JP2000026519A - Production of ethylene-cyclic olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer at low cost in high activity without the need of using any expensive catalytic component by copolymerization between ethylene and a cyclic olefin in the presence of a specific polymerization catalyst. SOLUTION: This copolymer is obtained by copolymerization between (D) ethylene and (E) a cyclic olefin such as 2-norbornene pref. at 90-190 deg.C under a pressure of 0.1-7 MPa normally for 1-180 min in the presence of a polymerization catalyst composed of (A) a transition metal complex such as biscyclopentadienylzirconium dichloride, (B) a clay-based compound (e.g. montmorillonite) preferably treated with an organoaluminum compound and/or organosilane compound (e.g. methylphenethylsilyl dichloride) and (C) a group IIb or IIIb organometallic compound (pref. an organoaluminum compound such as triisobutylaluminum).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ethylene-cyclic olefin copolymer, and more particularly, to a method for producing an inexpensive and highly active ethylene-cyclic olefin copolymer.

[0002]

2. Description of the Related Art A conventional method for producing an ethylene-cycloolefin copolymer has a problem that the production cost is high. For example, a large amount of expensive methylaluminoxane (hereinafter sometimes abbreviated as MAO) is used as a cocatalyst. Further, an expensive cocatalyst such as a boron compound containing a fluorine group, which is used in a small amount, is used. Further, a transition metal complex catalyst containing a complex and expensive ligand is used as a main catalyst, which causes an increase in production cost.

[0003] For example, Japanese Patent Application Laid-Open No. 61-221206 discloses ethylene-combination of MAO and a metallocene complex.
Although a method for producing a cyclic olefin copolymer is disclosed, MAO is synthesized using expensive trimethylaluminum as a raw material, and further has a molar equivalent of several hundred times to several thousand times the equivalent of transition metal in terms of aluminum during polymerization. MA
O is used, which causes an increase in cost when producing an ethylene-cyclic olefin copolymer.

[0004] Japanese Patent Application Laid-Open No. 5-262821 discloses an ethylene-based compound obtained by combining a boron compound and a metallocene complex.
A method for producing a cyclic olefin copolymer is disclosed.
In this production method, the amount of the boron compound used is as small as about one to several times that of the transition metal complex, and the cost reduction effect as a cocatalyst is excellent, but tetrakis (pentafluorophenyl) borate or the like is expensive. Therefore, further cost reduction is desired.

In addition, in the conventional production method, in order to reduce the amount of cocatalyst used, poisoning substances in the system which react with the catalyst or cocatalyst to lower the polymerization activity are added by adding an organic aluminum compound. For example, techniques for reducing or reducing the amount of cocatalyst used by removing or reducing the reaction have been attempted. However, there is a limit in reducing the amount of cocatalyst used.

On the other hand, JP-A-5-301917 discloses an example in which montmorillonite is treated with trimethylaluminum and used for homopolymerization of ethylene with zirconocene. In such a method, pretreatment of montmorillonite with expensive and highly dangerous trimethylaluminum, which is a raw material of MAO, is indispensable, and the activity per aluminum is not sufficient, and further improvement is required.

[0007] Under such circumstances, it has been desired to develop a production method using a less expensive co-catalyst and / or main catalyst.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and has as its object to provide an inexpensive and highly active method for producing an ethylene-cyclic olefin copolymer.
More specifically, an object of the present invention is to provide a method for producing an inexpensive and highly active ethylene-cyclic olefin copolymer without using an expensive ionizing agent such as MAO or a boron compound as a catalyst component.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the use of a reaction product of a clay compound and an organoaluminum compound and / or an organosilicon compound as a catalyst component allows the use of a low-cost catalyst component. The present inventors have found that a highly active ethylene-cyclic olefin copolymer can be produced, and have completed the present invention based on this finding.

That is, the present invention provides the following method for producing an ethylene-cyclic olefin copolymer. 1. Ethylene-cyclic olefin copolymerization of copolymerizing ethylene and cyclic olefin using a polymerization catalyst comprising (a) a transition metal complex, (b) a clay compound, and (c) an organometallic compound of Group IIb or IIIb of the Periodic Table. Manufacturing method of coalescence. 2. 2. The method for producing an ethylene-cyclic olefin copolymer according to the above 1, wherein (a) is any of transition metal complexes represented by the following general formulas (I) to (IV).

CpM ¹ R ¹ aR ² bR ³ c (I) Cp ₂ M ¹ R ¹ dR ² e (II) (Cp-A _f -Cp) M ¹ R ¹ dR ² e (III) M ¹ R ¹ gR ² hR ³ iR ⁴ j (IV) [In the formulas (I) to (IV), M ¹ is one atom selected from Ti, Zr and Hf atoms. Cp is one group selected from a cyclic unsaturated hydrocarbon group and a chain unsaturated hydrocarbon group bonded in an η ⁵ bonding mode. R ¹ , R ² , R ³ and R ⁴ are one ligand selected from a σ-binding ligand, a chelating ligand and a Lewis base ligand. A represents a covalent crosslink. a, b and c are each 0
A + b + c = (valence of M ¹ ) −1. d and e are each an integer of 0 to 2, and d + e
= (Valence of M ¹⁾ -2. f is an integer from 0 to 6, g,
h, i and j are each an integer of 0 to 4, and g + h +
i + j = (valence of M ¹ ). R ¹ , R ² , R ³ and R
⁴ may have two or more of them bonded to each other to form a ring. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ] 3. In the general formulas (I) to (IV), Cp represents cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group, substituted fluorenyl Any one of a cyclic unsaturated hydrocarbon group selected from the group consisting of R ¹ , R ² ,
R ³ and R ⁴ are each a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, and an arylalkyl group And 1 to 20 carbon atoms
A group of sigma-bonding ligands consisting of an acyloxy group, an allyl group, a substituted allyl group and a substituent containing a silicon atom, a group of chelating ligands consisting of an acetylacetonate group and a substituted acetylacetonate group, and The above-mentioned 2 which is any one ligand selected from the group of ligands of Lewis bases;
A method for producing the ethylene-cyclic olefin copolymer described in the above. 4. 2. The method for producing an ethylene-cyclic olefin copolymer according to the above 1, wherein (a) is a transition metal complex represented by the following general formula (V).

[0012]

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[0013] (wherein, M ¹ is Ti, .cp is any one atom selected from Zr and Hf atoms is cyclic unsaturated hydrocarbon group and a chain that binds with eta ⁵ bonding mode to M ¹ X ¹ represents a σ ligand, n is 1 or 2, and a plurality of X ^{1 s} may be the same or different; Also,
It may be bonded via any group. Y ¹ is a neutral two-electron donating ligand, and Z is SiR ₂ , CR ₂ ,
SiR ₂ SiR ₂ , CR ₂ CR ₂ , CR = CR, CRS
It is any one selected from iR ₂ , GeR ₂ , BR and BR ₂ . R is composed of a hydrogen atom, an alkyl group, an aryl group, a silyl group, an alkyl halide, an aryl halide, and any combination thereof, and has 20 or less non-hydrogen atoms. When there are a plurality of Rs, they may be the same or different. A ring may be formed between the R group and another R group, or between the R group and Y ¹ . ) 5. A cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group in which Cp in the general formula (V) is bonded to M ¹ in an η ⁵ bonding mode. Group, substituted hexahydroazulenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, tetrahydrofluorenyl group, substituted tetrahydrofluorenyl group, octahydrofluorenyl group, substituted octahydrofluorenyl group. Any one group, Y
¹ is O, S, NR, PR or CR ₂ ;
The method for producing an ethylene-cyclic olefin copolymer according to the above item 4, wherein the ethylene-cyclic olefin copolymer is a neutral two-electron donating ligand selected from R, SR, NR _{2 and} PR ₂ . 6. (1) wherein (b) is a clay compound treated with an organoaluminum compound and / or an organosilane compound;
A method for producing an ethylene-cyclic olefin copolymer according to any one of claims 1 to 5. 7. The method for producing an ethylene-cyclic olefin copolymer according to any one of the above 1 to 6, wherein (c) is an organoaluminum. 8. The method for producing an ethylene-cyclic olefin copolymer according to any one of claims 1 to 7, wherein the cyclic olefin is represented by the following general formula (VI).

[0014]

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(In the formula (VI), R^a~ R^lIs hydrogen
An atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom,
A substituent containing an oxygen atom or a nitrogen atom;
The following integers are shown. RⁱOr R^jAnd R^kOr R^lAnd each other
A ring may be formed. Also, R ^a~ R^mAre each other
They may be the same or different. )

[0016]

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for producing an ethylene-cyclic olefin copolymer using the above-mentioned polymerization catalyst. Hereinafter, the present invention will be described in detail. 1. Polymerization catalyst (a) Transition metal complex In the production method of the present invention, the transition metal complex (a) is selected from the groups IVB, VB, VIB, VIIB, VIII of the periodic table.
A transition metal compound containing a transition metal belonging to the group is used.
Examples of such transition metal compounds include various compounds, and as the transition metal, it is preferable to use titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum, etc., among which titanium, zirconium, hafnium, It is preferable to use nickel and palladium. In particular, compounds containing transition metals of groups IVB and VIII, particularly transition metal compounds containing transition metals selected from group IVB of the periodic table, ie, titanium (Ti), zirconium (Zr) or hafnium (Hf) are preferred. is there. In particular, the following general formula (I), (II) or (III)
Or a derivative thereof or a compound represented by the following general formula (IV) or a derivative thereof is suitable as the transition metal compound.

CpM¹R¹aR^TwobR^Threec… (I) Cp_TwoM¹R¹dR^Twoe ... (II) (Cp-A_f-Cp) M¹R¹dR^Twoe… (III) M¹R¹gR^TwohR^ThreeiR^Fourj… (IV) [wherein (I) to (IV), M¹Is a Ti, Zr or Hf atom
Is one atom selected from Cp is cyclic unsaturated carbon
One group selected from a hydrogen group or a chain unsaturated hydrocarbon group
It is. R¹, R^Two, R^ThreeAnd R^FourIs a σ-binding ligand,
Selected from chelating ligands or Lewis base ligands
Is the only ligand. A indicates covalent cross-linking
You. a, b and c are each an integer of 0 to 3;
b + c = (M ¹Valence) -1. d and e are each
Where d + e = (M ¹Valence) -2
is there. f is an integer of 0 to 6, and g, h, i and j are each
G + h + i + j = (M¹Valence)
It is. R¹, R^Two, R^ThreeAnd R^FourAre two or more of each other
They may combine to form a ring. Formulas (II) and (II)
In the formula (I), two Cp may be the same.
Alternatively, they may be different from each other. Preferably, Cp is a cyclopentadienyl group,
Lopentadienyl group, indenyl group, substituted indenyl
Group, tetrahydroindenyl group, substituted tetrahydroin
Benzyl, fluorenyl, substituted fluorenyl, octyl
Tahydrofluorenyl and substituted octahydrofluores
Any one of cyclic unsaturated hydrocarbons selected from nyl group
Group or chain unsaturated hydrocarbon group. Also preferred
Is R¹, R ^Two, R^ThreeAnd R^FourAre hydrogen and oxygen, respectively
Atom, halogen atom, alkyl group having 1 to 20 carbon atoms, charcoal
Alkoxy group having 1 to 20 primes, aryl having 6 to 20 carbon atoms
Group, alkylaryl group or arylalkyl
Group, acyloxy group having 1 to 20 carbon atoms, allyl group, substitution
Σ bond consisting of substituents containing allyl group and silicon atom
Group of ligands, acetylacetonate groups, and substituted acetyl
A group of chelating ligands consisting of luacetonate groups or
Any one of the Lewis base ligands
It is a child.

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. Specific examples of R ^{1 to} R ⁴ include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom as a halogen atom; a methyl group, an ethyl group, an n-propyl group and an iso group as an alkyl group having 1 to 20 carbon atoms.
-Propyl group, n-butyl group, octyl group, 2-ethylhexyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group as an alkoxy group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; A phenyl group as an alkylaryl group or an arylalkyl group,
Tolyl group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group, (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, tetrahydrofuran, etc. as Lewis base Ethers, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N,
Amines such as N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline and the like; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene; 1-hexene and derivatives thereof; cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof.

Examples of the crosslink by a covalent bond of A include methylene bridge, dimethylmethylene bridge, ethylene bridge,
Examples include 1,1′-cyclohexylene bridge, dimethylsilylene bridge, dimethylgermylene bridge, and dimethylstannylene bridge. Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compound of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyl Rukoniumu, (methylcyclopentadienyl) triphenyl zirconium, (methylcyclopentadienyl) tribenzyl zirconium, (methylcyclopentadienyl) trichloro zirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, compound of formula (II) bis (cyclo) Pentadienyl) dimethyl zirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium, compound of formula (III) ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichloro Zirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentane Dienyl) (9-fluorenyl) dimethyl zirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconi Arm, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclopentane Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylenebis (indenyl) dichlorozirconium Compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) also impair the effect. is not. Examples of such compounds include compounds of formula (IV) above, for example, tetramethylzirconium,
Tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy trichloro zirconium, dibutoxy dichloro zirconium, bis (2,5-di-t-
Butylphenoxy) dimethyl zirconium, bis (2,
One or more of an alkyl group, an alkoxy group, and a halogen atom such as 5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), or a compound obtained by replacing zirconium with hafnium or titanium. Zirconium compounds, hafnium compounds, and titanium compounds.

The transition metal compound containing a Group VIII transition metal is not particularly limited. Specific examples of the chromium compound include, for example, tetramethylchromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) ) Chromium, hydride tricarbonyl (cyclopentadienyl)
Chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl)
Chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like can be mentioned.

Specific examples of the manganese compound include, for example,
For example, tricarbonyl (cyclopentadienyl) manga
Pentacarbonylmethylmanganese, bis (cyclope
Antadienyl) manganese, manganese bis (acetylacetate)
And the like. Specific examples of nickel compounds
For example, dicarbonylbis (triphenylphospho
Fin) nickel, dibromobis (triphenylphosphine)
In) nickel, dinitrogen bis (bis (tricyclohexyl)
Ruphosphine) nickel), chlorohydride bis (tri
Cyclohexylphosphine) nickel, chloro (phenyl
Le) bis (triphenylphosphine) nickel, dimethyl
Rubis (trimethylphosphine) nickel, diethyl
(2,2'-bipyridyl) nickel, bis (allyl) di
Nickel, bis (cyclopentadienyl) nickel, bis
(Methylcyclopentadienyl) nickel, bis (pen
Tamethylcyclopentadienyl) nickel, allyl
Clopentadienyl) nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate
Acid salt, bis (cyclooctadiene) nickel, nickel
Bisacetylacetonate, allyl nickel chloride
De, tetrakis (triphenylphosphine) nickel
, Nickel chloride, (C₆H_Five) Ni ｛OC (C₆H_Five) CH = P (C₆H _Five)_Two｝
｛P (C₆H_Five)_Three｝, (C₆H_Five) Ni ｛OC (C₆H_Five) C (SO_ThreeNa) = P (C
₆H_Five)_Two｝ ｛P (C₆H_Five)_ThreeAnd the like.

Specific examples of the palladium compound include, for example, dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanate) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
(1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate and the like can be mentioned.

In the production method of the present invention, a transition metal compound represented by the following general formula (V) can be used.

[0024]

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[0025] (wherein, M ¹ is Ti, .cp is any one atom selected from Zr or Hf atom, cyclic unsaturated hydrocarbon group or chain binds with eta ⁵ bonding mode to M ¹ X ¹ represents a σ ligand, n is 1 or 2, and a plurality of X ^{1 s} may be the same or different; Also,
It may be bonded via any group. Y ¹ is a neutral two-electron donating ligand, and Z is SiR ₂ , CR ₂ ,
SiR ₂ SiR ₂ , CR ₂ CR ₂ , CR = CR, CRS
It is any one selected from iR ₂ , GeR ₂ , BR, BR ₂ . R is composed of a hydrogen atom, an alkyl group, an aryl group, a silyl group, an alkyl halide, an aryl halide, and any combination thereof, and has 20 or less non-hydrogen atoms. When there are a plurality of Rs, they may be the same or different. A ring may be formed between the R group and another R group, or between the R group and Y ¹ . Preferably, Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group bonded to M ¹ in an η ⁵ bonding mode,
An indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulenyl group, a tetrahydroindenyl group,
It is any one group selected from a substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group, an octahydrofluorenyl group, and a substituted octahydrofluorenyl group. Also preferably, Y ¹ is O, S, NR, PR or CR ₂ ,
Or any one of neutral neutral electron donating ligands selected from OR, SR, NR _{2 and} PR ₂ .

Here, the substituted cyclopentadienyl group is, for example, a cyclopentadienyl group substituted by one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3- Di (trimethylsilyl) cyclopentadienyl group; tert-butylcyclopentadienyl group;
1,3-di (tert-butyl) cyclopentadienyl group; a hydrocarbyl group having 1 to 20 carbon atoms, a halohydrocarbyl group and the like. Further, the substituted indenyl group is
For example, a methylindenyl group, a dimethylindenyl group,
A tetramethylindenyl group and a hexamethylindenyl group; examples of the substituted tetrahydroindenyl group include a 4,5,6,7-tetrahydroindenyl group;
A methyl-4,5,6,7-tetrahydroindenyl group;
2-methyl-4,5,6,7-tetrahydroindenyl group; 1,2-dimethyl-4,5,6,7-tetrahydroindenyl group; 1,3-dimethyl-4,5,6,7- Tetrahydroindenyl group; 1,2,3-trimethyl-
4,5,6,7-tetrahydroindenyl group;
3,4,5,6,7-heptamethyl-4,5,6,7-
Tetrahydroindenyl group; 1,2,4,5,6,7-
Hexamethyl-4,5,6,7-tetrahydroindenyl group; 1,3,4,5,6,7-hexamethyl-4,
5,6,7-tetrahydroindenyl group; 4,5,6
7-tetrahydro-1,2,3 trimethylindenyl group and the like, and the substituted fluorenyl group is, for example, a methylfluorenyl group, a dimethylfluorenyl group, a tetramethylfluorenyl group, an octamethylfluorenyl group. is there. A substituted tetrahydrofluorenyl group is, for example, 1,2,2
3,4-tetrahydrofluorenyl group; 9-methyl-
1,2,3,4-tetrahydrofluorenyl group,
The substituted octahydrofluorenyl group is, for example, a 9-methyl-octahydrofluorenyl group or the like. Examples of the substituted hexahydroazulenyl group include a 1-methylhexahydroazulenyl group, a 2-methylhexahydroazulenyl group, a 1,2-dimethylhexahydroazulenyl group,
1,3-dimethylhexahydroazulenyl group, 1,2,2
It is a 3-trimethylhexahydroazulenyl group.

X ¹ is a σ ligand. Specifically, hydride, halogen, alkyl, silyl, aryl, arylsilyl, amide, aryloxy, alkoxy, silyloxy, phosphide, sulfide,
Acyl, cyanide, azide, acetylacetonate, etc.
And combinations thereof. Specific compounds include (t-butylamide) (tetramethylcyclopentadienyl) 1,2-ethanediylzirconium dichloride and (t-butylamide) (tetramethylcyclopentadienyl) 1,2-ethanediyltitanium dichloride. , (Methylamide) (tetramethylcyclopentadienyl) 1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) 1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethylcyclopentadiyl (Enyl) -methylene titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride, (t-butylamido)
Dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dimethyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dimethyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dibenzyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) Silane titanium dichloride, (phenyl phosphide) dimethyl (tetramethyl cyclopentadienyl) silane zirconium dibenzyl, (t-butyl amide) dimethyl (tetramethyl cycle Pentadienyl) silane titanium dichloride, (dimethylaminoethyl) tetramethyl - cyclopentadienyl titanium (III) dichloride, 9-
(Dimethylaminoethyl) octahydro-fluorenyltitanium (III) dichloride, (di-n-butylaminoethyl) tetramethyl-cyclopentadienyltitanium (III) dichloride, (dimethylaminomethyl) tetramethyl-cyclopentadienyl Titanium (III) dichloride, (dimethylaminopropyl) tetramethyl-cyclopentadienyl titanium (III) dichloride, and the like. (B) Clay-based compound As the clay-based compound (b), the following clays or clay minerals or ion-exchange layered compounds can be used. Clay or clay mineral Clay is an aggregate of fine hydrated silicate minerals,
A substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. The clay mineral refers to a hydrated silicate that is a main component of clay. These are not limited to natural products, and may be artificially synthesized. Ion-exchangeable layered compound The ion-exchanged layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable. Some clay minerals are ion-exchangeable layered compounds.

For example, ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packing type, an antimony type, a cadmium chloride type, and a cadmium iodide type can be given. The ion-exchange layered compound is not limited to a natural product, and may be an artificially synthesized product. Specific examples of the above (b) include kaolin, bentonite, kibushi clay, gairome clay, allophane, hissingelite, pyrophyllite, talc, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite , Dickite, halloysite and the like. As the component (b), a pore volume having a radius of 20 ° or more measured by a mercury intrusion method is preferably 0.1 ml / g or more, particularly preferably 0.3 to 5 ml / g or more.

Among them, preferred as (b) is clay or clay mineral, and most preferred is montmorillonite. In some cases, the method (b) is used by removing impurities or changing its structure and function, and it is also preferable to perform a chemical treatment. Here, the chemical treatment refers to either the surface treatment for removing impurities adhering to the surface (b) or the treatment for affecting the surface and internal crystal structure. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned.

The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. The alkali treatment destroys the crystal structure, resulting in a change in the structure. In salt treatment and organic matter treatment, ion complex,
By forming a molecular complex, an organic complex, or the like, the surface area, the interlayer distance, and the like can be changed. By replacing the exchangeable ions between layers with another bulky ion by utilizing ion exchangeability, an interlayer material having an enlarged interlayer can be obtained.

The above (b) may be used as it is, or may be a water-added and newly-adsorbed one.
Alternatively, those subjected to heat dehydration treatment may be used. In the production method of the present invention, it is preferable to use the clay-based compound (b) that has been treated with an organoaluminum and / or an organosilane compound in the above chemical treatment. Treatment of Clay Compound with Organoaluminum and / or Organosilane Compound (a) Treatment of Clay Compound with Organoaluminum As the organoaluminum, an alkyl group-containing aluminum compound represented by the following general formula (VII), A linear aluminoxane represented by the general formula (VIII) or a cyclic aluminoxane represented by the following general formula (IX) or an aggregate of a cyclic aluminoxane can be used.

R ⁵ _m Al (OR ⁶ ) _n X _3-mn (VII) (wherein R ⁵ and R ⁶ each represent an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms) , X represents a hydrogen atom or a halogen atom, and m is 0 <m ≦ 3, preferably 2 or 3, most preferably 3, and n is 0 ≦
n <3, preferably 0 or 1. )

[0033]

Embedded image

(Wherein R ⁷ is an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ⁷ may be the same or different. )

[0035]

Embedded image

(Wherein R ⁷ and w are the same as those of the above-mentioned general formula (VIII)
The same as in. Further, n is a positive integer. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, etc. Aluminoxane such as alkylaluminum, methylalumoxane, ethylalumoxane, isobutylalumoxane, etc., of which halogen or alkoxy group is contained, among which triisobutylaluminum is particularly preferred.

When the clay compound is treated with the organoaluminum compound, the molar ratio of the transition metal in the component (a) to the hydroxyl group in the clay compound and the aluminum atom in the organoaluminum compound is 1: 0.1 to 100,000. : 0.1 ~
1,000,000, especially 1: 0.5-100
00: 0.5 to 10,000 is preferable. (A) Treatment of a clay compound with an organic silane compound As the organic silane compound, specifically, for example, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, tert-butyldiphenylsilyl chloride , Trialkylsilyl chlorides such as phenethyl dimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, bisdiphenethylsilyl dichloride, diphenylsilyl dichloride, dialkylsilyl dichloride such as ditolysilyl dichloride, etc. , Methylsilyl trichloride, ethylsilyl trichloride, isopropylsilyl trichloride, phenylsilyl trichloride , Alkylsilyl trichlorides such as mesitylsilyl trichloride, tolylsilyl trichloride, phenethylsilyl trichloride, halides in which the above-mentioned chloride portion is replaced by another halogen element, bis (trimethylsilyl) amide, bis (triethylsilyl) ) Amide, bis (triisopropylsilyl) amide, bis (dimethylethylsilyl) amide, bis (diethylmethylsilyl) amide, bis (dimethylphenylsilyl) amide, bis (dimethyltolylsilyl)
Disilazanes such as amide and bis (dimethylmesitylsilyl) amide; polysilanols commonly used for peralkylpolysiloxy polyols; tetraalkylsilanes such as dimethyldiphenylsilane, diethyldiphenylsilane and diisopropyldiphenylsilane; trimethylsilane Trialkylsilanes such as triethylsilane, triisopropylsilane, tri-t-butylsilane, triphenylsilane, tolylsilane, trimesitylsilane, methyldiphenylsilane, dinaphthylmethylsilane, bis (diphenyl) methylsilane, and tetrachloride And inorganic silicon compounds such as silicon and silicon tetrabromide. Among these, preferred are disilazanes, and more preferred are trialkylsilane chlorides. One of these may be used, but in some cases, two or more may be used in any combination.

When the clay compound is treated with the organosilane compound, the molar ratio of the transition metal in the component (a) to the hydroxyl group in the clay compound and the silicon atom in the organosilane compound is 1: 0.1 to 100,000. : 0.1 to 1,000,000, especially 1: 0.5 to 10000: 0.5 to 1
Preferably, the contact is at 0000. (C) Organometallic compound In the production method of the present invention, in addition to the above (a) and (b), if necessary, an organometallic compound can be used as the component (c).

Here, there are various organometallic compounds. For example, an alkyl group-containing aluminum compound represented by the general formula (VII) or a linear alumoxane represented by the general formula (VIII) And the cyclic alumoxane represented by the general formula (IX) or an aggregate of the cyclic alumoxane. Further, the following general formula (X): R ⁸ ₂ Mg (X) wherein R ⁸ represents an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms. Alkyl group-containing magnesium compound represented by], yet the general formula _{^{(XI) R 8 2 Zn ···}} (XI) wherein, R ⁸ is as defined above. And the like.

Of these alkyl group-containing compounds, alkyl group-containing aluminum compounds, particularly trialkylaluminum and dialkylaluminum compounds, are preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum Dialkylaluminum halides such as chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-t-butylaluminum chloride, dimethylaluminum methoxide;
Dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, dimethyl aluminum hydride,
And dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride. Further examples include dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium and butylmagnesium, and dialkylzinc such as dimethylzinc, diethylzinc, ethyl-n-propylzinc and diisopropylzinc. . Among these organometallic compounds, organoaluminum compounds are preferred, and among these, trialkylaluminum is preferred.

In the production method of the present invention, (a) a transition metal complex represented by the general formulas (I) to (V) wherein M is Zr, (b) a clay compound, and (c) Is preferably used. More preferably, (a) is a transition metal complex represented by general formulas (I) to (V) in which M is Zr, and (b) is a clay-based compound treated with an organic silane compound.
(C) is a case where a trialkylaluminum is used. 2. Production Method of Copolymer The production method of the present invention involves copolymerizing ethylene and a cyclic olefin using the above catalyst. In this case, ethylene may be ethylene alone, or ethylene and propylene, butene-1,4-methylpentene-1.
And mixtures with other α-olefins having 3 to 25 carbon atoms, such as The cyclic olefin is represented by the following general formula (VI).

[0042]

Embedded image

(In the formula (VI), R^a~ R^lIs hydrogen
An atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom,
A substituent containing an oxygen atom or a nitrogen atom;
Represents an integer greater than or equal to, preferably 0 or 1, and particularly preferably
Or 0. RⁱOr R^jAnd R ^kOr R^lIs a ring to each other
It may be formed. Also, R^a~ R^lAre the same as each other
It may be one or different. ) The odor of the cyclic olefin represented by the general formula (VI)
And R^a~ R^lAre hydrogen atom and charcoal, respectively,
A hydrocarbon group of 1 to 20 or a halogen atom, an oxygen atom
Alternatively, a substituent containing a nitrogen atom is shown.

Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, An alkyl group having 1 to 20 carbon atoms such as a hexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, a propylidene group; Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as an alkylidene group having 1 to 20 carbon atoms, a vinyl group and an allyl group. Note that R ^c , R ^d , R
If any ^g to R ^l are alkylidene group, the carbon atom to which it is attached does not have the other substituent.

Specific examples of the substituent containing a halogen atom include halogen substituents having 1 to 20 carbon atoms such as a halogen group such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, a C1-20 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a C1-20 carbon atom such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like.

Specific examples of the substituent containing a nitrogen atom include:
Examples thereof include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group. Specific examples of the cyclic olefin represented by the general formula (VI) include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene,
Methyl norbornene, 7-methyl norbornene, 5,
5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-fluoro-1,4,5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 1,5-dimethyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2-cyclohexyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,2
-Dihydrocyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned. Of these, norbornene or a derivative thereof is particularly preferred.

The polymerization method of the copolymer of the present invention is not particularly limited, but known methods such as slurry polymerization, gas phase polymerization, high pressure polymerization, and solution polymerization can be used, and these polymerization methods can be used alone or in combination. Multi-stage polymerization or pre-polymerization can also be used. Among them, solution polymerization is preferred. Although the polymerization temperature is not particularly limited, the polymerization temperature is usually 20
-250 ° C, preferably 70-220 ° C), more preferably 90-190 ° C. As for the polymerization pressure,
Although there is no particular limitation, 0.05 to 10 MPa is preferable,
More preferably, it is 0.1 to 7 MPa. The polymerization time is not particularly limited, but is usually 1 to 180 minutes.

The amount of the catalyst used is 0.001 to 1000 μmol / L, preferably 0.00 to 1000 μmol / L in terms of transition metal of the component (a).
1 to 100 μmol / L, particularly preferably 0.02 to 50
μmol / L. If the amount used is too large, it becomes difficult to remove the heat of the polymerization. On the other hand, if the amount is too small, sufficient activity is not exhibited. Component (b) is used in an amount of 0.0001 to 100 g, preferably 0.0, to 1 micromol of transition metal.
005 to 50 g, particularly preferably 0.001 to 10 g. The same applies to the case where the chemically treated component (b) is used. In either case, if the amount used is too large, there are problems such as high cost, increased residue in the copolymer, and reduced polymer physical properties. Conversely, if the amount is too small, sufficient catalytic activity cannot be obtained, resulting in high cost and deterioration of polymer properties.

When the organoaluminum compound (c) is used, the amount is 1 to 10000 times (molar ratio), preferably 5 to 5000 times, particularly preferably 1 to 1 times the transition metal.
The amount is from 0 to 5000 times. Methods for adjusting the molecular weight of the copolymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and fats such as pentane, hexane, heptane and octane Group hydrocarbons, halogenated hydrocarbons such as chloroform, dichloromethane and the like can be used. These solvents may be used alone or in a combination of two or more. Further, a monomer such as a cyclic olefin or an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the present invention, preliminary polymerization can be performed using the polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, a cyclic olefin, or a mixture thereof. It is advantageous to use the same olefin used in the polymerization.

The prepolymerization temperature is usually -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, aliphatic hydrocarbons, aromatic hydrocarbons, monomers and the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent.

In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and the transition metal component in the catalyst is used. The amount of the prepolymerized product per 1 mmol is from 1 to 10,000 g, especially from 10 to 10 g.
It is desirable to adjust the conditions so that the weight becomes 00 g. The ethylene-cyclic olefin copolymer can be efficiently obtained by the above production method.

[0054]

[Example 1]

(1) Chemical treatment of clay mineral 40 g of commercially available montmorillonite (Kunimine F, Kunipia F) was pulverized by a pulverizer for 4 hours. Pulverized montmorillonite 19.9 in a 500 ml four-necked flask
g of magnesium chloride hexahydrate was dispersed in 100 ml of deionized water in which 20 g of magnesium chloride hexahydrate was dissolved, and treated at 90 ° C. for 0.5 hour with stirring. After the treatment, the solid component was washed with water. This treatment operation was repeated once to obtain montmorillonite treated with magnesium chloride. After drying, it was dispersed in 160 ml of a 6% aqueous hydrochloric acid solution and treated under reflux with stirring for 2 hours. After the treatment, washing with water was repeated until the supernatant became neutral, followed by drying to obtain montmorillonite.

Next, 1 g of the above montmorillonite and 1.13 g of methylphenethylsilyl dichloride were placed in a Schlenk tube.
(5.2 mmol) and heated at 100 ° C. for 1 hour. Thereafter, the resulting powder was washed with toluene, and the liquid volume was adjusted to 50 ml with toluene to obtain a co-catalyst clay slurry (A) (5 ml of this slurry containing 0.1 g of montmorillonite). (2) Ethylene and norbornene Copolymerization In a 2-liter autoclave, dry toluene 900 m
l, 1.5 mmol triisobutylaluminum (TIBA), 750 mmol 2-norbornene
After the temperature was raised to 10 ° C., 4 MPa of ethylene was introduced.
30 ml of toluene, 1.5 mmol of TIBA, and 0.2 ml of the co-catalyst clay slurry (A) obtained in
g, 0.5 micromol of biscyclopentadienyl zirconium dichloride was charged, and the autoclave was pressure-fed with dry nitrogen. Then, ethylene was continuously supplied so that the ethylene partial pressure became 4 MPa, and copolymerization was performed for 5 minutes. After that, the polymerization was stopped by adding methanol. The polymer was transferred to an excess of methanol, separated by filtration, and 90 ° C. under reduced pressure.
After drying for 12 hours, 21 g of a copolymer was obtained. The activity per transition metal and the norbornene content determined by ¹³ C-NMR were 462 kg / gZr,
It was 5.8 mol%. [Example 2] (1) Chemical treatment of clay mineral In the chemical treatment of clay mineral of Example 1, 1.13 g (5.2 mmol) of methylphenethylsilyl dichloride was used.
Instead of 25 ml of a toluene solution of triisobutylaluminum (concentration: 0.5 mol / l) (1
Except for using 2.5 mmol), the same procedure as in Example 1 was carried out to obtain a co-catalyst clay slurry (B) (5 ml of this slurry containing 0.1 g of montmorillonite). (2) Copolymerization of ethylene and norbornene The amount of toluene was 700 ml, and the amount of 2-norbornene was 20.
(B) and biscyclopentadienyl zirconium dichloride in accordance with the method described in Example 2 of JP-A-3-16388. (Methylcyclopentadienyl) silane Titanium dichloride was used in the same manner as in Example 1 except that the substitution was performed. The results are shown in Table 1. Example 3 The amount of toluene was 800 ml, the amount of 2-norbornene was 250 mmol, the polymerization temperature was 130 ° C.,
The procedure was performed in the same manner as in Example 2 except that 0.5 micromol of (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride was changed to 1 micromol of tetrabutoxyzirconium. The results are shown in Table 1. Example 4 370 ml of dry hexane and triisobutylaluminum (TIB) were placed in a 1-liter autoclave.
A) 1.5 mmol, 1,4,5,8-dimethanone 1,
After loading 800 mmol of 2,3,4,4a, 5,8,8a-octahydronaphthalene and heating to 90 ° C,
0.8 MPa of ethylene was introduced. 30 ml of hexane, 0.5 mmol of TIBA, 0.2 g of the clay clay (B) for the cocatalyst were obtained in a catalyst introduction tube, and dimethylsilylbis (2- (2-dimethylsilylbis) (2-) obtained according to the method described in Example A of JP-A-6-100579. Methyl-4-phenylindenyl) zirconium dichloride (1 μmol) was charged to the autoclave with dry nitrogen, and the ethylene partial pressure was reduced to 4MP.
After ethylene was continuously supplied so as to obtain a and copolymerization was performed for 60 minutes, the polymerization was stopped by adding methanol. The polymer was transferred to an excess amount of methanol, separated by filtration, and dried under reduced pressure at 90 ° C. for 12 hours to obtain 27 g of a copolymer. Activity per transition metal, intrinsic viscosity measured in decalin at 135 ° C., 1,4,5,8-dimetano 1,2,3,4,4 determined by ¹³ C-NMR
The a, 5,8,8a-octahydronaphthalene content was 297 kg / gZr, 1,8 deciliter / g,
18.6 mol%. Example 5 1,4,5,8-Dimethanone 1,2,3
4,4a, 5,8,8a-octahydronaphthalene 80
The procedure was performed in the same manner as in Example 4 except that 0 mmol was changed to 170 mmol of 2-norbornene, the polymerization temperature was changed to 70 ° C., the clay slurry for the promoter was changed to (A), and the transition metal complex was changed to ethylenebis (indenyl) zirconium dichloride. Was. The results are shown in Table 1. Example 6 The amount of 2-norbornene was changed to 750 mmol,
At a polymerization temperature of 110 ° C, the co-catalyst clay slurry was added to (A)
In the same manner as in Example 3, except that 1 micromol of TBZ was changed to 2 micromol. The results are shown in Table 1. Reference Example 1 Triisobutylaluminum (TIBA)
Was not used, and the amount of 2-norbornene was 250
Mmol, the polymerization temperature to 130 ° C., the amount of the co-catalyst clay slurry (A) to 1 g, the biscyclopentadienyl zirconium dichloride 0.5 μmol to the biscyclopentadienyl dimethyl zirconium 50 μmol, and the ethylene component The procedure was performed in the same manner as in Example 1 except that the pressure was changed to 6 MPa and the polymerization time was changed to 10 minutes. The results are shown in Table 1. Reference Example 2 Triisobutylaluminum (TIBA)
Was not used and the amount of 2-norbornene was 750.
1 mmol of dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride and biscyclopentadienyl dimethylzirconium. 20 micromoles, ethylene partial pressure 0.8
The procedure was performed in the same manner as in Example 4 except that the polymerization time was changed to 60 minutes. The results are shown in Table 1.

[0056]

[Table 1]

[0057]

According to the production method of the present invention, a high molecular weight ethylene-cyclic olefin copolymer can be obtained efficiently and inexpensively because it has sufficient molecular weight controllability and polymerization activity even under high temperature polymerization conditions. Can be.

Continued on the front page F term (reference) 4J028 AA01A AB00A AB01A AC01A AC09A AC10A AC27A AC28A BA01B BA02B BB01B BB02B BC05B BC09B BC15B BC16B BC24B BC25B BC32B EA01 EB02 EB18 EB18 EC02 FA01 FA02 AR04A04A03 AR03 A03 AR03 A04A04 BA31R BB01R BC26R BC27R BC43R CA04 CA05 FA02 FA08

Claims (8)

[Claims] 1. Ethylene copolymerizing ethylene and a cyclic olefin using a polymerization catalyst comprising (a) a transition metal complex, (b) a clay compound, and (c) an organometallic compound of Group IIb or IIIb of the Periodic Table. -A method for producing a cyclic olefin copolymer. 2. The method according to claim 1, wherein (a) is a compound represented by the following general formulas (I) to (IV):
The method for producing an ethylene-cycloolefin copolymer according to claim 1, which is any one of transition metal complexes represented by the following formula: CpM ¹ R ¹ aR ² bR ³ c (I) Cp ₂ M ¹ R ¹ dR ² e (II) (Cp-A _f -Cp) M ¹ R ¹ dR ² e (III) M ¹ R ¹ gR ² hR ³ iR ⁴ j (IV) [In the formulas (I) to (IV), M ¹ is one atom selected from Ti, Zr and Hf atoms. Cp is one group selected from a cyclic unsaturated hydrocarbon group and a chain unsaturated hydrocarbon group bonded in an η ⁵ bonding mode. R ¹ , R ² , R ³ and R ⁴ are one ligand selected from a σ-binding ligand, a chelating ligand and a Lewis base ligand. A represents a covalent crosslink. a, b and c are each 0
A + b + c = (valence of M ¹ ) −1. d and e are each an integer of 0 to 2, and d + e
= (Valence of M ¹⁾ -2. f is an integer from 0 to 6, g,
h, i and j are each an integer of 0 to 4, and g + h +
i + j = (valence of M ¹ ). R ¹ , R ² , R ³ and R
⁴ may have two or more of them bonded to each other to form a ring. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ] 3. In the general formulas (I) to (IV), Cp
Is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, tetrahydroindenyl, substituted tetrahydroindenyl, fluorenyl, substituted fluorenyl, octahydrofluorenyl and substituted octahydro selected from a fluorenyl group is any one of the cyclic unsaturated hydrocarbon group, R ^1,
R ² , R ³ and R ⁴ each represent a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
0 alkoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group and arylalkyl group, and 1 carbon atom
A group of sigma-bonding ligands comprising an acyloxy group, an allyl group, a substituted allyl group and a substituent containing a silicon atom, and a chelating ligand consisting of an acetylacetonate group and a substituted acetylacetonate group. The method for producing an ethylene-cyclic olefin copolymer according to claim 2, wherein the ligand is any one selected from the group consisting of a group and a ligand of a Lewis base. 4. The method for producing an ethylene-cycloolefin copolymer according to claim 1, wherein (a) is a transition metal complex represented by the following general formula (V). Embedded image (Wherein, M ¹ is Ti, .cp is any one atom selected from Zr and Hf atoms is cyclic unsaturated hydrocarbon group and a chain binds with eta ⁵ bonding mode to M ¹ unsaturated hydrocarbons X ¹ is a σ ligand, n is 1 or 2, and a plurality of X ^{1 s} may be the same or different, and And Y ¹ is a neutral two-electron donating ligand, and Z is SiR ₂ , CR ₂ , SiR ₂ SiR
₂ , CR ₂ CR ₂ , CR = CR, CRSiR ₂ , GeR
_2, selected from BR and BR ₂ is any one.
R represents a hydrogen atom, an alkyl group, an aryl group, a silyl group,
It consists of an alkyl halide, an aryl halide and any combination thereof, and has 20 or less non-hydrogen atoms. When there are a plurality of Rs, they may be the same or different. A ring may be formed between the R group and another R group, or between the R group and Y ¹ . ) 5. Cp in the general formula (V) is η in M ¹
Cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, substituted fluorenyl group, hexahydroazulenyl group, substituted hexahydroazulenyl group, tetrahydroindenyl group bonded in a ^5- bond mode , A substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group, an octahydrofluorenyl group, a substituted octahydrofluorenyl group, wherein Y ¹ is O, S, NR, PR or CR ₂ or where oR, SR, claim 4 is a two-electron donating ligand of any one neutral selected from NR ₂ or PR ₂
A method for producing the ethylene-cyclic olefin copolymer described in the above. 6. The method according to claim 1, wherein (b) is an organoaluminum compound and / or
The method for producing an ethylene-cyclic olefin copolymer according to any one of claims 1 to 5, wherein the method is a clay-based compound treated with an organic silane compound. 7. The method for producing an ethylene-cyclic olefin copolymer according to claim 1, wherein (c) is an organoaluminum. 8. The cyclic olefin is represented by the following general formula (VI):
The ethylene according to any one of claims 1 to 7, wherein
A method for producing a cyclic olefin copolymer. Embedded image(In the formula (VI), R^a~ R^lIs hydrogen atom and carbon number respectively
1 to 20 hydrocarbon groups or halogen atoms, oxygen atoms,
Or a substituent containing a nitrogen atom, and n is an integer of 0 or more.
Show. RⁱOr R^jAnd R^kOr R^lAnd form a ring with each other
Is also good. Also, R ^a~ R^lAre the same or different
It may be. )