JP3314831B2 - Olefin polymerization catalyst and method for producing olefin polymer using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same. More specifically, the present invention provides a catalyst for olefin polymerization which has a high polymerization activity even in a non-aromatic solvent, and which is excellent in copolymerizability and which gives a polymer having a high molecular weight especially in high-temperature polymerization. The present invention relates to a method for efficiently producing an olefin-based polymer using the method.

[0002]

2. Description of the Related Art Heretofore, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known (JP-A-58-193).
09, JP-A-60-217209). In addition, it has been reported that cationic species are useful as active species of the soluble olefin polymerization catalyst [Journal of the American Chemical Society.
(J. Am. Chem. Soc.), Vol. 81, p. 81 (1959
82), p.1953 (1960), 10
7, 7219 (1985)]. Also, as an example of isolating this active species and applying it to olefin polymerization,
"Journal of the American Chemical Society (J. Am. Chem. Soc.)", 108, 7410
Page (1986), Japanese Translation of PCT International Publication No. 1-502636, Japanese Patent Application Laid-Open No. 3-139504, European Patent No. 4
No. 6,865, No. 1 and the like, as examples in which an organoaluminum compound is used in combination with this active species, see JP-A-3-20770.
No. 4, International Publication No. 92-1723, and the like.

[0003] However, the polymer formed by the complex having a cyclopentadienyl ligand used in these prior arts can be polymerized at a reaction temperature of 70 to 200 ° C, which is efficient in an industrial process, or higher. When it is carried out, there is a problem that the molecular weight of the obtained polymer is small. Further, in Japanese Laid-3-139504 discloses, for example, (t-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) (and M- [alkyl] complex) silane titanium dimethyl and the ionic complex A method for producing an olefin-based polymer using a catalyst system combining the above is disclosed. However, the "M- [alkyl] complex" generally comprises a halo-substituted compound,
For example, (t-butylamido) dimethyl (tetramethyl-
η ⁵ -cyclopentadienyl) silanetitanium dichloride, but the production process is complicated and the reaction yield is low, so the production cost is high, and it is not practical, and the activity is not sufficient. Has disadvantages. Furthermore, the method using these polymerization catalysts merely shows a method of polymerizing substantially using toluene as a catalyst, and has problems in safety, odor and the like based on an aromatic solvent. On the other hand, JP-A-5-178926 discloses an olefin polymerization catalyst comprising a transition metal complex component obtained by contacting a transition metal compound with an organic compound and an organoaluminum oxy compound. The activity is remarkably low, and there is no description about the molecular weight distribution of the obtained polymer.Moreover, only the homopolymerization of ethylene is performed, such as copolymerization of α-olefin or copolymerization of α-olefin and cyclic olefin. About not done. Furthermore, "J.Organomet. Chem"
Vol. 363, C12-14 (1989) contains Cp ₂
Zr (CF ₃ SO ₃ ) ₂ THF is shown, and a cationic compound as an active species is isolated. An electron donor such as tetrahydrofuran (THF) is added to such a cyclopentadienyl compound. When added, the polymerization activity is inevitably reduced.

[0004]

Under these circumstances, the present invention has a high polymerization activity even in a non-aromatic solvent, is excellent in copolymerizability, and has a high molecular weight especially in high-temperature polymerization. It is an object of the present invention to provide a catalyst for olefin polymerization which gives a polymer having a high olefin content, and a method for efficiently producing an olefin homopolymer or a copolymer using the catalyst.

[0005]

Means for Solving the Problems The present inventors have achieved the above object.
As a result of intensive research to achieve
From the genus compound, the transition metal compound or a derivative thereof,
A compound capable of forming a seed, a specific electron donating compound, and
Catalyst optionally containing an organoaluminum compound
Has found that the object can be achieved. The present invention
Has been completed based on such knowledge. Sand
The present invention relates to (A) a compound represented by the general formula (I) M¹R¹ _aR^Two _bR^Three _CR^Four _d... (I) (where M¹Is a transition metal of Group 4 of the periodic table, R¹~ R^Four
Are elements selected from groups 13 to 17 of the periodic table, respectively.
Ligands containing at least one of which is 16
Ligands in which group elements are σ-bonded or coordinated to transition metals
And R ¹~ R^FourEven if they are the same, they are different
Two or more of which may be linked to each other
May be formed. a to d are each an integer of 0 to 4
Is shown. (B) the transition metal compound represented by (A)
Cationic species from the transition metal compound or its derivative
A compound which can be formed, (C) a transition metal compound of the component (A)
Electron-donating compounds that do not cause a substitution reaction with ligands of
And optionally containing (D) an organoaluminum compound
Olefin polymerization catalyst, and the presence of the polymerization catalyst
Below, characterized in that olefin is polymerized or copolymerized.
And a method for producing an olefin polymer.
You.

In the polymerization catalyst of the present invention, as the component (A), a transition metal represented by the following general formula (I): M ¹ R ¹ _a R ² _b R ³ _C R ⁴ _d (I) Compounds are used. In the above general formula (I), M ¹ represents a transition metal of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium.
R ^{1 to} R ⁴ each represent a ligand containing an element selected from Groups 13 to 17 of the periodic table. Examples of such a compound include 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, and an alkyl group having 6 to 20 carbon atoms. Aryloxy group, alkylaryl group having 7 to 20 carbon atoms, arylalkyl group or arylalkoxy group, acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonate group, substituted acetylacetonate group, silicon A substituent containing an atom, a substituent containing a sulfur atom, a substituent containing a nitrogen atom, or a ligand such as carbonyl, an oxygen molecule, a nitrogen molecule, a Lewis base, a chain unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon; Show. The R ¹ ~
It is necessary that at least one of R ⁴ is a ligand in which a Group 16 element is σ-bonded or coordinated to a transition metal, and particularly, a Group 16 element is oxygen, and R ^{1 to} R ¹ It is preferable that at least one of ⁴ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an arylalkoxy group having 7 to 20 carbon atoms. The R ¹
To R ⁴ may be the same or different, or two or more of them may combine with each other to form a ring. a to d each represent an integer of 0 to 4.

Specific examples of R ^{1 to} R ⁴ include 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 isopropyl group as an alkyl group having 1 to 20 carbon atoms. Group, n-butyl group, octyl group, 2-ethylhexyl group, carbon number 1-2
Methoxy group; ethoxy group; propoxy group; butoxy group; hexyloxy group; 2-ethylhexyloxy group; ethyleneglycoxy group; diethyleneglycoxy group; 1,3-pentanedioxy group; Group; 1,5-pentanedioxy group; 1,3-
Butanedioxy group; 2,3-butanedioxy group; 2,
2'-dinitrilodiethoxy group; 2,2 ', 2 "-trinitrilotriethoxy group; 2,2'-dinitrilodipropoxy group, aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
A phenyl group, a tolyl group, a xylyl group, a benzyl group,
A phenoxy group as an aryloxy group having 6 to 20 carbon atoms; 2,6-dimethylphenoxy group; 2,6-diisopropylphenoxy group; 2,6-di-t-butylphenoxy group; 2,2′-biphenoxy group; A butyl catecholoxy group, a benzylalkoxy group as an arylalkoxy group having 7 to 20 carbon atoms; a 3-phenylpropoxy group;
A phenylbutoxy group, a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms, a trimethylsilyl group, a (trimethylsilyl) methyl group as a substituent containing a silicon atom, a methylthiolate group, an ethylthiolate group as a substituent containing a sulfur atom, Phenylthiolate group, ethyldithiolate group, substituents containing a nitrogen atom such as diethylamino group, dimethylamino group, N-methylanilinium group, Lewis bases such as dimethyl ether, diethyl ether, ethers such as tetrahydrofuran, and thioethers such as tetrahydrothiophene , Esters such as ethylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethylaniline; pyridine; 2,2'-bipyridine; amines such as phenanthroline; triethylphosphine; phosphines such as triphenylphosphine; 1-pentene; isoprene; pentadiene; 1-hexene and derivatives thereof, as cyclic unsaturated hydrocarbons, benzene; toluene; xylene; cycloheptatriene; cyclooctadiene; cyclooctatriene; And the like.

[0008] Specific examples of the transition metal compounds represented by the general formula (I), Te tiger methoxy zirconium; tetraethoxy zirconium; tetrabutoxyzirconium; tetra hexyloxy zirconium; tetra (2-ethylhexyloxy) zirconium; 2,2 '-Biphenoxydichlorozirconium;2,2'-biphenoxydimethylzirconium; catecholoxydichlorozil Catecholoxydimethyl zirconium; tributoxymethyl zirconium; tributoxychlorozirconium; triethoxymethyl zirconium; triethoxychlorozirconium; triphenoxychlorozirconium; dibutoxydichlorozirconium; dibutoxydimethylzirconium; diphenoxydichlorozirconium; diethoxydimethyl Zirconium; diethoxydichlorozirconium; (2,6-di-
(tert-butylphenoxy) trichlorozirconium; (2,6-di-tert-butylphenoxy) trimethylzirconium; bis (2,6-di-tert-butylphenoxy) dichlorozirconium; bis (2,6
-Di-tert-butylphenoxy) dimethylzirconium;) tetra (methylthiolate) zirconium; tri (methylthiolate) chlorozirconium; di (methylthiolate) dichlorozirconium; (methylthiolate) trichlorozirconium; bis (1,2-ethanedioxy) Zirconium; bis (1,3-propanedioxy) zirconium; bis (1,4-butanedioxy)
Zirconium; bis (1,3-butanedioxy) zirconium; bis (2,3-butanedioxy) zirconium; 1,2-ethanedioxydichlorozirconium;
1,2-ethanedioxydimethyl zirconium; 2,
2′-nitrileethoxyethoxydichlorozirconium; 2,
2,2 "-nitrilotriethoxychlorozirconium;
2,2,2 "-nitrilotriethoxymethylzirconium; tetra (3-phenylpropoxy) zirconium;
Examples thereof include tetra (4-phenylbutoxy) zirconium; tetra (2-phenylethoxy) zirconium, and the like, and compounds in which zirconium is replaced with titanium or hafnium. Among these, a zirconium compound and a titanium compound are preferable, and a compound having an alkoxy group or an arylalkoxy group is particularly preferable. The transition metal compound of the component (A) may be used alone or in combination of two or more.

In the polymerization catalyst of the present invention, the component (B)
From the transition metal compound or its derivative
A compound capable of forming a seed is used. This component (B)
And the transition metal compound of the component (B-1) (A)
An ionic compound which forms an ionic complex in response, (B
-2) Aluminoxane, (B-3) Lewis acid
Can be. As the component (B-1), the component (A)
Reacts with a transition metal compound to form an ionic complex
Any ionic compound can be used.
However, the following general formulas (II) and (III) ([L¹-R^Five]^{k +})_p([Z]^-)_q ... (II) ([L^Two]^{k +})_p([Z]^-)_q ... (III) (where L^TwoIs M^Three, R⁶R⁷M^Four, R⁸ _ThreeC or R⁹
M^FourIt is. [In formulas (II) and (III), L¹Is a Lewis base, [Z]
^-Is a non-coordinating anion [Z ¹]^-Or [Z^Two]^-This
Here [Z¹]^-Is an anion in which multiple groups are bonded to an element
That is, [M^TwoA¹A^Two... Aⁿ]^-(Where M^TwoIs
Group 5 to 15 element of the periodic table, preferably 13 of the periodic table
Group 15 elements are shown. A¹~ AⁿAre hydrogen atoms,
Halogen atom, alkyl group having 1 to 20 carbon atoms, 2 carbon atoms
Dialkylamino group having 1 to 40 carbon atoms and alcohol having 1 to 20 carbon atoms
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl aryl having 7 to 40 carbon atoms
Group, an arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
To 20 halogen-substituted hydrocarbon groups and 1 to 20 carbon atoms
Siloxy group, organic metalloid group, or 2 to 20 carbon atoms
Represents a hetero atom-containing hydrocarbon group. A¹~ AⁿOut of
Two or more may form a ring. n is [(central metal
M^Two+1)]. ), [Z^Two]
^-Means that the logarithm (pKa) of the reciprocal of the acid dissociation constant is -10 or less
Of Bronsted acid alone or Brønsted acid and Louis
Conjugated bases in combination with succinic acids, or generally with super strong acids
Shows the conjugate base defined. Also, the Lewis base is coordinated
May be. Also, R^FiveIs a hydrogen atom, carbon number 1-20
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl
An aryl group or an arylalkyl group;⁶And R
⁷Is cyclopentadienyl group, substituted cyclopen
Tadienyl group, indenyl group or fluorenyl group, R⁸
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
It represents an aryl group or an arylalkyl group. R⁹Is Tet
Macrocyclic arrangement of laphenylporphyrin, phthalocyanine, etc.
Indicates a ligand. k is [L¹-R^Five], [L^Two] Ion value
An integer of 1 to 3 in number, p is an integer of 1 or more, q = (k × p)
It is. M^ThreeAre periodic table Nos. 1-3, 11-13, and 17
Containing a group III element,^FourAre the 7th to 12th periodic tables
Indicates a group element. ] Is preferably used
Can be.

Here, specific examples of L ¹ include ammonia; methylamine; aniline; dimethylamine; diethylamine; N-methylaniline;
N, N-dimethylaniline; trimethylamine; triethylamine; tri-n-butylamine; methyldiphenylamine; pyridine; p-bromo-N, N-dimethylaniline; amines such as p-nitro-N, N-dimethylaniline; Triphenylphosphine; phosphines such as diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; acetonitrile; and nitriles such as benzonitrile. Specific examples of R ⁵ include hydrogen, a methyl group, an ethyl group, a benzyl group, and a trityl group. Specific examples of R ⁶ and R ⁷ include a cyclopentadienyl group, a methylcyclopentadienyl group , Ethylcyclopentadienyl group,
A pentamethylcyclopentadienyl group and the like can be mentioned. Specific examples of R ⁸ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ⁹ include tetraphenylporphine,
Examples include phthalocyanine, allyl, and methallyl. Specific examples of M ³ include Li, Na,
K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ⁴ include Mn, Fe, Co, Ni,
Zn and the like can be given.

[Z ¹ ] ^- , that is, [M ² A ¹ A]
² ... A ⁿ ], B and A are specific examples of M ^2.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of A ^1, A ² ~A ⁿ is dimethylamino group as a dialkylamino group, a diethylamino group, a methoxy group as an alkoxy group or an aryloxy group, an ethoxy group, n- butoxy group,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, hydrocarbon groups such as phenoxy
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group, as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , a fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the compound of the component (B-1), include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , Triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
Boric acid (1,1'-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, manganese tetrakis (pentafluorophenyl) borate porphyrin porphyrin, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned.

The component (B-1), an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), may be used alone or in combination of two or more. May be used. On the other hand, as the aluminoxane of the component (B-2), the general formula (IV)

[0015]

Embedded image

(Wherein, R ¹⁰ is each independently a group having 1 to 1 carbon atoms.
20 and preferably 1 to 12 represent a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a halogen atom, and may be the same or different. s indicates a degree of polymerization, and is usually 3 to 50, preferably 7 to
Aluminoxane represented by the general formula (V):

[0017]

Embedded image

(Wherein R ¹⁰ and s are the same as those described above). Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The means is not particularly limited, and the reaction may be performed according to a known method. 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 aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in a combination of two or more. (B-
The Lewis acid as the component 3) is not particularly limited, and may be an organic compound or a solid inorganic compound. As the organic compound, a boron compound or an aluminum compound is preferably used, and as the inorganic compound, a magnesium compound, an aluminum compound or the like is preferably used. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl and (1,1-bi-2-naphthoxy) aluminum methyl. Examples of the magnesium compound include magnesium chloride, Diethoxymagnesium and the like; aluminum compounds such as aluminum oxide and aluminum chloride; and boron compounds such as triphenylboron, tris (pentafluorophenyl) boron and tris [3,5-bis (trifluoromethyl) phenyl] boron , Tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl)
Boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tris [3,5-bis ( Trifluoromethyl) phenyl) boron, bis (pentafluorophenyl)
Fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoro Boron, ethyldifluoroboron, n
-Butyldifluoroboron and the like. One of these Lewis acids may be used, or two or more may be used in combination.

In the polymerization catalyst of the present invention, the use ratio of the catalyst component (A) to the catalyst component (B) is preferably a molar ratio when the compound (B-1) is used as the catalyst component (B). Is from 10: 1 to 1: 100, more preferably from 2: 1 to
When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 100.
0000, more preferably in the range of 1:10 to 1: 10000. The ratio of the catalyst component (A) to the catalyst component (B-3) is preferably in a molar ratio of 1: 0.1 to 1: 0.1.
1: 2000, more preferably 1: 0.2 to 1: 100
0, more preferably in the range of 1: 0.5 to 1: 500. As the catalyst component (B), (B-1),
(B-2) and (B-3) can be used alone or in combination of two or more. In the polymerization catalyst of the present invention, an electron donating compound is used as the component (C). The electron donating compound does not cause a substitution reaction with the ligand of the transition metal compound of the component (A),
In particular, those having a coordinating lone pair or having a conjugated π electron and having no active hydrogen group are preferable. That is, an active hydrogen group, and further, -CHO, -COO
Those having no R and -COX (where R represents an alkyl group and X represents a halogen atom) are used.

Specific examples of the electron-donating compound (C) include trimethylamine, triethylamine, tributylamine, tricyclohexylamine, triphenylamine, N, N-dimethylaniline, diphenylmethylamine, N, N, N Tertiary amines such as', N'-tetramethylethylenediamine, pyrroles such as N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, pyridine, methylpyridine, ethylpyridine, phenylpyridine, bromopyridine, tetrapyridone Pyridines such as fluoropyridine, N-methylpyrrolidine,
Other cyclic nitrogen-containing compounds such as quinoline, isoquinoline, N-methylindole, furan; tetrahydrofuran; 1,4-dioxane; 1,3-dioxane; 1,4
-Cineol; Pinolfuran; Methylfuran; Diphenylfuran; Dimethylfuran; Benzofuran; Coumaran; Phthalane; Tetrahydropyran; Pyran; Cyclic ethers such as dihydropyran; Ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone and benzoquinone; nitriles such as acetonitrile, benzonitrile and tolunitrile; trimethylphosphine; triethylphosphine; trin-butylphosphine; triphenylphosphine Diphenylmethylphosphine; tertiary phos such as 1,2-bis (diphenylphosphino) ethane Fins such, tetramethylsilane, tetraethylsilane, tetraphenyl silane, tetra Cyclohexylsilanes, tetra -t- butylsilane,
Trimethylphenylsilane, triethylphenylsilane, tricyclohexylphenylsilane, tri-t-butylphenylsilane, dimethyldiphenylsilane, diethyldiphenylsilane, dicyclohexyldiphenylsilane, di-t-butyldiphenylsilane, methyltriphenylsilane, ethyltriphenylsilane , Cyclohexyltriphenylsilane, t-butyltriphenylsilane, trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, and other alkylsilanes and arylsilanes, benzene, toluene, xylene, naphthalene, indene, anthracene, ethylbenzene, t Aromatic hydrocarbons such as -butylbenzene, chlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene; La tetrahydrothiophene, dimethyl sulfite, and the like thioethers such as diphenyl sulfite. Among them, particularly preferred are tetrahydrofuran, triphenylphosphine, dimethyldiphenylsilane and aromatic hydrocarbons. These electron donating compounds may be used alone or in a combination of two or more.

The ratio of the catalyst component (A) to the catalyst component (C) used in the polymerization catalyst of the present invention is as follows.
The catalyst component (C) is used in an amount of 0.1 to 50 mol, preferably 0.5 to 20 mol, more preferably 1 to 1 mol, per 1 mol of the catalyst component.
It is desirable to use 0 moles. In the polymerization catalyst of the present invention, if necessary, an organoaluminum compound can be used as the component (D) together with the catalyst components (A), (B) and (C). Here, as the organoaluminum compound of the component (D), a general formula (VI) R ¹¹ _r AlQ _3-r (VI) (wherein, R ¹¹ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Wherein r is an integer of 1 to 3).

Specific examples of the compound represented by the above general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The use ratio of the catalyst component (A) to the catalyst component (D) is preferably 1: 1 to 1: 100 in molar ratio.
00, more preferably 1: 5 to 1: 2000, even more preferably 1:10 to 1: 1000. By using the catalyst component (D), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, it is preferable that the catalyst components are brought into contact with each other before the polymerization, and then used for the polymerization. In the present invention, at least one of the catalyst components can be used by being supported on a suitable carrier.
The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, another inorganic carrier, and an organic carrier can be used. In particular, an inorganic oxide carrier or another inorganic carrier is preferable. As the inorganic oxide carrier, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , T
iO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, Ba
O, ThO ₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like can be mentioned. Among these, SiO ₂ , Al ₂ O
₃ is preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like. On the other hand, as carriers other than the above, MgCl ₂ , Mg (OC ₂ H ₅ ) ₂
General formula Mg represented by magnesium compounds such as
Magnesium compounds and their complex salts represented by R ¹² _{X X} ¹ _y can be exemplified. Here, R ¹² has 1 to 1 carbon atoms.
20 alkyl group, an aryl group, X ¹ having 6 to 20 alkoxy groups or carbon atoms having 1 to 20 carbon atoms is an alkyl group having a halogen atom or a C 1-20, x is 0 to 2, y is 0 2 and x + y = 2. Each R ¹² and each X ¹
May be the same or different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, starch, and carbon. The carrier used in the present invention is MgC
l ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , S
iO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of a hopper. The specific surface area of the support is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, and the pore volume is usually
It is 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). reference). Further, it is desirable that the above-mentioned carrier is used after being calcined usually at 150 to 1000 ° C, preferably 200 to 800 ° C.

When at least one of the catalyst components is supported on the carrier, at least one of the catalyst components (A) and (B), preferably the catalyst components (A) and (B)
It is desirable to support both of the catalyst components. On the carrier,
The method of supporting at least one of the component (A) and the component (B) is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with a carrier, an organic aluminum compound Or a method of treating with a halogen-containing silicon compound and then mixing with at least one of the component (A) and the component (B) in an inert solvent, the carrier and the component (A) and / or the component (B) and the organoaluminum compound or A method of reacting with a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A) with the component (A) and the component (B). For example, a method of mixing the contact reaction product with the carrier and the method of coexisting the carrier during the contact reaction between the component (A) and the component (B) can be used. In addition, in the above and the reactions of
An organoaluminum compound as the component (D) may be added.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, at least one of the components (A) and (B), a carrier, an electron-donating compound of the component (C) and, if necessary, an organoaluminum compound of the component (D) are added. cm ² , and a method of performing prepolymerization at −20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the compound (B-1)
The use ratio of the component and the carrier is preferably 1: 5 to 1: 1.
0000, more preferably 1:10 to 1: 500. The ratio of the component (B-2) to the carrier is preferably
The weight ratio is preferably from 1: 0.5 to 1: 1000, more preferably from 1: 1 to 1:50, and (B-
3) The use ratio of the component and the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 10: 1 by weight.
It is desirable to set 1: 500. When two or more catalyst components (B) are used as a mixture, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. Further, the use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by weight. (B)
Component [(B-1) component, (B-2) component or (B-3)
If the ratio of the component] to the carrier or the ratio of the component (A) to the carrier is outside the above range, the activity may be reduced. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 200 μm.
150 μm, particularly preferably 20 to 100 μm,
The specific surface area is usually from 20 to 1000 m ² / g, preferably from 50 to 500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase,
If it exceeds m, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the support is usually 0.05 to 10%.
g, particularly preferably 0.1 to 2 g. If the amount of the transition metal is outside the above range, the activity may be reduced.

By supporting on a carrier as described above, a polymer having a high bulk density and excellent particle size distribution, which are industrially advantageous, can be obtained. According to the method for producing an olefin polymer of the present invention, using the polymerization catalyst described above,
(1) homopolymerization of α-olefin, (2) two or more α-olefins
-Copolymerization of olefins, (3) copolymerization of α-olefins with cyclic olefins and / or cyclic dienes, (4) copolymerization of ethylene with other α-olefins and cyclic olefins and / or cyclic dienes, etc. Copolymerization of an α-olefin and a monomer having a ring structure (cyclic olefin, cyclic diene) can be suitably performed. The composition of the olefin-based copolymer can be appropriately selected according to its use. For example, in the case of a copolymer of an α-olefin and a cyclic olefin and / or a cyclic diene which requires a low elastic modulus and high elastic recovery, the content of the α-olefin unit is 80 to 99.9 mol%. Required, 80 mol%
If it is less than this, the low-temperature physical properties decrease. The content of each of the cyclic olefin unit and the cyclic diene unit must be in the range of 0 to 20 mol%, and the total amount must be in the range of 0.1 to 20 mol%.

In the case of a copolymer of ethylene, α-olefin and cyclic olefin, the content of ethylene unit / α-olefin unit / cyclic olefin unit is 5 to 99.
8 mol% / 75-0.1 mol% / 20-0.1 mol%, preferably 32-99 mol% / 50-0.5 mol% / 18-0.1 mol%
5 mol%, more preferably 55 to 98 mol% / 30 to 1
Desirably, it is in the range of mol% / 15 to 1 mol%. The above α-
As the olefin, an α-olefin having 2 to 20 carbon atoms is preferable. As the α-olefin, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4- Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. These may be used alone or in combination of two or more.

Examples of the cyclic olefin include norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; -Trimethylnorbornene;
5-phenylnorbornene; 5-benzylnorbornene; 5-ethylidene-2-norbornene; 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-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-hexyl-1,4,5,8-dimetano-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-dimetano-1,2,3,4,4a, 5,8, 8a-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-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene; 2-isobutyl-1,4,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene; 1,2-dihydrodicyclopentadiene; 5-chloronorbornene; 5,5-dichloronorbornene; 5-fluoronorbornene;
5,6-trifluoro-6-trifluoromethylnorbornene; 5-chloromethylnorbornene; 5-methoxynorbornene; 5,6-dicarboxynorbornene anhydrate; 5-dimethylaminonorbornene;
—Cyanonorbornene and the like, and these may be used alone or in combination of two or more. Further, as the cyclic diene, for example, norbornadiene; 1,3-cyclopentadiene; 1,3-cyclohexadiene; 1,4-cyclohexadiene; 5-ethyl-1,3-cyclohexadiene; 1,3-cycloheptadiene; 1,4-cycloheptadiene; 1,3-cyclooctadiene; 1,4-cyclooctadiene;
5-cyclooctadiene; 5-methylene-2-norbornene; dicyclopentadiene; dimethyldicyclopentadiene;

[0031]

Embedded image

[0032] These may be used alone or in combination of two or more.
Among the above cyclic olefins and cyclic dienes, particularly preferred are norbornene; norbornene derivatives; 5-ethylidene-2-norbornene; 5-vinylnorbornene; and dicyclopentadiene. The cyclic diene has at least 2
As long as it has two double bonds, for example, a cyclic triene is also included. In the present invention, other than these three components, other copolymerizable unsaturated monomers may be used. Examples of the other copolymerizable unsaturated monomers include vinyl aromatic compounds such as styrene, p-methylstyrene, isopropylstyrene, and t-butylstyrene.
Butadiene; isoprene; chain diolefins such as 1,5-hexadiene, monocyclic olefins such as cyclopentene and cycloheptene, unsaturated esters such as ethyl acrylate and methyl methacrylate, β-propiolactone, β-butyrolactone Lactones such as, γ-butyrolactone, lactams such as ε-caprolactam and δ-valerolactam, epoxypropane; and epoxides such as 1,2-epoxybutane.

In the present invention, the polymerization method is not particularly limited.
It does not matter whether solution polymerization or suspension polymerization is used.
And a batch method or a continuous method may be used. With the polymerization solvent
Is preferably a non-aromatic solvent, for example, cyclopentane
, Methylcyclopentane, cyclohexane, methyl
Alicyclic hydrocarbons such as cyclohexane and cyclooctane;
Xane, heptane, octane, decane, dodecane, etc.
Aliphatic hydrocarbons, chloroform, dichloromethane, etc.
Halogenated hydrocarbons and the like can be used. these
Of these, hexane and cyclohexane are preferred. this
These solvents may be used alone or in combination of two or more.
May be combined. Also, monomers such as α-olefins
May be used as a solvent. Regarding polymerization conditions,
The combined temperature is usually 50 to 250 ° C, preferably 70 to 220.
° C, more preferably 80 to 200 ° C. Also the reaction
The ratio of the catalyst to the raw material is as follows.
(A) The catalyst component (molar ratio) is preferably 1 to 10 ⁸, Special
100 to 10^FivePreferably, Further polymerization
The reaction time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg.
/ Cm^TwoG: preferably normal pressure to 50 kg / cm^TwoG
You. The adjustment of the molecular weight of the polymer is performed, for example, by using each catalyst component.
Amount, especially the amount of the catalyst component (C) used and the choice of polymerization temperature
Can be carried out by a polymerization reaction in the presence of hydrogen.
You. In the case of a copolymer, the composition is (C) a catalyst component.
Can be adjusted depending on the amount of
Wear. The concentration of the obtained polymer is 5 to 500 g / l.
Turtle is preferred, and 10 to 400 g / liter is further preferred.
preferable.

[0034]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. The physical properties of the obtained polymer were measured in the following manner. (1) Intrinsic viscosity [η] Measured in decalin at 135 ° C. (2) Melting point [Tm], melting energy [δH] 1 by DSC of PerkinElmer 7 series
The temperature was measured at a rate of 0 ° C./min in the range of −50 ° C. to 150 ° C. (3) 2-norbornene (abbreviated as NB) unit content The sum of a peak based on ethylene and a peak based on methylene at the 5th and 6th positions of norbornene and a norbornene appearing at around 32.5 ppm in ¹³ C-NMR. Of the 7-position methylene group. (4) Molecular weight distribution (Mw / Mn) Using ALC / GPC 150C manufactured by Waters (column: TSKHM + GMH-6 × 2 manufactured by Tosoh Corporation)
Solvent: 1,2,4-trichlorobenzene, temperature: 135
° C, measured in terms of polyethylene. (5) Melt index (MI) The measurement was performed at 190 ° C. and 2.16 kg according to JIS K-7210.

Preparation Example 1 Preparation of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium is reacted with 45 mmol of boron trichloride in hexane. And tris (pentafluorophenyl) boron as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of lithium pentafluorophenyl, and lithium tetrakis (pentafluorophenyl) boron was isolated as a white solid. Next, 16 mmol of lithium tetrakis (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride were reacted in water to obtain 11.4 mmol of dimethylanilinium tetraalkyl (pentafluorophenyl) borate as a white solid. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the target product.

Example 1 Under a nitrogen atmosphere, at room temperature, 400 ml of dry hexane, 0.6 mmol of triisobutylaluminum and 70 ml of 2-norbornene were placed in a 1 liter autoclave.
67 ml of a hexane solution containing 400 wt.
Mmol) in this order and the temperature was raised to 90 ° C. Next, 20 ml of dry hexane, 0.6 mmol of triisobutylaluminum, 0.2 mmol of tetrahydrofuran, 20 micromol of tetrabutoxyzirconium, and 40 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate were added to the catalyst charging tube in this order. Was. This catalyst mixed solution was introduced through a catalyst introduction tube, and immediately after the reaction, reaction was carried out for 30 minutes while continuously introducing ethylene so that the ethylene partial pressure became 6 kg / cm ² . After completion of the reaction, the polymer solution was poured into 1 liter of methanol to precipitate a polymer. The polymer was collected by filtration and dried to obtain a copolymer. Table 1 shows the polymerization results and the physical properties of the obtained polymer.

Examples 2 to 5 Copolymers were obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of tetrahydrofuran as the electron donating compound. Table 1 shows the polymerization results and the physical properties of the obtained copolymer.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that tetrahydrofuran was not used. Table 1 shows the polymerization results and the physical properties of the obtained copolymer. First
As is clear from the table, Example 1 was different from Comparative Example 1 in that
It can be seen that the copolymerizability and high molecular weight are remarkably excellent.

[0039]

[Table 1]

[0040]

[Table 2]

Example 6 (Copolymerization of ethylene and octene-1) 360 ml of dry hexane and octene-1 were placed in a 1-liter autoclave at room temperature under a nitrogen atmosphere.
Was added in this order with 40 ml and triisobutylaluminum 1 mmol, and the temperature was raised to 70 ° C. Next, 10 micromol of triisobutylaluminum, 10 micromol of triphenylphosphine, 1 micromol of tetrabutoxytitanium, and 2 micromol of dimethylallynium tetrakis (pentafluorophenyl) borate were previously mixed, and charged into an autoclave. The temperature rose. Thereafter, the reaction was carried out for 1 hour while introducing ethylene so that the ethylene partial pressure became 8 kg / cm ² . After completion of the reaction, the polymer solution was poured into 1 liter of methanol to precipitate a polymer, and the polymer was collected by filtration and dried to obtain a copolymer. Table 2 shows the polymerization results and the physical properties of the obtained copolymer.

Comparative Example 2 A copolymer was obtained in the same manner as in Example 6, except that triphenylphosphine was not used. Table 2 shows the polymerization results and the physical properties of the obtained copolymer.

[0043]

[Table 3]

Examples 7 and 8 In Example 1, the amount of tetrahydrofuran used was changed to the third
A copolymer was obtained in the same manner as in Example 1 except that the amount was changed as shown in the table and the amount of 2-norbornene used was 200 mmol. Table 3 shows the polymerization results and the physical properties of the obtained copolymer.

[0045]

[Table 4]

Examples 9 to 11 In Example 7, triphenylphosphine was used in place of tetrahydrofuran, 10 micromoles of tetrabutoxyzirconium, 20 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate were added, and triphenylphosphine was added. A copolymer was obtained in the same manner as in Example 7, except that the amount of phosphine used was as shown in Table 3. Table 4 shows the polymerization results and the physical properties of the obtained copolymer. It is apparent from these examples that the molecular weight can be controlled by the amount of the electron donating compound used.

[0047]

[Table 5]

Example 12 700 ml of dry hexane, 1.2 mmol of triisobutylaluminum and 70 ml of 2-norbornene were placed in a 2 liter autoclave at room temperature under a nitrogen atmosphere.
420 ml of a hexane solution containing 2% by weight (2-
2.1 mol as norbornene) in this order, 15
The temperature was raised to 0 ° C. Next, dry hexane 1
20 ml, triisobutylaluminum 0.6 mmol, tetrahydrofuran 30 micromol, tetrabutoxyzirconium 6 micromol, dimethylanilinium tetrakis (pentafluorophenyl) borate 12
Micromoles were added in this order. Next, ethylene was introduced so that the ethylene partial pressure became 53 kg / cm ² , then a catalyst solution was introduced from a catalyst introduction tube, and a reaction was carried out for 5 minutes while continuously introducing ethylene. After completion of the reaction, the polymerization was stopped with isopropyl alcohol, and the mixture was flashed on a flash drum to obtain a powdery copolymer. Table 5 shows the polymerization results and the physical properties of the obtained copolymer.

Example 13 A copolymer was obtained in the same manner as in Example 12, except that 60 μmol of triphenylphosphine was used instead of tetrahydrofuran. Table 5 shows the polymerization results and the physical properties of the obtained copolymer.

Comparative Example 3 A copolymer was obtained in the same manner as in Example 12, except that tetrahydrofuran was not added. Table 5 shows the polymerization results and the physical properties of the obtained copolymer.

[0051]

[Table 6]

[0052]

Industrial Applicability The olefin polymerization catalyst of the present invention has high polymerization activity even in a non-aromatic solvent, is excellent in copolymerizability, and can give a polymer having a high molecular weight especially in high temperature polymerization. it can. By using this polymerization catalyst, a homopolymer or copolymer of an olefin, particularly a copolymer of an α-olefin and a cyclic olefin and / or a cyclic diene can be efficiently produced.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-263815 (JP, A) JP-A-6-157634 (JP, A) JP-A-6-192316 (JP, A) JP-A-4-192 331210 (JP, A) JP-A-56-149405 (JP, A) WO 93/24541 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/64-4 / 685

Claims (8)

(57) [Claims] (A) General formula (I) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (I) wherein M ¹ is a transition metal of Group 4 of the periodic table, R ^{1 to} R ⁴ each represent a ligand containing an element selected from Groups 13 to 17 of the periodic table, and at least one of the ligands is a group 16 element having a σ bond or a coordination bond to a transition metal. And R ^{1 to} R ⁴ may be the same or different, and two or more of them may be bonded to each other to form a ring. a to d each represent an integer of 0 to 4), (B) a general formula (II) capable of forming a cationic species from the transition metal compound of the component (A) or a derivative thereof. And / or general
Formula (III) ([L ¹ -R ⁵ ] ^{k +} ) _p ([Z] ^- ) _q ... (II) ([L ² ] ^{k +} ) _p ([Z] ^- ) _q ... (III) ( However, L ² is ^{M 3, R 6 R 7 M} 4, R 8 3 C or R ⁹ M ⁴
is there. [Wherein L ¹ is a Lewis base,
[Z] ^- is a non-coordinating anion [Z ^{1] -} or [Z ^{2] -,}
Wherein [Z ^{1] -} is to anionic plurality of groups are bonded to an element
That is, [M ² A ¹ A ² ... ^An ] ^- (where M ² is a period
Group 5 to 15 element of the periodic table, preferably 13 to 1 of the periodic table
Shows Group 5 elements. A ¹ to A ⁿ are each a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 2 to 40 carbon atoms
Dialkylamino group, alkoxy having 1 to 20 carbon atoms
Group, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms
Reeloxy group, alkylaryl having 7 to 40 carbon atoms
Group, an arylalkyl group having 7 to 40 carbon atoms,
20 halogen-substituted hydrocarbon groups, 1 to 20 carbon atoms
Roxy group, organic metalloid group, or C2-20
Indicate a hetero atom-containing hydrocarbon group. 2 of the A ¹ ~A ⁿ
One or more may form a ring. n is [(center metal M
² ) +1]. ), [Z ^{2] -,} the acid
Brene whose logarithm (pKa) of the reciprocal of the dissociation constant is -10 or less
Sted acid alone or combination of Bronsted acid and Lewis acid
Combined conjugate base, or generally defined as a superacid
A conjugate base. Also, even if the Lewis base is coordinated
Good. R ⁵ is a hydrogen atom, an alkyl having 1 to 20 carbon atoms.
Group, aryl group having 6 to 20 carbon atoms, alkylaryl
R ⁶ and R ⁷ are each a group or an arylalkyl group.
Cyclopentadienyl group, substituted cyclopentadienyl
Group, an indenyl group or a fluorenyl group, R ⁸ has 1 carbon atom
20 to 20 alkyl, aryl, and alkylaryl groups
Or an arylalkyl group. R ⁹ is tetraphenyl
Shows macrocyclic ligands such as porphyrins and phthalocyanines
You. k is the ionic valence of [L ¹ -R ⁵ ], [L ² ] and is 1 to 3;
And p is an integer of 1 or more, and q = (k × p). M
³ is an element of Groups 1 and ³ , 11 to 13 and 17 of the periodic table
And M ⁴ represents an element in Groups 7 to 12 of the periodic table
Show. And (C) a π electron without causing a substitution reaction with the ligand of the transition metal compound of the component (A).
An olefin polymerization catalyst containing an electron-donating compound that is not possessed . (2) a transition metal compound represented by the general formula (I), (B) a general formula (II) capable of forming a cationic species from the transition metal compound of the component (A) or a derivative thereof; /or
The compound represented by (III), (C) the (A) without causing the ligand and the substitution reaction of the transition metal compound of the component, holding the π electrons
An olefin polymerization catalyst comprising an electron-donating compound having no compound and (D) an organoaluminum compound. 3. The transition metal compound of component (A), wherein
The group 6 element is oxygen, and at least one of R ^{1 to} R ⁴ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an arylalkoxy group having 7 to 20 carbon atoms. Or the catalyst for olefin polymerization according to 2 above. 4. (C) according to claim 1 or 2 wherein the olefin polymerization catalyst electron donor compound components are those having no active hydrogen group. 5. The amount of the electron-donating compound (C) used is from 0.1 to 50 per mole of the transition metal compound (A).
The catalyst for olefin polymerization according to claim 1 or 2, which is in moles. 6. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the catalyst according to any one of claims 1 to 5. 7. The olefin weight according to claim 6, wherein the components (A), (B) and (C) or the components (A), (B), (C) and (D) are brought into contact before polymerization. Manufacturing method of coalescence. 8. The process for producing an olefin polymer according to claim 6, wherein the polymerization is carried out in a non-aromatic solvent.