JPH06228378A - Cycloolefin copolymer composition - Google Patents

Abstract

(57) [Summary] [Structure] (b) At least one or more α having 2 or more carbon atoms
An olefin, and (b) a specific cyclic olefin,
(C) Obtained by copolymerizing with a non-conjugated diene compound having a carbon number in the range of 5 to 20, and in decalin,
Intrinsic viscosity [η] measured at 135 ° C is 0.10 to 5.0
The glass transition temperature (Tg) is 10 in the range of dl / g.
℃ or more, having a polymerizable carbon-carbon double bond,
Iodine value is 2 to 30 (g-iodine / 100g-polymer)
Cyclic Olefin Random Copolymer Component [A]
And a polypropylene component [B] obtained by polymerizing propylene in the presence of the cyclic olefin random copolymer component [A], the cyclic olefin copolymer composition [C] comprising: A cyclic olefin-based copolymer composition, wherein the component [A] is contained in the composition [C] in an amount of 1 to 99% by weight. [Effect] It is excellent in heat resistance, chemical resistance, rigidity and the like without impairing the properties of polypropylene and a cyclic olefin random copolymer, and is also excellent in toughness and compatibility with other resins.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin copolymer composition, and more specifically, to a cyclic olefin copolymer composition excellent in rigidity, impact resistance, heat resistance, toughness and compatibility with other resins. It relates to a coalescing composition.

[0002]

BACKGROUND OF THE INVENTION Crystalline polyolefins such as polypropylene are widely used, but their physical properties are remarkably changed depending on the crystallinity of the polyolefin. For example, if the crystallinity of the polyolefin used is low, the physical properties such as rigidity and heat resistance of the resulting molded article will not be sufficiently high.

Therefore, it is possible to produce a molded article having excellent properties such as rigidity, heat resistance and toughness without deteriorating the physical properties such as excellent weather resistance of the conventionally known polyolefins. The advent of polyolefin resins has been desired.

For example, a method of adding a nucleating material or a filler is known as a method of improving the heat resistance and rigidity of a molded product formed of polypropylene, but the sufficient effect is not always obtained. .

A cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene is excellent in transparency and has heat resistance, heat aging resistance, dielectric properties, rigidity, etc. It is known to exhibit excellent performance in the field of optical materials such as optical memory disks and optical fibers, or in the field of structural materials (for example, JP-A-60-168). , 708, JP 61-98,780, JP 61-115,
912, JP 61-115,916, JP 61-120,816, JP 62-25.
No. 2,407).

[0006] Therefore, if the excellent properties of the cycloolefin copolymer can be imparted to the obtained composition by mixing the polypropylene with the cycloolefin copolymer, the obtained composition or It is expected that the rigidity and heat resistance of the molded product made of the composition will be improved.

Further, the cyclic olefin copolymer is amorphous and may not have sufficient chemical resistance and solvent resistance,
By mixing polypropylene with an amorphous cyclic olefin copolymer and a crystalline resin, it is expected that a resin composition having excellent chemical resistance and solvent resistance in addition to rigidity and heat resistance will be obtained. To be done.

However, in practice, polypropylene and the cyclic olefin copolymer have extremely poor miscibility, and they cannot be uniformly mixed, and a desired resin excellent in rigidity and heat resistance cannot be obtained. .

The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems in the prior art. As a result, a specific cyclic olefin random copolymer component [A] and the cyclic olefin random copolymer are obtained. A cycloolefin copolymer composition comprising a polypropylene component [B] obtained by polymerizing propylene in the presence of the component [A], wherein the component [A] is contained in a specific amount. The cyclic olefin-based copolymer composition as described above has rigidity,
The inventors have found that they are excellent in impact resistance, heat resistance, toughness and compatibility with other resins, and have completed the present invention.

[0010]

An object of the present invention is to solve the problems in the prior art as described above, and to prevent the deterioration of the properties of polypropylene and cyclic olefin random copolymers. It is an object of the present invention to provide a cyclic olefin-based copolymer composition which has improved compatibility with a copolymer and can produce a molded product having improved rigidity, heat resistance and toughness.

[0011]

SUMMARY OF THE INVENTION The cyclic olefin copolymer composition according to the present invention comprises (a) at least one or more α-olefin having 2 or more carbon atoms, and (ii) the following general formula [I] or [I]:
[I] and the cyclic olefin represented by
It is obtained by copolymerizing with a non-conjugated diene compound in the range of 20, and the intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.10 to 5.0 dl / g and has a glass transition. It has a temperature (Tg) of 10 ° C or higher, has a polymerizable carbon-carbon double bond, and has an iodine value of 2 to 30.
(G-iodine / 100 g-polymer), a cycloolefin random copolymer component [A], and polypropylene obtained by polymerizing propylene in the presence of the cycloolefin random copolymer component [A]. Ingredient [B]
A cyclic olefin-based copolymer composition [C] comprising 1 to 99% by weight of the component [A] in the composition [C].
It is characterized by being included in the amount of.

[0012]

[Chemical 3]

(In the formula [I], n is 0 or 1, and m is
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
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 may have a double bond, and R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. );

[0014]

[Chemical 4]

(In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2,
R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
It is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ¹³ (or R ¹⁰ ) is bonded to the carbon atom to which R ¹³ or R ¹¹ is bonded. It may be bonded to the carbon atom 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. It may form a monocyclic or polycyclic aromatic ring. ).

The cyclic olefin-based copolymer composition according to the present invention as described above does not impair the properties of polypropylene and the cyclic olefin-based random copolymer,
It is possible to produce a molded product having excellent compatibility between polypropylene and a cyclic olefin-based copolymer and having improved rigidity, heat resistance and toughness.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The cycloolefin copolymer composition according to the present invention will be specifically described below. The cyclic olefin-based copolymer composition [C] according to the present invention comprises a cyclic olefin-based random copolymer component [A] and a polypropylene component [B], and the polypropylene component [B] is the above-mentioned cyclic olefin. It is obtained by polymerizing propylene in the presence of the system random copolymer component [A]. In the cyclic olefin-based copolymer composition [C] according to the present invention, the cyclic olefin-based random copolymer component [A] has a polymerizable carbon-carbon double bond. At least a part of the cyclic olefin-based random copolymer component [A] and the polypropylene component [B] are considered to be chemically bonded.

First, the cycloolefin random copolymer component having a polymerizable carbon-carbon double bond of the present invention will be described. Cyclic Olefin Random Copolymer Component [A] The cyclic olefin random copolymer component [A] used in the present invention is a copolymer having a polymerizable carbon-carbon double bond in the elastomer, (A) at least one or more α-olefin having 2 or more carbon atoms, (b) a cyclic olefin represented by the following general formula [I] or [II], and (c) a carbon number in the range of 5 to 20 The copolymer with the non-conjugated diene compound can be mentioned.

Examples of the α-olefin (a) having 2 or more carbon atoms include ethylene, propylene, 1-butene, 1-
C2-C20 alpha such as pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene Mention may be made of olefins.
Of these, ethylene is preferred.

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

[0021]

[Chemical 5]

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.

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

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

The monocycle or polycycle formed here is exemplified below.

[0027]

[Chemical 6]

In the above example, 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 and an isopropylidene group.

[0030]

[Chemical 7]

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 amyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group and octadecyl group.

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

Examples of the alkoxy group include 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]. The above formula [I] or [I
As the cyclic olefin represented by [I], specifically,
Bicyclo [2.2.1] hept-2-ene derivative, 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 derivative, 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 derivative, 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.

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

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.
(C) The non-conjugated diene having 5 to 20 carbon atoms specifically includes the non-conjugated dienes represented by the following general formulas [III] to [VI].

[0063]

[Chemical 30]

The non-conjugated dienes represented by the above formula [III] include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1, 9-
Examples include decadien, 1,11-dodecadiene, and 1,19-eicodiene.

As the diene represented by the above formula [IV],

[0066]

[Chemical 31]

Examples thereof include the following. As the non-conjugated diene represented by the above formula [V],

[0068]

[Chemical 32]

Examples include the following. The above formula [V
As the diene represented by [I],

[0070]

[Chemical 33]

Examples thereof include: In the above non-conjugated diene (C), the hydrogen atom bonded to carbon other than the carbon forming the double bond may be substituted with a hydrocarbon group.

Among the non-conjugated dienes (c) represented by the above formulas [III] to [VI], 1,5-hexadiene, 1,
7-octadiene, 1,9-decadiene, 5-vinyl-bicyclo
[2.2.1] Hept-2-ene, 8-vinyl-tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10 ] -3-dodecene, bicyclo [2.2.1] hept-2,
5-diene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3,8-dodecadiene are preferably used.

Specific examples of the cyclic olefin random copolymer component [A] having a polymerizable carbon-carbon double bond as described above are given below. First, as the cyclic olefin-based random copolymer component [A] having a unit derived from the non-conjugated diene represented by the formula [III], 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, ethylene / norbornene / 1,7-octadiene copolymer, ethylene / 5-
Methyl-2-norbornene-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, 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, ethylene / tetracyclododecene / 1,9-
Examples thereof include decadiene copolymer.

The cyclic olefin random copolymer component [A] having a unit derived from the non-conjugated diene represented by the formula [IV] includes ethylene / norbornene / vinyl norbornene copolymer and ethylene / 5-methyl. -2-norbornene / vinyl norbornene copolymer, ethylene / 5-
Ethyl-2-norbornene / vinylnorbornene copolymer, ethylene / 5-phenyl-2-norbornene / vinylnorbornene copolymer, ethylene / tetracyclododecene / vinylnorbornene copolymer, ethylene / norbornene / vinyltetracyclododecene Copolymer, ethylene / 5
-Methyl-2-norbornene / vinyltetracyclododecene copolymer, ethylene / 5-ethyl-2-norbornene / vinyltetracyclododecene copolymer, ethylene / 5-phenyl-2-norbornene / vinyltetracyclododecene Examples thereof include copolymers and ethylene / tetracyclododecene / vinyltetracyclododecene copolymers.

The cyclic olefin-based random copolymer component [A] having a unit derived from a non-conjugated diene represented by the formula [V] includes ethylene-norbornene-norbornadiene copolymer, ethylene-5-methyl- 2-norbornene / norbornadiene copolymer, ethylene / 5-ethyl-2-norbornene / norbornadiene copolymer, ethylene / 5-phenyl-2-norbornene / norbornadiene copolymer, ethylene / tetracyclododecene / norbornadiene copolymer , Ethylene-norbornene-tetracyclododecadienene copolymer, ethylene-5-methyl-2-norbornene-tetracyclododecadienene copolymer, ethylene-5-ethyl-2-norbornene-tetracyclododecadienene copolymer, ethylene・ 5-Phenyl-2-norbornene / tetracyclododecadene co-weight Examples of the combination include ethylene / tetracyclododecene / tetracyclododecadiene copolymer.

The cyclic olefin random copolymer component [A] having a unit derived from the non-conjugated diene represented by the formula [VI] is ethylene norbornene-1,2
-Bis (5-bicyclo [2.2.1] hept-2-enyl) ethane copolymer, ethylene-5-methyl-2-norbornene-1,2-bis (5-
Bicyclo [2.2.1] hept-2-enyl) ethane copolymer, ethylene-5-ethyl-2-norbornene-1,2-bis (5-bicyclo [2.2.1] hept-2-enyl) ethane copolymer Combined, ethylene-5-phenyl-2-norbornene-1,2-bis (5-bicyclo [2.
2.1] hepta-2-enyl) ethane copolymer, ethylene / tetracyclododecene-1,2-bis (5-bicyclo [2.2.1] hepta-
Examples thereof include 2-enyl) ethane copolymer.

The cyclic olefin random copolymer component [A] contains the unit derived from α-olefin in an amount of usually 40 to 95 mol%, preferably 42 to 90 mol%. The unit derived from the cyclic olefin is contained in an amount of 5 to 60 mol%, preferably 10 to 58 mol%, and the unit derived from the non-conjugated diene compound is contained in an amount of 10 mol% or less. Has been. However, the total of the α-olefin unit, the cyclic olefin unit and the non-conjugated diene unit is 100 mol%.

The intrinsic viscosity [η] of this cyclic olefin random copolymer component [A] measured in decalin at 135 ° C. is 0.1 to 5.0 dl / g, preferably 0.1.
It is 5 to 4.5 dl / g. The glass transition temperature (Tg) of the cyclic olefin-based random copolymer component [A] measured by DSC is 10 to 250 ° C., preferably 70 to 2
The temperature is 00 ° C., and the iodine value is in the range of 2 to 30 (g-iodine / 100 g-polymer), preferably 2 to 20 (g-iodine / 100 g-polymer).

Cyclic Olefin Random Copolymer Component
Production of [A] The cyclic olefin random copolymer component [A] as described above includes, for example, (I) a ligand having a cyclopentadienyl skeleton, a transition of Group IVB or lanthanide of the periodic table. A catalyst comprising a metal compound, (II) an organoaluminum oxy compound, and optionally (III) an organoaluminum compound (hereinafter sometimes referred to as "metallocene catalyst"), or (IV) a soluble vanadium compound , (V) in the presence of a catalyst composed of an organoaluminum compound (hereinafter sometimes referred to as a vanadium-based catalyst), (a) an α-olefin having 2 or more carbon atoms, and (b)
At least one cyclic olefin represented by the above formula [I] or [II], and (c) the above formula [II
It can be produced by copolymerizing with a non-conjugated diene compound represented by I], [V] or [VI].

First, the metallocene catalyst will be described. Periodic Table IV containing a ligand having a cyclopentadienyl skeleton forming a metallocene catalyst as described above.
Examples of the transition metal compound (I) of Group B or lanthanide include compounds represented by the following formula [IX].

ML _X ... [IX] In the above formula [IX], M is a transition metal selected from Group IVB and lanthanides of the periodic table, and specifically, zirconium, titanium, hafnium, neodymium. ,
Samarium or ytterbium, L is a ligand that coordinates to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and a ligand having a cyclopentadienyl skeleton L has a carbon number of 1
~ 12 hydrocarbon groups, alkoxy groups, aryloxy groups,
A halogen atom, a trialkylsilyl group, SO ₃ R (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom,
x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group,
Alkyl-substituted cyclopentadienyl group such as butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group or indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, etc. Can be illustrated. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Of these ligands which coordinate to the transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above formula [IX] contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, and isopropylidene. , A substituted alkylene group such as diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, a substituted silylene group such as a methylphenylsilylene group, and the like.

Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group It is illustrated.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. A phenoxy group etc. are illustrated as an aryloxy group.

Halogen includes fluorine, chlorine, bromine,
Examples thereof include iodine. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

The compound represented by the above general formula [IX] is more specifically represented by the following general formula [X] when the valence of the transition metal is 4, for example. R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [X] (In the general formula [X], M is zirconium,
Titanium, hafnium, neodymium, samarium or ytterbium, R ¹ is a group having a cyclopentadienyl skeleton, and R ² , R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group. , Aryl group, aralkyl group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group, S
It is O ₃ R or a hydrogen atom, a is an integer of 1 or more, and a + b + c + d = 4. In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the above general formula [X] is a group having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopentadienyl skeletons A transition metal compound which is a group having is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene, substituted methylphenylsilylene groups and the like. It may be bound via a silylene group or the like. R ³ and R ⁴ are a group having a 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, SO ₃ R or a hydrogen atom. Is.

In the present invention, a zirconocene compound having a ligand containing at least two cyclopentadienyl skeletons and forming a bridge structure is preferably used.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) ) Dimethyl zirconium, dimethyl silylene bis (cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (methyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadiene) (Enyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bi Sus (indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) ) Zirconium dichloride, methylphenylsilylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclo Pentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium,
Bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluene) Sulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) Zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) dimethyl zirconium, bis (eth Rucyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene (Enyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl)
Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples of the transition metal compound,
The disubstituted forms of the cyclopentadienyl ring include 1,2- and 1,3-substituted products, and the trisubstituted products include 1,2,3- and 1,2,4-substituted products. Alkyl groups such as propyl and butyl are n-,
Includes isomers such as i-, sec-, and tert-.

In the present invention, in the zirconium compound as described above, a transition metal compound in which the zirconium metal is replaced with titanium metal, hafnium metal, neodymium metal, samarium metal or ytribium metal can also be used.

The organoaluminum oxy compound (II) which forms the above metallocene catalyst 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.

[0094]

[Chemical 34]

(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.) Here, the aluminoxane is represented by the formula [OAl (R
¹ )] and an alkyloxyaluminum unit represented by the formula [OAl (R ² )] [wherein R ¹ and R ² are the above R 1
And R ¹ and R ² represent different groups], and may be formed from a mixed alkyloxyaluminum unit.

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 the hydrocarbon medium suspension and reacted. (2) A method in which water is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) To an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene,
A method of reacting an organic tin compound such as dimethyltin oxide or dibutyltin oxide.

Among these methods, the method (1) is preferably adopted. It should be noted that the aluminoxane may contain a small amount of an organometallic component other than aluminum. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and trialuminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums, tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums, dimethylaluminum Dialkyl aluminum halides such as 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, diethyl aluminum Examples thereof include dialkylaluminum aryloxides such as aluminum phenoxide.

Isoprenylaluminum represented by the following general formula can also be used. (I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z (In the formula, x, y and z are positive numbers and z ≧ 2x.) Of these, trialkylaluminum is particularly preferable. .

The above organoaluminum compounds may be used alone or in combination. As the solvent used in the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, decane, dodecane, hexadecane and octadecane. Of hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Hydrocarbon solvents such as halides, especially chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran can be mentioned. Of these, aromatic hydrocarbons are particularly preferably used.

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

[0102] 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 0.0
It is preferably in the range of 4 to 0.07.

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

[0104]

[Chemical 35]

In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. As such a hydrocarbon group, specifically,
Methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, pentyl group, hexyl group,
Examples thereof include 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.

[0107]

[Chemical 36]

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

When containing an oxyaluminum unit, an organoaluminum oxy having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more. Compounds are desirable.

The organoaluminum oxy compound (II) 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 a carrier compound.

An organoaluminum compound (II) is optionally used as a catalyst for forming the above metallocene catalyst.
Examples of I) include organic aluminum compounds represented by the following general formula [XI].

R ⁵ _n AlX _3-n ... [XI] (However, in the general formula [XI], R ⁵ has 1 to 1 carbon atoms.
2 is a hydrocarbon group, X is a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula [XI], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

As such an organoaluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (III), a compound represented by the following general formula [XII] can also be used. R ⁵ _n AlY _3-n ... [XII] (In the general formula [XII], R ⁵ is the same as above, and Y is —OR ⁶ group, —OSiR ⁷ ₃ group, —OAlR.
⁸ ₂ group, -NR ⁹ ₂ group, -SiR ¹⁰ ₃ group or -N (R ¹¹⁾ Al
R 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 and the like,
R ⁹ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁰
And R ¹¹ is a methyl group, an ethyl group or the like. ) As such an organoaluminum compound, the following compounds are specifically used. (I) compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (ii) R ⁵ _n Al (OSiR ⁷ ₃ ) _3- a compound represented by _n , such as Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂
Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), and other compounds represented by (iii) R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , for example Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ Al
(Iv) R ⁵ _n Al (NR ⁹ ₂ ) _3-n, such as OAl (iso-Bu) ₂
A compound represented by, for example, Me ₂ AlNEt ₂ , Et ₂
AlNHMe, Me ₂ AlNHEtEt ₂ AlN (SiM
_{e 3) 2, (iso-} Bu) 2 AlN (SiMe 3) 2 , etc., (V) R ⁵ _n
A compound represented by Al (SiR ¹⁰ ₃ ) _3-n , for example (is
o-Bu) ₂ AlSi Me _3, etc.,

[0115]

[Chemical 37]

Among the organoaluminum compounds represented by the above general formulas [V] and [VI], the general formula R ⁵ ₃ Al,
Preferred examples include the organoaluminum compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n and R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , wherein R ⁵ is an isoalkyl group and n = 2 is particularly preferable. Two or more kinds of these organoaluminum compounds can be mixed and used.

The metallocene catalyst as described above is prepared by a transition metal compound (I) of Group IVB or lanthanide containing a ligand having a cyclopentadienyl skeleton.
The organoaluminum oxy compound (II) and the organoaluminum compound (III) may be separately fed into the polymerization vessel, or may be contacted with each other outside the polymerization vessel in advance.

The catalyst concentration of the transition metal compound (I) of Group IVB or lanthanide is 10 ^-8 to 10 ^-2 mol / liter, preferably 10 ^-6 to 10 ^-3 mol / liter, The catalyst concentration of the compound is preferably 1 to 10 ⁴ equivalents of the transition metal compound. The catalyst concentration of the organoaluminum compound used as necessary is preferably 0.01 to 100 equivalents of the aluminum atom of the organoaluminum oxy compound.

Next, the vanadium catalyst will be described. Soluble vanadium compounds (I
V) is specifically represented by the following formula.

Formula VO (OR) _a X _b or formula V (OR) _c X _d . However, in the above formula, R is a hydrocarbon group, and X is
Is a halogen atom, and a, b, c and d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c, respectively.
The relationship is ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4.

Examples of these vanadium compounds include:
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 , VO (O-n-C ₄
H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ ,
VOCl ₂ , VO (O-n-C ₄ H ₉ ) ₃ and VCl ₃・ 2
(OC ₈ H ₁₇ OH) and the like. These vanadium compounds can be used alone or in combination.

Further, the soluble vanadium compound (i) is
As shown by the following formula, a vanadium compound having a tertiary alkoxy group may be used. ^{_{VO (OCR 1 3) a X}} b or ^{_{V (OCR 2 3) c X}} d proviso, R ^1, R ² in the above formula is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, X is It is a chlorine atom or a bromine atom. Also, a, b, c, d are 0.5 ≦
a ≦ 3, 0 ≦ b ≦ 2.5, 2 ≦ a + b ≦ 3, 0.5 ≦ c ≦
4, 0 ≦ d ≦ 3.5, 3 ≦ c + d ≦ 4 are satisfied.

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

V (tert-butyloxy) Cl ₃ , V (tert-butyloxy) ₂ Cl ₂ V (tert-butyloxy) ₃ Cl V (2,3-dimethyl-2-butyloxy) Cl ₃ V (2,3-dimethyl 2-Butyloxy) ₂ Cl ₂ V (2,3-dimethyl-2-butyloxy) ₃ Cl and the like.

V (tert-butyloxy) Cl ₃ V (tert-butyloxy) ₂ Cl ₂ V (tert-butyloxy) ₃ Cl and the like.

Of these vanadium compounds having a tertiary alkoxy group, VO (alkoxy group) Cl ₂ is preferable. Further, the soluble vanadium compound (i) may be a vanadium compound having β-diketone as a ligand, as represented by the following formula.

VO (acac) _e Y _f or V (mmh) _g Y _h However, in the above formula, acac represents an acetylacetonato group represented by the following formula, and mmh is 2-methyl-1,3-butanedionate. Represents a group. Y is an alkyl group, an alkoxy group or a halogen atom, and e, f, g and h are 1 ≦.
e ≦ 2, 0 ≦ f ≦ 1, 2 ≦ e + f ≦ 3, 1 ≦ g ≦ 3, 0
≦ h ≦ 3, 3 ≦ g + h ≦ 4 are satisfied.

[0128]

[Chemical 38]

Specific examples of the soluble vanadium compound having the β-diketone represented by the above formula as a ligand include the compounds described below. In the formula shown below, X represents Cl, F, Br, I, an alkyl group, a primary alkoxy group, or a secondary alkoxy group, but Cl is preferable.

VO (acac) ₂ , VO (mmh) ₂ , VO (aca
c) X ₂ , VO (acac) X, VO (mmh) X ₂ , VO (mm
h) X etc. V (acac) ₃ , V (mmh) ₃ , V (acac) ₂ X
₂ , V (acac) ₂ X, V (mmh) ₂ X ₂ , V (mmh) ₂ X, etc.

In the soluble vanadium compounds having these β-diketones as ligands, VO (acac) ₂ and VO (m
mh) ₂ , V (acac) ₃ and V (mmh) ₃ are preferred. Further, the vanadium compound may be an adduct obtained by adding an electron donor to the vanadium compound represented by the above formula.

Examples of electron donors that form adducts with the above vanadium compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acids. Anhydrous and oxygen-containing electron donor such as alkoxysilane,
And nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

Specific examples of the compound used as such an electron donor include methanol, ethanol,
C1-18 such as propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol Alcohols; C1-18 such as trichloromethanol, trichloroethanol and trichlorohexanol
Halogen-containing alcohols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol (these phenols may have a lower alkyl group) ); Acetone, methyl ethyl ketone, methyl isobutyl ketone,
C3-C15 ketones such as acetophenone, benzophenone and benzoquinone; acetaldehyde,
C2-C15 aldehydes such as propyl aldehyde, octyl aldehyde, benzaldehyde, trialdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, ethyl 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 Carbon number 2 such as ethyl benzoate, methyl aliceate, ethyl aliceate, ethyl ethoxybenzoate, γ-butyl lactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate.
30 organic acid esters; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and alice acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole And 2 to 2 carbon atoms such as diphenyl ether
0 ethers; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; alkoxysilanes such as ethyl silicate and diphenylmethoxysilane; acetic acid N, N-
Acid amides such as dimethylamide, benzoic acid N, N-dimethylamide and toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine,
Mention may be made of amines such as tribenzylamine and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile; and pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine. These electron donors can be used alone or in combination.

Further, the above-mentioned soluble vanadium compound (IV)
The organoaluminum compound (V) used with
It is a compound having at least one Al-carbon bond in the molecule.

Examples of the organoaluminum compound include compounds represented by the following formulas (a) and (b). (A) An organoaluminum compound represented by the formula R ¹ _m Al (OR ² ) _n H _p X _q .

Here, R ¹ and R ² are hydrocarbon groups having a carbon number of usually 1 to 15, preferably 1 to 4, which may be the same or different. X is halogen, m
Is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.

[0137] (ii) Part I of the formula M ¹ AlR ¹ ₄
Complex alkylated product of group metal and aluminum. Where M ¹
Is Li, Na or K, and R ¹ has the same meaning as described above.

Specific examples of the organoaluminum compound represented by the above formula (a) include the compounds described below. A compound represented by the formula R ¹ _m Al (OR ² ) _3-m ... (1); wherein R ¹ and R ² have the same meanings as described above, and m is preferably 1.5 ≦ m <3. Is a number.

A compound represented by the formula R ¹ _m AlX _3-m (2); wherein R ¹ has the same meaning as described above, X is a halogen atom, and m is preferably 0 <m <3. .

A compound represented by the formula R ¹ _m AlH _3-m (3); wherein R ¹ has the same meaning as described above, and m is preferably 2 ≦ m <3.

A compound represented by the formula R ¹ _m Al (OR ² ) _n X _q (4); wherein R ¹ and R ² have the same meanings as described above, X is a halogen atom, and 0 <m ≦ 3, 0 ≦ n
<3, 0 ≦ q <3, and m + n + q = 3.

Specific examples of the organoaluminum compound represented by the above formula (1) include trialkylaluminums such as triethylamminium and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; diethylaluminum ethoxide. And dialkyl aluminum alkoxides such as dibutyl aluminum butoxide; ethyl aluminum sesquiethylide, butyl aluminum sesquibutoxide and the formula R ¹ _2.5 Al (OR ² ) _0.5 etc. (R ¹ ,
R ² is a partially alkoxylated alkylaluminum having an average composition represented by an alkyl group.

Specific examples of the organoaluminum compound represented by the above formula (2) include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; ethylamylnium sesquichloride, butylaluminum sesquichloride. And alkylaluminum sesquihalides such as ethylaluminum sesquibromide; partially halogenated alkylaluminums such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminium dibromide.

Specific examples of the organoaluminum compound represented by the above formula (3) include dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and ethylaluminum dihydride and propylaluminum dihydride. Partially hydrogenated alkyl aluminums are mentioned.

Specific examples of the organoaluminum compound represented by the above formula (4) include a partially alkoxylated and halogenated alkyl such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide and ethylaluminum ethoxy bromide. Aluminum can be used.

Further, the organoaluminum compound may be a compound similar to the compound represented by the formula (a), such as an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom.

Specific examples of such compounds include:
_{(C 2 H 5) 2 AlOAl} (C 2 H 5) 2, (C 4 H 9) 2 Al
OAl (C ₄ H _{9) 2} and _{(C 2 H 5) 2 AlN} (C 6 H 5)
Al (C ₂ H _{5) 2} and the like.

An example of the organoaluminum compound represented by the above formula (B) is LiAl (C ₂ H ₅ ) ₄
And LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.

As the organoaluminum compound (V) forming the vanadium catalyst, an organoaluminum oxy compound (aluminoxane) can be used. This aluminoxane may be a conventionally known aluminoxane or a benzene-insoluble aluminoxane. These aluminoxane are
It has already been described in the section of metallocene catalyst.

In the present invention, the soluble vanadium compound (IV) and the organoaluminum compound (V) described above are
It can be used as it is or can be used by supporting it on a carrier. Here, as the carrier compound, S
iO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO,
Inorganic carrier compounds such as TiO ₂ , ZnO, ZnO ₂ , SnO, BaO, ThO, polyethylene, polypropylene,
Poly-1-butene, poly-4-methyl-1-pentene, styrene
-A resin such as vinylbenzene copolymer can be used. These carrier compounds can be used alone or in combination.

The above-mentioned copolymerization reaction of the α-olefin (a) having 2 or more carbon atoms, the cyclic olefin (b) and the non-conjugated diene compound (c) is usually carried out in a liquid phase, and the soluble vanadium compound (IV ) And the organoaluminum compound (V) are usually diluted with the reaction solvent and supplied to the polymerization solution.

The catalyst concentration of the soluble vanadium compound (IV) is 10 ^-8 to 10 ^-2 mol / liter, preferably 10 ^-6 to 10 ^-3 mol / liter, and the catalyst concentration of the organoaluminum compound is It is preferably used in an amount of 1 to 10 ⁴ equivalents of the transition metal compound.

When copolymerizing an α-olefin (a) having 2 or more carbon atoms, a cyclic olefin (b) and a non-conjugated diene compound (c) in the presence of the above-mentioned metallocene catalyst or vanadium catalyst. Polymerization forms include solution polymerization, monomer solvent polymerization, and slurry polymerization.

Examples of the polymerization solvent used in the above copolymerization include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene and xylene. Examples thereof include aromatic hydrocarbons and the like. These solvents can be used alone or as a mixture.

The polymerization temperature is -50 to 230 ° C, preferably -30 to 200 ° C, more preferably -20 to 20 ° C.
The temperature is in the range of 150 ° C., and the polymerization reaction time is 2 minutes to 5 hours, preferably 5 minutes to 3 hours. The pressure during the polymerization reaction is in the range of more than 0 and 1000 kg / cm ² , preferably more than 0 and 50 kg / cm ² .

The supply concentration ratio of each component of the α-olefin (a) having 2 or more carbon atoms, the cyclic olefin (b) and the non-conjugated diene compound (c) is ((b) + (c)) / ((b) )
The value of + (b) + (c)) is preferably in the range of 0.60 to 0.99, and particularly preferably in the range of 0.70 to 0.98. Regarding the ratio between (b) and (c), the value of (c) / (b) + (c) is 0.01 to
It is preferably in the range of 0.80, and 0.01 to 0.
A range of 50 is particularly preferable.

The molecular weight of the cyclic olefin copolymer obtained as described above depends on whether hydrogen is present in the polymerization system or
Alternatively, it can be adjusted by changing the polymerization temperature.

The polypropylene component [B] of the present invention will be described. Polypropylene Component [B] The polypropylene component [B] of the present invention is obtained by polymerizing propylene in the presence of the cyclic olefin random copolymer component [A] having a polymerizable double bond as described above. .

In the polypropylene component [B], other α may be used as long as the properties of the propylene component are not impaired.
-It is also possible to carry out addition polymerization of olefins. More specifically, as other α-olefins, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Mention may be made of α-olefins having 2 to 20 carbon atoms such as pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Cyclic Olefin Copolymer Composition [C] Cyclic Olefin Copolymer Composition [C] According to the Present Invention
Comprises a cyclic olefin-based random copolymer component [A] and a polypropylene component [B] as described above. In the composition [C], the cyclic olefin-based random copolymer component [A] is included. Is 1 to 95% by weight, preferably 5 to 9
It is present in an amount of 5% by weight.

The cyclic olefin-based copolymer composition [C] according to the present invention comprises a cyclic olefin-based random copolymer component [A] having a polymerizable carbon-carbon double bond and the cyclic olefin. The composition comprises a polypropylene component [B] obtained by polymerizing propylene in the presence of a system random copolymer component [A]. In the composition [C], the polypropylene component [B] and the cyclic olefin are included. It is considered that at least a part of the system random copolymer component [A] is chemically bonded. This means that the cycloolefin copolymer composition [C] according to the present invention has a polypropylene component [B] obtained by polymerizing propylene in the absence of the cycloolefin random copolymer component [A]. It is also shown that the toughness is superior to the cyclic olefin copolymer composition obtained by simply blending the above cyclic olefin random copolymer component [A]. Therefore, the dispersibility of the cyclic olefin-based random copolymer component [A] phase and the polypropylene component [B] phase becomes good, and the copolymer composition [C] having improved heat resistance and toughness can be obtained.

Here, the polypropylene component [B] is a component other than the component [A] in the cycloolefin copolymer composition [C] produced in the presence of the cyclic olefin random copolymer component [A]. However, in the cyclic olefin copolymer composition [C] of the present invention, the compatibility between the component [B] and the cyclic olefin random copolymer component [A] is actually good. It is not possible to take out all of the polypropylene component [B] from the product [C].

The cyclic olefin copolymer composition [C] according to the present invention comprises the cyclic olefin random copolymer component [A] and the copolymer component [A] in the presence of the cyclic olefin random copolymer component [A] as described above. It comprises a polypropylene component [B] obtained by polymerizing propylene, and a polymerization catalyst used in the production of such a cyclic olefin-based copolymer composition [C] and these catalysts. The polymerization method used will be specifically described.

Production of Cyclic Olefin Copolymer Composition In the present invention, the term "polymerization" may be used not only as a homopolymerization but also as a copolymerization, and also as a "polymer". The term may be used to include not only a homopolymer but also a copolymer.

The method for producing the composition of the cyclic olefin copolymer of the present invention, that is, the propylene polymerization in the presence of the component [A] is carried out by the catalyst component [P] transition metal compound and the organometallic compound [Q] as described below. This is performed using a catalyst component and, if necessary, an electron donor [R].

First, the [P] transition metal compound catalyst component will be described. In the present invention, the [P] transition metal compound catalyst component may be a compound containing a transition metal selected from Groups III to VIII of the Periodic Table, preferably Ti,
Examples thereof include compounds containing at least one transition metal selected from Zr, Hf, Nb, Ta, Cr and V.

As such a [P] transition metal compound catalyst component, a known catalyst component can be used, and specific examples thereof include a solid titanium catalyst component containing titanium and halogen. . More specifically, as an example of the solid titanium catalyst component, titanium, magnesium, halogen and preferably an electron donor (a)
The solid titanium catalyst component [P-1] containing

Such solid titanium catalyst component [P-1]
Details of the method for preparing are described in, for example, the following publications. JP-A-51-28
1189, JP-A-50-126590, JP-A-51
-92885, JP-B 57-45244, JP-B 5
7-26613, JP-B-61-5483, JP-A-5-
6-811, Japanese Patent Publication No. 60-37804, Japanese Patent Publication No. 59
-50246, JP 58-83006, JP 4
8-16986, JP-A-49-65999, JP-A-49-86482, JP-B-56-39767, JP-B-56-322322, JP-A-55-29591, JP-A-53-146292. JP-A-57-63310
JP-A-57-63311 and JP-A-57-6331.
2, JP-A-62-273206, JP-A-63-69.
804, JP-A-61-211109, JP-A-63-2
64607, JP-A-60-23404, JP-A-60
-44507, JP-A-60-158204, JP-A-61-55104, JP-A-2-28201, JP-A-58-196210, JP-A-64-54005, and JP-A-59-149905. No. JP-A-61-145206
JP-A-63-302, JP-A-63-225605
JP-A-64-69610, JP-A-1-16870.
7, JP-A-62-104810, JP-A-62-10
4811, JP-A-62-104812, JP-A-62.
-104813, etc.

The solid titanium catalyst component [P-1] is prepared, for example, by using a tetravalent titanium compound, a magnesium compound and preferably the electron donor (a) and bringing these compounds into contact with each other.

As such a tetravalent titanium compound,
The compound represented by the following formula can be mentioned. In the formula Ti (OR) _g X _4-g , R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.

Specific examples of such a compound include T
Tetrahalogenated titanium such as iCl ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On
-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H
₉ ) Trihalogenated alkoxy titanium such as Br ₃ , Ti (O
_{CH 3) 2 Cl 2, Ti} (OC 2 H 5) 2 Cl 2, Ti (On-C 4 H 9)
₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ and other dihalogenated dialkoxy titanium, Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ C
1, monohalogenated trialkoxy titanium such as Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₄ ,
Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄
Examples thereof include tetraalkoxytitanium such as H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Alternatively, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

Examples of the magnesium compound used for preparing the solid titanium catalyst component [P-1] include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Examples of the magnesium compound having reducing ability include organomagnesium compounds represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2 and R is hydrogen or carbon number 1
To 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different, and X is halogen.

Specific examples of the organomagnesium compound having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium and ethyl butyl magnesium, alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halides, butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium, and butyl magnesium hydride.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, and magnesium methoxy chloride.
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halides such as methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-oct Examples thereof include alkoxymagnesium such as xymagnesium and 2-ethylhexoxymagnesium, allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium carboxylates such as magnesium laurate and magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is used as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen. It may be brought into contact with a containing compound or a compound having an OH group or an active carbon-oxygen bond.

The above-mentioned magnesium compound having reducing ability and magnesium compound having no reducing ability are
It may form an organometallic compound described later, for example, a complex compound with another metal such as aluminum, zinc, boron, beryllium, sodium and potassium, a double compound, or a mixture with another metal compound. Good. Further, the magnesium compound may be used alone, or two or more kinds of the above compounds may be combined, and may be used in a liquid state or a solid state. When the magnesium compound is a solid, alcohols, carboxylic acids, aldehydes, amines, metal acid esters and the like, which will be described later, can be used as the electron donor (a) to bring it into a liquid state.

As the magnesium compound used for preparing the solid titanium catalyst component [P-1], many magnesium compounds other than those mentioned above can be used, but the solid titanium catalyst component [P- In the above [1], it is preferable to take the form of a halogen-containing magnesium compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Of these, magnesium compounds having no reducing ability are preferable, halogen-containing magnesium compounds are particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride and aryloxy magnesium chloride are preferable.

In preparing the solid titanium catalyst component [P-1], the electron donor (a) is preferably used. Such electron donors (a) 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 alkoxysilanes, ammonia,
Examples thereof include nitrogen-containing electron donors such as amines, nitriles, pyridines and isocyanates. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl. C1-C18 alcohols such as alcohol, C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol , Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as naphthol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and the like having 2 to 15 carbon atoms
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, crotonic acid 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 benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-
C2-C18 organic acid esters such as butyrolactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate, C2-C15 such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride
C2-20 ethers such as acid halides, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide , Toluic acid
Acid amides such as N, N-dimethylamide, trimethylamine, triethylamine, tributylamine, tribenzylamine, amines such as tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile and trinitrile, pyridine, methylpyridine, ethylpyridine, Examples thereof include pyridines such as dimethyl pyridine, acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride.

As a preferred example of the organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be given.

[0183]

[Chemical Formula 39]

(Wherein R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or It is an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other to form a cyclic structure. When the hydrogen groups R ^{1 to} R ⁶ are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C—O.
-C, COOR, COOH, OH, SO 3 H, -C-N
It has a group such as —C— and NH ₂ . ) As such a polyvalent carboxylic acid ester, specifically, an aliphatic polycarboxylic acid ester, an alicyclic polycarboxylic acid ester,
Examples thereof include aromatic polycarboxylic acid esters and heterocyclic polycarboxylic acid esters.

Preferred specific examples are n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-phthalate. Butyl, di-2-phthalate
Examples thereof include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Examples of particularly preferable polyvalent carboxylic acid esters include phthalic acid esters. Further, examples of the polyether compound include compounds represented by the following general formula.

[0187]

[Chemical 40]

(In the formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. It is a substituent having an element, and any R ¹ to
R ²⁶ , preferably R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) As a preferred specific example, 2,2-
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3 -Dimethoxypropane and the like can be exemplified.

Two or more electron donors (a) as described above can be used in combination. The solid titanium catalyst component [P-1] used in the present invention is, in addition to the compound as described above, an organic compound containing silicon, phosphorus, aluminum and the like used as a carrier compound and a reaction aid during preparation. It may be prepared by contacting with an inorganic compound or the like.

As such a carrier compound, Al ₂ O is used.
₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Zn
Resins such as O, SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Al ₂
O ₃ , SiO ₂ , and a styrene-divinylbenzene copolymer are preferable.

The solid titanium catalyst component [P-1] used in the present invention is prepared by bringing the above-mentioned titanium compound, magnesium compound and preferably the electron donor (a) into contact with each other.

The method for preparing the solid titanium catalyst component [P-1] using these compounds is not particularly limited, but this method will be briefly described below with several examples. (1) A method in which a solution containing a magnesium compound, an electron donor and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, a solution is contacted with a titanium compound. (2) A method in which a complex consisting of a magnesium compound and an electron donor (a) is reacted with an organometallic compound and then a titanium compound is subjected to a catalytic reaction. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method of catalytically reacting a titanium compound and preferably an electron donor (a). At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound. (4) Magnesium compound, electron donor (a), a mixture of a solution optionally containing a hydrocarbon solvent and an inorganic or organic carrier to obtain a magnesium compound-supported inorganic or organic carrier, and then a titanium compound How to contact. (5) Magnesium compounds, titanium compounds, electron donors
(a) A method of obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution optionally containing a hydrocarbon solvent with an inorganic or organic carrier. (6) A method of reacting an organomagnesium compound in a liquid state with a halogen-containing titanium compound by catalytic reaction. (7) A method of contacting a titanium compound after a liquid reaction of an organomagnesium compound with a halogen-containing compound. (8) A method in which an alkoxy group-containing magnesium compound is catalytically reacted with a halogen-containing titanium compound. (9) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor (a) is catalytically reacted with a titanium compound. (10) A method in which a complex consisting of an alkoxy group-containing magnesium compound and an electron donor (a) is contacted with an organometallic compound and then contacted with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor (a), and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor (a) and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound.

In this method, it is preferable to use the electron donor (a) at least once. (12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor (a) to precipitate a solid magnesium-titanium complex. (13) A method of further reacting a titanium compound with the reaction product obtained in (12). (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor (a) and a titanium compound. (15) Magnesium compound and preferably electron donor (a)
And a titanium compound are pulverized to obtain a solid product, which is treated with halogen, a halogen compound or an aromatic hydrocarbon. It should be noted that this method may include a step of pulverizing only the magnesium compound, the complex compound composed of the magnesium compound and the electron donor (a), or the magnesium compound and the titanium compound. Further, after pulverization, pretreatment with a reaction auxiliary agent and then treatment with halogen or the like may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds. (16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound. At this time, it is preferable to use an electron donor (a) or a reaction aid during pulverization and / or contact / reaction. (17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with the electron donor (a) and a titanium compound. (19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor (a). (20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor (a). At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound. (21) Solid magnesium obtained by reacting a liquid magnesium compound having no reducing ability with an organometallic compound.
A method of depositing a metal (aluminum) complex and then reacting the electron donor (a) with a titanium compound.

Such solid titanium catalyst component [P-1]
Is usually -70 ° C to 200 ° C, preferably -50
It is carried out at a temperature of ℃ to 150 ℃. The solid titanium catalyst component [P-1] thus obtained contains titanium, magnesium, halogen and preferably an electron donor (a).

In this solid titanium catalyst component [P-1], the halogen / titanium (atomic ratio) is 2 to 200, preferably 4 to 90, and the magnesium / titanium (atomic ratio) is 1 to 100, It is preferably 2 to 50.

Also preferably the electron donor (a) is usually
The electron donor (a) / titanium (molar ratio) is 0.01 to 10
It is contained at a ratio of 0, preferably 0.05 to 50. In the present invention, the solid titanium catalyst component [P-1] as described above is used.
With regard to the above, an example using a titanium compound has been described, but in the above titanium compound, titanium may be replaced with zirconium, hafnium, vanadium, niobium, tantalum or chromium.

In the present invention, as another example of the solid titanium catalyst component mentioned as the [P] transition metal compound catalyst component, the conventionally known [P-2] titanium trichloride-based catalyst component may be used.

Details of the method for preparing such a [P-2] titanium trichloride-based catalyst component are described in, for example, the following publications. JP-A-56-3
4711, JP-A-61-287904, and JP-A-63.
-75007, JP-A-63-83106, JP-A-5
9-13630, JP-A-63-108008, JP-A-63-27508, JP-A-57-70110, JP-A-58-219207, JP-A-1-144405.
No. 1, JP-A 1-292901, JP-A 1-292901
No. 1 etc.

Specific examples of [P-2] titanium trichloride catalyst component include titanium trichloride. As this titanium trichloride, for example, titanium tetrachloride is reduced by bringing it into contact with hydrogen or a metal such as magnesium metal, aluminum metal, or titanium metal or an organometallic compound such as an organomagnesium compound, an organoaluminum compound or an organozinc compound. The titanium trichloride obtained is preferably used. Further, such titanium trichloride is used as the electron donor described above.
It can be used together with (a) and / or a tetravalent titanium compound or after being brought into contact with them.

Further, in the present invention, a [P-3] metallocene compound may be used as the [P] transition metal compound catalyst component. Details of the method for preparing such a [P-3] metallocene compound are described in, for example, the following publications.

JP-A-61-221207 and JP-A-62.
-121707, JP-A-63-66206, JP-A-2-22307, JP-A-2-173110, JP-A-2-302410, JP-A-1-129003, JP-A-1-210404, JP-A-3. -66710, JP-A-3-70710, JP-A-1-207248, JP-A-63-222177, JP-A-63-222178.
JP-A-63-222179, JP-A 1-1240
7, JP-A-1-301704, JP-A-1-3194
89, JP-A-3-74412, JP-A-61-264.
010, JP-A-1-275609, JP-A-63-2
51405, JP-A-64-74202, JP-A-2-
No. 41303, JP-A-2-131488, JP-A-3-
56508, JP-A-3-70708, JP-A-3-7
0709 etc.

As such a [P-3] metallocene compound, specifically, the compound of the formula [IX]: ML used in the production of the cyclic olefin random copolymer component [A] is used.
The transition metal compound (I) of Group IVB or lanthanide of the periodic table represented by x can be mentioned.

In the zirconium compound specifically exemplified as the compound represented by the formula [IX]: MLx, a compound in which zirconium is replaced by titanium, hafnium, vanadium, niobium, tantalum or chromium can be used.

In the present invention, a metallocene compound having a central metal atom of zirconium is preferably used as the metallocene compound [P-3]. These compounds may be used alone or in combination of two or more. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

The [P-3] metallocene compound as described above can also be used by supporting it on a carrier by bringing it into contact with a particulate carrier compound. As a carrier compound, SiO ₂
, Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, Ti
Inorganic carrier compounds such as O ₂ , ZnO, SnO ₂ , BaO, and ThO, and resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. it can.

These carrier compounds can be used in combination of two or more kinds. Of these, SiO ₂ , Al
₂ O ₃ and MgO are preferably used. Next, the organometallic compound catalyst component [Q] containing a metal selected from Group I to Group III of the periodic table that forms the polymerization catalyst [I] will be described.

Such an organometallic compound catalyst component [Q]
Are, for example, [Q-1] organoaluminum compounds, complex alkyl compounds of Group I metal and aluminum,
Organometallic compounds of Group II metals and the like can be used.

Examples of such [Q-1] organoaluminum compounds include, for example, the compound of the formula [XI] shown in the production of the cyclic olefin random copolymer component [A]:
An organoaluminum compound represented by R ⁵ _n AlX _3-n or an organoaluminum compound represented by the formula [XII]: R ⁵ _n AlY _3-n can be used.

Examples of complex alkylated products of Group I metals and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (provided that M ¹ is Li, Na, K, and R ^j has 1 carbon atom)
Specifically, LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄
And so on.

Examples of the organometallic compound of Group II metal include compounds represented by the following general formula. R ^k R ^l M ² (provided that R ^k and R ^l are a hydrocarbon group having 1 to 15 carbon atoms or halogen, and they may be the same or different from each other, but when they are both halogens, M ² Is M
g, Zn, Cd) Specifically, diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, etc. are mentioned.

Two or more of these compounds can be used in combination. Specific examples of the [Q-2] organoaluminum oxy compound include aluminoxanes similar to those used in the production of the cyclic olefin random copolymer component [A]. can do.

That is,

[0213]

[Chemical 41]

The aluminoxane is represented by the formula [O
Al (R ¹ )] alkyloxyaluminum units and formula [OAl (R ² )] alkyloxyaluminum units [wherein R ¹ and R ²
May be the same hydrocarbon group as R above,
R ¹ and R ² represent different groups] and mixed alkyloxyaluminum units. In that case, a methyloxyaluminum unit (O
Aluminoxane formed from mixed alkyloxyaluminum units containing Al (CH ₃ )) in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is suitable.

The [Q-2] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound found by the present applicants. May be.

The method for producing such an aluminoxane is as described in detail in the section for producing the cyclic olefin-based random copolymer component [A]. In the present invention, when the [P] transition metal compound catalyst component is [P-1] solid titanium catalyst component or [P-2] titanium trichloride catalyst component, [Q] organometallic compound catalyst component Is
[Q-1] An organoaluminum compound is preferred, and when the [P] transition metal compound catalyst component is a [P-3] metallocene compound, the [Q] organometallic compound catalyst component is [Q-2 ] It is preferable that it is an organic aluminum oxy compound.

Further, by using such a [P] transition metal compound catalyst component and [Q] organometallic compound catalyst component,
When polymerizing propylene in the presence of the component [A],
If necessary, the above-mentioned electron donor (a) or the following electron donor (b) may be used.

As such an electron donor (b), 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 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethylsilane Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchid, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. It is preferably used.

These organosilicon compounds can be used in combination of two or more kinds. Further, in the present invention, as the electron donor (b), 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N' Substituted methylenediamines such as N, N'-tetraethylmethylenediamine, nitrogen-containing electron donors such as 1,3-dibenzylimidazolidine, substituted methylenediamines such as 1,3-dibenzyl-2-phenylimidazolidine, triethylphos Phosphorus-containing electron donors such as phosphites such as phyto, tri-n-propyl phosphite, tri-isopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite It is also possible to use oxygen-containing electron donors such as 2,2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.

Two or more electron donors (b) as described above can be used in combination. Next, the propylene polymerization catalyst used in the present invention will be described. The propylene polymerization catalyst used in the present invention comprises a polymerization catalyst [P] obtained as described above, and an organometallic compound catalyst component [Q] containing a metal selected from Group I to Group III of the periodic table. Formed from. This propylene polymerization catalyst may be formed from a [P] polymerization catalyst, a [Q] organometallic compound catalyst component, and a [R] electron donor.

As the electron donor [R], the above-mentioned electron donor (a) or electron donor (b) is used. These electron donors (a) and (b) may be used in combination.
In the present invention, the propylene polymerization catalyst may contain, in addition to the above-mentioned components, other olefin components useful for the polymerization of propylene within a range not deviating from the object of the present invention.

In the propylene polymerization method employed in the present invention, propylene is polymerized in the presence of the above-mentioned propylene polymerization catalyst [P]. In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

Polymerization of propylene is carried out in a solution state or a slurry state by dissolving the cyclic olefin random copolymer component [A] in a hydrocarbon solvent.
In the propylene polymerization, the cyclic olefin random copolymer component [A] is preferably used in an amount of 0.1 g / l to 200 g / l.

In the polymerization method of the present invention, the polymerization catalyst [P] is usually converted to about 0.001 to 10 in terms of the transition metal atom in the polymerization catalyst [P] per liter of the polymerization volume.
It is used in an amount of 0 mmol, preferably about 0.005 to 20 mmol. In the organometallic compound catalyst component [Q], the metal atom in the catalyst component [Q] is usually about 1 to 2 relative to 1 mol of the transition metal atom in the prepolymerization catalyst [P] in the polymerization system.
It is used in an amount of 000 moles, preferably about 2-500 moles.

When the electron donor [R] is used,
The electron donor [R] is generally used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the metal atom of the organometallic compound catalyst component [Q].

If hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted and a polymer having a high melt flow rate can be obtained. In the polymerization method of the present invention, the polymerization is usually carried out under the following conditions.

The polymerization temperature is usually about 20 to 300 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is atmospheric pressure to 1 ° C.
00 kg / cm ² , preferably about ² to 50 kg / cm ² . In the polymerization method of the present invention, the propylene polymerization,
It can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Using the propyne polymerization catalyst as described above, a cyclic olefin-based random copolymer component [A],
When propylene is polymerized in the presence of the component [A], a cyclic olefin copolymer composition composed of the cyclic olefin random copolymer component [A] and the polypropylene component [B] is produced with high polymerization activity. can do.

As described above, the cycloolefin random copolymer component [A] and the polypropylene component [B] obtained by polymerizing propylene in the presence of the random copolymer component [A]. A solution containing the cyclic olefin-based copolymer composition [C] is obtained. In such a solution, the cyclic olefin-based copolymer composition [C] is
Usually, it is contained at a concentration of 10 to 500 g / liter and 10 to 300 g / liter. This solution is treated by a conventional method to obtain the cyclic olefin-based copolymer composition [C].

In the cyclic olefin copolymer composition [C] thus obtained, the cyclic olefin random copolymer component [A] is 1 to 99% by weight, preferably 5 to 95% by weight. Included in the amount by weight. However, the total of the component [A] and the polypropylene component [B] is 100
Weight%

Melt flow rate (MFR: 260 ° C., 2.16 k) of such a cyclic olefin copolymer composition [C]
(measured under g load) is usually 50.0 to 0.01 g / 10
Min, preferably 20.0 to 0.05 g / 10 min, and the heat distortion temperature (HDT) is usually 50 to 300 ° C., preferably 7
0-200 ℃, flexural modulus (FM) is usually 170
00-35000 kg / cm ² , preferably 18000-3
2000 kg / cm ² and tensile elongation (EL) is usually 10
% Or more, preferably 15% or more.

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, plastifier, 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 [C] of the present invention further improves the impact strength of the cyclic olefin copolymer composition [C] within a range not impairing the object of the present invention. Or a heat resistant stabilizer, weather resistant stabilizer, antistatic agent, slip agent, antiblocking agent, antifog agent, lubricant, dye, pigment, natural oil, synthetic oil, wax, etc. be able to.

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

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

In the present invention, propylene is polymerized (main polymerization) in the presence of the component [A] by the method as described above, but preliminary polymerization may be carried out prior to such propylene polymerization. . In such prepolymerization, for example, the [P] transition metal compound catalyst component and the [Q] organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table have carbon numbers. 3 or more α-olefins and polyene compounds are used as the [P] transition metal compound catalyst component 1
The prepolymerized catalyst obtained by prepolymerization is used in an amount of 0.01 to 2000 g per g.

In the present invention, the cyclic olefin copolymer composition is provided with silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, and hydroxide within a range not impairing the object of the present invention. Aluminum, 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, silicon carbide fiber, α-olefin fiber having 2 or more polycarbons, polypropylene fiber, polyester fiber,
A filler such as polyamide fiber may be blended.

[0240]

The cyclic olefin copolymer composition [C] obtained in the present invention is a cyclic olefin random copolymer component [A] having a polymerizable carbon-carbon double bond.
And a polymer component [B] obtained by polymerizing propylene in the presence of the random copolymer component [A]. The cyclic olefin-based random copolymer component [A] and the polypropylene component [B]. ], It is considered that at least a part is chemically bonded (chemical bond between polymers).

Therefore, in this cyclic olefin-based copolymer composition [C], the dispersion of the cyclic olefin-based random copolymer component [A] phase and the polypropylene component [B] phase became good, and the polypropylene and cyclic olefin-based copolymer composition [C] It has excellent heat resistance, chemical resistance, rigidity, etc., without impairing the properties of the random copolymer, and also has excellent toughness and compatibility with other resins.

[0242]

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

The methods for measuring and evaluating 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 / liter) using an Ubbelohde viscometer. (2) Glass transition point (Tg) The glass transition point (Tg) was measured using a DSC-220C manufactured by Seiko Instruments Inc. in a N2 atmosphere at a temperature rising rate of 10 ° C / min. (3) Monomer composition ratio in polymer Measured by 13 C-NMR. (4) Iodine value Measured by the iodine monochloride method according to JIS K3331. (5) MFR According to ASTM D1238, measured at 260 ° C. under a load of 2.16 kg. (6) 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.

The test pieces were left for 48 hours at room temperature after molding and then supplied for measurement. Molding conditions: Cylinder temperature: 230 ° C., mold temperature: 60 ° C., injection pressure primary / secondary = 1000/800 kg / cm ² (7) Izod impact strength (Iz) Measured according to ASTM D256.

Test temperature: 23 ° C. (8) Heat distortion temperature (HDT) Tested according to ASTM D648.

Load: 264 psi (9) Tensile elongation (EL) Measured according to ASTM-D-638. (10) Flexural modulus (FM) The flexural modulus was measured according to ASTM-D-790.

[0247]

[Production Example of Cyclic Olefin Random Copolymer Component [A]] The production example of the cyclic olefin random copolymer component [A] used in the present invention is shown below.

[0248]

[Production Example of Cyclic Olefin Random Copolymer Component [A]: (1)] Using a 1-liter glass polymerization vessel equipped with a stirring blade, ethylene tetracyclo [4.4.0.1]
^2,5 . 1 ^7,10 ] -3-Dodecene (hereinafter abbreviated as TCD) -1,
The copolymerization reaction of 9-decadiene (hereinafter abbreviated as 1,9-DD) was continuously performed by the following method.

From the top of the polymerization vessel, TCD and 1,9-DD
Was continuously fed so that the TCD feed concentration in the polymerization vessel was 54.1 g / liter and the 1,9-DD feed concentration was 5.2 g / liter. . As catalyst from the polymerization vessel top, VO and (O · ethyl) Cl2 cyclohexane solution, so that the vanadium concentration in the polymerization vessel becomes 0.5 mmol / l, ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) cyclohexane solution was continuously fed into each of the polymerization reactors so that the aluminum concentration in the polymerization reactor was 4.0 mmol / liter. In addition, ethylene was added to the polymerization system by using a bubbling tube.
The amount of hydrogen was 6.0 liter / hour, nitrogen was 33.0 liter / hour, and hydrogen was 3.0 liter / hour.

Copolymerization reaction was carried out while circulating the heating medium in the jacket attached to the outside of the polymerization vessel to keep the polymerization system at 10 ° C. Generated by the above copolymerization reaction,
Continuously polymerize the cyclic olefin-based random copolymer component [A] from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel is always 1 liter (that is, the average residence time is 0.5 hours). I extracted it. Cyclohexane / isopropyl alcohol (1:
1) The mixed solution was added to stop the polymerization reaction. afterwards,
An aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water was brought into contact with the polymerization liquid at a ratio of 1: 1 using a homomixer under vigorous stirring to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand still, the aqueous phase was separated and removed, and then washed twice with distilled water to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3 times the amount of acetone under strong stirring to precipitate the cyclic olefin random copolymer component [A], and the solid portion was collected by filtration to obtain acetone. Thoroughly washed with. In addition, unreacted TCD and 1,5-
In order to extract HD, this solid part was put into acetone so as to have a concentration of 40 g / liter, and then extraction operation was carried out at 60 ° C. for 2 hours. After the extraction process, the solid part was collected by filtration, and 12 at 130 ° C and 350 mmHg under nitrogen flow.
Dried for hours.

Ethylene.T obtained as described above
The CD · 1,9-DD copolymer component [A] is [η] 0.
85 dl / g, Tg 131 ° C., TCD content 32.
It was 5 mol% and the iodine value was 6.3 g iodine / 100 g polymer.

The results are shown in Table 3.

[0254]

[Production Example of Cyclic Olefin Random Copolymer Component [A]: (2)] In a nitrogen atmosphere, ethylenebis (indenyl) zirconium dichloride (Table 2 shows Et (Ind) ₂ ZrCl ₂
20.1 mg was collected, and a toluene solution of methylalumoxane (described as MAO in Table 2) (1.54 mm
6.2 ml of (ol / ml) was added and dissolved at room temperature.

In a 1 liter-stainless steel autoclave containing 260 ml of toluene, NB was placed at room temperature under a nitrogen stream.
317 g and 1,9-DD32.7 ml were added, and the mixture was stirred for 5 minutes. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. Keep the internal temperature of the autoclave at 20 ° C and use ethylene to increase the internal pressure to 4 kg / c
Pressurized to m ² . After stirring for 10 minutes, 5.2 ml of a toluene solution containing ethylenebis (indenyl) zirconium dichloride and methylalumoxane prepared above was added to the system to copolymerize ethylene, TCD, and 1,5-hexadiene. The reaction was started. At this time, the catalyst concentration was 0.10 for ethylene bis (indenyl) zirconium dichloride based on the whole system.
Mmol / l, and methylalumoxane is 20
It is mmol / liter. During the polymerization, the internal pressure was maintained at 4 kg / cm ² by continuously supplying ethylene into the system. After 20 minutes, the polymerization reaction was performed with isopropyl alcohol.
It was stopped by adding After depressurization, the polymer solution was taken out and brought into contact with an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water with a homomixer at a ratio of 1: 1 under vigorous stirring to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further 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, and then a solid part (copolymer) was collected by filtration and washed sufficiently with acetone. did. Further, in order to extract unreacted NB existing in the polymer, this solid part was put into acetone at 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid portion was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

Ethylene / N obtained as described above
The B · 1,9-DD copolymer has a [η] of 1.33 dl / g, T
g 144 ° C., NB content was 46.1 mol%, iodine value was 7.3 g / 100 g copolymer.

The results are shown in Table 2.

[0259]

[Example of production of cyclic olefin-based random copolymer component:
(3) Ethylene was produced in the same manner as in Production Example (1) except that TCD was supplied at 60.0 g / liter and Diene was not supplied in Production Example (1) of Component [A]. A TCD.1,9-DD copolymer component was produced.

The results are shown in Table 2.

[0261]

[Example of production of cyclic olefin-based random copolymer component:
(4) In the production example (1) of the component [A], norbornene (hereinafter abbreviated as NB) was supplied at 7.8 g / liter instead of TCD, and 1,9-DD was added at 1.
An ethylene / NB / 1,9-DD copolymer component was produced in the same manner as in Production Example (1) except that the amount was 0 g / liter.

The results are shown in Table 1.

[0263]

Example 1 “Preparation of solid titanium catalyst component” 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a uniform solution, which was then added to this solution. 21.3 g of phthalic anhydride was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve the phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was added dropwise to 200 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added.
Was added and the mixture was kept stirring for 2 hours at the same temperature.

After completion of the reaction, a solid portion was collected by hot filtration,
After resuspending this solid part in 275 ml of titanium tetrachloride, the resulting suspension was heated again at 110 ° C. for 2 hours. After the reaction was completed, the solid part was collected again by hot filtration.
It was thoroughly washed with decane and hexane at 0 ° C. until no free titanium compound was detected in the solution.

The solid titanium catalyst component prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component thus obtained was titanium 2.
4% by weight, 60% by weight chlorine, 20% by weight magnesium,
It was 13.0% by weight of DIBP.

[0266]

[Preparation of composition] In an autoclave having an internal volume of 1 liter, 375 ml of cyclohexane containing 15.5 g of cyclic olefin copolymer 1 dissolved therein was charged, and 6
Triethylaluminum 0.375 mmol, cyclohexylmethyldimethoxysilane (CMMS) 0.375 mmol, and the prepared solid titanium catalyst in a propylene atmosphere at 0 ° C. were converted to 0.00
Charge 75 mmol Ti.

100 ml of hydrogen was introduced at 70 ° C.
After the temperature was raised to 1, the temperature was maintained for 20 minutes to carry out propylene polymerization. The pressure during the polymerization was kept at 8 kg / cm ² . After the completion of the polymerization, the slurry containing the polymerization product was brought into contact with 3 times the amount of acetone under strong stirring to precipitate the copolymer, and then the solid part (copolymer) was collected by filtration, and acetone was sufficient. Washed. After that, the solid part is collected by filtration,
It was dried at 130 ° C. and 350 mmHg for 12 hours under nitrogen flow.

As described above, 47.0 g of a cyclic olefin-based copolymer composition was obtained, in which 33% by weight of the cyclic olefin-based random copolymer component [A] and polypropylene component [B] were used. ] Was contained in a proportion of 67% by weight. The MFR of the cyclic olefin-based copolymer composition [C] was 0.1 g / 10 minutes. This composition [C] has a heat distortion temperature of 92 ° C. and a flexural modulus of 200.
It was 00 kg / cm ² . The elongation in the tensile test was 18%. As described above, since the tensile elongation, that is, the toughness is improved, it was shown that the compatibility of both [A] and [B] is good.

The results are shown in Table 2.

[0270]

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that the cyclic olefin copolymer component [A] was not used. 33.0 g of copolymer was obtained.

The results are shown in Table 4. It was shown that polypropylene alone had low heat resistance, rigidity and toughness.

[0272]

Comparative Example 2 The physical properties of the copolymer component [A] shown in Production Example (1) were measured. The results are shown in Table 4.

It was shown that, although the heat resistance was excellent, the toughness was low and the compatibility of both components [A] and [B] was poor.

[0274]

COMPARATIVE EXAMPLE 3 Polypropylene obtained in Comparative Example 13.
6 g of 4 g and the copolymer component [A] shown in Production Example (1).
Solution blended in 6 g, 1000 ml para-xylene at 135 ° C. After 2 hours, the heating was stopped, and the hot solution was brought into contact with a large amount of acetone with vigorous stirring to cause precipitation.
The solid part was collected by filtration to obtain a blend.

The evaluation results are shown in Table 4. It was shown that merely blending the cyclic olefin-based copolymer component [A] and polypropylene is incompatible and only a mixture having low toughness can be obtained.

[0276]

Example 2 A composition was produced by polymerizing propylene in the same manner as in Example 1 except that the amount of hydrogen was 150 ml. 48.4 g of composition was obtained.

The results are shown in Table 4. Although the MFR of the composition was high, it showed a high tensile elongation, indicating that the components [A] and [B] were compatible with each other.

[0278]

Example 3 Triethylaluminum 0.160 mmol CMMS 0.1 added at the time of polymerization in Example 1.
Polymerization of propylene was carried out in the same manner as in Example 1 except that 60 mmol and the prepared solid titanium catalyst was used in an amount of 0.0032 mmol Ti in terms of titanium atom to prepare a composition. 21.1 g of composition was obtained.

The results are shown in Table 4. It was shown that when the ratio of the component [A] increased, the heat resistance was greatly improved as compared with polypropylene.

[0280]

[Example 4] In Example 1, instead of the copolymer component [A] shown in Production Example (1) as the cyclic olefin-based copolymer [A] component, the copolymer component shown in Production Example (2) was used. Propylene was polymerized in the same manner as in Example 1 except that was used to prepare a composition. 51.7 g of composition was obtained.

The results are shown in Table 4. NB instead of TCD as the cyclic olefin component of the cyclic olefin copolymer
It was shown that even when is used, the composition has excellent heat resistance, rigidity and toughness.

[0282]

COMPARATIVE EXAMPLE 4 In Example 1, the copolymer component shown in Production Example (3) was used as the cyclic olefin copolymer [A] component instead of the copolymer component shown in Production Example (1). Propylene was polymerized in the same manner as in Example 1 except that. Four
8.4 g of product was obtained.

The results are shown in Table 4. When a copolymer containing no diene component was used as the cyclic olefin-based copolymer, toughness was not exhibited and the compatibility of both components [A] and [B] was low.

[0284]

Comparative Example 5 In Example 1, except that the copolymer component shown in Production Example (4) was used as the cyclic olefin copolymer [A] component instead of the copolymer component shown in Production Example (1). Was polymerized with propylene in the same manner as in Example 1. 5
0.0 g of product was obtained.

The results are shown in Table 4. It was shown that when the Tg of the cyclic olefin copolymer component is out of the claimed range, the rigidity and the heat resistance are significantly lowered.

[0286]

[Table 1]

[0287]

[Table 2]

[0288]

[Table 3]

[0289]

[Table 4]

Claims (1)

[Claims] 1. An (a) at least one or more α-olefin having 2 or more carbon atoms, (b) a cyclic olefin represented by the following general formula [I] or [II], and (c) a carbon number 5
Obtained by copolymerizing with a non-conjugated diene compound in the range of 20 to 20, the intrinsic viscosity [η] measured at 135 ° C in decalin is in the range of 0.10 to 5.0 dl / g, and the glass It has a transition temperature (Tg) of 10 ° C or higher, has a polymerizable carbon-carbon double bond, and has an iodine value of 2 to 3
It is obtained by polymerizing cycloolefin-based random copolymer component [A], which is 0 (g-iodine / 100 g-polymer), and propylene in the presence of the cycloolefin-based random copolymer component [A]. A cyclic olefin-based copolymer composition [C] comprising a polypropylene component [B], wherein the component [A] is contained in the composition [C].
Is contained in an amount of 1 to 99% by weight, and a cyclic olefin-based copolymer composition; (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, It is a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle has a double bond. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group.); (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, or an aliphatic carbon atom. A hydrogen atom, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ (or R ¹⁰ ) is bonded and 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 to form a monocycle or It may form a polycyclic aromatic ring.).