JP3207891B2 - Method for producing cyclic olefin polymer - Google Patents

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 a cyclic olefin polymer, and more particularly, to a cyclic olefin homopolymer and a cyclic olefin / α-olefin copolymer obtained by polymerizing a cyclic olefin without ring opening. And a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Cyclic olefins are known to polymerize with Ziegler-Natta catalysts, but ring-opened polymers are often obtained. On the other hand, as means for polymerizing a cyclic olefin without ring opening, there are the following examples (a) to (e). (A) JP-A-64-66216 discloses a catalyst comprising a stereorigid metallocene compound, particularly ethylenebis (indenyl) zirconium dichloride and aluminoxane, as a means for isotactically polymerizing a cyclic olefin without opening the ring. Are described. (B) JP-A-61-271308 discloses a method using a catalyst comprising a soluble vanadium compound and an organoaluminum compound as a means for copolymerizing a cyclic olefin and an α-olefin without opening the cyclic olefin. Is described.

(C) JP-A-61-221206, JP-A-64-221206
No. 106 describes a method using a catalyst comprising a transition metal compound and an aluminoxane as a means for copolymerizing a cyclic olefin and an α-olefin without opening the cyclic olefin. (D) JP-A-62-25240
No. 6 discloses that an ethylene content of 40 is obtained using a catalyst comprising a soluble vanadium compound and an organoaluminum compound.
It is described to produce ~ 90 mol% ethylene / cyclic olefin random copolymer. (E) JP-A-3-45612 discloses a method for producing homopolymers and copolymers of polycyclic olefins using a catalyst comprising a specific metallocene compound and an aluminoxane.

However, the above-mentioned polymerization methods (a) and (c) both use aluminoxane in a large amount.
A large amount of metal remains in the product after polymerization, causing deterioration, coloring, and the like. For this reason, there is a problem in productivity and the like that the product must be sufficiently demineralized after the polymerization. Further, the catalysts of (b) and (d) have a drawback that the activity is extremely low. Moreover, the ethylene-rich copolymer obtained with the catalyst (d) has a distinct melting point and poor randomness. Further, in the publication of (e), it is not shown in Examples that a copolymer having a cyclic olefin content of 40 mol% or more can be produced, and there is a disadvantage that a large amount of aluminoxane is used.

On the other hand, the polymerization of olefins with cationic transition metal complexes has been studied for a long time, and many reports have been made as shown in the following (f) to (h). There's a problem. (F) Natta et al. Report that ethylene is polymerized using titanocene dichloride / triethylaluminum as a catalyst (J. Polymer Sci., 26 , 120 (1964)). Also,
Breslow et al. Report the polymerization of ethylene by titanocene dichloride / dimethylaluminum chloride catalyst (J. Am. Chem. Soc., 79 , 5072 (1957)). In addition, Dyac
hkovskii et al. reported that the polymerization activity of ethylene with a titanocene dichloride / dimethylaluminum chloride catalyst was
It is suggested that it is due to titanocene monomethyl cation (J. Polymer Sci., 16 , 2333 (1967)). However, the ethylene activity in these methods is extremely low.

(G) Jordan et al. Disclose zirconocene dimethyl
Of biscyclope by the reaction of
Nantadienyl zirconium methyl (tetrahydrofura
N)] [tetraphenyl boric acid]
Reported the polymerization of ethylene by it (J. Am. Ch.
em.Soc.,108, 7410 (1986)). In addition, Jordan et al.
Nosenedibenzyl and ferrocenium tetraphenylborate
[Biscyclopentadienyl zirconium
Umbenzyl (tetrahydrofuran)] [tetraphenyl
Ruboric acid] has been synthesized and isolated (J. Am. Chem. Soc.,Ten
9, 4111 (1987)). However, these catalysts do not
Although polymerization was confirmed to be slight, the polymerization activity
Sex is extremely low.

(H) Turner et al. Describe a boron complex containing a specific amine such as triethylammonium tetraphenylborate, triethylammonium tetratolylborate or triethylammonium tetrakis (pentafluorophenyl) borate, and a metallocene compound as a catalyst. A polymerization method has been proposed (Japanese Patent Publication No. 1-502036). However, there is no description in these publications regarding polymerization of cyclic olefins or copolymerization of α-olefins with cyclic olefins. Further, these methods have extremely low activities and cannot be used industrially.

The present invention has been made in view of the above circumstances, and a cyclic olefin homopolymer or a cyclic olefin / α-olefin copolymer obtained by polymerizing without using a large amount of an organometallic compound and without opening the cyclic olefin. An object of the present invention is to provide a method capable of efficiently producing a polymer.

[0009]

According to the present invention, in order to achieve the above object, the present invention relates to homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an α-olefin with the following compounds (A) and (B). Provided is a method for producing a cyclic olefin-based polymer, which is performed using a catalyst containing a main component or a catalyst containing the following compounds (A), (B), and (C) as a main component. (A) Transition metal compound (B) Compound which reacts with a transition metal compound to form an ionic complex (C) Organoaluminum compound In particular, according to one embodiment of the present invention, the following compounds (A) and (B) or A cycloolefin-based polymer characterized by performing homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an α-olefin using a catalyst containing the following compounds (A), (B) and (C) as main components: Is provided. (A) a transition metal compound containing a tetravalent transition metal selected from group IVB of the periodic table (B) (A) a compound which reacts with the transition metal compound to form an ionic complex Excluding reaction products of (i) a bis (cyclopentadienyl) group IVB metal compound represented by the following general formulas 1-4 and (ii) an activator compound represented by the following general formula 5 .

Embedded image In the above formula, M is a Group IVB metal, and (A-Cp)
Is either (Cp) (Cp ^* ) or Cp-A'-Cp ^* , wherein Cp and Cp ^* are the same or different, substituted or unsubstituted cyclopentadienyl groups, and A 'is a covalent cross-linked L is an olefin, diolefin or alliin ligand; X ₁ and X ₂ are each independently a hydride group, hydrocarbyl group, substituted hydrocarbyl group or organic metalloid group; X ′ ₁ and X ′ ₂ Are bonded together to a metal to form a metal ring, and the metal atoms M and X ′
But ₁ and X _'2 is intended to form a hydrocarbon ring of from about 3 to about 20 carbon atoms, and R is bonded to the metal atom M in the substituent groups present in one cyclopentadienyl group is there. 5. [(L'-H) ⁺ ] _d [(M ') ^{m +} Q ₁ Q ₂ ... Q _n ] ^{d-In the} above formula, L' is a neutral Lewis base, H is a hydrogen atom, and [( L′-H)] is a Bronsted acid, and M ^′
Is a metal or metalloid selected from each group of VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA;
Q ₁ to Q _n independently represent a hydride group, a dialkylamide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a substituted hydrocarbyl group or an organic metalloid group, and any one of Q ₁ to Q _n One (but only one) may be a halide group, and m is 1 to 7
Where n is an integer of 2 to 8, and nm = d. (C) Organoaluminum Compound In the above production method, a compound not included in the above general formula 5 can be used as the compound (B). In particular,
Ferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate,
And compounds such as trityl tetrakis (pentafluorophenyl) borate.

Hereinafter, the present invention will be described in more detail.
FIG. 1 shows the manufacturing method of the present invention. In the present invention,
A transition metal compound is used as the compound (A). Here, as the transition metal compound, a transition metal compound containing nickel and a transition metal belonging to Group IVB of the periodic table can be used. Specifically, titanium, zirconium, and hafnium are preferable as the transition metals belonging to Group IVB.

Such transition metal compounds include various compounds. In particular, compounds containing a transition metal of Group IVB and nickel, particularly a transition metal selected from Group IVB of the periodic table, ie, titanium (Ti) , Zirconium (Zr) or hafnium (Hf) -containing compounds can be suitably used, and particularly the following general formulas (I) and (II)
Alternatively, a cyclopentadienyl compound represented by (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. As a compound containing nickel, nickel bis (acetylacetonate) can be given. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 d R 2 e ... (II) (Cp-A f -Cp) M 1 R 1 d R 2 e ... (II
_{^{I) M 1 R 1 g R}} 2 h R 3 i R 4 j ... (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr
Or Hf atom, Cp is a cyclopentadienyl group,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl 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, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
Σ-binding ligands such as aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, substituents containing silicon atoms, acetylacetonate groups, A chelating ligand such as a substituted acetylacetonate group or a ligand such as a Lewis base is shown, and A represents a crosslink by a covalent bond.
a, b and c are each an integer of 0-3, d and e are each an integer of 0-2, f is an integer of 0-6, and g, h, i and j are each an integer of 0-4. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

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 as a Lewis base Ethers 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 the covalent bond of A include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a 1,1′-cyclohexylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethylstannylene crosslink.

Examples of such compounds include the following compounds and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compounds 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) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
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,

Compounds of the formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
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

The compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) do not impair the effects. Examples of such compounds include compounds of formula (IV) above, for example, tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium,
Tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2
5-di-t-butylphenoxy) dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), or hafnium,
Zirconium compounds, hafnium compounds, and titanium compounds having one or more of an alkyl group, an alkoxy group, and a halogen atom such as a compound replaced with titanium.

[0018]

[0019]

[0020]

[0021]

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bonded anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bonded to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or R ¹¹ M ⁶⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are groups VB, VIB and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, VIII
Family, IA Group, IB, Group IIA, element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 carbon atoms
Aryloxy group having 20 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms an acyloxy group, an organic metalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7; n is an integer of 2 to 8; k is an integer of 1 to 7 as an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ are B, Al, Si, P, As, Sb , etc., M ⁵
Specific examples of Li, Na, Ag, Cu, Br, I,
Specific examples of M ⁶ such as I _{3 and the} like are Mn, Fe, Co, Ni,
Zn and the like can be mentioned. Specific examples of Z ¹ to Z ⁿ may, for example, dimethylamino group as a dialkylamino group, a diethylamino group; methoxy group as an alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group; carbons 6-2
0 aryloxy groups such as phenoxy, 2,6-dimethylphenoxy, and naphthyloxy;
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group as 0 alkyl group; aryl group having 6 to 20 carbon atoms, alkylaryl group or aryl Examples of the alkyl group include phenyl, p-tolyl, benzyl, 4-tert-butylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl, and 2,3-dimethylphenyl. Dimethylphenyl group;
Examples of the 20 halogen-substituted hydrocarbon groups include p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, 3,4,5-trifluorophenyl, pentafluorophenyl, and 3,5-bis (trifluoro Methyl) phenyl group; F, Cl, B as halogen atoms
r, I: Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include the same as those described above. R ⁸
And specific examples of the substituted cyclopentadienyl group for R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. here,
The alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected from an integer of 1 to 5.
Among the compounds of the formulas (V) and (VI), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V) Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenyltetraborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-tetrakis (pentafluorophenyl) borate)
Butyl) ammonium, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrabutylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate Butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate tetrakis (pentafluorophenyl) Dimethylammonium borate, Anilinium tetrakis (pentafluorophenyl) borate, Teto Methylanilinium lakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), tetrakis Dimethyl (pentafluorophenyl) borate (p-bromoanilinium), pyridinium tetrakis (pentafluorophenyl) borate, p-cyanopyridinium tetrakis (pentafluorophenyl) borate, N-methylpyridinium tetrakis (pentafluorophenyl) borate ), Tetrakis (pentafluorophenyl) borate (N-benzylpyridinium), tetrakis (pentafluorophenyl) borate (o-cyano-N-methylpirate) Dinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis Benzyldimethylsulfonium (pentafluorophenyl) borate, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [3,5-bis (trifluoromethylphenyl)] borate, triethylammonium hexafluoroarsenate,

[0027]Compound of formula (VI)  Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin man
Cancer), ferroseni tetrakis (pentafluorophenyl) borate
, Tetrakis (pentafluorophenyl) borate (1,1 ′
-Dimethylferrocenium, decamethyl tetrakis (pentafluorophenyl) borate
Ferrocenium, acetyltetrakis (pentafluorophenyl) borate
Ferrocenium, formylph tetrakis (pentafluorophenyl) borate
Ferrocenium, cyanotetrakis (pentafluorophenyl) borate
Rosenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate
Tetrakis (pentafluorophenyl) borate (tetraf
Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraf
Phenylporphyrin iron chloride), tetrakis (pentafluorophenyl) borate (tetraf
Zinc porphyrin), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate,

Compounds other than formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used. is there.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following formulas (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisobutyl Examples include aluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0030]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization and is usually from 3 to 50.)

[0031]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3 to 50.) A cyclic alkylaluminoxane having a repeating unit represented by the formula: Among the compounds of the formulas (VII) to (IX),
Preferred are compounds of the formula (VII), particularly preferred are compounds of the formula (VII) with r = 3, among which trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum.

As a method for producing the aluminoxane, a method in which an alkylaluminum is brought into contact with a condensing agent such as water may be mentioned. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminoxane with a trialkylaluminum, and further reacting water.

The catalyst used in the present invention comprises the above component (A) and component (B) or the above component (A), component (B) and component (C) as main components. in this case,
The use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.
01 to 1: 100, particularly 1: 0.5 to 1:10, preferably 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of component (C) used is generally 0 to 2,000 mol, preferably 5 to 2000 mol per mol of component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable. The use form of the catalyst is not limited. For example, the components (A) and (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. May be used.
Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance. The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system.

In the production method of the present invention, the homopolymerization of a cyclic olefin or the copolymerization of a cyclic olefin and an α-olefin is carried out using the above catalyst. In this case, examples of the cyclic olefin include the following. Monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene; substituted monocyclic olefins such as 3-methylcyclopentene and 3-methylcyclohexene; norbornene;
1,2-dihydrodicyclopentadiene, 1,4,5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Polycyclic olefins such as octahydronaphthalene;

1-methylnorbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 5-chloronorbornene, 5-chloronorbornene Fluoronorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5-chloromethylnorbornene,
5-methoxynorbornene, 7-methylnorbornene,
5,6-dimethylnorbornene, 5,5-dichloronorbornene, 5,5,6-trimethylnorbornene, 5,
5,6-trifluoro-6-trifluoromethylnorbornene, 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-
Substituted polycyclic olefins such as 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Among these, polycyclic olefins, particularly norbornene or derivatives thereof, are particularly preferred.

As the α-olefin to be copolymerized with the cyclic olefin, for example, those having 2 to 25 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene are preferably used. Can be. Particularly preferred among these is ethylene. Further, in the production method of the present invention, a copolymerizable unsaturated monomer component other than those described above may be used, if necessary. As such unsaturated monomers that may be optionally copolymerized, specifically, those not previously used among α-olefins, those not previously used among cyclic olefins,
Examples thereof include cyclic dienes such as ethylidene norbornene, dicyclopentadiene and norbornadiene, and chain dienes such as butadiene, isoprene and 1,5-hexadiene.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is preferably -100 to 250C, particularly preferably -50 to 200C. The ratio of the catalyst to the reaction raw material is such that the raw material monomer / component (A) (molar ratio) or the raw material monomer / component (B) (molar ratio) is 1 to 1.
0 ^9, it is preferable that the particular 100 to 10 ^7. Further, the polymerization time is usually from 1 minute to 10 hours, and the reaction pressure is from normal pressure to
100 kg / cm ² G, preferably normal pressure to 50 kg / c
m ² G. As a method for adjusting the molecular weight of the polymer, the amount of each catalyst component used, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can be performed.

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 combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent.

According to the production method of the present invention, a cyclic olefin
When an α-olefin copolymer is produced, the ratio of the structural unit derived from the α-olefin to the structural unit derived from the cyclic olefin is from 0.1: 99.9 to 99.9: 0.
In 1, it is possible to obtain a copolymer in which each structural unit is randomly arranged and is substantially linear. The fact that the copolymer is substantially linear can be confirmed by completely dissolving the copolymer in decalin at 135 ° C. In this case, a copolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 20 dl / g can be obtained.

[0041]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, physical properties were measured as follows. Mw, Mn, Mw / Mn JPC's GPC-880 [column; TSK's TSK
GMH-6 × 1, GL-A120 × 1, G made by Hitachi, Ltd.
LA-130 × 1], solvent; chloroform, temperature; 23
° C, measured in terms of polystyrene. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Norbornene content From the ratio of the sum of a peak based on ethylene and a peak based on methylene at the 5th and 6th positions of norbornene and a peak based on a methylene group at 7th position of the norbornene appearing at around 32.5 ppm, in ^13C -NMR, I asked. Crystallinity Using a test piece prepared by hot pressing, X at room temperature
It was determined by a line diffraction method.

As a glass transition temperature (Tg) measuring device, Vibron II- manufactured by Toyo Boulding Co., Ltd.
Using EA type, width 4mm, length 40mm, thickness 0.1m
m heating rate 3 ° C. / min measurement piece, measured at a frequency 3.5 Hz, the heating was determined from the peak of loss modulus at this (E "). The softening temperature (TMA) copolymer to 250 ° C. Then, a test sheet was cut out from the sheet, and its softening temperature (TMA) was measured using a TMA-100 manufactured by Seiko Denshi Co., Ltd. applying a load of area per 3 g / mm @ 2, by 10 ° C. / heated at a heating rate of minute sheet was temperature in broken. crystallization temperature Perkin Elmer 7 Series DSC, 1
The temperature was raised to 150 ° C at 0 ° C / min, and after holding for 60 seconds, 10 ° C
The temperature was lowered to −50 ° C./min. It carried out according to JIS-K7113 using the tensile characteristic autograph. Total light transmittance, Haze Digital Haze Computer (DIGITAL HAZE COMPU
TER) (manufactured by Suga Test Instruments Co., Ltd.)
The measurement was performed according to 7105.

[0043]Example 1  (1) Tritetrakis (pentafluorophenyl) borate
Preparation of ethylammonium Bromopentafluorobenzene (152 mmol) and
Pentaph prepared from butyllithium (152) mmol
Fluorophenyllithium with 45 mmol of boron trichloride
The reaction was performed in hexane. Tris (pentafluorofe
Nyl) boron was obtained as a white solid. Tris obtained
Pentafluorophenyl) boron (41 mmol) and penta
Reacted with fluorophenyllithium (41 mmol)
To make tetrakis (pentafluorophenyl)
L) Lithium borate was isolated as a white solid. Next,
Lithium trakis (pentafluorophenyl) borate (1
6 mmol) and triethylamine hydrochloride (16 mmol)
With tetrakis (pe)
N-fluorophenyl) triethylammonium borate
12.8 mmol were obtained as a white solid.

The fact that the product is the desired product means that ¹ H-
Confirmed by NMR and ¹³ C-NMR. ¹ H-NMR (THFd ₈ ): -CH ₃ 1.31 ppm -CH ₂ -3.27 ppm ¹³ C-NMR: -C ₆ F ₅ 150.7, 147.5, 140.7, 1
_{38.7,137.4,133.5ppm - C H 2 - 48.2ppm -} C H 3 9.1ppm

(2) Preparation of catalyst 1 mmol of (cyclopentadienyl) trimethylzirconium and 1 mmol of triethylammonium tetrakis (pentafluorophenyl) borate were mixed with 50 ml of toluene.
For 4 hours at room temperature. After evaporating the solvent, the solid was washed with 20 ml of petroleum ether. After drying toluene 5
It was dissolved in 0 ml to obtain a catalyst solution.

(3) Polymerization In a 100 ml flask, 25 mmol of cyclopentene, 0.05 mmol of a catalyst as a transition metal component and 25 ml of toluene were added and reacted at 20 ° C. for 4 hours. The reaction mixture was poured into methanol, and the precipitated white solid was collected by filtration, washed with methanol and dried. The yield was 0.61 g. The polymerization activity is 0.13 kg / gZr (12 kg / mol
-Zr). As a result of molecular weight measurement by GPC, Mw
Was 8200 and Mw / Mn was 2.6. In addition, ¹ H
From -NMR, no absorption based on the carbon-carbon double bond was observed at 5.7 ppm, and further, from the infrared absorption spectrum, it was found that polymerization was carried out while retaining the ring.

[0047]Example 2  In a 100 ml flask, 25 mM cyclopentene
, (Cyclopentadienyl) tribenzylzirconium
0.05 mmol, tetrakis (pentafluorofe
Nyl) 0.05 mmol of triethylammonium borate
The reaction was carried out in 50 ml of toluene. Reaction at 20 ° C for 4 hours
After that, pour the reaction mixture into 100 ml of methanol.
Was. The white precipitate was collected by filtration and washed with 50 ml of methanol.
After drying under reduced pressure, 0.58 g of a white powder was obtained. Heavy
The total activity is 0.13 kg / gZr (12 kg / mol-Zr).
Was. As a result of measuring the molecular weight by GPC, Mw was 940.
0, Mw / Mn was 2.6.

[0048]Example 3  In a 100 ml flask, 25 mmol of norbornene
(However, norbornene is the same solvent as the polymerization solvent.
It was used after being diluted to weight%. The same applies to the following examples and comparative examples.
), (Pentamethylcyclopentadienyl) tri
0.05 mmol of methyl zirconium, tetrakis (pe
(Nantafluorophenyl) triethylammonium borate
0.05 mmol was reacted in 50 ml of toluene.
After stirring for 4 hours at 20 ° C., the reaction mixture was
A white solid precipitated upon opening to 00 ml. After filtering this
Upon drying, 0.51 g of solid was obtained. The polymerization activity is
It was 0.11 kg / gZr (10 kg / mol-Zr). G
As a result of molecular weight measurement by PC, Mw was 12000, Mw
/ Mn was 2.3.

[0049]Example 4  200ml dry toluene in a 500ml glass container
After charging 21 mmol of norbornene, ethylene gas was flowed.
And kept at 50 ° C. for 10 minutes. After that, screw
Clopentadienyl) dimethyl zirconium 0.05mm
Limol, tetrakis (pentafluorophenyl) borate
Addition of 0.05 mmol of triethylammonium and polymerization
Started. After polymerization for 1 hour at 50 ° C.,
The polymerization was stopped with a tool. This was collected by filtration and dried.
8 g of the copolymer was obtained. Polymerization activity is 0.39 kg / gZ
r (36 kg / mol-Zr). The intrinsic viscosity [η] is 1.
38 dl / g, norbornene content was 12 mol%.
Was.

[0050]Reference Example 3  (1) Preparation of catalyst Ethylene bis (indenyl) dimethyl zirconium
Limol and tetrakis (pentafluorophenyl) borate
1 mmol of riethyl ammonium and 50 ml of toluene
The reaction was carried out at 20 ° C. for 4 hours. The solvent was distilled off
Afterwards, the solid was washed with 20 ml of petroleum ether. After drying
It was dissolved in 50 ml of ruene to prepare a catalyst solution.

(2) Polymerization In a 100 ml flask, 25 mmol of cyclopentene, 0.05 mmol of a catalyst as a transition metal component, and 25 ml of toluene were added and reacted at 20 ° C. for 4 hours. The reaction mixture was poured into methanol, and the precipitated white solid was collected by filtration. The yield was 0.84 g. Polymerization activity is 0.18k
g / gZr (16.8 kg / mol-Zr). As a result of measuring the molecular weight by GPC, Mw was 7,800 and Mw / Mn was 2.8. 5.7 ppm from ¹ H NMR.
No absorption based on a carbon-carbon double bond was observed, and it was found from the infrared absorption spectrum that the polymer was polymerized while retaining the ring.

[0052]Reference example 4  In a 100 ml flask, 25 mM cyclopentene
, Ethylenebis (indenyl) dimethylzirconium
0.05 mmol, tetrakis (pentafluorophenyl)
G) triethylammonium borate 0.05 mmol
The reaction was carried out in 50 ml of Ruen. Reaction at 20 ° C for 4 hours
After that, the reaction mixture was poured into 100 ml of methanol.
The white precipitate was collected by filtration, washed with 50 ml of methanol, and
Drying yielded 0.63 g of a white powder. The polymerization activity is
0.14 kg / g Zr (12.6 kg / mol-Zr)
Was. As a result of molecular weight measurement by GPC, Mw was 9000,
Mw / Mn was 2.7.

[0053]Reference example 5  In a 100 ml flask, 25 ml of norbornene
Limol, ethylenebis (indenyl) dimethyl zirconi
0.05 mmol, tetrakis (pentafluorop
Enyl) trimethylammonium borate 0.05 mmol
Was reacted in 50 ml of toluene. Stir at 20 ° C for 4 hours
After stirring, pour the reaction mixture into 100 ml of methanol
, A white solid precipitated. After this is filtered and dried,
0.49 g of a solid was obtained. Polymerization activity is 0.11kg / g
Zr (9.8 kg / mol-Zr). GPC molecules
As a result of the measurement, Mw was 10500 and Mw / Mn was 2.1.
Met.

[0054]Example 8  Triethyl tetrakis (pentafluorophenyl) borate
Instead of ammonium tetrakis (pentafluorophene)
Nil) Same as Reference Example 5 except that ferrocenium borate was used.
Was performed in the same manner. The yield was 0.82 g. The polymerization activity is
0.18 kg / gZr (16.4 kg / mol-Zr)
Was. As a result of molecular weight measurement by GPC, Mw was 9800,
Mw / Mn was 2.6.

[0055]Example 9  Triethyl tetrakis (pentafluorophenyl) borate
Instead of ammonium tetrakis (pentafluorophene)
Nil) except that silver borate was used.
Was. The yield was 0.56 g. Polymerization activity is 0.12k
g / gZr (11.2 kg / mol-Zr). GPC
As a result of molecular weight measurement, Mw was 8900 and Mw / Mn was
2.4.

[0056]Example 10  Triethyl tetrakis (pentafluorophenyl) borate
Instead of ammonium tetrakis (pentafluorophene)
Nyl) except that trityl borate was used.
became. The yield was 0.64 g. The polymerization activity is 0.1
It was 4 kg / gZr (12.8 kg / mol-Zr). GP
As a result of molecular weight measurement by C, Mw was 9100, Mw / M
n was 2.3.

[0057]Reference Example 6  100 ml of toluene in a glass container replaced with argon,
Cyclopentene 25 mmol, tetrakis (pentaflu
Orophenyl) triethylammonium borate 0.01
Limol, 0.2 mmol of triisobutylaluminum,
Ethylene bis (indenyl) dimethyl zirconium
After adding 01 mmol and reacting at 20 ° C. for 1 hour,
The reaction was stopped with methanol. Dry the white solid after filtering
Then, 0.85 g of an individual was obtained. The polymerization activity is 0.93kg
/ GZr (85 kg / mol-Zr). Minutes by GPC
As a result of the measurement of the molecular weight, Mw was 11,000 and Mw / Mn was
2.3.

[0058]Example 12  200ml dry toluene in a 500ml glass container
After charging 25 mmol of norbornene, ethylene gas
And kept at 50 ° C. for 10 minutes. Then Echile
Nbis (indenyl) dimethyl zirconium 0.01
Limol, tetrakis (pentafluorophenyl) borate
Addition of 0.01 mmol of triethylammonium, polymerization
Started. After polymerization for 1 hour at 50 ° C.,
The polymerization was stopped with a tool. This was filtered and dried, and 2.1 g of
A copolymer was obtained. The polymerization activity was 2.3 kg / gZr (21
0 kg / mol-Zr). The intrinsic viscosity [η] is 1.40d
1 / g, norbornene content was 10 mol%.

[0059]Example 13  200 ml of dry toluene in a 500 ml glass container,
Norbornene 21 mmol, triisobutylaluminum
0.2 mmol, ethylenebis (indenyl) dimethy
Luzirconium 0.01 mmol, tetrakis (penta
Fluorophenyl) triethylammonium borate 0.0
1 mmol was added and kept at 50 ° C. for 10 minutes. That
Thereafter, ethylene gas was passed, and polymerization was carried out for 1 hour. Me
The polymerization was stopped with ethanol, and the resulting copolymer was collected by filtration and dried.
Drying yielded 6.3 g of solid. The polymerization activity is 6.9 kg /
gZr (630 Kg / mol-Zr). Intrinsic viscosity [η]
Is 2.15 dl / g and the norbornene content is 8 mol%.
Was.

[0060]Example 14  200ml dry toluene in a 500ml glass container
After charging 25 mmol of norbornene, ethylene gas
And kept at 50 ° C. for 10 minutes. After that,
Tylsilylenebis (cyclopentadienyl) dimethyldi
Ruconium 0.05 mmol, tetrakis (pentaflu
Orophenyl) triethylammonium borate 0.05
Limol was added to initiate polymerization. Polymerization at 50 ° C for 1 hour
After that, polymerization was stopped with methanol. Filter this
After drying, 4.0 g of a copolymer was obtained. The polymerization activity is 0.
It was 88 kg / gZr (80 kg / mol-Zr). Extreme viscosity
The degree [η] is 1.36 dl / g and the norbornene content is 38.
Mole%.

Comparative Example 1 100 ml of toluene was placed in a glass container replaced with argon.
25 mmol of cyclopentene, 0.2 mmol of aluminoxane and 0.05 mmol of ethylenebis (indenyl) dichlorozirconium were added. The reaction was carried out at 20 ° C. for 1 hour, but no polymer was obtained.

Comparative Example 2 After 200 ml of dry toluene and 21 mmol of norbornene were charged into a 500 ml glass container, ethylene gas was passed through the container, and the mixture was kept at 20 ° C. for 10 minutes. Subsequently, 0.2 mmol of aluminoxane and 1.25 × 10 ^-2 mol of bis (cyclopentadienyl) dichlorozirconium were added to initiate polymerization, and polymerization was performed at 20 ° C. for 1 hour.
No polymer was obtained.

Comparative Example 3 A 500 ml glass container was charged with 200 ml of dry toluene and 21 mmol of norbornene, and 0.2 mmol of aluminoxane and 0.01 mmol of dimethylsilylenebis (cyclopentadienyl) dichlorozirconium were added. For 10 minutes. Thereafter, ethylene gas was passed and polymerization was carried out for 1 hour, but no polymer was observed.

[0064]Example 15  (1) [Cp_TwoFe] [B (C₆F_Five)_Four(Jolly, W.L.The Synthesis and Characterization of I
norganic Compounds; Prentice-Hall: Englewood Cliff
s, NJ, synthesized by 1970, P487) Ferrocene (3.7 g, 2
0.0 mmol) and 40 ml of concentrated sulfuric acid at room temperature for 1 hour.
Upon reaction, a dark blue solution was obtained. This one liter
The resulting solution was poured into water and stirred, and the resulting deep blue aqueous solution was subjected to Li [B
(C₆F_Five)_Four] (13.7 g, 20.0 mmol: J. Org
anometal.Chem.,Two(Synthesized by the method of (1964) 245)
The solution was added to 500 ml. The falling pale blue precipitate is collected by filtration.
After washing 5 times with 500 ml of water,
The desired product [tetrakis (pentafluorofur
Enyl) ferrocenium borate] 14.7 g (17 mmol
Le) was obtained.

(2) Polymerization In a 1-liter autoclave, dry toluene 400 m
l, 0.05 mmol of ferrocenium tetrakis (pentafluorophenyl) borate, 0.05 mmol of bis (cyclopentadienyl) dimethylzirconium, and 100 mmol of norbornene, 50 ° C., ethylene pressure 5k
When polymerization was performed at g / cm ² for 4 hours, 5.3 g of a copolymer was obtained. The polymerization activity was 1.2 kg / gZr. The norbornene content is 2 mol%, the intrinsic viscosity [η] is 2.24.
dl / g and crystallinity were 8%.

[0066]Example 16  400 m of dry toluene in a 1 liter autoclave
1, 0.6 mmol of triisobutylaluminum, tet
Lakis (pentafluorophenyl) borate ferrocenium
0.03 mmol, bis (cyclopentadienyl) dim
0.03 mmol of tilzirconium, norbornene 20
0 mmol, 50 ° C., ethylene pressure 5 kg / cm
^TwoAfter polymerization for 0.5 hour, stop the polymerization with methanol
Was. This was filtered and dried to obtain 71 g of a copolymer.
Polymerization activity, norbornene content, [η] and crystallinity
26 kg / g Zr, 7 mol%, 2.10 dl /
g, 6%.

[0067]Example 17  In Example 16, tetrakis (pentafluorophenyl)
F) Tetrakis (pentaf) instead of ferrocenium borate
Fluorophenyl) boric acid (1,1′-dimethylferrocenic)
The polymerization was carried out in the same manner except that
4 g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] and crystallinity were 23 kg / gZr and 7
%, 1.72 dl / g and 7%.

[0068]Example 18  In Example 16, tetrakis (pentafluorophenyl)
F) Tetrakis (pentaf) instead of ferrocenium borate
Fluorophenyl) dimethylanilinium borate
Polymerization was performed in the same manner except that the total time was changed to 4 hours.
Then, 30 g of a copolymer was obtained. Polymerization activity, norbornene
The content, [η] and crystallinity were each 11 kg / gZ
r, 7 mol%, 1.54 dl / g, 8%.

[0069]Example 19  400 m of dry toluene in a 1 liter autoclave
1, 0.4 mmol of triisobutylaluminum, tet
Lakis (pentafluorophenyl) boric acid (1,1'-di
Methyl ferrocenium) 0.02 mmol, bis (sic)
Lopentadienyl) dimethyl zirconium 0.02mm
Mol, norbornene 260 mmol, 50 ° C,
Ethylene pressure 5kg / cm^TwoPolymerization for 1 hour
5 g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] and crystallinity were 52 kg / gZr and 7
%, 1.69 dl / g and 7%.

Example 20 Polymerization was carried out under the same conditions as in Example 16 except that the amount of norbornene charged was 250 mmol and the polymerization temperature was 70 ° C., to obtain 105 g of a copolymer. Polymerization activity,
The norbornene content, [η] and crystallinity were 38
kg / g Zr, 5 mol%, 2.15 dl / g, 8%.

Example 21 Polymerization was carried out under the same conditions as in Example 20 except that the amount of norbornene was changed to 350 mmol.
g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] and crystallinity were 23 kg / gZr and 10 kg, respectively.
Mole%, 1.89 dl / g, 5%.

Example 22 Polymerization was carried out under the same conditions as in Example 16 except that bis (pentamethylcyclopentadienyl) dimethylzirconium was used instead of bis (cyclopentadienyl) dimethylzirconium, and the polymerization time was changed to 4 hours. As a result, 85 g of a copolymer was obtained. The polymerization activity, norbornene content, [η], and crystallinity were 31 kg / g Zr, respectively.
4 mol%, 2.32 dl / g, 9%.

Example 23 Polymerization was carried out under the same conditions as in Example 16 except that bis (cyclopentadienyl) dimethylhafnium was used instead of bis (cyclopentadienyl) dimethylzirconium. As a result, 53 g of a copolymer was obtained. I got The polymerization activity, norbornene content, [η], and crystallinity were each 1
It was 0 kg / gHf, 7 mol%, 1.77 dl / g, 7%.

Example 24 Polymerization was carried out under the same conditions as in Example 16 except that bis (cyclopentadienyl) dimethylbenzylzirconium was used in place of bis (cyclopentadienyl) dimethylzirconium. A coalescence was obtained. The polymerization activity, norbornene content, [η], and crystallinity were 27 kg / g Zr, 6 mol%, 1.85 dl / g, and 8%, respectively.
Met.

Example 25 Polymerization was carried out under the same conditions as in Example 22 except that dimethylsilylenebis (cyclopentadienyl) dimethylzirconium was used instead of bis (pentamethylcyclopentadienyl) dimethylzirconium.
g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] and crystallinity were 14 kg / g Zr, 72 mol%, 2.11 dl / g, and 0%, respectively.

[0076]Comparative Example 4  In Example 15, tetrakis (pentafluorophenyl)
G) Example 1 except that ferrocenium borate was not used.
Performed similarly to 5. As a result, no polymer was obtained.

Comparative Example 5 The procedure of Example 15 was repeated except that bis (cyclopentadienyl) dimethylzirconium was not used. As a result, no polymer was obtained.

Example 26 Polymerization was carried out under the same conditions as in Example 16 except that bis (cyclopentadienyl) dimethylzirconium was used instead of bis (cyclopentadienyl) dimethylzirconium. I got The polymerization activity, norbornene content, [η], and crystallinity were 17 kg / g Zr, 7 mol%, 2.74 dl / g, and 6%, respectively.
Met.

[0079]Example 27  400 m of dry toluene in a 1 liter autoclave
1, triisobutylaluminum 0.6 mmol, bis
(Cyclopentadienyl) dichlorozirconium 0.0
After stirring and stirring, tetrakis (pentaf
(Fluorophenyl) ferrocenium borate 0.045 mmol
And 200 mmol of norbornene, and add
Len pressure 5kg / cm^TwoWas polymerized for 0.5 hour at 6
5 g of the copolymer was obtained. Polymerization activity, including norbornene
The amount, [η] and crystallinity were 48 kg / gZr and 8 kg, respectively.
Mol%, 2.30 dl / g, 5%.

[0080]Example 28  In Example 24, bis (cyclopentadienyl) di
Benzyl zirconium, tetrakis (pentafluorop
Enyl) ferrocenium borate 0.015 mm each
The polymerization was carried out under the same conditions except that the moles were used.
4 g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] and crystallinity are 62 kg / gZr and 6 mol, respectively.
%, 2.13 dl / g and 6%.

Example 29 Polymerization was carried out under the same conditions as in Example 27 except that bis (cyclopentadienyl) monochloromonohydride zirconium was used instead of bis (cyclopentadienyl) dichlorozirconium. A polymer was obtained. The polymerization activity, norbornene content, [η], and crystallinity were 45 kg / gZr, 8 mol%, 2.34 d, respectively.
1 / g, 5%.

Example 30 Polymerization was carried out under the same conditions as in Example 16 except that (cyclopentadienyl) trimethylzirconium was used instead of bis (cyclopentadienyl) dimethylzirconium, and 68 g of the copolymer was obtained. Obtained. Polymerization activity,
The norbornene content, [η] and crystallinity are each 25k
g / gZr, 7 mol%, 2.22 dl / g, 6%.

Example 31 Polymerization was carried out under the same conditions as in Example 22 except that tetrabenzylzirconium was used instead of bis (pentamethylcyclopentadienyl) dimethylzirconium. As a result, 50 g of a copolymer was obtained. The polymerization activity, norbornene content, [η], and crystallinity were each 18 kg / gZ.
r, 6 mol%, 2.50 dl / g, 8%.

[0084]Example 32  In Example 16, tetrakis (pentafluorophenyl)
F) Tetrakis (pentaf) instead of ferrocenium borate
Polymerization was carried out in the same manner except that silver (fluorophenyl) borate was used.
Then, 48 g of a copolymer was obtained. Polymerization activity,
The rubornene content, [η] and crystallinity are each 18 kg
/ GZr, 7 mol%, 1.94 dl / g, 6%
Was.

Example 33 In Example 16, 1,4,4 was used instead of norbornene.
5,8-Dimethano-1,2,3,4,4a, 5,8,8
Polymerization was carried out under the same conditions except that 100 mmol of a-octahydronaphthalene was used to obtain 35 g of a copolymer. Polymerization activity, cyclic olefin content, [η], and crystallinity were 13 kg / g Zr, 5 mol%, 1.5 mol, respectively.
7 dl / g, 9%.

Example 34 Polymerization was carried out under the same conditions as in Example 33 except that dimethylsilylenebis (cyclopentadienyl) dimethylzirconium was used instead of bis (cyclopentadienyl) dimethylzirconium, and the polymerization time was changed to 4 hours. Was carried out to obtain 14 g of a copolymer. The polymerization activity, cyclic olefin content, [η], and crystallinity were each 5 kg / gZ.
r, 39 mol%, 1.61 dl / g, 0%.

[0087]Example 35  400 m of dry toluene in a 1 liter autoclave
1, 0.6 mmol of triisobutylaluminum, tet
Lakis (pentafluorophenyl) borate ferrocenium
0.03 mmol, bis (cyclopentadienyl) dim
0.03 mmol of tilzirconium, norbornene 23
0 mmol and 2 kg / cm of propylene at 50 ° C.
^TwoIs introduced and the total pressure of ethylene is 5 kg / cm^TwoTo be
When continuously fed and polymerized for 1 hour, 41 g
A coalescence was obtained. Polymerization activity, norbornene content, [η],
The crystallinity was 15 kg / gZr, 7 mol%, 1.4, respectively.
7 dl / g, 0%.

[0088]Example 36  400 m of dry toluene in a 1 liter autoclave
1, triisobutylaluminum 0.6 mmol, bis
(Cyclopentadienyl) dichlorozirconium 0.0
After stirring and stirring, tetrakis (pentaf
Benzyl (fluorophenyl) borate (4-cyano) pyridini
0.01 mmol, norbornene 200 mmol
In addition, 90 ° C, ethylene pressure 9Kg / cm^Two0.5 hours in
Upon polymerization, 33 g of a copolymer was obtained. Polymerization activity,
Norbornene content and [η] are each 72 Kg / gZ.
r, 6 mol%, 2.01 dl / g.

[0089]Example 37  In Example 36, tetrakis (pentafluorophene)
Benzyl) for benzyl (4-cyano) pyridinium
Methyl tetra (pentafluorophenyl) borate (2
Example 36 except that -cyano) pyridinium was used.
When polymerization was carried out in the same manner, 15 g of a copolymer was obtained.
Was. The polymerization activity, norbornene content, and [η] were each 3
3 kg / g Zr, 5 mol%, 2.34 dl / g
Was.

[0090]Example 38  In Example 36, tetrakis (pentafluorophene)
Benzyl) for benzyl (4-cyano) pyridinium
And tetrakis (pentafluorophenyl) borate (teto
Laphenylporphine manganese)
When polymerization was carried out in the same manner as in Example 36, 58 g of
A coalescence was obtained. The polymerization activity, norbornene content, and [η]
127 Kg / gZr, 6 mol%, 1.95 dl /
g.

[0091]Example 39  400 ml of dry hexane in a 1 liter autoclave
And 10 ml of toluene and triisobutyl alcohol
Luminium 0.6 mmol, bis (cyclopentadienyl
G) 0.006 mmol of dichlorozirconium, tetra
Dimethylanilini-kis (pentafluorophenyl) borate
Catalyst solution prepared by premixing 0.006 mmol of
The solution was added, and after stirring, 200 mmol of norbornene was added.
90 ℃, ethylene pressure 5Kg / cm^Two0.4 hours heavy
When combined, 10 g of the copolymer was obtained. Polymerization activity,
The rubornene content and [η] are each 18 kg / gZr,
16 mol%, 0.42 dl / g.

Example 40 Polymerization was carried out in the same manner as in Example 39 except that a mixed solvent of 200 ml of hexane and 200 ml of toluene was used instead of 400 ml of dry hexane, and 59 g of the copolymer was obtained. Obtained. The polymerization activity, norbornene content, and [η] were 108 kg / gZr, respectively.
2 mol%, 1.14 dl / g.

[0093]Example 41  In Example 39, dry hexane was used instead of dry hexane.
Using bis (cyclopentadienyl)
0.03 mmol of dichlorozirconium, tetrakis
Dimethylanilinium (pentafluorophenyl) borate
Was changed to 0.03 mmol in the same manner as in Example 39.
As a result of the polymerization, 67 g of a copolymer was obtained. polymerization
The activity, norbornene content, and [η] are each 24 kg /
gZr, 7.2 mol%, 1.26 dl / g.

[0094]Example 42  In Example 16, a substitute for triisobutylaluminum was used.
Instead, trimethylaluminum is replaced by bis (cyclopentane
Bis (cyclo) instead of dienyl) dimethyl zirconium
Lopentadienyl) dichlorozirconium with tetrakis
Substitute for ferrocenium (pentafluorophenyl) borate
Dimethyl tetrakis (pentafluorophenyl) borate
Example 16 was repeated except that luanilinium was used.
When polymerization was carried out in the same manner, 33 g of a copolymer was obtained.
Was. The polymerization activity, norbornene content, and [η] were each 1
2 kg / g Zr, 10 mol%, 2.00 dl / g
Was.

Example 43 Example 42 was repeated except that triethylaluminum was used instead of trimethylaluminum.
Polymerization was carried out in the same manner as in the above to obtain 17 g of a copolymer. The polymerization activity, norbornene content, and [η] were 6.2 Kg / gZr, 10 mol%, and 1.92 dl / g, respectively.

[0096]Example 44  400 m of dry toluene in a 1 liter autoclave
1, triisobutylaluminum 0.4 mmol, bis
(Cyclopentadienyl) dichlorozirconium 0.0
After stirring and stirring, tetrakis (pentaf
Fluorophenyl) methyldiphenylammonium borate
0.006 mmol, norbornene 260 mmol
, 90 ° C, ethylene pressure 6Kg / cm^Two0.5 hours
As a result, 57 g of a copolymer was obtained. Polymerization activity,
The rubornene content and [η] are each 208 kg / gZ.
r, 7.9 mol%, 1.13 dl / g.

Example 45 Polymerization was carried out in the same manner as in Example 42 except that methylaluminoxane was used instead of trimethylaluminum. As a result, 53 g of a copolymer was obtained. The polymerization activity, norbornene content, and [η] were each 1
It was 9 Kg / gZr, 8 mol%, 1.83 dl / g.

[0098]Example 46  400 m of dry toluene in a 1 liter autoclave
l, 0.6 mmol of triisobutylaluminum, bis
(Cyclopentadienyl) dihydrido zirconium
After stirring, tetrakis (pentane) was added.
Fluorophenyl) dimethylanilinium borate 0.00
4 mmol and 200 mmol of norbornene were added, and 90
° C, ethylene pressure 7Kg / cm^TwoFor 0.5 hours
As a result, 48 g of a copolymer was obtained. Polymerization activity, nor
Bornene content and [η] are 263 Kg / gZr, respectively.
It was 4.7 mol%, 1.46 dl / g.

Example 47 In Example 42, except that triisobutylaluminum was used instead of trimethylaluminum and bis (cyclopentadienyl) dimethyltitanium was used instead of bis (cyclopentadienyl) dichlorozirconium.
When polymerization was carried out in the same manner as in Example 42, 31 g of a copolymer was obtained. Polymerization activity, norbornene content, [η]
Are 11 kg / g Ti, 3.6 mol%, 1.83, respectively.
dl / g.

Example 48 Example 42 was repeated except that triisobutylaluminum was used instead of trimethylaluminum and 5-methylnorbornene was used instead of norbornene.
Polymerization was carried out in the same manner as in the above to obtain 38 g of a copolymer. The polymerization activity, cyclic olefin content, and [η] were 14 kg / gZr, 7 mol%, and 1.97 dl / g, respectively.

Example 49 Example 4 was repeated except that 5-benzylnorbornene was used instead of 5-methylnorbornene.
When polymerization was carried out in the same manner as in Example 8, 13 g of a copolymer was obtained. The polymerization activity, cyclic olefin content, and [η] were 4.8 kg / g Zr, 11 mol%, 2.15 dl /
g.

Example 50 Polymerization was carried out in the same manner as in Example 42 except that triisobutylaluminum was used instead of trimethylaluminum and propylene was used instead of ethylene. Obtained. Polymerization activity,
The norbornene content and [η] are each 6.2 kg / gZ.
r, 6.4 mol%, 0.62 dl / g.

[0103]Example 51  400 m of dry toluene in a 1 liter autoclave
l, 0.6 mmol of triisobutylaluminum, bis
(Cyclopentadienyl) dichlorozirconium 0.0
After stirring and stirring, tetrakis (pentaf
Fluorophenyl) dimethylanilinium borate 0.006
And 200 mmol of norbornene,
℃, ethylene pressure 9.5Kg / cm^Two0.5 hours polymerization
As a result, 53 g of a copolymer was obtained. Polymerization activity,
The norbornene content and [η] are each 97 kg / gZ.
r, 5 mol%, 1.43 dl / g.

[0104]Example 52  In Example 51, tetrakis (pentafluorophene)
Nyl) 0.012 mmol of dimethylanilinium borate
Except for using, polymerization was carried out in the same manner as in Example 51.
However, 97 g of a copolymer was obtained. Polymerization activity, norvol
The nene content and [η] were 177 Kg / gZr and 5
%, 1.45 dl / g.

Example 53 Polymerization was carried out in the same manner as in Example 51 except that 1.8 mmol of triisobutylaluminum was used. As a result, 78 g of a copolymer was obtained. The polymerization activity, norbornene content, and [η] were each 143 kg.
/ GZr, 4 mol%, 1.67 dl / g.

[0106]Example 54  In Example 39, tetrakis (pentafluorophene)
Nyl) 0.012 mmol of dimethylanilinium borate
Use, ethylene pressure 30Kg / cm^Two10 minutes weight
Polymerization was carried out in the same manner as in Example 39 except that the polymerization was carried out.
As a result, 78 g of a copolymer was obtained. Polymerization activity, nor
Bornene content and [η] are respectively 143 Kg / gZr,
It was 3 mol% and 1.39 dl / g.

Example 55 Polymerization was carried out in the same manner as in Example 54 except that the polymerization temperature was changed to 130 ° C.
2 g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] is 22 kg / gZr, 4 mol%, 1.6, respectively.
It was 5 dl / g.

[0108]Example 56  (1) Preparation of catalyst solution 500 ml of dry toluene was placed in a 2 liter glass container,
Triisobutylaluminum 10 mmol, bis (six
Lopentadienyl) dichlorozirconium 0.2 mmol
Di, tetrakis (pentafluorophenyl) borate
Add 0.3 mmol of luanilinium to make a catalyst solution.
Was. (2) Continuous polymerization Dry toluene in a 2-liter continuous polymerization autoclave
1 liter, 90 ml of the catalyst solution prepared in (1), nor
Pre-loaded with 360 mmol of Bornene, 90 ° C, ethyl
Pressure 5Kg / cm^TwoFor 0.5 hours. That
After that, 1 liter / hour of toluene and 90 m / hour of the catalyst solution
1, feed norbornene at a rate of 360 mmol / h
At the same time, the amount of polymerization solution in the polymerization
It was continuously extracted so as to be always 1 liter. Ma
In addition, the partial pressure of ethylene in the polymerization vessel is always 5 kg / cm.^TwoTona
While continuously supplying ethylene so that
The temperature was kept at 90C. As a result, 158 g / h
A polymer was obtained. Polymerization activity, norbornene content, [η]
48 Kg / gZr, 5 mol%, 1.64 dl /
g.

Example 57 Example 50 was repeated with the exception that ethylene bis (indenyl) dichlorozirconium was used in place of bis (cyclopentadienyl) dichlorozirconium.
Polymerization was carried out in the same manner as in the above to obtain 23 g of a copolymer. The polymerization activity, norbornene content, and [η] were 8 kg / g Zr, 7 mol%, and 0.76 dl / g, respectively.

Example 58 The procedure of Example 50 was repeated, except that isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium was used instead of bis (cyclopentadienyl) dichlorozirconium. As a result of polymerization, 21 g of a copolymer was obtained. The polymerization activity, norbornene content, and [η] were 8 kg / g Zr and 6, respectively.
8 mol%, 0.54 dl / g.

[0111]Example 59  400 m of dry toluene in a 1 liter autoclave
1, triisobutylaluminum 0.6 mmol, bis
(Cyclopentadienyl) dichlorozirconium 0.0
After stirring and stirring, tetrakis (pentaf
Fluorophenyl) dimethylanilinium borate 0.006
Mmol and norbornene 400 mmol, and 90
° C, ethylene pressure 6Kg / cm^Two, Hydrogen pressure 2Kg / cm^Twoso
When polymerization was performed for 0.5 hour, 8 g of a copolymer was obtained.
Was. The polymerization activity, norbornene content, and [η] are each 2
9 kg / g Zr, 7 mol%, 0.06 dl / g
Was.

[0112]Example 60  In Example 16, bis (cyclopentadienyl) di
Instead of methyl zirconium (cyclopentadienyl
Le) trichlorozirconium, tetrakis (pentaflu
Orophenyl) instead of ferrocenium borate
Dimethylanilinium di (pentafluorophenyl) borate
The polymerization was carried out in the same manner as in Example 16 except that a polymer was used.
As a result, 66 g of a copolymer was obtained. Polymerization activity, nor
Bornene content and [η] were 24 Kg / gZr and 8 respectively.
Molar% was 2.34 dl / g.

Example 61 In Example 60, (pentamethylcyclopentadienyl) trichlorozirconium was used instead of (cyclopentadienyl) trichlorozirconium.
When polymerization was carried out in the same manner as in Example 60, 68 g of a copolymer was obtained. Polymerization activity, norbornene content, [η]
Are 25 kg / g Zr, 6 mol%, 2.51 dl, respectively.
/ G.

Example 62 In Example 60, (pentamethylcyclopentadienyl) trimethylzirconium was used instead of (cyclopentadienyl) trichlorozirconium.
When polymerization was carried out in the same manner as in Example 60, 71 g of a copolymer was obtained. Polymerization activity, norbornene content, [η]
Are 26 Kg / gZr, 7 mol%, 2.47 dl, respectively.
/ G.

Example 63 Polymerization was carried out in the same manner as in Example 60 except that (pentamethylcyclopentadienyl) trimethoxyzirconium was used instead of (cyclopentadienyl) trichlorozirconium. But 65g
Was obtained. Polymerization activity, norbornene content,
[Η] is 24 kg / gZr, 6.5 mol%,
It was 2.68 dl / g.

Example 64 Example 46 was repeated except that 0.002 mmol of tetrabenzylzirconium was used in place of zirconium bis (cyclopentadienyl) dihydride.
Polymerization was carried out in the same manner as in the above to obtain 62.7 g of a copolymer. The polymerization activity, norbornene content, and [η] were 344 g / g Zr, 6.5 mol%, 1.76 dl /, respectively.
g.

Example 65 Polymerization was carried out in the same manner as in Example 64 except that 0.002 mmol of tetrabutoxyzirconium was used instead of tetrabenzylzirconium, and 37.1 g of copolymer was obtained. I got The polymerization activity, norbornene content, and [η] were each 203 g / gZr,
5.5 mol%, 1.89 dl / g.

Example 66 Polymerization was carried out in the same manner as in Example 64 except that 0.002 mmol of tetrachlorozirconium was used instead of tetrabenzylzirconium, and 69.1 g of a copolymer was obtained. I got The polymerization activity, norbornene content, and [η] were 379 g / g Zr and 5, respectively.
It was 5 mol% and 1.71 dl / g.

[0119]Example 67  In Example 51, bis (cyclopentadienyl) di
Bis (cyclopentadiene) instead of chlorozirconium
Nil) dimethylzirconium, tetrakis (pentaflu
Orophenyl) instead of dimethylanilinium borate
Other than using ris (pentafluorophenyl) boron
Was polymerized in the same manner as in Example 51.
2 g of the copolymer was obtained. Polymerization activity, norbornene content,
[Η] is 22 kg / gZr, 8 mol%, 1.6, respectively.
It was 4 dl / g.

Comparative Example 6 In a nitrogen atmosphere, 400 ml of toluene, 8 mmol of ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) were placed in a 1 liter autoclave,
(OC ₂ H ₅ ) Cl ₂ 0.8 mmol, norbornene 13
After adding 0 mmol and raising the temperature to 40 ° C., the reaction was carried out for 60 minutes while continuously feeding ethylene so that the ethylene partial pressure became 3 kg / cm ² . The yield was 6.16 g. The polymerization activity, norbornene content, and [η] were 0.15 kg / gV, 12 mol%, 1.20 dl / g, respectively.
Met.

Example 68 Polymerization was carried out in the same manner as in Example 34 except that the ethylene pressure was 4 kg / cm ² and the polymerization temperature was 70 ° C., and 17 g of a copolymer was obtained. Was.
The polymerization activity, norbornene content, and [η] are each 6.2.
Kg / gZr, 57 mol%, 1.47 dl / g.

[0122]Example 69  30 ml of dry toluene in a 500 ml glass container
Liisobutyl aluminum 5 mmol, nickel bis
(Acetylacetonate) 25 micromol, tetrakis
Dimethylanilinium di (pentafluorophenyl) borate
25 micromoles and 500 millimoles of norbornene
The polymerization reaction was carried out at 50 ° C. for 1 hour.
8 g of the copolymer was obtained. The polymerization activity is 6.53 Kg / gN
i. Mw is 1,210,000 and Mw / Mn is
2.37.

[0123]Example 70  In Example 16, tetrakis (pentafluorophene) was used.
Tetrakis (pen) instead of ferrocenium borate
Tafluorophenyl) dimethylanilinium borate 0.0
Except for using 3 mmol, the weight was the same as in Example 16.
After the combination, 26.4 g of a copolymer was obtained. Heavy
The total activity was 10 kg / gZr. Norbo of copolymer
The ruthenium content is 7.0 mol%, and the intrinsic viscosity [η] is 3.94.
dl / g. This weight is obtained by DSC (temperature drop measurement).
The crystallization temperature of the coalescence was measured. The results are shown in FIG.
You. The measurement was performed using a PerkinElmer 7 series DSC.
Temperature to 150 ° C at a rate of 10 ° C / min.
After that, the temperature was lowered to -50 ° C at 10 ° C / min.

Comparative Example 7 400 ml of toluene, 8 mmol of ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) and VO (O
After adding 0.8 mmol of C ₂ H ₅ ) Cl ₂ and 130 mmol of norbornene, the temperature was raised to 40 ° C., and the reaction was carried out for 180 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7 kg / cm ^2. Done. After completion of the reaction, the polymer solution was poured into 1 liter of methanol to precipitate a polymer, which was collected by filtration and dried. As a result, 35.9 g of a copolymer having a norbornene content of 6.8 mol% and an intrinsic viscosity [η] of 3.28 dl / g was obtained. The polymerization activity is 0.88 kg /
gV. The DSC temperature of the copolymer was measured in the same manner as described above. The results are shown in FIG. From the comparison between FIG. 2 and FIG. 3, the copolymer obtained by the method of the present invention was found to be DSC
In the crystallization peak by (temperature decrease measurement), there is a sub-peak on the high temperature side of the main peak, and it is understood that the resin is a resin having different physical properties from a copolymer obtained by a known catalyst system.

[0125]Example 71  (1) Tritetrakis (pentafluorophenyl) borate
Preparation of ethylammonium Tetrakis (pentafluorophene)
(Nil) 12.8 mol of triethyammonium borate was prepared.
This was suspended in 1280 ml of toluene and the catalyst solution
And (2) dimethylsilylenebis (cyclopentadienyl)
Preparation of dichlorozirconium 1.73 g (9.
19 mmol) of dicyclopentadienyldimethylsila
And 1.55 mol / l of butyl resin
12.0 ml (18.6 mM
Over 1 hour while cooling to -75 ° C
did. After stirring for 30 minutes, the temperature was raised to 0 ° C. this
In addition, 2.14 g of zirconium tetrachloride (9.18 mmol
Liquid) dissolved in 50 ml of dehydrated tetrahydrofuran
Was added dropwise over 1 hour and then stirred at room temperature overnight.
Was. After heating at 50 ° C. for 2 hours, the solvent was distilled off and the solid
Was washed with a small amount of cold pentane. Extracted with methylene chloride
Thereafter, concentration recrystallization was performed, and 2.20 g (6.31 mmol
Dimethylsilylenebis (cyclopentadienyl)
Dichlorozirconium was obtained (ref .: Inorg, Chem., Chapter 24).
Vol. 2539 (1985)). This into 631 ml of toluene
The suspension was used as a catalyst solution.

(3) Copolymerization of norbornene / ethylene In a 500 ml glass-made autoclave purged with nitrogen,
200 ml of toluene and triisobutylaluminum
Then, 10 mmol of dimethylsilylenebis (cyclopentadienyl) dichlorozirconium obtained in the above (2) and 10 micromol of triethylammonium tetrakis (pentafluorophenyl) borate obtained in the above (1) are added thereto. Mole was added. Subsequently, 22 mmol of norbornene was added, and after the temperature was raised to 50 ° C., ethylene gas was passed at 40 L / hr,
Polymerization was performed at normal pressure for 1 hour. The polymerization proceeded in a homogeneous solution state. After completion of the reaction, the reaction solution was poured into 1 liter of hydrochloric acid-acidic methanol to precipitate a copolymer, and then the catalyst component was decomposed and removed, followed by washing and drying to obtain 1.47 g of the copolymer. The polymerization activity was 1.6 kg / gZr. The copolymer has a norbornene content of 68 mol%, an intrinsic viscosity [η] of 0.3 dl / g, and a glass transition temperature (T
g) was 182 ° C., the softening temperature (TMA) was 175 ° C., the total light transmittance of the sheet was 94.0%, and the haze was 3.2%.

Example 72 Example 71 (3) was repeated except that the amount of norbornene used was changed to 44 mmol.
In the same manner as in the above, 1.64 g of a copolymer was obtained. The polymerization activity was 1.8 kg / gZr. The norbornene content of the obtained copolymer was 74 mol%, and the intrinsic viscosity [η] was 0.49.
dl / g, glass transition temperature (Tg) 199 ° C, TMA
Was 190 ° C., the total light transmittance of the sheet was 94.5%, and the haze was 3.0%.

Example 73 Example 71 (3) was repeated except that the amount of norbornene used was changed to 33 mmol.
In the same manner as in the above, 2.44 g of a copolymer was obtained. The polymerization activity was 2.7 Kg / gZr. The resulting copolymer had a norbornene content of 72 mol% and an intrinsic viscosity [η] of 0.50.
dl / g, glass transition temperature (Tg) 193 ° C, TMA
Was 185 ° C. The tensile strength is 260 kg / c.
m ² , elongation 1%, tensile modulus 29,000 Kg / c
m ² , the total light transmittance was 93%, and the haze was 3%.

Example 74 (1) Preparation of dimethylsilylenebis (indenyl) dichlorozirconium In Example 71 (2), instead of dicyclopentadienyldimethylsilane, 2.65 g (9.2) of diindenyldimethylsilane was used. ) 0.61 g (1.36) of dimethylsilylenebis (indenyl) dichlorozirconium in the same manner as in (2) of Example 71 except that mmol was used.
(Ref.:Angew.Chem.Int.Ed.Engl., No.
28, 1511 (1989)). This was suspended in 136 ml of toluene to obtain a catalyst solution. (2) Copolymerization of norbornene-ethylene In (3) of Example 71, 10 μmol of dimethylsilylenebis (indenyl) dichlorozirconium was used instead of dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, and norbornene was used. Example 7 except that the amount of used was 66 mmol.
3.38 g of a copolymer was obtained in the same manner as in 1 (3).
The polymerization activity was 3.7 Kg / gZr. The resulting copolymer had a norbornene content of 67 mol% and an intrinsic viscosity [η].
Is 1.4 dl / g, and the glass transition temperature (Tg) is 176.
C., TMA is 168.degree. C., and the total light transmittance of the sheet is 94.degree.
0% and haze were 3.1%.

Example 75 The procedure of Example 74 (2) was repeated except that the amount of norbornene used was changed to 100 mmol.
2.88 g of a copolymer was obtained in the same manner as described above. The polymerization activity was 3.2 Kg / gZr. The obtained copolymer had a norbornene content of 72 mol% and an intrinsic viscosity [η] of 1.2 d.
l / g, glass transition temperature (Tg) was 205 ° C, and TMA was 195 ° C.

[0131]Comparative Example 8  In (3) of Example 71, triisobutylaluminum
Ethyl aluminum sesquichloride (A
l (C_TwoH_Five)_1.5Cl_1.5) In toluene solution (1 mol / l)
And 1.0 ml (1.0 mmol) of
Dimethylsilylenebis (cyclopentadienyl) di
VO (OC) instead of chlorozirconium_TwoH_Five) Cl_Two
0.25 ml of toluene solution (1 mol / l)
(0.25) mmol, and tetrakis (pen
(Trifluorophenyl) triethylammonium borate
Not used and the amount of norbornene used was 100 mmol
Other than that described above, in the same manner as (3) of Example 71,
1.38 g of a polymer were obtained. Polymerization activity is 0.11Kg / g
Zr. The norbornene content of the obtained copolymer is
48 mol%, intrinsic viscosity [η] is 1.2 dl / g, glass
The transition temperature (Tg) was 104 ° C and TMA was 98 ° C.
Was.

Example 76 The procedure of Example 46 was repeated, except that 0.003 mmol of (3,5-dimethylphenoxy) trichlorozirconium was used instead of bis (cyclopentadienyl) dihydridozirconium. As a result, 53.7 g of a copolymer was obtained. Polymerization activity is 29
It was 5 kg / gZr. The copolymer had a norbornene content of 4.9 mol% and an intrinsic viscosity [η] of 1.88 dl / g.

[0133]Reference Example 1  In Example 13, a substitute for triisobutylaluminum was used.
Instead, use 2.0 mmol of methylaluminoxane,
Triethyl tetrakis (pentafluorophenyl) borate
Example 13 except that no ammonium was used.
When polymerization was carried out in the same manner as described above, 0.96 g of the copolymer was obtained.
I got The polymerization activity was 1.05 kg / gZr. Profit
The intrinsic viscosity [η] of the obtained copolymer was 2.32 dl / g,
The norbornene content was 11.5 mol%.

[0134]Reference Example 2  In Example 27, instead of triisobutylaluminum,
Instead, use 3.0 mmol of methylaluminoxane,
Ferroseni, tetrakis (pentafluorophenyl) borate
Except that no uranium was used.
Upon polymerization, 10.4 g of a copolymer was obtained. Heavy
The total activity was 7.4 kg / gZr. Copolymer obtained
Intrinsic viscosity [η] of the body is 2.19 dl / g, norbornene
The content was 8.5 mol%.

[0135]

As described above, the catalyst used in the present invention exhibits excellent polymerization activity in homopolymerization of cyclic olefin or copolymerization of cyclic olefin and α-olefin. In particular, the catalyst using the organoaluminum compound (C) shows a very high polymerization activity by using a small amount of the organoaluminum compound. Therefore, according to the production method of the present invention, a cyclic olefin homopolymer or a cyclic olefin / α-olefin polymerized without using a large amount of an organometallic compound, omitting the deashing step, and opening the cyclic olefin without ring opening. The copolymer can be produced efficiently. In the production of the copolymer, a resin having high randomness and excellent physical properties can be produced.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a manufacturing method of the present invention.

FIG. 2 is a DSC (temperature drop measurement) chart of the copolymer of Example 70.

FIG. 3 is a DSC (temperature decrease measurement) chart of the copolymer of Comparative Example 7.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References Table 5-505838 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 32 / 00-32/08

Claims (14)

(57) [Claims] 1. A cyclic olefin-based polymer comprising conducting homopolymerization of a cyclic olefin or copolymerizing a cyclic olefin with an α-olefin using a catalyst containing the following compounds (A) and (B) as main components. Manufacturing method of coalescence. (A) a transition metal compound containing a tetravalent transition metal selected from Group IVB of the periodic table (B) (A) a compound which reacts with the transition metal compound to form an ionic complex (provided that the above catalyst Excluding reaction products of (i) a bis (cyclopentadienyl) group IVB metal compound represented by the following general formulas 1-4 and (ii) an activator compound represented by the following general formula 5 Embedded image In the above formula, M is a Group IVB metal, and (A-Cp)
Is either (Cp) (Cp ^* ) or Cp-A'-Cp ^* , wherein Cp and Cp ^* are the same or different, substituted or unsubstituted cyclopentadienyl groups, and A 'is a covalent cross-linked L is an olefin, diolefin or alliin ligand; X ₁ and X ₂ are each independently a hydride group, hydrocarbyl group, substituted hydrocarbyl group or organic metalloid group; X ′ ₁ and X ′ ₂ Are bonded together to a metal to form a metal ring, and the metal atoms M and X ′
But ₁ and X _'2 is intended to form a hydrocarbon ring of from about 3 to about 20 carbon atoms, and R is bonded to the metal atom M in the substituent groups present in one cyclopentadienyl group is there. 5. [(L'-H) ⁺ ] _d [(M ') ^{m +} Q ₁ Q ₂ ... Q _n ] ^{d-In the} above formula, L' is a neutral Lewis base, H is a hydrogen atom, and [( L′-H)] is a Bronsted acid, and M ^′
Is a metal or metalloid selected from each group of VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA;
Q ₁ to Q _n independently represent a hydride group, a dialkylamide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a substituted hydrocarbyl group or an organic metalloid group, and any one of Q ₁ to Q _n One (but only one) may be a halide group, and m is 1 to 7
Where n is an integer of 2 to 8, and nm = d. ) 2. The production of the cyclic olefin polymer according to claim 1, wherein the compound (A) is a cyclopentadienyl transition metal compound containing a tetravalent transition metal selected from Group IVB of the periodic table. Method. 3. The compound (A) is represented by the following general formula: M ¹ R ¹ R ² R ³ R ⁴ [wherein M ¹ is a transition metal selected from Group IVB of the periodic table, R ¹ , R ² , R ³ and R ⁴ each represent a σ-binding ligand, a chelating ligand or a Lewis base, which may be the same as or different from each other. And a transition metal compound represented by the formula:
3. The method for producing a cyclic olefin polymer according to item 1. 4. The compound (B) is a compound of the periodic table IIIB
Group, IVB group, VB group, VIB group, VIIB group, VIII group, IA
Group, group IB, group IIA, group IIB, group VIB and VIB of the periodic table
, VIIB, VIII, IB, IIB, IIIA, IVA
The method for producing a cyclic olefin polymer according to claim 3, wherein the compound is a compound comprising an anion bonded to an element selected from Group IV and Group VA. 5. A cyclic olefin polymer, comprising homopolymerizing a cyclic olefin or copolymerizing a cyclic olefin with an α-olefin using a catalyst containing the following compounds (A) and (B) as main components. Manufacturing method of coalescence. (A) at least a transition metal compound containing a tetravalent transition metal selected from Group IVB of the periodic table represented by either of the following general formulas (I) or (IV): CpM ¹ R ¹ _a R ² _b R ³ _c (I) M ¹ R ¹ _g R ² _h R ³ _i R ⁴ _j (IV) [In the general formula (I) or (IV), M ¹ is Ti, Zr or H
indicates f atom, Cp represents a cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, a fluorenyl group or substituted fluorenyl group, R ^1, R ² , R ³ and R ⁴ each represent a σ-binding ligand, a chelating ligand or a Lewis base, two or more of which may combine with each other to form a ring; Represents an integer of 0 to 3, and g, h, i, and j each represent an integer of 0 to 4. (B) (A) a compound which reacts with a transition metal compound to form an ionic complex 6. A cyclic olefin-based polymer comprising conducting homopolymerization of a cyclic olefin or copolymerizing a cyclic olefin with an α-olefin using a catalyst containing the following compounds (A) and (B) as main components. Manufacturing method of coalescence. (A) At least a transition metal compound containing a tetravalent transition metal selected from the group IVB represented by either of the following general formulas (II) or (III): Cp ₂ M ¹ R ¹ _d R ² _e (II) ( ^{_{Cp-a f -Cp) M 1}} R 1 d R 2 e (III) [ general formula (II) or (III), M ¹ represents a Ti, Zr or Hf atom, Cp is different identical, or together cycloalkyl A pentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group, wherein R ¹ and R ² are a halogen atom, Two or more of which represent a C1 to C20 alkoxy group, a C1 to C20 acyloxy group, a chelating ligand or a Lewis base which may combine with each other to form a ring; Shows crosslinking and d Fine e is 0 to 2, respectively integer, f is an integer of 0 to 6. (B) (A) a compound which reacts with a transition metal compound to form an ionic complex 7. A cyclic olefin-based polymer comprising conducting homopolymerization of a cyclic olefin or copolymerizing a cyclic olefin with an α-olefin using a catalyst containing the following compounds (A) and (B) as main components. Manufacturing method of coalescence. (A) Nickel bis (acetylacetonate) (B) (A) Compound that reacts with a transition metal compound to form an ionic complex 8. The method according to claim 1, wherein (C) homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an α-olefin is carried out using a catalyst further containing an organoaluminum compound as a main component. A method for producing the cyclic olefin polymer according to any one of the preceding claims. 9. The method for producing a cyclic olefin polymer according to claim 5, wherein the compound (B) is a compound comprising a cation and an anion having a plurality of groups bonded to an element. 10. The compound (B) is at least one boron compound selected from tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and triphenylboron. A method for producing the cyclic olefin polymer according to any one of claims 5 to 8. 11. A method for producing a cyclic olefin polymer, comprising copolymerizing norbornene and ethylene using a catalyst containing the following compounds (A) and (B) as main components. (A) a transition metal compound containing a tetravalent transition metal selected from Group IVB of the periodic table (B) (A) a compound which reacts with the transition metal compound to form an ionic complex 12. The process for producing a cyclic olefin polymer according to claim 11, wherein the copolymerization of norbornene and ethylene is carried out using a catalyst further comprising (C) an organoaluminum compound as a main component. 13. The following general formula: M ¹ R ¹ R ² R ³ R ^{4 wherein} M ¹ is a transition metal selected from Group IVB of the periodic table, and R ¹ , R ² , R ³ and R ⁴ are Each represents a σ-binding ligand, a chelating ligand, or a Lewis base, which may be the same as or different from each other. And a compound which reacts with the transition metal compound to form an ionic complex. 14. The catalyst according to claim 13, further comprising an organoaluminum compound as a main component.