is bonded, which is a hydrocarbon group or an alkoxy group, may be bonded directly or via an alkylene group of a carbon atom, and R ¹⁵ and R ¹² or R ¹⁵ And R ¹⁹ are bonded together to form a monocyclic or polycyclic aromatic ring when n and m are zero.

Method for producing a cycloolefin copolymer composition according to the present invention

(a) α-olefins having 2 or more carbon atoms,

(b) a hydrocarbon elastomer (A-1) component having no polymerizable double bond and having an intrinsic viscosity [η] of 0.05-10 dl / g and a glass transition temperature (Tg) of 10 DEG C or less measured in decalin at 135 DEG C; In the presence of the above, the cycloolefin represented by the above-mentioned formula [1] or [2] is copolymerized in a liquid phase to obtain a composition containing 1-50% by weight of the hydrocarbon elastomer (a-1) component.

The cycloolefin copolymer composition of the present invention has the inherent properties of the cycloolefin random copolymer, namely excellent transparency, chemical resistance and rigidity, and particularly excellent impact resistance.

Detailed description of the invention

The cycloolefin copolymer composition of the present invention and its preparation method are described in detail below.

[Cycloolefin copolymer composition]

The cycloolefin copolymer composition of the present invention comprises (a) an α-olefin having 2 or more carbon atoms in the presence of a hydrocarbon elastomer (A-1) without a polymerizable double bond and the cycloolefin represented by the above formula [1] or [2] ( It is obtained by copolymerization of b).

First, a hydrocarbon elastomer without a polymerizable double bond will be described below.

[Hydrocarbon Elastomer (A-1)]

The hydrocarbon elastomer (A-1) used in the present invention is an elastomer without a polymerizable double bond and specifically includes (i) α-olefin copolymer and (ii) α-olefin / cycloolefin copolymer.

These hydrocarbon elastomers (A-1) are explained in more detail.

(Iii) α-olefin copolymer

The α-olefin copolymer is a random copolymer obtained from at least two kinds of α-olefins.

Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-exene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Α-olefins having 2 to 20 carbon atoms such as hexadecene, 1-octadecene and 1-aircosene.

As a specific example of the α-olefin copolymer,

Ethylene / flofilene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer,

Ethylene / 1-dodecene copolymer, ethylene / 1-octene copolymer, ethylene / 1-decene copolymer, ethylene / 1-tetradecene copolymer, ethylene / 1-hexadecene copolymer, ethylene / 1-octadecene air Copolymer, ethylene / 1-eicosene copolymer, propylene / 1-butene copolymer, propylene / 1-pentene copolymer, propylene / 1-hexene copolymer, propylene / 4-betayl-1-pentene copolymer, propylene / 1 Octene copolymer, propylene / 1-decene copolymer, propylene / 1-dodecine copolymer, propylene / 1-tetradecene copolymer, propylene / 1-hexadecene copolymer, propylene / 1-octadecene copolymer, propylene / 1-eicosene copolymer, and the like.

The α-olefin copolymer has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.05 to 10 Pa / g, preferably 0.1 to 5 Pa / g and a glass transition temperature (Tg) of 10 ° C. or less. Is 0 degrees C or less.

(Ii) α-olefin / cycloolefin copolymer

The α-olefin / cycloolefin copolymer is a random copolymer formed from at least one kind of α-olefin and cycloolefin.

Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Α-olefins having 2 to 20 carbon atoms such as hexadecene, 1-octadecene and 1-aircosene.

Cycloolefin includes the cycloolefin shown by the above-mentioned formula [1] or [2].

Specific examples of the α-olefin / cycloolefin copolymer are as follows.

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 / tetracyclodocene copolymer,

Ethylene / 1-decene / norbornene copolymer,

Ethylene / 1-decene / 5-betayl-2-norbornene copolymer,

Ethylene / 1-decene / 5-ethyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-propyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-butyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-pentyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-hexyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-heptyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-octyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-nonyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-decyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-undecyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-dodecyl-2-norbornene copolymer,

Ethylene / 1-decene / 5-phenyl-2-norbornene copolymer,

Ethylene / 1-decene / tetracyclododecene copolymer.

The α-olefin / cycloolefin copolymer has an intrinsic viscosity [?] measured in decalin at 135 ° C. of 0.05 to 10 Pa / g, and a glass transition temperature (Tg) of 10 ° C. or less, preferably 0 ° C.

The cycloolefin copolymer composition according to the present invention copolymerizes an α-olefin (a) having 2 or more carbon atoms and a cycloolefin (b) in the presence of the hydrocarbon elastomer (A-1) component and the component (A-1). It is formed from the obtained cycloolefin random copolymer (B-1).

Examples of α-olefins (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 and 1-eicosene.

Of these, ethylene or propylene is preferable.

The cycloolefin shown by following formula [I] and / or the cycloolefin shown by following formula [II] is used as cycloolefin (b).

Wherein n is 0 or 1, m is 0 or a positive integer q is 0 or 1, when q is 1, R ^a and R ^b represent the following atoms or hydrocarbon groups, respectively, and q is 0 , Two bonds are bonded together to form a 5-membered ring.

R ¹ -R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group.

Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms.

Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms.

Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl.

Specific examples of the cycloalkyl group are cyclohexyl groups.

These groups may be substituted with halogen atoms.

In formula [I], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁸ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are bonded together (or The monocyclic or polycyclic groups formed by cooperating with each other) may form a monocyclic or polycyclic group.

Examples of monocyclic or polycyclic groups are as follows.

Carbon atoms having the numerals 1 or 2 above are carbon atoms in which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) forms an alicyclic structure in which the bond is shown in formula [I].

R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ together may form an alkylidene group. The alkylidene group is generally an alkylidene group having 2 to 20 carbon atoms, and examples of such alkylidene groups include ethylidene group, propylidene group, and isopropylidene group.

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

R ¹ to R ¹⁹ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group.

The halogen atom in the formula [II] is a halogen atom as described in the formula [I].

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

Examples of the alicyclic hydrocarbon group include alicyclic hydrocarbon groups having 3 to 15 carbon atoms such as cyclohexyl groups.

Examples of the aromatic hydrocarbon group include aralkyl groups and aryl groups such as phenyl group, tolyl group, naphthyl group, benzyl group and phenylethyl group.

These groups have lower alkyl groups.

Alkoxy groups include methoxy group, ethoxy group, and propoxy group.

These groups may be substituted with halogen atoms. The carbon atom to which R ⁹ and R ¹⁰ are bonded may be bonded directly to a carbon atom to which R ¹³ is bonded or to a carbon atom to which R ¹¹ is bonded, or via an alkylene group having 1 to 3 carbon atoms.

That is, the above-mentioned two carbon atoms are bonded to each other by the group represented by the alkylene group R ⁹ and the group represented by R ¹³ or the group represented by R ¹⁰ and the group represented by R ¹¹ cooperate with each other to form a methylene group (-CH _2- ), an ethylene group ( An alkylene group is formed between -CH ₂ CH _2- ) and a propylene group (-CH ₂ CH ₂ CH _2- ).

In the case of n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded together to form a monocyclic or polycyclic aromatic ring. Examples of monocyclic or polycyclic aromatic rings include the following groups in which R ¹⁵ and R ¹² together form an aromatic ring when n = m = 0.

Q is the same as q of the formula [II].

For example, the cycloolefin represented by the formula [I] or [II] is:

Bicyclo [2.2.1] hepto-2-ene derivatives,

Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives,

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives,

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene derivatives,

^Pentacyclo [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14 ] -4-hexadecene derivatives,

^Pentacyclo [6.5.1.1 ^{3,6 2,7} .0 ^9,13 ] -4- ^pentadecene derivatives,

Pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3- ^pentadecene derivatives,

Pentacyclo pentadecadiene derivatives,

Pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-hexadecene derivatives,

The hectare bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] -4- hepta-decene derivative,

Heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,16 ] -4-eicosene derivatives,

The cyclo hepta ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3,8 .0 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,

Octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17 ] -5- ^docosene derivatives,

Na of cyclo ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .1} 3,8 .0 2,10 .0 12,21 .0 14,19] -5- penta Hill derivative,

Nonacyclo [10.10.1.1.1 ^5,8 .1 ^14,21 .1 ^18,19 .0 ^2,11 .0 ^4,9 .0 ^13,22 .0 ^15,20 ] -6-hexacosene derivatives,

1,4-methano-1,4,4a, 9a-tetrahydrofuroene derivatives,

1,4-methano-1,4,4a, 5,10,10a-hexahydroandracene derivatives,

Cyclopentadiene-dasenaphthylene adducts and the like.

For example:

Bicyclo [2.2.1] hepto-2-ene derivatives as follows;

The cycloolefin (b) represented by the formula [I] or [II] can be produced by the Diels Alder reaction of cyclopentadiene and the corresponding olefin.

These cycloolefins (b) can be used individually or in combination of 2 or more types.

[Cycloolefin copolymer composition]

The cycloolefin copolymer composition of the present invention is a cycloolefin represented by the above formula [I] and / or a cycloolefin represented by the above formula [II] in the presence of a hydrocarbon elastomer (a-1) without a polymerizable double bond. ) And an addition polymer obtained by polymerizing α-olefin (a) having 2 or more carbon atoms.

That is, the siroolefin copolymer composition of the present invention is composed of a hydrocarbon elastomer (A-1) component, a cycloolefin random copolymer (B-1) composed of α-olefin (a) and cycloolefin (b) having 2 or more carbon atoms. Resin composition.

This cycloolefin copolymer composition contains 1 to 50% by weight, preferably 3 to 40% by weight of the above-mentioned hydrocarbon elastomer (A-1).

The hydrocarbon elastomer (A-1) is finely dispersed in a cycloolefin random copolymer (B-1) formed from α-olefin (a) and cycloolefin (b). This is because the cycloolefin copolymer composition as described above is produced by copolymerization of an alpha -olefin (a) having 2 or more carbon atoms and a cycloolefin (b) in the presence of a hydrocarbon elastomer (A-1).

The cycloolefin copolymer composition of the present invention described above is simply melt kneaded with a cycloolefin random copolymer obtained by copolymerization of a hydrocarbon elastomer without a polymerizable double bond, an alpha -olefin (a) having at least 2 carbon atoms, and a cycloolefin (b). It is excellent in impact resistance than the cycloolefin copolymer composition obtained by this.

In the cycloolefin copolymer composition of the present invention, the cycloolefin random copolymer (B-1) is other cycloolefin in an amount which does not impair the properties of the composition other than α-olefin (a) and cycloolefin (b) having 2 or more carbon atoms, that is, And copolymers obtained by addition polymerization of cycloolefins (other cycloolefins) other than the cycloolefins represented by the aforementioned formula [I] or [II].

As used herein, another cycloolefin means a broad concept cycloolefin including unsaturated polycyclic hydrocarbon compounds other than the cycloolefin represented by the formula [I] or [II].

More specifically, examples of other cycloolefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methelbutyl) -1-cyclohexene, styrene, α Methyl styrene and 3a, 5, 6, 7a-tetrahydro-4,7-methano-1H-indene and the like.

The cycloolefin copolymer composition of the present invention is a cycloolefin (b) represented by the above-mentioned formula [I] or [II] in a liquid phase in a hydrocarbon solvent in the presence of the aforementioned hydrocarbon elastomer (A-1) and α- having 2 or more carbon atoms. The copolymerization of an olefin (a) can produce the copolymer composition containing 1-50 weight% of hydrocarbon elastomers (A-1).

When performing a copolymerization reaction, the transition metal type catalyst containing the following specifically, is used.

(Iii) a catalyst formed from a soluble vanadium compound and an organoaluminum compound (1), or (ii) a metallocene compound or a lanthanide-based and organoaluminum oxy compound of a transition metal selected from Group 4b of the Periodic Table and, if necessary, Catalyst formed from

Specific examples of the soluble vanadium compound forming the catalyst include the following formulae.

VO (OR) _a X _b or V (OR) _c X _d

Wherein R is a hydrocarbon group, X is a halogen atom, a, b, c, and d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 The relationship of? D? 4 and 3? C + d? 4 is satisfied.

Examples of the soluble vanadium compound are as follows.

VOCL ₃ ,

VO (OC ₂ H ₅ ) ₂ Cl,

VO (OC ₂ H ₅ ) ₂ Cl,

VO (O-iso-C ₃ H ₇ ) Cl ₂ ,

VO (OnC ₄ H ₉ ) Cl ₂ ,

VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ ,

VO (OnC ₄ H ₉ ) ₃ and

VOCl ₃ · 2 (OC ₈ H ₁₇ OH).

These compounds can be used individually or in combination of 2 or more types.

The soluble vanadium compound described above can be used in the form of an electron donor adduct obtained by contacting the electron donors described below and the soluble vanadium compound described above.

Electron donors include, for example, hydrogen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic or inorganic acid esters, ethers, diethers, acid amides, acid anhydrides, alkoxysilanes, ammonia, amines, Nitrogen-containing electron donors such as nitrile, pyridine, isocyanate and the like, and more specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, C1-C18 alcohols, such as oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, and carbon atoms, such as trichloromethanol, trichloroethanol, and trichlorohexanol 1 A phenol having 6 to 20 carbon atoms having a halogen containing alcohol of 18 to 18, and a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, Ketones having 3 to 15 carbon atoms, such as cetone, methyl ethyl keron, methyl isobutyl kerone, acetophenone, benzophenone, and benzoquinone; and carbon sources such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde Aldehydes of embroidery 2 to 15, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloro Acetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarbonate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, Methyl toluate, ethyl toluate, amyl tolu Organic acids of 2 to 18 carbon atoms, such as ethyl, benzoate, methyl aniseate, ethyl aniseate, ethoxyethyl benzate, γ-butyrolactone, δ-valerolactone, cumin, phthalide, and ethyl carbonate Esters, acid halides having 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluic acid chloride, aniseic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydro hulan, Ethers having 2 to 20 carbon atoms such as anisole and diphenyl ether, acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride, alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane, and N, N-acetic acid Acid amides such as dimethylamide, benzoic acid N, N-dimethylamide, toluic acid N, N-dimethylamide, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethyl There are ethylene diamine, such as amine and acetonitrile, benzonitrile, nitriles such as acetonitrile and the tree, such as pyridine, such as pyridine, methylpyridine, ethylpyridine, dimethylpyridine.

In the preparation of the electron donor adduct of the soluble vanadium compound, the electron donors exemplified above may be used alone or in combination of two or more thereof.

The organoaluminum compound (1) which can be used for the catalyst used with a soluble vanadium compound contains the compound containing at least 1 A-C bond in a molecule | numerator.

Examples of the organoaluminum compound include compounds represented by the following formulas (a) and (b).

(a) R ¹ _m Al (OR ² ) _n H _p X _q

Wherein R ¹ and R ² are each usually a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, they are the same or different from each other, X is a halogen atom, m, n, p and q Is a number that satisfies the conditions of 0≤m≤3, 0≤n≤3, 0≤p≤3, 0≤q≤3 and m + n + p + q = 3.

Alkyl complex compound of group I metal and aluminum

(b) M ¹ AℓR ₄ ¹

In the formula, M ¹ is Li, Na or K, R ¹ is the same as defined in the formula (a).

Specific examples of the organoaluminum compound represented by the formula (a) are as follows.

(1) R ¹ _m Al (OR ² ) _3-m

In the above formula, R ¹ and R ² are the same as in the above formula (a), and m is a number of 1.5m≤3.

(2) R ¹ _m AlX _3-m

Wherein R is the same as in formula (a), X is halogen and m is a number of 0 m 3.

(3) R ¹ _m AlH _3-m

Wherein R ¹ is the same as in the formula (a), and is a number of 2 ≦ m 3.

(4) R ¹ _m Al (OR ² ) _n X _q

Wherein R ¹ and R ² are the same as in formula (a), X is halogen, m, n and q are 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3 and m + n + A number satisfying the condition of q = 3.

The organoaluminum compound represented by the formula (a) is specifically as follows.

Trialkylaluminum such as triethylaluminum and tributylaluminum, trialkenylaluminum such as triisopropenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide, and formula R ¹ _2, Some alkoxylated alkylaluminum, butylaluminum sesquiburoxide and ethylaluminum sesquiethoxide with an average composition represented by ₅ Al (OR ² ) _0.5 .

The specific thing of the organoaluminum compound represented by said Formula (2) is as follows.

Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide, and ethyl aluminum Some halogenated alkylaluminum such as dichloride, propylaluminum dichloride and butylaluminum dibromide.

Specific examples of the organoaluminum compound represented by the formula (3) are as follows.

Dialkyl aluminum hydrides, such as diethyl aluminum hydride and dibutyl aluminum hydride, and partially hydrogenated alkyl aluminum, such as ethyl aluminum dihydride and propyl aluminum dihydride.

Specific examples of the organoaluminum compound represented by the formula (4) are as follows.

Some alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxychloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxy bromide.

The organoaluminum compound may be a compound similar to the compound represented by formula (a) such as an organoaluminum compound in which two or more aluminums are bonded through an oxygen element or a nitrogen element.

Examples of such compounds are as follows.

In addition, the compounds belonging to the above-described formula (b) is such as LiAl (C ₂ H _{5) 4} and _{LiAl (C 7 H 15) 4} .

Of the organoaluminum compounds described above, alkylaluminum halides, alkylaluminum dihalides and mixtures thereof are preferably used.

Next, a catalyst (ii) formed from a metallocene compound, an organoaluminum oxy compound of a transition metal selected from the group IVB or the lanthanide series of the periodic table and, if necessary, the organoaluminum compound (2) used in the present invention will be described.

Examples of the metallocene compound of the transition metal selected from the group IVB of the periodic table and the rattanide system include compounds represented by the following formula (a).

ML _x (a)

In the formula [a], M is a transition metal selected from the group IVB of the periodic table and the rattanide system, and specific examples of M include zirconium, titanium, hafnium, neodymium, samarium, and yttrium. L is a ligand that coordinates to the transition metal, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton.

A ligand (L) other than a ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy key, a halogen element, a trialkylsilyl group, or a SO ₃ R group (R is a substituent such as halogen) Is a hydrocarbon group having 1 to 8 carbon atoms) or a hydrogen atom, and X is a valence of a transition metal atom.

The ligand having a cyclopentadienyl skeleton is, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethyl Cyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclo Cyclopentadienyl groups, alkyl or cycloalkyl substituted cyclopentadienyl groups, such as a pentadienyl group, a methyl benzyl cyclopentadienyl group, an ethylbutyl cyclopentadienyl group, an ethylhexyl cyclopentadienyl group, and a methylcyclohexyl cyclopentadienyl group Or an indenyl group, 4,5,6,7-tetrahydroindenyl group, and furuorenyl group.

Groups as described above may be substituted with halogen atoms or trialkylsilyl groups.

Ligands other than those having a cyclopentadienyl skeleton include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, and a sulfone-containing group (-SO ₃ R ^a ; R ^a is an alkyl group or a halogen atom substituted with a halogen atom). Or a aryl group or an aryl group substituted with a halogen atom or an alkyl group), a halogen atom or a hydrogen atom. The hydrocarbon group having 1 to 12 carbon atoms is a group such as an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

More specifically, the alkyl group is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group and dode And a cycloalkyl group, such as a cyclopentyl group and a cyclohexyl group, an aryl group is a petyl group and a tolyl group, and an aralkyl group is a benzyl group and a neophil group.

The alkoxy group is a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy and octoxy group, etc. The oxy group is a phenoxy group and the like, and the sulfone-containing group (-SO ₃ R ^a ) includes a methanesulfonate group, a P-toluenesulfonate group, a trifluoromethanesulfonate group and a P-chlorobenzenesulfonate group. Are fluorine, chlorine, bromine and iodine.

When the transition metal atom is 4, for example, the transition metal compound represented by the formula [a] is represented by the following formula in more detail.

Wherein M is zirconium, titanium, hafnium, neodymium, samarium or yttrium, R ¹ is a group having a cyclopentadienyl skeleton, R ² , R ³ and R ⁴ are each a group having a cyclopentadienyl skeleton, Alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group, SO ₃ R group or hydrogen atom, a is an integer of 1 or more, a + b + c + d = 4 to be.

In the present invention, the transition metal compound having the formula (a) is a group having at least one of R ² , R ³ and R ⁴ having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopentadienyl skeletons. Groups having are preferred. The group having the cyclopentadienyl skeleton described above may be substituted with an alkylene group such as ethylene or propylene, an alkylidene group such as isopropylidene, a substituted alkylene group such as diphenylmethylene, a silylene group or dimethylsilylene, diphenylsilylene or methylphenylsil. It may be bonded together through a substituted silylene group such as ylene. R ³ and R ⁴ each represent a group having an cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, an SO ₃ R group or a hydrogen atom to be.

Illustrated below are metallocene compounds of transition metals where M is zirconium.

Bis (cyclopentadienyl) zirconium monochloride monohydride,

Bis (cyclopentadienyl) zirconium dichloride,

Bis (cyclopentadienyl) zirconium dibromide,

Bis (cyclopentadienyl) methylzirconium monochloride,

Bis (cyclopentadienyl) ethylniconium monochloride,

Bis (cyclopentadienyl) cyclohexyl zirconium monochloride,

Bis (cyclopentadienyl) phenylzirconium monochloride,

Bis (cyclopentadienyl) benzylzirconium monochloride,

Bis (cyclopentadienyl) methylzirconium monochloride,

Bis (cyclopentadienyl) dimethylzirconium

Bis (cyclopentadienyl) diphenylzirconium

Bis (cyclopentadienyl) dibenzylzirconium

Bis (cyclopentadienyl) zirconium phenoxymonochloride,

Bis (metalcyclopentadienyl) zirconium dichloride,

Bis (ethylcyclopentadienyl) zirconium dichloride,

Bis (propylcyclopentadienyl) zirconium dichloride,

Bis (butylcyclopentadienyl) zirconium dichloride,

Bis (hexylcyclopentadienyl) zirconium dichloride,

Bis (octacyclopentadienyl) zirconium dichloride,

Bis (indenyl) zirconium dichloride,

Bis (indenyl) zirconium bis (P-toluenesulfonate)

Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Bis (indenyl) zirconium dibromide,

Bis (cyclopentadienyl) zirconium dimethyl,

Bis (cyclopentadienyl) zirconium methoxychloride,

Bis (cyclopentadienyl) zirconium ethoxychloride,

Bis (furuorenyl) zirconium dichloride,

Bis (cyclopentadienyl) zirconium bis (methanesulfonide),

Bis (cyclopentadienyl) zirconium bis (P-toluenesulfonate),

Bis (cyclopentadienyl) zirconium bis (trifuromethanesulfonate),

Bis (methylcyclopentadienyl)) zirconium bis (trifluoromethanesulfonate),

Bis (dimethylcyclopentadienyl) dimethylniconium,

Bis (methylcyclopentadienyl)) zirconium bis (methanesulfonate),

Bis (ethylcyclopentadienyl) zirconium bis (trifuromethanesulfonate),

Bis (propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),

Bis (butylcyclopentadienyl) zirconium bis (trifluoromethylethanesulfonate),

Bis (hexylcyclopentadienyl) zirconium bis (trifuromethanesulfonate),

Bis (dimethylcyclopentadienyl) zirconium bis (trifuromethanesulfonate),

Bis (methylethylcyclopentadienyl) zirconium bis (trifluoromethylethanesulfonate),

Bis (methylpropylcyclopentadienyl) zirconium bis (trifuromethanesulfonate),

Bis (methylbutylcyclopentadienyl) zirconium bis (trifluoromethylethanesulfonate),

Bis (dimethylcyclopentadienyl) zirconium dichloride,

Bis (dimethylcyclopentadienyl) zirconium ethoxychloride,

Bis (methylethylcyclopentadienyl) zirconium dichloride,

Bis (methylpropylcyclopentadienyl) zirconium dichloride,

Bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylhexylcyclopentadienyl) zirconium dichloride,

Bis (methyloctylcyclopentadienyl) zirconium dichloride,

Bis (ethylbutylcyclopentadienyl) zirconium dichloride,

Bis (trimethylcyclopentadienyl) zirconium dichloride,

Bis (tetramethylcyclopentadienyl) zirconium dichloride,

Bis (pentamethylcyclopentadienyl) zirconium dichloride,

Bis (hexylcyclopentadienyl) zirconium dichloride,

Bis (methylbenzylcyclopentadienyl) zirconium dichloride,

Bis (ethylhexylcyclopentadienyl) zirconium dichloride,

Bis (methylcyclohexylcyclopentadienyl) zirconium dichloride,

Ethylenebis (indenyl) dimethylzirconium,

Ethylenebis (indenyl) zirconium dichloride,

Ethylenebis (indenyl) diphenyl zirconium,

Ethylenebis (indenyl) methylzirconium monochloride,

Ethylenebis (indenyl) zirconium bis (trifuromethanesulfonate),

Ethylenebis (indenyl) zirconium bis (methylmethanesulfonate),

Ethylenebis (indenyl) zirconium bis (P-toluenesulfonate),

Ethylenebis (indenyl) zirconium bis (P-chlorobenzenesulfonate,

Ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-furuorenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-furuorenyl) dimethyl zirconium,

Isopropylidene (cyclopentadienyl-indenyl) zirconium dichloride,

Isopropylidene (methylcyclopentadienyl-furuorenyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium bis (trifuromethanesulfonate),

Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl-fluoroenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Methylphenylsilylenebis (indenyl) zirconium dichloride,

Among these, the following compounds are preferably used.

Bis (indenyl) zirconium dichloride,

Bis (indenyl) zirconium dibromide,

Bis (indenyl) zirconium bis (P-toluene sulfonate),

Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Bis (furuorenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dibromide,

Ethylenebis (indenyl) dimethyl nironium,

Ethylenebis (indenyl) diphenyl zirconium,

Ethylenebis (indenyl) methyl zirconium monochloride,

Ethylenebis (indenyl) zirconium bis (methane sulfonate),

Ethylenebis (indenyl) zirconium bis (P-toluene supportonate),

Ethylenebis (indenyl) zirconium bis (trifuromethanesulfonate),

Ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-furuorenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-furuorenyl) dimethyl zirconium,

Isopropylidene (cyclopentadienyl-indenyl) zirconium dichloride,

Isopropylidene (methylcyclopentadienyl-furuolenyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis ((dimethylcyclopentadienyl) zirconium dichloride,,

Dimethylsilylenebis ((trimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium bis (trifuromethanesulfonate),

Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl-fluoroenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Methylphenylsilylenebis (indenyl) zirconium dichloride,

Bis (trimethylsilylcyclopentadienyl) zirconium dichloride,

In the transition metal compounds exemplified above, the di-substituted cyclopentadienyl rings are 1,2- and 1,3-substituted compounds and the like, and the tri-substituted cyclopentadienyl rings are 1,2,3- and 1,2,4- Substituted compounds;

Alkyl groups such as propyl or butyl are isomers such as n-, i-, sec- and tert- compounds.

In the present invention, a zirconium metal substituted with titanium metal, hafnium metal, neodymium metal, samarium or yttrium in the above-described zirconium compound may be used as the transition metal compound. These compounds may be used alone or in combination of two or more thereof. These compounds may also be used after dilution in hydrocarbons or halogenated hydrocarbons.

In the present invention, the metallocene compound is preferably used after dilution in a hydrocarbon medium. The metallocene compound as described above may be supported on the carrier by contact with the particle carrier compound.

Examples of carrier compounds include inorganic carriers such as Sio ₂ , Al ₂ Ob, B ₂ O ₃ , Mg), ZrO ₂ , CaO, TiO ₂ , ZnO, SnO ₂ , BaO, and ThO, and polyethylene, polypropylene, poly-1- Resins such as butene, poly-4-methyl-1-pentene and styrene / divinylbenzene copolymers.

This carrier compound can be used in combination of 2 or more type.

In the present invention, a zirconocene compound containing zirconium as a heavy metal atom and containing at least two ligands having a cyclopentadienyl skeleton is preferably used as the metallocene compound.

Next, the organoaluminum oxy compound used in the preparation of the catalyst (ii) is described below.

The organoaluminum oxy compound used in the present invention may be a known aluminoxane or a benzene insoluble organic aluminum oxy compound.

Known aluminoxanes are specifically represented by the following formulas.

Wherein R is a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrocarbon group such as a methyl group or an ethyl group, especially a methyl group, and m is an integer of 2 or more, preferably 5 to 40.

This aluminoxane can be formed from a mixture of an alkyloxyaluminoxane unit represented by the formula OA1 (R ¹ ) and an alkyloxyaluminoxane unit represented by the formula OAl (R ² ).

Wherein R ¹ and R ² are each hydrocarbon groups, for example the same as for R, but R ¹ and R ² are different.

Known aluminoxanes can be prepared, for example, by the following process, and the final aluminoxane is generally obtained in the form of the aluminoxane solution in aromatic hydrocarbon medium.

(1) React with one another by adding an organoaluminum compound such as trialkylaluminum to an aromatic hydrocarbon suspension of a water-absorbing compound or a crystal water-containing salt such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or nickel hexachloride. (2) water, ice, or steam directly to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydro hurane in the aluminoxane solution type in an aromatic hydrocarbon medium. (3) organoaluminum compounds such as trialkylaluminum and organic tins such as dimethyltin oxide and dibutyltin oxide in a solvent such as decane, benzene or toluene in the aluminoxane solution type in an aromatic hydrocarbon medium. A method comprising reacting an oxide.

Of these methods, method (1) is preferably used.

Specific examples of organoaluminum compounds that can be used to prepare aluminoxane solutions include triethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-sec-butyl Trialkyl aluminum such as aluminum, tri-tert-butyl aluminum, tripentyl aluminum trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, and tricycloalkyl aluminum such as tricyclohexyl aluminum, tricyclohexyl aluminum and tricyclooctyl aluminum and,

Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride,

Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide;

Dialkyl aluminum aryl oxides, such as diethyl aluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.

Moreover, what can be used as an organoaluminum compound is isoprenyl aluminum represented by a following formula.

(iC ₄ H ₉ ) xAly (C ₅ H ₁₀ ) _z

Wherein x, y and z are each positive integers and z &gt;

The organoaluminum compounds exemplified above may be used alone or in combination.

Benzene-insoluble organoaluminum oxycompounds can be obtained, for example, by contacting the aluminoxane solution with water or active hydrogen containing compounds or by contacting the organoaluminum compounds with water.

When the benzene-insoluble organoaluminumoxy compound was analyzed by an infrared spectrometer (IR), the ratio of absorption at about 1260 cm ^-1 (D ₁₂₆₀ ) and absorption at about ₁₂₂₀ cm ^-1 (D ₁₂₂₀ ) (D ₁₂₆₀ / D ₁₂₂₀ ) Preferably it is 0.09 or less, More preferably, it is 0.08 or less, Especially preferably, it is in the range of 0.04-0.07.

The benzene insoluble organoaluminumoxy compound as described above is assumed to have an alkyloxyaluminum unit represented by the following formula.

In the above formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group. . Among them, the methyl group and ethyl group are good, and the methyl group is particularly good.

In addition to the alkyloxy aluminum units represented by the above formula, the benzene insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula.

Wherein R ⁸ is an aryloxy group, a hydroxyl group, a halogen or hydrogen atom of the alkoxy group, a 6 to 20 carbon atoms in the hydrocarbon group, 1 to 12 carbon atom number of 1 to 12 carbon atoms.

The group represented by R ⁸ in the above formula is different from the group represented by R ⁷ in the above formula.

When the organoaluminum oxycompound contains oxyaluminum units, the organoaluminum oxycompound contains at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol% of alkyloxyaluminum units.

The organoaluminum oxy compound 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 being supported on the above-mentioned carrier compound.

As an organoaluminum compound (2) used as needed by this invention, the organoaluminum compound shown by following formula [b] is mentioned, for example.

R ⁵ _n AlX _3-n ...

Wherein R ⁵ is a hydrocarbon having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3;

In formula [b], R <^5> is a C1-C12 hydrocarbon group, such as an alkyl group, a cycloalkyl group, or an aryl group, Specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group, a pen And a methyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Examples of the organoaluminum compound include compounds described below.

Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri-2-ethylhexyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, Dialkylaluminum halides such as diethylaluminum chloride, diisobutylaluminum chloride, diisopropylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquilolide, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butyl Alkyl aluminum sesquihalides such as aluminum sesquichloride and ethyl acetquibromide; alkyl aluminum di halides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; Ethyl aluminum hydride and diisobutyl aluminum hydride, such as beads of an alkyl aluminum hydride.

As the organoaluminum compound, a compound represented by the following formula [b '] can also be used.

R ⁵ _n ALY _3-n ·········· [b ']

Wherein R ⁵ is as above, Y is —OR ⁶ group, —OSiR ⁷ ₃ group, —OAlR ³ ₂ group, —NR ³ ₂ group, —SiR ¹⁰ ₃ group or —N (R ¹¹ ) AlR ¹² ₂ group , n is 1 to 2, R ⁶ , R ⁷ , R ⁸ and R ¹² are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, trimethylsilyl group and the like, and R ⁹ is hydrogen atom, methyl group, Ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., R <^10> and R <^11> are methyl group, ethyl group, etc., respectively.

An organoaluminum compound is as specifically mentioned later.

(Iii) dimethyl aluminum methoxide,

Diethyl aluminum ethoxide,

Diisobutyl aluminum methoxide,

A compound of the formula R ⁵ _n AL (OR ⁶ ) _{3-n such} as

(Ii) Et ₂ Al (OSiMe ₃ ),

(iso-Bu) ₂ Al (OsiMe ₃ ),

(iso-Bu) ₂ Al (OsiEt ₃ )

A compound of the formula R ⁵ _n A1 (OSiR ⁷ ₃ ) _{3-n such} as

(Iii) Et ₂ AlOAlEt ₂ ,

(iso-Bu) ₂ AlOAl (iso-Bu) ₂

Compounds of the formula R ⁵ _n L (OR ⁸ ₃ ) _3-n , etc.,

(Ⅳ) Me ₂ AlNEt ₂ ,

Et ₂ AlNHMe,

Me ₂ AlNJEt,

Et ₂ AlN (SiNe ₃ ) ₂ ,

(iso-Bu) ₂ AlN (SiMe ₃ ) ₂

A compound of the formula R ⁵ _n AL (NR ⁹ ₂ ) _{3-n such} as

(Iii) a compound of the formula R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n such as (iso-Bu) ₂ AlSiMe _3;

Among the organoaluminum compounds represented by the formulas [b] and [b '], an organoaluminum compound represented by R ₈ Al, R ₈ Al (OR ₆ ) _3-n R ₈ / Al (OAlR ₈ ) _3-n is preferable.

In particular, a compound in which R ⁵ is an isoalkyl group and n is 2 is preferable. This organoaluminum compound can also be used in combination of 2 or more.

The organoaluminum compound may also be supported on the carrier organoaluminum compound described above.

As described above, the cycloolefin copolymer (B-1) of the present invention is a liquid phase transfer in a hydrocarbon solvent in the presence of a hydrocarbon elastomer (A-1) using the catalyst (i) or (ii) described above [ The cycloolefin represented by [I] or [II] and the alpha olefin of 2 or more carbon atoms can be copolymerized, and it can manufacture.

Hydrocarbon solvents used in this case include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene, and halogen derivatives thereof.

Alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane and their halogen derivatives,

Aromatic hydrocarbons such as benzene, toluene and xylene and halogen derivatives such as chlorobenzene. In the above-mentioned copolymerization reaction, alpha -olefin or cycloolefin itself can also be used as a hydrocarbon solvent. These solvents can also be mixed and used.

In the present invention, it is preferable to perform the above-mentioned copolymerization in the presence of the aforementioned hydrocarbon solvent, and when using a mixture of hydrocarbon solvents, cyclohexane / hexane, cyclohexane / heptane, cyclohexane / pentane, toluene / hexane, toluene / heptane, toluene / It is preferable to perform the above copolymerization in the presence of a mixed solvent such as pentane.

Although either a branch method or a continuous method may be employed, it is preferable to copolymerize by the continuous method.

In this case, the concentration of the catalyst used is as follows.

When the catalyst (i) is used, the amount of the soluble vanadium compound to be supplied to the polymerization system is usually 0.01 to 5 mmol, preferably 0.05 to 3 mmol, per 1 liter of the polymerization liquid, and the amount of the organoaluminum compound is the amount of aluminum atoms present in the polymerization system ( 2 or more, preferably 2 to 50, and particularly preferably 3 to 20, in terms of the ratio A1) to the vanadium atom (V).

When the copolymerization is carried out in a continuous method, the soluble vanadium compound is supplied at a concentration of 10 times or less, preferably 1 to 7 times, particularly preferably 1 to 5 times, of the soluble vanadium compound present in the polymerization system.

Typically, the soluble vanadium compound and the organoaluminum compound are supplied to the polymerization system after dilution with the liquid monomer and / or the hydrocarbon solvent described above.

In this case, the soluble vanadium compound to be supplied is preferably diluted in the above-described concentration range, and the organoaluminum compound is supplied at a concentration of, for example, 50 times or less of the concentration of the polymerization system.

In the case of using the catalyst (ii), the amount of the metallocene compound supplied in the polymerization system is preferably about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, per 1 liter of the polymerization solution, and the organoaluminum oxy compound has its aluminum atom. The amount of about 1 to 10000 moles, preferably 10 to 5000 moles per mole of the transition metal atom of the metallocene compound is good.

Further, if necessary, the atomic ratio (Al-1 / Al-2) of the aluminum atom (Al-1) of the organoaluminum compound and the aluminum atom (Al-2) of the organoaluminum oxy compound is usually 0.02 to 3, preferably 0.05-1.5.

In the presence of the catalyst (iii) or (ii) described above, the copolymerization reaction is usually carried out at -50 deg. C to 150 deg. C, preferably -30 deg. C to 100 deg. C, particularly preferably -20 deg. C to 70 deg. Is 0-50 kg / cm <2>, Preferably it is 0-20 kg / cm <2>.

The reaction time (average holding time when copolymerization is carried out by the continuous method) is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours, depending on the type of monomer, the catalyst concentration, and the use conditions such as polymerization temperature.

In the above-mentioned copolymerization reaction, the α-olefin (a) having 2 or more carbon atoms and the cycloolefin (b) represented by the above formula [I] or [II] are 1/99 to 90/10, preferably 5/95 to It feeds into a polymerization system at the molar ratio (a) / (b) of 50/50.

When copolymerizing, a chain transfer agent such as hydrogen may be used for molecular weight control such as hydrogen.

When copolymerizing α-olefin (a) having 2 or more carbon atoms and cycloolefin (b) represented by the above formula [I] or [II] in the presence of a hydrocarbon elastomer (A-1) component in the above-described manner, a hydrocarbon elastomer The solution containing the cycloolefin copolymer composition which consists of (A-1) component and a cycloolefin copolymer (b-1) component is obtained. The concentration of cycloolefin in such a solution is usually 10-500 g / l, preferably 10-300 g / l. This solution is treated by conventional methods to obtain the desired cycloolefin copolymer composition.

More specifically, in the preparation of the cycloolefin copolymer composition of the present invention, a hydrocarbon elastomer (A-1) prepared in advance, for example, an elastomer pellet or a lump is dissolved in a hydrocarbon solvent, and then α-olefin having 2 or more carbon atoms in this solution ( copolymerizing a) with cycloolefin (b) or first preparing the above-mentioned hydrocarbon elastomer (A-1) and then copolymerizing α-olefin (a) having 2 or more carbon atoms and cycloolefin (b) in the polymer solution. A step polymerization technique can also be used.

The cycloolefin copolymer composition prepared according to the present invention is a single screw extruder, a belt extruder, a twin screw extruder, a conical twin screw extruder, a coneader, a platicater, a mixtruder, a conical 2 Shaft extruders, planetary extruders, geared extruders and shaftless extruders can be used to form by conventional methods such as extrusion, injection molding, blow molding and rotational molding.

The cycloolefin copolymer composition according to the present invention can be used in various additives such as heat stabilizers, weather stabilizers, antistatic agents, anti-slip agents, antiblocking agents, anti-rust agents, lubricants, pigments, It may contain dyes, natural oils, synthetic oils and waxes. Stabilizers used as needed are, for example, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate] methane, β- (3,5-di Phenolic properties such as -t-butyl-4-hydroxyphenyl) propionic acid and 2,2'-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Aliphatic metal salts such as antioxidants, zinc stearate, calcium stearate and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate Fatty acid esters of polyhydric alcohols such as latex and pentaerythritol tristearate.

These stabilizers may be used alone or in combination.

One of the combination examples is the combination of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate] methane, zinc stearate and glycerin monostearate .

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of polyhydric alcohol. The fatty acid ester of the polyhydric alcohol is preferably a fatty acid ester of polyhydric alcohol obtained by esterifying a part of the alcoholic hydroxyl group of the polyhydric alcohol having three or more hydroxyl groups.

Specific examples of fatty acid esters of polyhydric alcohols include aliphatic esters of glycerin such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate and glycerin distearate, pentaerythritol monostearate, Fatty acid esters of pentaerythritol such as pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate.

The phenolic stabilizer is used in an amount of 0 to 10 parts by weight, preferably 0 to 2 parts by weight, based on 100 parts by weight of the cycloolefin resin.

The fatty acid ester of polyhydric alcohol is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the cycloolefin resin.

In addition, the cycloolefin random copolymer composition in the present invention is silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloons, aluminum hydroxide, magnesium hydroxide, basic, so long as the object of the invention is not impaired. Magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asmestos, glass fiber, glass chips, glass pellets, calcium silicate, montmorillonite, bentonite, graphite, Fillers such as aluminum powder, molybdenum sulfide, boron fibers, silicon carbide fibers, polymer fibers of? -Olefins having 2 or more carbon atoms, polypropylene fibers, polyester fibers and polyamide fibers may be contained.

[Effects of the Invention]

The cycloolefin copolymer composition of the present invention is a hydrocarbon elastomer (A-1) component without a polymerizable double bond and the α-olefin (a) and cycloolefin having 2 or more carbon atoms in the presence of the hydrocarbon elastomer (A-1) component. It is formed from the cycloolefin random copolymer (B-1) obtained by the copolymerization of b), whereby the dispersion obtained in the cycloolefin random copolymer (B-1) phase on the elastomer (A-1) is good, so Excellent impact

Hereinafter, the present invention will be described with reference to Examples. However, the present invention is not limited to the embodiments.

Various physical properties and evaluation methods used in the present invention are shown below.

(1) limit viscosity [η]

It was measured with Ubbelohde viscometer in decalin at 135 ° C.

(2) Glass transition temperature (Tg)

It measured by Seiko Density DSC-220C in nitrogen atmosphere at the heating rate of 10 degree-C / min.

(3) Softening temperature (TMA)

Thermal deformation of a sheet having a thickness of 1 mm was measured by a DuPont Thermomechanical Analyzer. That is, a load of 49 g was applied to a quartz needle placed vertically on the sheet, and the temperature of the sheet was increased at a rate of 5 ° C./min, whereby the sheet temperature when the needle penetrated into the sheet by 0.635 mm was measured by TMA. As.

(4) Id value

It measured according to JIS K3331 by the iodine monochloride method.

(5) MFR

It measured according to ASTM D1238 at 260 degreeC under the load of 2.16 kg.

(6) Production of sample

The tax was prepared using an injection molding machine 1S50EPN manufactured by Toshiba Corp. and a mold for a sample. After molding, the sample was measured after standing at room temperature for 48 hours.

(7) Bending test (FM)

Tested according to ASTM D790. Shape of Sample: 5 × 1/2 × 1/8 inch Width: 51mm

(8) Izod impact test

It measured according to ASTM D256. Shape of the sample: 5/2 x 1/8 x 1/2 inch (notch) Test temperature: 23 ℃

(9) Light transmittance

The transmittance | permeability in 780 mm wavelength visible light obtained by measuring the 2 mm-thick press sheet used as a sample with the Shimadzu Corporation spectrophotometer MSP-2000 was made into the light transmittance.

EXAMPLE

2 L glass reactor with mixed vanes, ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecation (hereinafter abbreviated as TCD) in the presence of a hydrocarbon elastomer without polymerizable double bonds according to the following method ) Copolymerization was carried out continuously.

A hexane / propylene copolymer ([η]: 2.1 kPa / g, Tg: -31 ° C) cyclohexane solution was continuously supplied from the top of the reactor so that the concentration of the ethylene / propylene copolymer in the reactor was 1.2 g / l. Next, the reactor was continuously fed with 0.4 L / hr of cyclohexane solution of TCD so that the TCD concentration in the reactor was 65.7 g / L.

A cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst from the top of the reactor was continuously fed at a rate of 0.7 l / hr (where the concentration of vanadium to be supplied is 2.86 times the concentration of vanadium present in the reactor). The concentration of vanadium was 0.5 mmol / L, and the catalyst was continuously supplied with 0.4 ml / hr of cyclohexane solution of ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) at a rate of 0.4 m / hr. It was made to mol / L, and ethylene, nitrogen, and hydrogen were supplied to the polymerization system via a bubble tube in an amount of 30.0 L / hr 7.0 L / hr and 3.0 L / hr.

The copolymerization was carried out while maintaining the polymerization system at 10 ° C by circulating the refrigerant through a jacket provided outside the reactor. The solution of the ethylene / propylene copolymer and the cycloolefin copolymer composition composed of the ethylene / TCD copolymer from the above-mentioned copolymerization is continuously taken out from the top of the reactor so that the volume of the polymerization solution in the reactor is 1 liter (ie, average residence flow). Made time to 0.5 hours).

A mixture of cyclohexane / isopropyl alcohol (1: 1) was added to the polymerization solution to stop the polymerization reaction. Thereafter, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymer solution were contacted by a steel stirring in a ratio of 1: 1 with a homomixer to allow the catalyst residue to move to the aqueous phase, and then the contacted mixture was left to stand. The aqueous phase was then separated and the remaining polymer phase was washed twice with distilled water to purify the polymerization solution phase and then separated.

The thus purified polymer solution is brought into contact with the stirring solution in three times the acetone of the polymerization solution, and the solids are collected by filtration and washed with acetone. In addition, in order to extract the TCD present in the polymer, the washed solids were put in acetone to 40 g / L and the extraction was performed at 60 ° C for 2 hours.

After the extraction treatment, the solids were collected by filtration and dried in a nitrogen stream at 350 mmHg, 130 ° C. for 24 hours.

In the manner described above, the amount of 81.4 g / hr, that is, 40.7 g / l, of the cycloolefin copolymer composition composed of the ethylene / propylene copolymer (component (A-1)) and the ethylene / TCD copolymer (B-1) component Got as. The proportion of the component (A-1) contained in the final copolymer composition was 2.9% by weight.

Table 1 shows the polymerization conditions, and Table 2 shows the results obtained in the bending test, the impact resistance test and the TMA softening test.

Example 2

The cycloolefin copolymer composition of the ethylene / propylene copolymer and the ethylene / TCD copolymer was prepared in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1.

A sample was prepared from the copolymer composition thus obtained, and its physical properties were evaluated, and the results are shown in Table 2.

Example 3-5

The same procedure as in Example 1 was repeated except that the component (A-1) was changed as shown in Table 1 to prepare a sample from the cycloolefin copolymer composition consisting of a hydrocarbon elastomer and an ethylene / TCD copolymer to obtain physical properties thereof. It evaluated and the result was shown in Table 2.

When various elastomers were used, the impact resistance was improved in every case.

Example 6

The same procedure as in Example 1 was repeated except that 1,4-methano-1,4,4a, 9a-tetrahydrofurouene (hereinafter referred to as MTHF) was used instead of TCD and the ethylene / propylene copolymer and ethylene / MTHF A cycloolefin copolymer composition made of a copolymer was prepared, a sample was prepared from the prepared composition, and physical properties thereof were evaluated, and the results are shown in Table 2.

Example 7

Ethylenebis (indenyl) zirconium dichloride [Et (Ind) ₂ ZrCl ₂ , concentration in the polymerization system: 0.2 mmol / l] and methylaluminoxane [MAO, Al concentration in the polymerization system: 20.0 mmol / l] The cycloolefin copolymer composition of the ethylene / propylene copolymer and the ethylene / TCD copolymer was prepared by repeating the same procedure as in Example 1, except that it was used as a polymer and the polymerization conditions were changed to those shown in Table 1.

Samples were prepared from the prepared compositions, their physical properties were evaluated, and the results are shown in Table 2.

In these examples, the effect of improving the impact strength was apparent by performing the copolymer in the presence of the elastomer.

Comparative Example 1

An ethylene / TCP copolymer was prepared by repeating the procedure of Example 1 except that cyclohexane was added to the polymerization system instead of a cyclohexane solution of ethylene / propylene copolymer.

Samples were prepared from the prepared copolymers, and their physical properties were evaluated, and the results are shown in Table 3.

Comparative Example 2

The procedure of Example 6 was repeated except that cyclohexane was added to the polymerization system instead of the cyclohexane solution of ethylene / propylene copolymer to prepare an ethylene / MTHF copolymer.

Samples were prepared from the prepared copolymers, and their physical properties were evaluated, and the results are shown in Table 3.

Comparative Example 3

Ethylene / TCD copolymer (TCD component 30.1 mol%, 450 g) and ethylene / propylene copolymer (50 g) were melt-mixed with a twin screw extruder (Plastic Kogaku Genkyuso Co., Ltd. 1 / D = 42) at a cylinder temperature of 270 ° C. Pelletized with a maker.

The pellets thus obtained were prepared and their physical properties were evaluated, and the results are shown in Table 3.

Comparative Examples 4 to 6

The procedure of Comparative Example 3 was repeated except that the elastomers listed in Table 3 were used instead of the ethylene / propylene copolymer.

Samples were prepared from the prepared compositions, their physical properties were evaluated, and the results are shown in Table 3.

Claims (2)

[A] a hydrocarbon elastomer (A-1) component having no polymerizable double bond and an intrinsic viscosity [η] measured in decalin at 135 ° C of 0.05 to 10 dl / g and a glass transition temperature (Tg) of 10 ° C or less; [B] Cycloolefin air composed of cycloolefin random copolymer (B-1) obtained by copolymerizing α-olefin (a) having 2 or more carbon atoms and cycloolefin (b) represented by the following formula [1] or [2]: In the copolymer composition, the hydrocarbon elastomer (A-1) component is present in the composition 1 to 50% by weight, and the cycloolefin random copolymer (B-1) component is airborne in the presence of the hydrocarbon elastomer (A-1) component. Cycloolefin copolymer composition characterized by the obtained. Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ -R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ¹⁵ -R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ together may form an alkylidene group. Wherein p and q are each an integer of 0 or 1 or more, m and n are each 0, 1 or 2, and R ¹ -R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. Or an alkoxy group, a carbon atom to which R ⁹ (or R ¹⁰ ) is bonded, and a 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 R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded together to form a monocyclic or polycyclic aromatic ring when n and m are 0. The α-olefin (a) having 2 or more carbon atoms and the cycloolefin (b) represented by the following formula [I] or [II] do not have a polymerizable double bond and have an intrinsic viscosity [η] measured in decalin at 135 ° C of 0.05. And copolymerize in the presence of a hydrocarbon elastomer (A-1) having a glass transition temperature (Tg) of 10 ° C. or less and 10 ° C./g or less, wherein the hydrocarbon elastomer (A-1) is present in the composition in an amount of 1 to 50% by weight. A method for producing a cycloolefin copolymer composition characterized by the above-mentioned. Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ -R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^15- R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ together may form an alkylidene group. Wherein p and q are each an integer of 0 or 1 or more, m and n are each 0, 1 or 2, and R ¹ -R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. Or an alkoxy group, a carbon atom to which R ⁹ (or R ¹⁰ ) is bonded, and a carbon atom to which R ¹³ or R ¹¹ is bonded may be bonded directly or by an alkylene group having 1 to 3 carbon atoms, and R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded together to form a monocyclic or polycyclic aromatic ring when n and m are 0.