JPH06228237A - Cycloolefin copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having excellent impact resistance, transparency and heat-resistance and useful for optical material, etc., by copolymerizing respective specific alpha-olefin, cycloolefin and non-conjugate diene compound in the presence of a specific catalyst. CONSTITUTION:The objective copolymer having an intrinsic viscosity of 0.1-5.0dl/g and a Tg of -10 to +250 deg.C can be produced by copolymerizing (A) a >=2C alpha-olefin, (B) one or more kinds of cycloolefins of formula I (n and q are 0 or 1; m is >=0; R<1> to R<18>, R<a> and R<b> are H, halogen, hydrocarbon group, etc.) or formula II (p and q are >=0; m and n are 0-2; R<1> to R<19> are H, halogen, hydrocarbon group, etc.) and (C) an alpha,omega-nonconjugated diene compound of formula III (Y<1> is 2-3C alkylene) in the presence of a catalyst composed of a transition metal compound of group IV B metal or lanthanide metal of the periodic table and containing a ligand having cyclopentadienyl skeleton, an organic aluminum oxy compound and, as necessary, an organic aluminum compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin random copolymer and a method for producing the same, and more particularly to a cyclic olefin copolymer excellent in impact resistance, transparency and heat resistance and a method for producing the same. .

[0002]

TECHNICAL BACKGROUND OF THE INVENTION The present applicant has previously found that a cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene is excellent in transparency and heat resistance. Resistance, heat aging resistance, chemical resistance,
It has been found that it is a synthetic resin having well-balanced solvent resistance, dielectric properties, and rigidity, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers, and has already been disclosed in JP-A-60-168708. JP, JP-A-61-98780, JP-A-61-11591
No. 2, JP 61-115916, and JP 6
It is proposed in JP-A No. 1-120816 and JP-A No. 62-252407. The cyclic olefin random copolymers described in these publications are also known to exhibit excellent performance in the field of structural materials.

However, although these cyclic olefin-based copolymers are particularly excellent in heat resistance and rigidity, there is room for improvement in impact resistance, and the transparency which these cyclic olefin-based copolymers have is Further improvement of impact resistance is required while maintaining heat resistance.

Therefore, the present inventors have conducted diligent research to obtain a cyclic olefin random copolymer having excellent impact resistance, and include a ligand having a cyclopentadienyl skeleton.
Presence of a catalyst (b) consisting of a transition metal compound of Group IVB or lanthanide of the periodic table, an organoaluminum oxy compound, and optionally an organoaluminum compound, or a catalyst consisting of soluble vanadium and organoaluminum (b) Below, by transparently copolymerizing α-olefin, a specific cyclic olefin, and a specific non-conjugated diene compound having 6 to 20 carbon atoms, the conventional cyclic olefin random copolymer has a transparent property. The inventors have found that a cyclic olefin-based copolymer having an excellent balance between impact resistance and heat resistance can be obtained without impairing the properties, and have completed the present invention.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has the heat resistance and transparency which conventional cyclic olefin random copolymers have. In addition, it is an object of the present invention to provide a cyclic olefin-based random copolymer having an excellent balance between impact resistance and heat resistance.

[0006]

The first cyclic olefin copolymer according to the present invention comprises [A] an α-olefin having 2 or more carbon atoms,
[B] A random copolymer of at least one cyclic olefin represented by the following formula [I] or [II] and [C] a non-conjugated diene compound having 6 to 20 carbon atoms. The structural units derived from the respective components [A], [B] and [C] forming
[B]: [C] = 30 to 90: 5 to 70: 1 to 60
(The total of [A], [B] and [C] is 100)
And the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 5.0 dl / g.
Glass transition temperature (Tg) measured by
It is characterized by being 50 ° C.

[0007]

[Chemical 16]

(However, in the above formula [I], n is 0.
Or 1, m is 0 or a positive integer, and 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, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring is It may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. )

[0009]

[Chemical 17]

(However, in the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1
Or a 2, R ¹ to R ¹⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ¹⁰ are attached, R ¹³
May be bonded to the carbon atom to which R is bonded or to the carbon atom to which R ¹¹ is bonded, directly or through 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 may be bonded to each other to form a monocyclic or polycyclic aromatic ring. The second cyclic olefin-based copolymer according to the present invention comprises [A] an α-olefin having 2 or more carbon atoms and [B] at least 1 represented by the above formula [I] or [II]. [C-1] CH ₂ ═CH—Y ¹ —CH═CH ₂ ... [III] (in the above formula [III], Y ¹ has 2 or 3 carbon atoms).
Is an alkylene group of) having 6 or 7 carbon atoms
Which is a random copolymer with an α, ω-non-conjugated diene compound, and the structural units derived from the respective components [A], [B] and [C-1] which form the copolymer are The molar ratio is [A]: [B]: [C-1] = 30 to 90: 5 to 7.
It exists in the ratio of 0: 5-60 (the total of [A], [B] and [C-1] is 100), and at least 5 mol% or more of the constitutional units of the copolymer is [C-1. ] The constituent unit represented by the following formula [IV] derived from the component:
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.1
˜5.0 dl / g, and the glass transition temperature (Tg) measured by DSC is −10 to 250 ° C.

[0011]

[Chemical 18]

(However, in the above formula [IV], Y ¹
Is an alkylene group having 2 or 3 carbon atoms. )further,
The third cyclic olefin-based copolymer according to the present invention is
[A] an α-olefin having 2 or more carbon atoms, [B] at least one cyclic olefin represented by the above formula [I] or [II], and [C-2] the following formula [V] CH ₂ (in the above formula [V], Y ² is a hydrocarbon group having 4 to 16 carbon ^{atoms) = CH-Y 2 -CH =} CH 2 ··· [V] nonconjugated 8 to 20 carbon atoms represented by A non-conjugated diene compound represented by a diene compound or a random copolymer with a non-conjugated diene compound represented by the following formula [VI-a], [VI-b] or [VI-c] and having 9 to 20 carbon atoms. There is a constitutional unit derived from each of the above components [A], [B] and [C-2] which form this copolymer in a molar ratio of [A]: [B]: [C-2]. =
Present in a proportion of 30-90: 5-70: 1-10 (the sum of [A], [B] and [C-2] is 100).
At least 1 mol% or more of the constitutional units of the copolymer is [C
-1] component derived from the following formula [VII] or [VI]
II-a], [VIII-b] or [VIII-
c] is a constitutional unit, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 5.0 dl /
g, and the glass transition temperature (T
g) is -10 to 250 ° C.

[0013]

[Chemical 19]

[0014]

[Chemical 20]

(In the above formula [VII], Y ² is a hydrocarbon group having 4 to 16 carbon atoms.)

[0016]

[Chemical 21]

The above-mentioned second and third cyclic olefin-based copolymers according to the present invention correspond to the above-mentioned first cyclic olefin-based copolymer according to the present invention. The first method for producing a cyclic olefin copolymer according to the present invention is (I) a transition metal compound of Group IVB or lanthanide of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (II) )
Organoaluminum oxy compound, and optionally (II
I) in the presence of a catalyst (a) consisting of an organoaluminum compound or (IV) a soluble vanadium compound and (V) a catalyst consisting of an organoaluminum compound (b),
[A] an α-olefin having 2 or more carbon atoms, [B] at least one cyclic olefin represented by the above formula [I] or [II], and [C-1] the following formula [III] CH ₂ ^{= CH-Y 1 -CH = CH} 2 ··· [III] ( in the above formula [III], Y ¹ is 2 or 3 carbon atoms
Is an alkylene group of) having 6 or 7 carbon atoms
It is characterized in that it is copolymerized with the α, ω-non-conjugated diene compound.

According to this production method, the above-mentioned second cyclic olefin-based copolymer according to the present invention can be obtained. Also,
A second method for producing a cyclic olefin-based copolymer according to the present invention is (I) a transition metal compound of Group IVB or lanthanide of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (II) ) In the presence of a catalyst (b) comprising an organoaluminum oxy compound and, if necessary, (III) an organoaluminum compound, or (IV) a soluble vanadium compound and (V) an organoaluminum compound. [A] an α-olefin having 2 or more carbon atoms, [B] at least one cyclic olefin represented by the above formula [I] or [II], and [C-2] the following formula [V]: CH ₂ ═CH—Y ² —CH═CH ₂ ... [V] (in the above formula [V], Y ² is a hydrocarbon group having 4 to 16 carbon atoms) and having 8 to 20 carbon atoms. Non-coexistence represented by non-conjugated diene compound Diene compound, or the following formula [VI-a], is characterized by copolymerizing a non-conjugated diene compound [VI-b] or carbon atoms represented by [VI-c] 9~20.

[0019]

[Chemical formula 22]

According to this production method, the third cyclic olefin copolymer according to the present invention can be obtained. The cyclic olefin-based copolymer according to the present invention has heat resistance and transparency that a conventional cyclic olefin-based random copolymer has, and has an excellent balance between impact resistance and heat resistance. There is.

[0021]

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

First, the cycloolefin copolymer according to the present invention will be described. The cyclic olefin-based copolymer according to the present invention comprises an α-olefin [A] having 2 or more carbon atoms,
It is a random copolymer of a specific cyclic olefin [B] and a specific non-conjugated diene compound [C].

Specific examples of the α-olefin [A] having 2 or more carbon atoms used in the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4
-Methyl-1-pentene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene, 1-hexadecene, 1
-Octadecene, 1- Eicosene, etc. 2 to 20 carbon atoms
Α-olefins of Of these, ethylene and propylene are particularly preferably used.

The cyclic olefin [B] used in the present invention
Is represented by the following general formula [I] or [II].

[0025]

[Chemical formula 23]

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

In the above formula [I], 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, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group usually has 1 carbon atom.
To 20 alkyl groups, C3 to C15 cycloalkyl groups or aromatic hydrocarbon groups. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

The cycloalkyl group includes a cyclohexyl group, and the aromatic hydrocarbon group includes a phenyl group and a naphthyl group. Furthermore, the above formula [I]
, R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R
¹⁷ and R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R
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.

Specific examples of the monocycle or polycycle formed here include the following.

[0031]

[Chemical formula 24]

In the above exemplification, carbon atoms numbered 1 and 2 are respectively represented by R in the formula [I].
^It represents a carbon atom to which ¹⁵ (R ¹⁶ ) or 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 is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0034]

[Chemical 25]

In the above formula [II], p and q are 0.
Alternatively, it is a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the above formula [I]. The hydrocarbon group is usually an alkyl group having 1 to 20 carbon atoms, or 3 to carbon atoms.
There may be mentioned 15 cycloalkyl groups or aromatic hydrocarbon groups. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group, examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, Examples thereof include a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Where R ⁹
Or the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded,
They may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. 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 —), which forms 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. Specifically, n = m = 0
In this case, the following aromatic ring formed by R ¹⁵ and R ¹² can be mentioned.

[0040]

[Chemical formula 26]

Here, q is the same as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] include a bicyclo [2.2.1] -2-heptene derivative (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 [6.5.1.1 ^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, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivative, hexacyclo [6.6.1.1 ^{3, 6} .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo-5-eicosene derivatives,
Heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7.
0 ^11,16] -4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, heptacyclo [8.8.0.1 ^4,7 .1 ^11,18.
1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8. 0
^12,17 ] -5-Dococene derivative, nonacyclo [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, cyclopentadiene - acenaphthylene adduct, 1,
4-methano-1,4,4a, 9a-tetrahydrofluorene derivative,
1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative and the like can be mentioned.

In the following, the above formula [I] or [I
Specific examples of the cyclic olefin represented by [I] are shown below.

[0043]

[Chemical 27]

[0044]

[Chemical 28]

[0045]

[Chemical 29]

[0046]

[Chemical 30]

[0047]

[Chemical 31]

[0048]

[Chemical 32]

[0049]

[Chemical 33]

[0050]

[Chemical 34]

[0051]

[Chemical 35]

[0052]

[Chemical 36]

[0053]

[Chemical 37]

[0054]

[Chemical 38]

[0055]

[Chemical Formula 39]

[0056]

[Chemical 40]

[0057]

[Chemical 41]

[0058]

[Chemical 42]

[0059]

[Chemical 43]

[0060]

[Chemical 44]

[0061]

[Chemical formula 45]

[0062]

[Chemical formula 46]

[0063]

[Chemical 47]

General formula [I] or [II] as described above
The cyclic olefin represented by can be produced by subjecting cyclopentadiene and olefins having a structure corresponding to cyclopentadiene to a Diels-Alder reaction.

These cyclic olefins can be used alone or in combination of two or more kinds. The non-conjugated diene compound used in the present invention has 6 to 20 carbon atoms, and specifically, an α, ω-non-conjugated diene compound having 6 or 7 carbon atoms represented by the following formula [III]: [V]
A non-conjugated diene compound having 8 to 20 carbon atoms and a non-conjugated diene compound having 9 to 20 carbon atoms represented by the following formula [VI-a], [VI-b] or [VI-c] is preferably used. .

CH ₂ ═CH—Y ¹ —CH═CH ₂ ... [III] In the above formula [III], Y ¹ is an alkylene group having 2 or 3 carbon atoms. The non-conjugated diene compound represented by the above formula [III] is specifically 1,5-hexadiene or 1,6-heptadiene.

CH ₂ ═CH—Y ² —CH═CH ₂ ... [V] In the above formula [V], Y ² is a hydrocarbon group having 4 to 16 carbon atoms. Specific examples of the non-conjugated diene compound represented by the above formula [V] include 1,7-octadiene,
1,8- Nonadiene, 1,9- Decadiene, 1,10-
Undecadiene, 1,11- Dodecadiene, 1,12-
Tridecadiene, 1,13- tetradecadiene, 1,1
4-pentadecadiene, 1,15-hexadecadiene,
Chain dienes such as 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicodiene, 3-methyl-1,5-hexadiene, 1-vinyl-2- (2- Propenyl) benzene, 1-
Examples thereof include aromatic-containing dienes such as vinyl-3- (2-propenyl) benzene, 1,2-di (2-propenyl) benzene and 1,3-di (2-propenyl) benzene.
Of these, 1,7-octadiene and 1,9-decadiene are particularly preferably used.

[0068]

[Chemical 48]

As the non-conjugated diene represented by the above formula [VI-a],

[0070]

[Chemical 49]

Examples thereof include: Further, as the non-conjugated diene represented by the above formula [VI-b],

[0072]

[Chemical 50]

Examples thereof include: The above formula [V
I-c] represents a non-conjugated diene,

[0074]

[Chemical 51]

Examples thereof are as follows. These [V
Of the dienes represented by [Ia], [VI-b], and [VI-c], 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, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3,8-dodecadien is preferably used.

In the above non-conjugated diene [C],
The hydrogen atom bonded to carbon other than the carbon forming the carbon-carbon double bond may be substituted with a hydrocarbon group. In the cyclic olefin-based copolymer according to the present invention, the structural units derived from the α-olefin [A] having a carbon number of 2 or more, the cyclic olefin [B], and the non-conjugated diene compound [C] are in a molar ratio. Then, [A]: [B]:
It exists in the ratio of [C] = 30 to 90: 5 to 70: 1 to 60. However, the sum of [A], [B] and [C] is 1
00. Furthermore, the preferable ratio of [A], [B], and [C] varies depending on the structure of the [C] component unit, as described later.

The α, ω-non-conjugated diene compound [C-1] in which the non-conjugated diene compound [C] is represented by the above formula [III] is included in the above-mentioned α-olefin [A] having 2 or more carbon atoms. , The structural units derived from the cyclic olefin [B] and the α, ω-non-conjugated diene compound [C-1] are [A]: [B]: [C-1] = 30-
90: 5 to 70: 5 to 60, preferably [A]:
[B]: [C-1] = 40 to 80:15 to 60:10
60, and more preferably [A]: [B]: [C-1] =
It exists in the ratio of 40-65: 20-55: 15-60.

When the component [A] is in this range, the molecular weight can be easily extended, and when the component [B] is in this range, the heat resistance of the copolymer is maintained. When the component [C-1] is in this range, the impact resistance of the copolymer is improved while maintaining the heat resistance.

When such an α, ω-non-conjugated diene compound [C-1] is used, it is at least 5 mol% or more, preferably 10 mol% or more of the constitutional units of the cyclic olefin copolymer. Have a structural unit of a cyclized structure of an α, ω-non-conjugated diene compound represented by the following formula [IV].

[0080]

[Chemical 52]

In the above formula [IV], Y ¹ has 2 carbon atoms.
Alternatively, it is an alkylene group of 3. Further, the non-conjugated diene compound is represented by the above formula [V] or [VI-a], [VI-b].
Alternatively, the non-conjugated diene compound [C-2] represented by [VI-c] includes the above-mentioned α-olefin [A] having 2 or more carbon atoms, cyclic olefin [B] and non-conjugated diene compound [C-2]. Molar ratios of the structural units respectively derived from [A]: [B]: [C-2] = 30 to 90: 5.
~ 70: 1 to 10, preferably [A]: [B]: [C-
2] = 40-80: 15-60: 1.5-8, and more preferably [A]: [B]: [C-2] = 40-65: 1.
It exists in the ratio of 9-55: 1.5-5.

When the component [A] is in this range, molecular weight extension is easy, and when the component [B] is in this range, the heat resistance of the copolymer is maintained. When the component [C-2] is in this range, heat resistance and melt fluidity are maintained,
The impact resistance of the copolymer is improved.

When such a non-conjugated diene compound [C-2] is used, at least 1 mol% or more, preferably 1.5 mol% or more 5 mol of the constitutional unit of the cyclic olefin copolymer. The following is represented by the following formula [VII] or [VIII-a], [VIII-b] or [VI]
II-c].

[0084]

[Chemical 53]

In the above formula [VII], Y ² is a hydrocarbon group having 4 to 16 carbon atoms.

[0086]

[Chemical 54]

A method for determining the composition and structure of the above cyclic olefin copolymer will be described below. A) Second cyclic olefin-based copolymer set according to the present invention
Determination of formation and structures [A] alpha-olefin, the [B] cyclic olefins, and [C-1] α having 6 or 7 carbon atoms, the random copolymer of ω- nonconjugated diene compound, GPC-viscosity The long-chain branching parameter g'was measured using a meter to examine the presence or absence of long-chain branching. In the case of this copolymer, the value of g ′ was almost close to 1, which confirmed that long chain branching was not generated.

Next, from the monomer conversion rate (quantified by gas chromatography) and polymer yield at the time of copolymer synthesis, [A] α-olefin, [B] cyclic olefin, and [C-1] carbon number 6 or The composition ratio of the α, ω-non-conjugated diene compound of 7 could be obtained.

By measuring the iodine value of the copolymer, the ratio of the structure having a double bond in the structure derived from the component [C-1] was determined. Among the structures derived from the [C-1] component, the remaining component, that is, the cyclized polymerized structure [IV] was identified by ¹³ C-NMR to have the structure in which the [C-1] component was cyclopolymerized. Was done.

As described above, the composition of the copolymer and the ratio of the structure in which the component [C-1] was cyclopolymerized could be determined. This method was used in the present invention. Furthermore, in some cases, the composition of the copolymer and the ratio of the structure in which the [C-1] component is cyclopolymerized can be directly determined by ¹³ C-NMR.

A ) Third cyclic olefin system according to the present invention
Method for Determining Composition and Structure of Copolymer ¹³ C-NMR was measured for a random copolymer composed of [A] α-olefin, [B] cyclic olefin, and [C-2] non-conjugated diene compound, It was confirmed that the C-2] component had no cyclopolymerized structure.

Next, the [A] α-olefin, [B] cyclic olefin, and [C-2] non-conjugated diene compound were determined from the monomer conversion rate (determined by gas chromatography) and polymer yield during copolymer synthesis. It was possible to determine the composition ratio of.

By measuring the iodine value of the copolymer, the ratio of the structure having a double bond in the structure derived from the component [C-2] was determined. Of the structures derived from the [C-2] component, the remaining components were identified as having a long-chain branched structure.

As described above, the composition of the copolymer and the ratio of the long-chain branched structure could be determined. This method was used in the present invention. Further, in some cases, ¹³ C-NM
It is also possible to directly determine the composition of the copolymer by R.

The cyclic olefin copolymer according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1-5.0 dl / g, preferably 0.3-4.
5 dl / g, more preferably 0.4 to 4.0 dl / g
Is.

The cyclic olefin copolymer according to the present invention has a glass transition temperature (Tg) measured by DSC.
Is -10 to 250 ° C, preferably 50 to 250 ° C, more preferably 70 to 250 ° C.

The cyclic olefin-based copolymer as described above according to the present invention comprises, for example, a transition metal compound of Group IVB of the periodic table or a lanthanide containing (I) a ligand having a cyclopentadienyl skeleton. , (II) an organoaluminum oxy compound and, if necessary, a (III) organoaluminum compound (a) (hereinafter sometimes referred to as a metallocene catalyst), or (IV) a soluble vanadium compound, ( V) In the presence of a catalyst (b) comprising an organoaluminum compound (hereinafter sometimes referred to as a vanadium-based catalyst), [A] an α-olefin having 2 or more carbon atoms and [B] the above formula [I] ] Or [II] and at least one cyclic olefin and [C] a non-conjugated diene compound represented by the above formula [III], [V] or [VI]. It can be prepared by.

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 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.

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 transition metal compounds,
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 above zirconium compound, 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) forming 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.

[0111]

[Chemical 55]

(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 an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice, or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent.

Of these methods, the method (1) is preferably adopted. As the organoaluminum compound used in producing the solution of aluminoxane,
Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, tri Trialkylaluminums such as octylaluminum, tridecylaluminum, tricyclohexylaluminum and tricyclooctylaluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; diethylaluminum hydride, diisobutylaluminum hydride, etc. Dialkyl Rumi bromide hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide;
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

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

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

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

[0118] 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.

[0120]

[Chemical 56]

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.

[0123]

[Chemical 57]

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, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, n -Propyl group,
Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

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 ^{1 1)} 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.,

[0131]

[Chemical 58]

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 can be prepared by using 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 Group IVB or lanthanide transition metal compound (I) is 0.00005 to 1.0 mmol / liter, preferably 0.0001 to 0.3 mmol / liter. The catalyst concentration of the compound is preferably 1 to 10 ⁴ equivalents of the transition metal compound. Further, the catalyst concentration of the organoaluminum compound used as necessary is preferably 0.01 to 100 equivalents relative to the aluminum atom of the organoaluminum oxy compound.

Next, the vanadium-based 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.

[0144]

[Chemical 59]

Specific examples of the soluble vanadium compound having a 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.

Here, examples of the electron donor that forms an adduct with the above vanadium compound 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.

[0153] (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 dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; ethyl amylnium sesquichloride, butyl aluminum 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 partially alkoxylated and halogenated alkyls such as ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide and ethyl aluminum 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-based 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.

The soluble vanadium compound (IV) and the organoaluminum compound (V) described above in the present invention 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 the 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 0.01 to 5 mmol / liter, preferably 0.05 to 3 mmol / liter, and the catalyst concentration of the organoaluminum compound is that of the transition metal compound. 1 to 1
It is preferred to use 0 ⁴ equivalents.

When the copolymerization of the α-olefin [A] having 2 or more carbon atoms, the cyclic olefin [B] and the non-conjugated diene compound [C] is carried out in the presence of the above 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]) / ([A ]
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 preferably in the range of 0.01 to 0.80. When [C] is [C-1], the ratio between [B] and [C] is [C] / [B] +
The value of [C] is particularly preferably in the range of 0.10 to 0.70.

When [C] is [C-2],
The ratio of [B] and [C] is particularly preferably such that the value of [C] / [B] + [C] is in the range of 0.10 to 0.50. The molecular weight of the cyclic olefin copolymer obtained as described above can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

The α-olefin [A] having 2 or more carbon atoms, the cyclic olefin [B], and the α, ω-non-conjugated diene compound [C-1] represented by the above formula [III],
When copolymerized in the presence of the above metallocene catalyst, a structural unit represented by the following formula [IV] is recognized.

[0176]

[Chemical 60]

(Y ¹ in the formula is an alkylene group having 2 or 3 carbon atoms.) Further, the above α-olefin [A] having 2 or more carbon atoms, the cyclic olefin [B] and the above formula [III] When the α, ω-non-conjugated diene compound [C-1] represented by the following formula is copolymerized in the presence of the above vanadium-based catalyst, the above formula [I
V] and the structural unit represented by the following formula [XIII] are recognized, but the structural unit represented by the formula [IV] is more abundant.

[0178]

[Chemical formula 61]

(Y ¹ in the formula is an alkylene group having 2 or 3 carbon atoms.) Further, the α-olefin [A] having 2 or more carbon atoms, the cyclic olefin [B], and the above formula [V]. Or [VI-
In the copolymerization with the non-conjugated diene compound [C-2] represented by a], [VI-b] or [VI-c],
Regardless of whether the metallocene catalyst is a vanadium catalyst, the above formulas [VII] and [VIII-
Only constitutional units represented by a], [VIII-b] or [VIII-c] are accepted.

[0180]

The cyclic olefin copolymer according to the present invention is a random copolymer of an α-olefin having 2 or more carbon atoms, a specific cyclic olefin, and a specific non-conjugated diene compound. Having a specific ratio of structural units derived from the components, and having a specific intrinsic viscosity and a specific glass transition temperature, it has heat resistance and transparency that conventional cyclic olefin random copolymers have. In addition, it has an excellent balance between impact resistance and heat resistance.

Further, the method for producing a cyclic olefin-based copolymer according to the present invention is characterized by the presence of a specific metallocene-based catalyst or a specific vanadium-based catalyst in the presence of α having 2 or more carbon atoms.
-Since an olefin, a specific cyclic olefin, and a specific non-conjugated diene compound are copolymerized, a cyclic olefin-based copolymer having the above effects can be obtained.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. First, methods for measuring and evaluating various physical property values in Examples and Comparative Examples are shown below. (1) Intrinsic viscosity [η] It was measured in a decalin solution at 135 ° C using an Ubbelohde viscometer. (2) Glass transition point (Tg) The glass transition point was measured using a DSC-220C manufactured by Seiko Instruments Inc. in a nitrogen atmosphere at a temperature rising rate of 10 ° C / min. (3) Monomer composition ratio in polymer Same as the method for determining the composition and structure of the second and third cyclic olefin-based copolymers according to the present invention described above. (4) Izod impact strength Measured according to ASTM D256.

Test piece shape: 5/2 in. × 1/8 in. × thickness 1/2 in. (With notch) Test temperature: 23 ° C.

[0184]

Example 1 A 1 liter capacity glass polymerization vessel equipped with a stirring blade was used, and ethylene containing a metallocene catalyst was used.
Tetracyclo [4.4.0.1 ^2,5 . Copolymerization of 1 ^7,10 ] -3-dodecene (hereinafter abbreviated as TCD) and 1,5-hexadiene (hereinafter abbreviated as 1,5-HD) was continuously carried out by the following method.

A toluene solution of TCD and 1,5-HD was added from the upper part of the polymerization vessel so that the TCD concentration in the polymerization vessel was 96.2 g / liter and the 1,5-HD concentration was 12.3 g / liter. And as a catalyst from the top of the polymerization vessel,
Ethylene bis (indenyl) zirconium dichloride [hereinafter sometimes abbreviated as Et (Ind) ₂ ZrCl ₂ ] and methylalumoxane [hereinafter sometimes abbreviated as MAO]
Was continuously supplied to the polymerization vessel such that the zirconium concentration in the polymerization vessel was 0.1 mmol / liter and the aluminum concentration was 20.0 mmol / liter. Also, using a bubbling tube for the polymerization system, 54.0 liters / hour of ethylene,
Nitrogen was supplied at a rate of 18.0 l / h. The refrigerant was circulated in a jacket attached to the outside of the polymerization vessel to carry out a copolymerization reaction while maintaining the polymerization system at 20 ° C.

The polymerization solution of the ethylene / TCD / 1,5-HD copolymer produced by the above-mentioned copolymerization reaction was constantly adjusted so that the polymerization solution in the polymerization vessel was 1 liter from the upper part of the polymerization vessel (that is, the average retention time). It was continuously withdrawn (for a time of 0.5 hours). A toluene / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to terminate the polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were mixed in a ratio of 1: 1.
The mixture was contacted with a homomixer with strong stirring under strong stirring to transfer the catalyst residue to the aqueous phase. After leaving this contact mixture still, the aqueous phase was separated and removed, and further washed twice with distilled water to purify and separate the polymerization liquid phase.

Next, the purified and separated polymerization liquid was contacted with 3 times the amount of acetone under strong stirring to precipitate a copolymer, and then this solid part (copolymer) was collected by filtration, and acetone was sufficient. Washed. Furthermore, in order to extract unreacted TCD and 1,5-HD existing in the copolymer, after pouring this solid part into acetone so as to be 40 g / liter, the conditions were 60 ° C. and 2 hours. An extraction operation was performed. After the extraction treatment, the solid part was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

Ethylene.T obtained as described above
The CD / 1,5-HD copolymer has an intrinsic viscosity [η] of 0.
67 dl / g, Tg of 120 ° C., TCD content of 28.7 mol%, 1,5-HD content of 8.7 mol%,
The constitutional unit content of the cyclized structure of 1,5-HD was 6.9 mol%. The Izod impact strength of the press sheet was 2.0 kg · cm / cm.

The results are shown in Table 1.

[0190]

Example 2 In the polymerization of Example 1, TCD was 14
Polymerization was carried out in the same manner as in Example 1 except that 2.3 g / liter and 1,5-HD were supplied at 27.4 g / liter to obtain ethylene / TCD / 1,5-HD.
A copolymer was prepared and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0192]

Example 3 In the polymerization of Example 1, TCD was 14
Polymerization was carried out in the same manner as in Example 1 except that 4.3 g / liter and 1,5-HD were fed so as to be 42.3 g / liter to obtain ethylene / TCD / 1,5-HD.
A copolymer was prepared and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0194]

Example 4 In the polymerization of Example 1, as a catalyst, isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride [hereinafter, iPr (Cp) (Flu) ZrCl] was used.
_It may be abbreviated as ₂ ], so that the zirconium concentration in the polymerization vessel is 0.01 mmol / liter and the aluminum concentration is 10.0 mmol / liter. Supply, TCD 90.5 g / l, 1,5-HD 1
Except that it was fed at 1.5 grams / liter,
Polymerization was conducted in the same manner as in Example 1 to obtain ethylene / TCD
A 1,5-HD copolymer was prepared, and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0196]

Example 5 In the polymerization of Example 4, TCD was 96.
2 grams / liter, 1,5-HD 12.3 grams /
Polymerization was performed in the same manner as in Example 4 except that the amount was supplied so that the ethylene / TCD / 1,5-HD copolymer was prepared, and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0198]

[Comparative Example 1] A 1-liter capacity glass polymerization vessel equipped with a stirring blade was used, and ethylene containing a vanadium catalyst was used.
Copolymerization of TCD was continuously carried out by the following method.

A cyclohexane solution of TCD was continuously fed from the top of the polymerization vessel so that the concentration of TCD fed in the polymerization vessel was 60 g / liter. Further, a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ was used as a catalyst from the upper part of the polymerization vessel, and the vanadium concentration in the polymerization vessel was 0.
A cyclohexane solution of ethylaluminum sesquichloride [Al (C ₂ H ₅ ) _1.5 Cl _1.5 ] was added so that the concentration was 5 mmol / liter, and the aluminum concentration in the polymerization vessel was 4.
It was continuously fed into the polymerization vessel so that the concentration became 0 mmol / liter. Also, using a bubbling tube in the polymerization system, 36.0 liter / hour of ethylene and 33.0 of nitrogen were used.
L / hour and hydrogen were supplied at an amount of 3.0 liter / hour.

Copolymerization reaction was carried out while the polymerization system was kept at 10 ° C. by circulating a heating medium in a jacket attached to the outside of the polymerization vessel. Generated by the above copolymerization reaction,
The polymerization solution of the cyclic olefin-based copolymer was continuously withdrawn from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel was always 1 liter (that is, the average residence time was 0.5 hours). A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to terminate the polymerization reaction. The subsequent processing is the first embodiment.
Polymerization was carried out in the same manner as above to prepare an ethylene / TCD copolymer, and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0202]

Comparative Example 2 In the polymerization of Comparative Example 1, a cyclohexane solution of TCD was supplied so that the concentration of TCD supplied in the polymerization vessel was 35.0 g / l, and ethylene was added at 36.0 l / hr. Polymerization was carried out in the same manner as in Comparative Example 1 except that nitrogen was supplied at a rate of 12.0 liters / hour and hydrogen was supplied at a rate of 0.3 liters / hour.
A TCD copolymer was prepared and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0204]

Comparative Example 3 In the polymerization of Example 1, Example 1 was repeated except that TCD was supplied at a concentration of 120.0 g / l in the polymerization vessel and 1,5-HD was not supplied. Polymerization is performed in the same manner as for ethylene / TCD
A copolymer was prepared and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0206]

Example 6 In the polymerization of Comparative Example 1, a cyclohexane solution of TCD was supplied and a toluene solution of 1,5-HD was added so that the supply concentration of TCD in the polymerization vessel was 48.0 g / l. , 1,5-HD is fed at a concentration of 6.2 g / l, nitrogen is 35.0 l / h, and hydrogen is 1.0 l / l.
Polymerization was carried out in the same manner as in Comparative Example 1 except that the amount of time was supplied to prepare an ethylene / TCD / 1,5-HD copolymer, and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0208]

Example 7 Under a nitrogen atmosphere, 20.1 mg of ethylenebis (indenyl) zirconium dichloride was collected, and a toluene solution of methylalumoxane (1.54 mmol /
(6.2 ml) was added and dissolved at room temperature.

To a 1-liter stainless steel autoclave containing 156 ml of toluene, 204 ml (210 g) of TCD and 40 ml (27 g) of 1,5-HD were added and stirred at room temperature under a nitrogen stream 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 /
Pressurized to be cm 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 obtain ethylene,
The copolymerization reaction of TCD and 1,5-HD was started. At this time, the catalyst concentration was 0.10 mmol / liter of ethylenebis (indenyl) zirconium dichloride and 20 mmol / liter of methylalumoxane with respect to the whole system. During the polymerization, the internal pressure was maintained at 4 kg / cm ² by continuously supplying ethylene into the system. Two
After 0 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. 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 leaving the contact mixture still, the aqueous phase was separated and removed, and further washed with distilled water for 2 times.
The polymerization liquid phase was purified and separated.

Next, the purified and separated polymerization liquid is contacted with 3 times the amount of acetone under strong stirring to precipitate the copolymer, and then the solid part (copolymer) is collected by filtration, and acetone is sufficient. Washed. Further, in order to extract unreacted TCD existing in the polymer, this solid part was put into acetone so as to be 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction process, the solid part is collected by filtration, under nitrogen flow, at 130 ° C., 350 mm
It was dried with Hg for 12 hours.

Ethylene.T obtained as described above
The CD / 1,5-HD copolymer has an intrinsic viscosity [η] of 0.
87 dl / g, Tg is 121 ° C., TCD content is 2
9.9 mol%, 1,5-HD content is 9.1 mol%, 1,
The content of constitutional units in the 5-HD cyclized structure was 7.3 mol%. The Izod impact strength of the obtained copolymer was 2.2 kg · cm / cm.

The results are shown in Table 2.

[0213]

Example 8 In the polymerization of Example 7, the polymerization temperature was set to 70.
Polymerization was carried out in the same manner as in Example 7 except that the temperature was set to 0 ° C. and the polymerization was carried out for 30 minutes, and an ethylene / TCD / 1,5-HD copolymer was prepared, and various physical properties were determined by the methods described above.

The results are shown in Table 2.

[0215]

Example 9 In the polymerization of Example 7, 8.6 mg of isopropylene (9-fluorenyl) cyclopentadienylzirconium dichloride was used as a catalyst, and 13.0 ml of a toluene solution of methylalumoxane (1.54 mmol / ml) was used. In addition, 2.6 ml of it was dissolved in advance at room temperature. Isopropylene (9-
The concentrations of fluorenyl) cyclopentadienylzirconium dichloride and methylalumoxane are 0.01 mmol / ml and 10.0 mmol, respectively, based on the total system.
/ Ml. Then, polymerization was carried out in the same manner as in Example 7 except that the polymerization was carried out at 20 ° C. for 30 minutes.
A TCD-1,5-HD copolymer was prepared and its physical properties were determined by the methods described above.

The results are shown in Table 2.

[0217]

Example 10 In the polymerization of Example 7, 124.0 g of norbornene (hereinafter abbreviated as NB) was used in place of TCD, 40 ml of 1,5-HD and 23 of toluene were used.
Polymerization was conducted in the same manner as in Example 7 except that 6 ml was used and the polymerization was conducted at 70 ° C. for 20 minutes.
-An HD copolymer was prepared and various physical properties were determined by the above methods.

The results are shown in Table 2.

[0219]

Examples 11 to 13 Polymerization was carried out in the same manner as in Comparative Example 1 except that the conditions shown in Table 3 were changed in the polymerization operation of Comparative Example 1 to obtain ethylene / TCD / 1,9-decadiene (hereinafter, Abbreviated as 1,9-DD) copolymer, ethylene / T
A CD / vinyl norbornene (hereinafter abbreviated as VNB) copolymer and an ethylene / TCD / 1,7-octadiene (hereinafter abbreviated as 1,7-OD) copolymer were prepared, and their physical properties were determined by the above methods. I asked.

The results are shown in Table 3.

[0221]

[Table 1]

[0222]

[Table 2]

[0223]

[Table 3]

[0224]

[Table 4]

[0225]

[Table 5]

[0226]

[Table 6]

Claims (5)

[Claims] 1. An [A] α-olefin having 2 or more carbon atoms,
[B] A random copolymer of at least one cyclic olefin represented by the following formula [I] or [II] and [C] a non-conjugated diene compound having 6 to 20 carbon atoms. The constitutional units derived from the respective components [A], [B] and [C] forming the above are in a molar ratio of [A]: [B]: [C] = 30 to 90: 5 to 70: 1. ~
60 (total of [A], [B] and [C] is 100), and the intrinsic viscosity [η] measured in decalin at 135 ° C.
0.1 to 5.0 dl / g, and the glass transition temperature (Tg) measured by DSC is -1.
A cyclic olefin-based copolymer characterized by having a temperature of 0 to 250 ° C .; (However, in the above 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 respectively 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 a polycycle, and the monocycle or the polycycle is a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , A hydrocarbon group or an alkoxy group, wherein 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 carbon atom. 3 to 3 may be bonded via an alkylene group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be formed). 2. An [A] α-olefin having 2 or more carbon atoms,
[B] at least one cyclic olefin represented by the following formula [I] or [II], and [C-1] the following formula [II]
_{I] CH 2 = CH-Y} 1 -CH = CH 2 ··· [III] ( In the above formula [III], Y ¹ is 2 or 3 carbon atoms
Is an alkylene group of) having 6 or 7 carbon atoms
Which is a random copolymer with an α, ω-non-conjugated diene compound, and which forms the copolymer [A], [B] and [C] above.
The structural unit derived from each component of [-1] has a molar ratio of [A]: [B]: [C-1] = 30 to 90: 5 to 70:
5 to 60 (the total of [A], [B] and [C-1] is 1
Is present in the copolymer, and at least 5 mol% or more of the constitutional units of the copolymer is [C
−1] is a constitutional unit represented by the following formula [IV] derived from the component, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is:
0.1 to 5.0 dl / g, and the glass transition temperature (Tg) measured by DSC is -1.
A cyclic olefin-based copolymer characterized by having a temperature of 0 to 250 ° C .; (However, in the above 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 respectively 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 a polycycle, and the monocycle or the polycycle is a double bond. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , A hydrocarbon group or an alkoxy group, wherein 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 carbon atom. 3 to 3 may be bonded via an alkylene group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be formed), and (However, in the above formula [IV], Y ¹ is an alkylene group having 2 or 3 carbon atoms). 3. [A] an α-olefin having 2 or more carbon atoms,
[B] represented by the following formula [I] or [II], and at least one cyclic olefin, [C-2] below equation _{[V] CH 2 = CH-} Y 2 -CH = CH 2 ··· [ V] (in the above formula [V], Y ² is a hydrocarbon group having 4 to 16 carbon atoms), a non-conjugated diene compound represented by a non-conjugated diene compound having 8 to 20 carbon atoms, or the following formula VI-a], [VI-b] or [VI
-C] is a random copolymer with a non-conjugated diene compound having 9 to 20 carbon atoms, and the above-mentioned [A], [B] and [C] forming this copolymer.
-2], the constitutional unit derived from each component has a molar ratio of [A]: [B]: [C-2] = 30 to 90: 5 to 70:
1-10 (the total of [A], [B] and [C-2] is 1
00)) and at least 1 mol% or more of the constitutional units of the copolymer is [C
-2] derived from the following formula [VII] or [VI]
II-a], [VIII-b] or [VIII-
c] is a constitutional unit represented by the following formula, and the intrinsic viscosity [η] measured in decalin at 135 ° C.
0.1 to 5.0 dl / g, and the glass transition temperature (Tg) measured by DSC is -1.
A cyclic olefin-based copolymer characterized by having a temperature of 0 to 250 ° C .; (However, in the above 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 respectively 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 a polycycle, and the monocycle or the polycycle is a double bond. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , A hydrocarbon group or an alkoxy group, wherein 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 carbon atom. 3 to 3 may be bonded via an alkylene group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be formed), and [Chemical 9] (In the above formula [VII], Y ² is a hydrocarbon group having 4 to 16 carbon atoms), 4. A transition metal compound of Group IVB of the periodic table or a lanthanide, which comprises (I) a ligand having a cyclopentadienyl skeleton, (II) an organoaluminumoxy compound, and optionally (III ) In the presence of a catalyst (a) composed of an organoaluminum compound or (IV) a soluble vanadium compound and a catalyst (b) composed of (V) an organoaluminum compound, [A] an α-olefin having 2 or more carbon atoms. If, [B] represented by the following formula [I] or [II], and at least one cyclic olefin, [C-1] following formula _{[III] CH 2 = CH-} Y 1 -CH = CH 2 ·· [III] (In the above formula [III], Y ¹ has 2 or 3 carbon atoms.
Is an alkylene group of) having 6 or 7 carbon atoms
The method for producing a cyclic olefin-based copolymer according to claim 2, wherein the α, ω-non-conjugated diene compound is copolymerized; (However, in the above 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 respectively 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 a polycycle, and the monocycle or the polycycle is a double bond. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , A hydrocarbon group or an alkoxy group, wherein 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 carbon atom. 3 to 3 may be bonded via an alkylene group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be formed). 5. (I) A transition metal compound of Group IVB of the periodic table or a lanthanide, which contains a ligand having a cyclopentadienyl skeleton, (II) an organoaluminum oxy compound, and optionally (III ) In the presence of a catalyst (a) composed of an organoaluminum compound or (IV) a soluble vanadium compound and a catalyst (b) composed of (V) an organoaluminum compound, [A] an α-olefin having 2 or more carbon atoms. And [B] at least one cyclic olefin represented by the following formula [I] or [II], and [C-2] the following formula [V] CH ₂ ═CH—Y ² —CH═CH ₂ ... A non-conjugated diene compound represented by [V] (in the above formula [V], Y ² is a hydrocarbon group having 4 to 16 carbon atoms) and having 8 to 20 carbon atoms; or Formulas [VI-a], [V -b] or [VI
-C] is copolymerized with a non-conjugated diene compound having 9 to 20 carbon atoms, and the method for producing a cyclic olefin-based copolymer according to claim 3, wherein (However, in the above 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 respectively 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 a polycycle, and the monocycle or the polycycle is a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , A hydrocarbon group or an alkoxy group, wherein 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 carbon atom. 3 to 3 may be bonded via an alkylene group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be formed),