WO1996004317A1

WO1996004317A1 - Transition metal compound, olefin polymerization catalyst, olefin polymer produced by using the catalyst, and process for producing the polymer

Info

Publication number: WO1996004317A1
Application number: PCT/JP1995/001530
Authority: WO
Inventors: Takuji Okamoto; Masatoshi Uemura; Masami Watanabe
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 1994-08-02
Filing date: 1995-08-02
Publication date: 1996-02-15

Abstract

A novel transition metal compound represented by general formula (I) (wherein each symbol is as defined in the specification), and an olefin polymerization catalyst containing (A) the transition metal compound (I), (B) an active cocatalyst such as a compound capable of reacting with the metal compound or a derivative thereof to give an ionic complex, and, if necessary, (C) an organoaluminum compound. The transition metal compound is useful as a component of the olefin polymerization catalyst, and the olefin polymer produced by using this catalyst has a narrow molecular weight distribution and a comparatively wide composition distribution.

Description

Specification

TECHNICAL FIELD The present invention relates to a transition metal compound, an orphan polymerization catalyst, an orphan polymer using the catalyst, and a method for producing the same.

The present invention relates to a transition metal compound, a novel catalyst for polymerization of olefin, an olefin polymer using the catalyst, and a method for producing the same. More specifically, the present invention relates to a transition metal compound useful as a component of an olefin polymerization catalyst, and an olefin polymer containing the transition metal compound having a narrow molecular weight distribution and a relatively wide composition distribution. Or a highly active polymerization catalyst that gives highly regular polypropylene, an olefin homopolymer or copolymer obtained using the polymerization catalyst, and an olefin polymer. It relates to a method for efficiently manufacturing. Background art

Conventionally, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane is known (Japanese Patent Application Laid-Open No. 58-19309). And Japanese Patent Application Laid-open No. Sho 60-217720). In addition, it has been reported that cationic species are useful as active species in soluble polymerization catalysts [Journal of Ob-A-American, Chemical, and Society]. Am. Chem. Soc.) ”, Volume 81, Page 81 (1959), Volume 82, Page 195 (1960), Volume 107, Volume 7 Page (1985)]. Also, as an example of singulating this active species and adapting it to orphan polymerization, ΓJournal of OBJ 'America' · Can. Chem. Canole カ 'Society (J. Am. Chem. Soc.) Vol. 108, pp. 7410 (1986), Japanese Translation of PCT International Publication No. Japanese Unexamined Patent Publication No. Hei 3 (1990) -3,095,054 and European Patent Publication No. 468,651 are examples of the use of an organic aluminum compound in combination with this active species. 0 4 JP, International Patent Publication 9 2 - like 1 7 2 3 No., also - S 0 ₃ transition metal compound having a ligand containing R groups and consisting of an organoaluminum O alkoxy compounds of Orefi emissions polymerization catalyst As an example, European Patent Publication No. 519746 may be mentioned.

However, the catalytic activity, copolymerizability, or the distribution of the composition or molecular weight of the obtained polymer for the polymerization of the olefin were not always satisfactory. Moreover, in the polymerization of propylene, those that improve the regularity have been limited.

Disclosure of the invention

Under such circumstances, the present invention provides a novel transition metal compound useful as a component of an orefene polymerization catalyst, an orefin-based polymer having a narrow molecular weight distribution and a relatively wide composition distribution, or a highly ordered polymer. To provide a highly active polymerization catalyst for giving polypropylene, and an olefin polymer or copolymer having a narrow molecular weight distribution and a relatively wide composition distribution obtained by using the polymerization catalyst; and The purpose of the present invention is to provide a polypropylene polymer having a high melting point because there is almost no heterogeneous bond due to 2,1-insertion in the chain.

The present inventors have conducted intensive studies to achieve the above object, and consequently found that a novel transition metal compound having a specific structure is useful as a component of a catalyst for polymerization of olefins, and that the transition metal A polymerization catalyst containing a compound and an activation co-catalyst, for example, a compound capable of forming an ionic complex by reacting with the transition metal compound or a derivative thereof, and optionally an organic aluminum compound has high activity. Having a narrow molecular weight distribution and a relatively broad composition distribution. It was found that the pyrene was given efficiently. The present invention has been completed based on such findings.

That is, the present invention provides a compound represented by the general formula (I):

(In the formula, M is a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, X represents a σ-binding ligand bonded to M, and when there are a plurality of Xs, They may be the same or different, and may be crosslinked with an indenyl ring or Υ. Υ represents a Lewis base, and when there are a plurality of Υ, a plurality of Υ may be the same or different and may be cross-linked to an indenyl ring or X. Α represents a crosslinking group, p is an integer of 1 to 20, q is an integer of 1 to 5, [(valency of M) 12], and r is an integer of 0 to 3. R ^{1 to} R ⁸ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a heteroatom-containing group. However, they may be the same or different, or may form a ring with an adjacent group. Also, three R ^{4 's} may be the same or different, and three R ⁸ ' s may be the same or different. ]

And (A) a transition metal compound represented by the general formula (I) and an activating co-catalyst, for example, ( B) a compound characterized by containing a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof, and optionally (C) an organic aluminum compound. An object of the present invention is to provide a polymerization catalyst, and an olefin-based polymer obtained by using these polymerization catalysts for an olefin.

In addition, the orefin-based polymer of the present invention may be obtained by homopolymerizing orefins with orefins and other orefins and / or other monomers in the presence of the above-mentioned catalyst for orefin polymerization. It can be produced by copolymerization. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a chart of the proton nuclear magnetic resonance ('H-NMR) of compound group A1 obtained in Example 1 (1), and FIG. 2 is a chart of Example 1 (2). Fig. 3 is a chart of the proton nuclear magnetic resonance ('H-NMR) of the obtained compound group A2. Fig. 3 shows the compound group A3 proton nuclear magnetic resonance obtained in Example 1 (3). FIG. 4 is a chart of proton nuclear magnetic resonance (Ή-NMR) of compound group A4 obtained in Example 1 (4). BEST MODE FOR CARRYING OUT THE INVENTION

The transition metal compound of the present invention has the general formula (I)

Is a novel compound having a structure represented by

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanide series, and specific examples include titanium, zirconium, hafnium, and y. Examples include tritium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanide-based metals. Among them, catalysts for polymerization of olefins are group 4 elements. Certain titanium, zirconium and hafnium are preferred. X represents a sigma-binding ligand bonded to M. When there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked to an indenyl ring or Υ. Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a carbon atom. Amido groups of 1 to 20 carbon atoms, silicon-containing groups of 1 to 20 carbon atoms, phosphide groups of 1 to 20 carbon atoms, sulfide groups of 1 to 20 carbon atoms, 1 to 20 carbon atoms 20 acyl groups and the like.

Υ represents a Lewis base, and when there are a plurality of Υ, a plurality of Υ may be the same or different and may be cross-linked to an indenyl ring or X. Examples of this type include amines, ethers, phosphines, thioethers, esters, and nitriles.

Specific examples of Υ include ammonia, methylamine, aniline, Chillamine, Jethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, trin-butylamine, methyldiphenylamine , Pyridine, amines such as p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine Examples include phosphines such as quinine, teaters such as tetrahydrothiophene, esters such as ethyl benzoate, and nitriles such as acetonitrile and benzonitrile. be able to.

A represents a cross-linking group, and a specific structure is represented by the formula (R'nQ). Here, Q is an atom selected from the 13th, 14th, 14th, 15th and 16th groups of the periodic table, and n is 2 when the Q force is 14 the group, 1 when the 13th and 15th groups are 1, 0 when the group is 6 These _{structures, R '2 C, R'} 2 S i, R '2 G e, R' 2 S n, R 'A 1, R' P, R 'N, oxygen (- 0 -), sulfur (-S-), selen (-Se-) [where R 'is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon When n is 2, R's may be the same or different. O

(A) p [p represents an integer of 1 to 20. Examples of the above are methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylidene, dimethylsilylene, tetramethyldisilylene, dimethylgermiene. Len, dimethylsevenylene, methylborylidene (CH ₃ — B =), methylalkylidene (CH ₃ — Al =), phenylphospholidene (P h— P =), phenylphospholidene (Ρh PO =), ethylene (one CH = CH—), 1, 2-phenylene, bi Nilene, vinylidene, ethenylidene (CH ₂ = C =), methyl imide, oxygen (-0-), sulfur (-S-), selenium ( ₁ -Se), etc. , Methylene, ethylene, ethylidene, and isopropylidene are preferred in terms of ease of synthesis and yield. q represents an integer of 1 to 5 and represents [(valence of M) 1 2], and r represents an integer of 0 to 3. R ^{1 to} R ⁸ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group, They may be the same or different, or may form a ring with an adjacent group. Also, three R ^{4 's} may be the same or different, and three R ⁸ ' s may be the same or different.

Specific examples of R ′, R ^{1 to} R ⁸ include, in addition to a hydrogen atom, a halogen atom such as C 1, Br, F, I, methyl, ethyl, n-propyl, n-butyl, C1-C20 hydrocarbon groups such as isopropyl, isobutyl, and n-decyl; halogen-containing hydrocarbon groups such as trifluoromethyl; trimethylsilyl and dimethyl (t-butyl) silyl; Examples include a silicon-containing group, a heteroatom-containing group such as methoxy, ethoxyquin, and dimethylamino.

Specific examples of the transition metal compound represented by the general formula (I) include rac — [and 2-ethylenebis (7 — (4-t-butylindenyl))] zirconium dichloride, rac — [ 1,2—ethylenebis (71- (4-methylindenyl))] zirconium dichloride, rac— [1,2—ethylenebis (7— (2,4—dimethylindenyl))] zirconium dichloride, rac — [shi 2 -ethylenebis (6 — (2,3-dimethylindenyl))] zirconium dichloride, rac 1 [shi 2 -ethylenbis (7 — (shi 4 -dimethylindenyl)) Zirconium dichloride, rac— [isopropylidenebis (7— (4-t-butylindul))] zirconium dichloride, rac—isopropylidenebis (7— (4—1 Methylindenyl)))) Zirconium dichloride, rac — [Isopropylidene bis (7— (2,4-dimethylindyl))] zirconium dichloride, rac— [Isopropylidene bis (7 — (1,4-dimethylindenyl))) zirconium dichloride, rac — [methylene bis (7 — (4 — t-butylindenyl))] zirconium dichloride, rac — [Methylene bis (7- (4-methylindenyl))] zirconium dichloride, rac- [Methylene bis (7- (2,4-dimethylindenyl)) ] Zirconium dichloride, rac — [methylenebis (7- (d4-dimethylindul))] zirconium dichloride, rac — [methylenbis (6— (2-methylindenyl) )))] Zirconium dichloride, rac — [dimethylsilylene bis (6— (2—methylindenyl))]] zirconium dichloride, rac— [1,2—ethylene bis (7— ( 2 — phenyl-1-41-methylindenyl))) zirconium dichloride lid, rac — [and 2 — ethylenebis (6 — (2 — methyl-3 — phenylindenyl))] zirconium dichloride , Rac — [isopropylidenebis (7 — (2 — phenyl-41 -methylindenyl))] zirconium dichloride, rac — [methylenebis (7 — (2 — Phenyl-41-methylindenyl)))) zirconium dichloride, rac- [1,2—ethylenebis (7— (2—phenylindenyl));) zirconium dichloride, rac— [dimethyl Tyrsilylene bis (7- (4-t-butylindenyl)))] zirconium dichloride, rac— [dimethylsylylene bis (7— (4-methylindenyl))] zirconium dichloride , Rac — [Dimethylsilyl sulfide (7 — (2, 4 — Dimethylindenyl))) zirconium dichloride, rac — [1,2-ethylenebis (7-indenyl)] zirconium dichloride, rac — (trans —1,2-cyclohexylenebis (7 — ( 4t-butylindenyl)))] zirconium dichloride, rac—C trans—l, 2—cyclohexylenebis (7— (4-methylindenyl))) zirconium dichloride, rac— [trans— 1,2-cyclohexylenebis (7— (2,4—dimethylindenyl))] zirconium dichloride, rac— !: trans-1,2—cyclohexylenebis (7— (1,4—dimethylidyl) Ndenyl)))] zirconium dichloride, rac — [1,2—ethylenbis (4-fluorenyl)] zirconium dichloride, rac — [1,2—ethylene (4- (11-methylfluorenyl))] zirconium dichloride and the like, and those obtained by substituting the racemic form in these compounds with meso forms, and those in which zirconium in these compounds is substituted by titanium or hafnium Of course, the compound is not limited to these, and may be a similar compound of a metal element of another group or a lanthanide series.

The catalyst for polymerization of olefins of the present invention comprises (A) a transition metal compound represented by the above general formula (I) and an activation co-catalyst, for example, (B) a transition metal compound of the component (A) or a derivative thereof. It is a catalyst containing a compound capable of forming an ionic complex by reacting with an organism and, if necessary, (C) an organic aluminum compound.

In the above polymerization catalyst, the transition metal compound represented by the general formula (I) used as the component (A) may be used alone or in combination of two or more. In the polymerization catalyst of the present invention, the component (A) and the activating cocatalyst are used. There is no particular limitation on the activation promoter, For example, as the component (B), a transition metal compound of the component (A) or a compound capable of forming an ionic complex by reacting with a derivative thereof is used.

The component (B) includes (B-1) an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), (B-2) luminoxane, (B-3) Lewis acids can be mentioned.

As the component (B-1), any of ionic compounds capable of forming an ionic complex by reacting with the transition metal compound of the component (A) can be used. II), (III)

([I-R ⁹ ] ^{k +} ) · ([Z]-) _b · · ·

([I] ^{k +} ), ([Z]-) _b

[However, L ² is ^{^{^{M 2, R, 0 R 1}}} 'Μ 3, R' 2 3 C or R ¹³ M ³ o

[In the formulas (II) and (III), L ′ represents a Lewis base, and [Z] − represents a non-coordinating dione [Ζ ′] − or [Ζ ² ] −. Here, [Ζ ']-is an anion in which multiple groups are bonded to an element, that is, [IV! ¹ G ¹ G ² ■ · · G ^f )-

(Here, M 'is fifth to 1 V element of the periodic table, preferably a first 3-1 V element of the periodic table. G' ~G ^f are each a hydrogen atom, a halogen atom, Alkyl group having 2 to 20 carbon atoms, dialkylamino group having 2 to 40 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, carbon Alkyl aryl group having 7 to 40 carbon atoms, aryl alkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, organic metalloid group Or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms, wherein two or more of G ^{1 to} G ^f may form a ring, and f is [(atom of central metal M ′ ) + 1], and [Z ² ] 1 represents a Brents state whose logarithm (pK a) of the reciprocal of the acid dissociation constant is −10 or less. It indicates a conjugate base composed of a single acid or a combination of a Brentsted acid and a Lewis acid, or a conjugate base generally defined as a superacid. Further, a Lewis base may be coordinated. Also, R ^e represents a hydrogen atom, an alkyl group having 1 to 2 0 carbon atoms, the number of 6-2 0 § Li Lumpur group carbon, Arukirua Li Lumpur groups or § Li Ruarukiru group, R ¹ * "and R ¹¹ is a cyclopentenyl group, a substituted cyclopentenyl group, an indenyl group or a fluorenyl group, and R ¹² is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl group. R ¹³ represents a macrocyclic ligand such as tetrafdinyl porphyrin, phthalocyanine, etc. k represents the ionic valence of [L ¹ -R ⁹ ], CL ² ]. 1-3 integer, a is an integer of 1 or more, b = a (k X a). M ² is one comprising a first, periodic table 3, 1 1 to 1 3, 1 7 group elements, M ³ represents an element in Groups 7 to 12 of the periodic table.]

It is possible to suitably use those represented by

Here, specific examples of L ′ include ammonia, methylamine, aniline, dimethylamine, getylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, Trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, ρ-bromo-N, N-dimethylaniline, p—dinitro-N, N-dimethylaniline Amines, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiothiophene, esters such as ethyl benzoate, and acetates. Examples include nitriles such as tonitrile and benzonitrile.

Specific examples of R ⁹ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ^{1 G} and R ¹ ′ include: Examples include cyclopentenyl group, methylcyclopentenyl group, ethylcyclopentenyl group, and pentamethylcyclopentagenenyl group. Specific examples of R ¹² include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹³ include tetraphenylborfyl Phthalocyanine, aryl, and methallyl. Specific examples of M ² include Li, Na, K, Ag, C g, Br, I, and I _3. Specific examples of M ³ include Can be listed as Mn, Fe, Co, Ni, and Zn.

Also, [Zeta '] -, namely [M'^{^{'in, Μ G 1 G 2 · ·}} · 〇]' is a specific example of Β, A 1, Si, P , A s, such as S b, preferred Or B1 and A1. Further, as a specific example of G '~G ^f, Jimechirua Mi cyano group as a Jiarukirua Mi amino group, etc. Jechirua Mi amino group, an alkoxy group Wakashi Ku is main butoxy group and a § re Ruokishi group, Ethoxy, n-butoxy, phenoxy and other hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n- Octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenyl, etc. , Bromine, iodine, and heteroatom-containing hydrocarbon groups such as P-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, 3,4,5-trifluorophenyl, and pentafluorophenyl Group, 3, 5—Bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, and other organic methyl groups such as pentamethylantimony, trimethylnyl, and trimethylgermyl groups , Diphenylarsine group, dicyclohexylantimony group, diphenylboron and the like. Further, specific examples of the non-coordinating anion, that is, the conjugated salt group [Z ² ] − of a blended acid alone or a combination of a blended acid and a Lewis acid having a pKa of −10 or less are given below. , Application Benefits Furuoro main evening Nsuruhon acid § d on (CF ₃ S 0) -, bis (g Li Furuoro meth Nsuruhoniru) method Chirua two on, bis (g Li Furuorometa Nsuruhoniru) Benjirua two on, bis (g Li Furuoro meth Nsuruhoniru) A Mi de, perchlorate § d on (C 1 0 ₄₎ -, Application Benefits Furuoro acetate anion _{_{(CF 3 C 0 2) -}} , the hexa full O b antimony § anions (S b F _e) -, Furuorosuru acid Anion (FS 0 ₃₎ -, Anion chlorosulfonic acid _{(C 1 S 0 3) -} , Furuorosuruhon acid Anion Z 5-full Tsu antimony (FS 0 / S b F) -, Furuorosuruhon acid Anion 5—Fluoride _{(FS 0 3 / A s F} ) -, Application Benefits Furuorome data Nsuruhon acid Z 5-off Kkaa Nchimon _{_{(CF 3 S 0 3 ZS b}} F 5) - and the like can and Ageruko.

An example of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, a specific example of the compound of the component (B-1) is triethyl tetraphenylborate. Ammonium, tri-n-butylammonium tetratetraborate, trimethylammonium tetrabutylborate, tetramethylammonium tetraphenylborate, methyl tetratetraborate n-butyl) ammonium, benzyltetrabutyl borate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetrabutylborate, triphenylphenylborate (methyl) ammonium, tributylphenylborate Methylanilinium, Methylpyridinium tetraphenylborate, Tetraphenylboron Benzylpyridinium acid, methyl tetraphenylborate (2-cyanopyridinium), Tetrakis (fluorophenyl phenyl) Triethylammonium borate, Tetrakis

) Tri-n-borate, butylammonium, tetrakis (fluorene phenyl) Triphenylborate, tetrakis (fluorene pentyl) Tetra n-borate, n-butylammonium, tetrakis Pentaphenylammonium borate, tetraethylammonium borate, tetraxammonium (phenylphenylphenyl) benzoyl borate (tri-n-butyl) ammonium, tetrakis (phenylphenylammonium), methyldiphenylammonium borate , Tetrakis (pentafluorophenyl) triphenyl (methyl) ammonium borate, tetrax (phenylfluorophenyl) methylanilinium borate, tetrakis (pentaphenylphenyl) phenyldimethylborate, dimethylanilinium borate, Tetrakis (Penyu fluorophenyl) Trimethylanilinium borate, Tetrakis (pentafluorophenyl) Methylpyridinium borate, Tetrakis (pentafluorophenyl) Benzylpyridinium borate, Tetrakis (pentanofluorophenyl) Methyl borate (2-cyano) Pyridinium), tetrakis (pentafluorofluorophenyl) benzoyl borate (2-cyanopyridinium), tetrakis (pentanofluorophenyl) methyl borate (41 cyanopyridinium), tetrakis (pentafluorofluorophenyl) Triphenylphosphonium borate, Tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, Tetraf Xnylfluorosenium borate, Tetraphenyl silver borate, Tetraphenyl silver Trityl traphenylborate, Tetrafue Tetraphenyl porphyrin manganese ruborate, Tetrakis (pentafluorophenyl) borate ferrocene, tetrakis (pentafluorophenyl) borate (1,1'-dimethylphenate), Tetrakis (pentafluorophenyl) borate Decamethylferrosenium, Tetrakis (Pentafluorophenyl) Silver borate, Tetrakis (Penya) Fluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) thiolaphenyl borphyrin manganese borate, silver tetrafluoroborate, Examples include silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

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. Is also good.

On the other hand, as the aluminoxane of the component (B-2), the general formula (IV)

T] 4 ϋ 1

/ A 1-O-fA 1-0-> ^-A 1

R ¹⁴

[In the formula, R ¹⁴ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a halogen atom having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms. And w represent the degree of polymerization and are usually integers of 3 to 50, preferably 7 to 40. Note that each R ¹⁴ may be the same or different. ].

A chain-bound aluminoxane represented by the general formula (V)

Wherein R ¹⁴ and W are the same as above. ]

And the cyclic aluminoxane represented by

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 reaction is not particularly limited, and may be carried out according to a known method. For example, (1) a method in which an organic aluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organic aluminum compound is initially added during polymerization and water is added later, and (3) a metal salt is contained. Reaction of the water of crystallization, water adsorbed on organic or organic substances with organic aluminum compounds, and reaction of tetraalkylaluminum with trialkylaluminoxane and further reaction with water. is there. In addition, toluene may be insoluble in aluminum.

These aluminoxanes may be used alone or in combination of two or more.

The Lewis acid as the component (B-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 or an aluminum compound is preferably used. As the aluminum compound, for example, bis (2,6-di-t-butyl-4-methylphenoxy) aluminum-methyl, (shi-11-b2-naphthoxy) aluminummethyl, etc. Examples of the aluminum compound include magnesium chloride and magnesium magnesium, examples of the aluminum compound include aluminum oxide and aluminum chloride, and examples of the boron compound include triphenylboron and trisium. Boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, trisー n-butylboron, 'tris (fluoromethyl) boron, tris (pentachlorofluoroethyl) boron, tris (Nonafluorobutyl) boron, tris (2,4,6—trifluorophenyl) boron, tris (3,5—difluoro) boron, tris [3,5—bis (trif Fluoromethyl) phenyl] boron, bis (pentafluorofluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorofluorophenyl) cycloborane, dimethylfluoroboron, getylfluoroboron, di-n-butylfluoroboron, penta Examples thereof include fluorophenyl difluoroboron, phenyl difluoroboron, penfluorofluorophenyl dichloroboron, methyl difluoroboron, ethyl difluoroboron, and n-butyl difluoroboron.

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 (A) catalyst component to the (B) catalyst component is preferably 1 mole in the case of using the (B-1) compound as the (B) catalyst component. The ratio is preferably in the range of 0: 1 to 1: 100, more preferably in the range of 2: 1 to 1:10, and when the compound (B-2) is used, the molar ratio is preferably 1: 1: A range of 1-1: 1.000,000, more preferably 1: 10-1: 100,000 is desirable.

The use ratio of the catalyst component (A) to the catalyst component (B-3) is preferably from 1: 0.1 to 1: 200, more preferably from 1: 0.2, in a molar ratio. 1: 100, more preferably in the range of 1: 0.5 to 1: 500. When the component (B) is out of the above range, the catalyst cost per unit weight of the polymer increases, which is not practical. As the catalyst component (B), (B-1), (B-2), (B-3) and the like can be used alone or in combination of two or more.

The polymerization catalyst of the present invention may contain the above components (A) and (B) as main components, or may contain the components (A), (B) and (C) organic components. It contains aluminum compound as a main component and is excellent Here, the organoaluminum compound of the component (c) is represented by the general formula (VI)

R ^{1 5} v A 1 J 3-ν (VI)

[In the formula, R ^{1 S} represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom. , V is an integer of 1 to 3. ]

Can be used.

Specific examples of the compound represented by the general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylbutylaluminum, dimethylaluminum chloride. , Getyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, getyl aluminum hydride, ethyl aluminum sesquichloride, etc. No.

These organoaluminum compounds may be used alone or in combination of two or more.

The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10.00000, more preferably 1: 5 to 1: 2. , 0000, more preferably in the range of 1:10 to 1: 1,000. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, when the amount is too large, the organic aluminum compound is wasted and a large amount of the organic aluminum compound is contained in the polymer. It remains and is not preferred.

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, other inorganic carriers and an organic carrier can be used. Particularly, from the viewpoint of morphology control, the inorganic oxide carrier and the like can be used. Or other inorganic carriers are preferred.

Is an inorganic oxide support, _{specifically, S i 0 2, A 1} 2 0 3, M g 0, Z r 02, T i 02, F e 2 0 3, B 2 0 3, C a O, ZnO, BaO, Th02 and mixtures thereof, for example, silica alumina, zeolite, bright, glass fiber and the like. The inorganic oxide carrier may contain a small amount of a carbonate, a nitrate, a sulfate, or the like.

On the other hand, as a carrier other than the _{above, M g C l 2, U} g C \ (0 C 2 H 5), M g (0 C 2 H 5) one represented by magnesium compounds such as ₂ general formula such as M g R ¹⁶ _{x X} 'magnesium represented by _y compound or a complex salt can and Ageruko. Here, R ¹⁶ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ is a halogen atom or 1 to 2 carbon atoms. Represents an alkyl group of 0, X is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁶ and each X ¹ may be the same or different.

Examples of the organic carrier include polymers such as polystyrene, styrene-divinyl benzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, and starch and carbon. And so on.

The carrier used in the present _{invention, M g C l 2, g} C 1 (0 C 2 H 5), M g (OC 2 H 5) 2, S i 02, A 1 2 0 3 , etc. is good or arbitrary . The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually l to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. 0 / zm.

If the particle size is small, the fine powder in the polymer increases, and if the particle size is large, the coarse particles in the polymer increase and the bulk density decreases, which causes clogging of the hot pot. The ratio surface穑of carrier is usually ^{1 ~ 1 0 0 O m 2} Zg, favored properly is ^{5 0~ 5 0 0 m 2 Zg} , pore volume is usually 0. 1 ~ 5 cm ³ Zg, preferred and rather Is 0.3 to 3 cm ³ Zg.

If either the specific surface area or the pore volume deviates from the above range, the catalyst activity may decrease. The specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method. (Journal of “OB”, “American”, “Chemical” Society, Vol. 60 , P. 309 (see 1983).

Further, it is desirable that the above-mentioned carrier is used after being calcined usually at 150 to 1000, preferably at 200 to 800'C.

When at least one of the catalyst components is supported on the carrier, at least one of (A) the catalyst component and (B) the catalyst component, preferably both (A) the catalyst component and (B) the catalyst component are used. It is desirable to carry it.

The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, the method of mixing at least one of the component (A) and the component (B) with the carrier is not limited. (2) A method in which a carrier is treated with an organic aluminum compound or a halogen-containing gay compound, and then mixed with at least one of the components (A) and (B) in an inert solvent. (3) The carrier and (A) A method of reacting the component and the component (B) with the organoaluminum compound or the halogen-containing gayne compound; ④ After the component (A) or the component (B) is supported on a carrier, the component (B) orと A method of mixing the contact product of the component (A) with the component (B) with the carrier, ⑥ A method of coexisting the carrier in the contact reaction of the component (A) with the component (B). Etc. can be used.

In the above reactions (1), (2) and (3), an organic aluminum compound as the component (C) 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 produced by carrying out loading operation of at least one of the components (A) and (B) on a carrier in a polymerization system. For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and a olefin such as ethylene is added at normal pressure to 20 kg / cm ² , A method in which prepolymerization is performed at 120 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the use ratio of the compound (B-1) component and the carrier is preferably 1: 5 to 1: 100, more preferably 1:10 to 1: 1, by weight. The ratio is preferably 500, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 100, more preferably 1: 1, by weight. The ratio of the component (B-3) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1: 1 by weight. 0 to 1: It is desirable to set it to 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 in the above range. The ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10,000, more preferably 1:10 to 1: 500, by weight. It is desirable. The (B) component! If the proportion of the component (B-1), the component (B-2) or the component (B-3), and the carrier, or the proportion of the component (A) and the carrier deviates from the above range, the activity is reduced. May drop. The average particle size of the polymerization catalyst of the present invention thus prepared is usually from 2 to 200 m ^. Properly 1 0-1 5 0 〃 m, is properly especially preferred is 2 0-1 0 O m, specific surface area, typically 2 0-1 0 0 O m ² Zg, is favored properly 5 0-5 0 0 m ² Zg. If the average particle size is less than 2 m, fine powder in the polymer may increase, and if it exceeds 200 im, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² , the activity may decrease, and if it exceeds 100 O m ² Zg, the density of the polymer may decrease. Further, in the catalyst of the present invention, the amount of transition metal in 100 g of the support is usually 0.05 to 1 Og, preferably 0.1 to 2 g. If the amount of the transition metal is out of the above range, the activity may decrease.

By supporting on a carrier in this manner, an industrially advantageous polymer having a high bulk density and an excellent particle size distribution can be obtained.

According to the method for producing an olefin polymer of the present invention, homopolymerization of olefins, or olefins and other olefins, using the polymerization catalyst described above. Copolymerization with Z or another monomer (for example, copolymerization of different olefins with each other, copolymerization of olefins with other monomers, or (Copolymerization between fins and other monomers) can be suitably performed.

The olefins are not particularly limited, but α-olefins having 2 to 20 carbon atoms are preferred. This one-year-old refin includes, 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-tetradecen, 1-hexadecene, 1-octadecene, 1 eicosene, styrene, ρ-methylstyrene, isopropylstyrene, t-butylstyrene, etc. Can be mentioned. In addition, the above-described other classes may be appropriately selected from the above-mentioned classes. In the present invention, the above-mentioned orifices may be used alone or in combination of two or more. When copolymerizing two or more kinds of orifices, the above-mentioned orifices can be arbitrarily combined. For example, when propylene and ethylene, or ethylene and α-olefin having 3 to 10 carbon atoms are copolymerized, propylene and ethylene, or ethylene and carbon are used. The co-polymerization ratio (molar ratio) with α-olefin of Formulas 3 to 10 is usually 99.9: 0.1 to 0.1: 99.9, preferably 99.5: 0. 5-75.0: Selected in the range of 25.0.

Further, in the present invention, the above-mentioned olefins and other monomers may be copolymerized, and the other monomers used in this case include, for example, Bugen Gen: Isoprene. 1,5—Chain diolefins such as hexadiene; norbornane; 1,4,5,8 —Dimethanones 2,3,4,4a, 5,8,8a — Cytahydronaphthalene; cyclic olefins such as 2-norbornene, norbornadiene, 5-bornyldenenoruborene, 5-vinylvinylnorbornene, and cyclic cycloolefins such as dicyclopentene, acrylic. Unsaturated esters such as ethyl ester and methyl methacrylate, and lactones such as / S-propiolactone, / S-butyrolactone and 7-butyrolactone , £ Ichiriki Pro Lactum, ά Arm, epoxy propane; 1, 2 - epoxy pigs emissions of which epoxides and the like can and Ageruko.

The polymerization catalyst of the present invention can be used not only for the polymerization of the above-mentioned olefins, but also for polymerization of other than the olefins.

In the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Polymerization and gas phase polymerization are particularly preferred. The polymerization 'condition, the polymerization temperature is usually one ^{1 0 0~ 2 5 0 e C} , Shi preferred Te Ku Her 5 0-2 0 0, more preferred properly is 0~ 1 3 0 ^e C. The proportion of the catalyst to the reaction raw material, the raw material monomer Z component (A) (molar ratio) is preferable properly 1 to 1 0 ^8, in particular 1 0 0-1 0 ⁵ become this and is favored arbitrary. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to SOO kgZcm ² G, particularly preferably normal pressure to 100 kg / cm ² G.

Methods for adjusting the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, quinylene, and ethylbenzene, alicyclic hydrocarbons such as cyclo π-pentane, cyclohexane, and methylcyclohexane, pentane, hexane Aliphatic hydrocarbons such as octane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. One of these solvents may be used alone, or two or more thereof may be used in combination. In addition, a monomer such as Hishinsai Refine may be used as a solvent. Depending on the polymerization method, the reaction can be carried out without solvent.

The molecular weight of the polymer obtained in this way is not particularly limited, but the intrinsic viscosity [7?] (Measured in 135′C decalin) is 0.1 deciliter / g. The above is preferable, and in particular, 0.2 g / g or more Zg or more is preferable.

In the present invention, preliminary polymerization can be performed using the polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of an orifice into contact with the solid catalyst component, for example, but the method is not particularly limited, and a known method can be used. There is no particular limitation on the orifice used in the prepolymerization, and the same as those exemplified above, for example, Examples thereof include ethylene, one-year-old olefin having 3 to 20 carbon atoms, and a mixture thereof. It is advantageous to use the same olefin as used in the polymerization.

The prepolymerization temperature is usually from 120 to 200, preferably from -10 to 130, more preferably from 0 to 80. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Further, the prepolymerization may be performed without a solvent.

In the prepolymerization, the intrinsic viscosity [7?] (Measured in 135 ° C decalin) of the prepolymerized product is more than 0.2 deciliters, especially more than 0.5 deciliters, in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product per 1 mol of the transition metal component is 1 to 1000 g, particularly 100 to 100 g.

In this manner, the olefin polymer of the present invention having a narrow molecular weight distribution and a relatively wide composition distribution can be efficiently obtained.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1

[Ethylene bis (7- (4-methylindenyl))] Production of zirconium dichloride (Compound (A))

(1) In a 1-liter three-necked flask purged with nitrogen, 29 g (0.213 mol) of anhydrous aluminum chloride and 50 milliliters of anhydrous carbon disulfide were added and stirred.

Into this, a solution of 13.5 g (0.0469 mole) of carbon disulfide (70 milliliters) of pionyl chloride of 3-chlorope was added dropwise. Next, 10 g (0.048 mol) of 4,4'-dimethyldibenzyl An elemental (120 milliliter) solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the reaction, the mixture was poured into 500 milliliters of ice water to separate a carbon disulfide layer. The remaining solution was extracted three times with 50 milliliters of dichloromethane. The carbon disulfide solution and the dichloromethane extract were combined, washed twice with a saturated sodium hydrogen carbonate aqueous solution (250 milliliters), and then dried over sodium sulfate.

The residue obtained by evaporating the solvent under reduced pressure was purified by column chromatography using silica gel to give the intermediate product (the following compound group A1) as a white solid in a quantity of 14.3 g (0. 0.37 mol, yield: 77%).

When 'H-NMR was determined for this product, the following results were obtained. The 'H-NMR chart is shown in Fig. 1.

. Ή - NMR (9 0 MH z, CDC 1 3, δ): 2. 3 2~2 · 4 5 (6 H, C Η 3) 2. 8 8~ 3. 8 9 (2 H, CH 2) , 7.10 to 7.39 (m, 6H, aromatic H) This indicates that this is a mixture of the following compound group A1.

Compound group A 1

CH ₃ — (O /-• CH ₂ -CH _2-

0

C 1 C 1 CH 3— θ) ~ CH 2-CH 2— <0) ~~ CH

(2) 14.3 g (0.07 mol) of the compound group A obtained in (1) was added to 50 milliliters of concentrated sulfuric acid under a nitrogen stream, and the mixture was heated at 80 to 1 hour. Heat and stir. After allowing to cool, the reaction was poured into 500 milliliters of cold water. Extraction was performed five times with 100 ml of dichloromethane. The dichloromethan extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution (250 milliliters) and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain an off-white solid. Purification by column chromatography using silica gel gave 7.8 g (0.024 mol, yield: 67%) of the target intermediate (compound group A2) as a white solid. Was.

'Η-NMR of this product gave the following results. Fig. 2 shows the Η-NMR chart.

.. Ή - NMR (9 0 ΜΗ Ζ, CDC 1 3, δ): 2. 3 3~3 3 8 (1 8 Η, CH 3 and _{CH 2), 6 · 9 8~7} 3 8 (m, 4 H, aromatic H) This indicates a mixture of the following compound group A2. Compound group A 2

H

(3) Lithium aluminum hydride 1.65 g (0.043 mol) of tetrahydrofuran (THF) (300 milliliters) turbid solution was cooled to ice under a nitrogen stream. While cooling, 7.8 g (0.024 mol) of the compound group A 2 obtained in (2) was added little by little. After the addition was completed, the mixture was heated under reflux for 30 minutes. Under ice cooling, 10 milliliters of water was added little by little. After distilling off THF from the reaction solution under reduced pressure, 200 milliliters of diluted hydrochloric acid was added. Extraction was further performed four times with 50 milliliters of getyl ether. The extract is dried over sodium sulfate and evaporated under reduced pressure to give the intermediate product of interest.

(The following compound group A3) as a colorless solid, 4.1 g (0.013 mol, yield)

: 52%).

The following results were obtained when 'Η— NMR of this product was determined. FIG. 3 shows the 'H-NMR chart.

Ή - NMR (9 0 MH z , CDC 1 3, δ): 2. 2 3~ 3. 0 4 (2 OH, CH 3, CH 2, OH), 5. 1 0~ 5. 4 0 (2 H , CH-0 H), 6.9 3-7.20 (4 H, aromatic H)

This indicates that it is a mixture of the following compound group A3.

(4) A compound group A 34.1 g (0.013 mol) obtained in (3) was dissolved in dimethyl ether 200 milliliters, and iodine fragments 1.1 g were added. And stirred in the greenhouse for 200 hours. Based on the reaction solution, the aqueous solution was washed twice with 100 ml of a saturated aqueous solution of sodium thiosulfate, and then dried with sodium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by column chromatography using silica gel to obtain the target intermediate (compound group A4 below) as a yellow-white solid. g (0.006 mol, yield: 47%).

'Η-NMR analysis of this product gave the following results. FIG. 4 shows the Η-NMR chart.

. 'H - NMR (. 9 0 MH z, CDC 1 3 <5): 2. 3 3~2 4 0 (m, 6 H, CH 3), 2. 9 6~ 3. 2 3 (m, 8 H, CH ₂ ), 6.45 to 6.59 (m, 4 H, CH), 6, 92 to 7.28 (m, 4 H, aromatic H) Compound group A 4 indicating a mixture of 4

(5) Production of compound (A)

Compounds A 4 0. 7 0 g (2. 4 4 Mi Rimoru) After the was dissolved in TH F 5 0 millimeter Li Tsu Torr, this one 7 8 ^e C n-butyl lithium 4.8 millimeter mol (1.6 molar hexane solution in hexane) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, after the solvent was distilled off, the residue was washed once with hexane (20 milliliters) and dried to obtain a pale orange powder. This solid was suspended in 50 milliliters of toluene, 0.57 g (2.4 millimoles) of zirconium tetrachloride was added at 120 "C, and the mixture was stirred at room temperature for 12 hours. The obtained solid was evaporated to dryness to obtain [ethylenebis (7- (4-methylindenyl)) zirconium dichloride (compound A) as a yellow solid. 'H-NMR indicated a mixture of 57:43 two isomers.

The obtained solid was extracted with 20 milliliters of toluene at room temperature, filtered, concentrated to 5 milliliters, and then cooled to 120 milliliters to obtain a racemic mixture. [Ethylenebis (7- (4-methylindenyl))] zirconium dichloride (compound (A11)) (70 m) was obtained as yellow crystals.

'Η-NMR of this product gave the following results. Ή - NMR (9 0 MH z , CDC 1 3, δ): 2. 5 2 (6 Η, s, CH 3 -), 3. 2 1 (H, m, - CH 2 - CH 2 -), 4 . 48 (2H, dd, Cp ring), 6.74 (4H, m, Cp ring), 7.14 (4H, m, aromatic H)

3 o From the extraction residue, compound A12, which is considered to be a meso form, was obtained as a yellow powder by extraction with dichloromethane 20 milliliters.

'H-NMR measurement of this product gave the following results.

Ή - NMR (9 0 H z , CDC 1 3, δ): 2. 3 8 (6 H, s, CH 3 -), 3. 3 8 (4 H, m, - CH 2 one CH ₂ -), 6.5 0 — 6.80 (6 H, m, one C p-ring), 7.05 — 7.2 0 (4 H, m, aromatic H)

From these, it is presumed that Compound A is a mixture of racemic body: meso body = 57: 43.

Example 2

A heated vacuum dried 1 Li Tsu Toruo preparative click Loew, under a nitrogen atmosphere at room temperature, toluene 4 0 0 ml and Mechiruaru Mi Nokisan 2 3 Mi temperature of Li molar placed stirring solution 0 ^e C After that, 2 micromoles of rac— [ethylenbis (7— (4—methylidenyl))] zirconium dichloride (compound (A1 1)) obtained in Example 1 was added. 5 0 ^e C in continuously introduced while maintaining the pro pyrene 7 atm were 3 0 minutes polymerization.

After completion of the reaction, the reaction product was poured into a methanol-hydrochloric acid solution, stirred sufficiently, then separated, washed sufficiently with methanol, and dried to obtain Volima-2.7. Was. Its melting point is 104.2. The intrinsic viscosity [η] is 0.20 d 1 g [135. C, measured in decalin].

Example 3

Heat and dry under reduced pressure 1 liter autoclave in a nitrogen atmosphere at room temperature with toluene 360 milliliter, 1-octene 40 milliliter and triisobutylaluminum (TIBA) 1 milliliter. Then, the temperature of the solution was brought to 60 t with stirring, and then the solution was obtained at 60 in Example 1. The transition metal厲錯body (Compound A) 1 My Kuromoru and Te tetrakis (pen evening fluorophenyl) borate N, N - put dimethyl § two linear ©厶1 micro mol, and the temperature was raised to 8 0 ^e C. 8 0 ^e want C at such keeping ethylene in to 8 atm, while introducing continuously performed for 10 minutes polymerization.

After the completion of the reaction, the reaction product was poured into a methanol-hydrochloric acid solution, stirred sufficiently, separated, further washed sufficiently with methanol, and dried to obtain a polymer. Table 1 shows the results of measuring the yield and various properties of the obtained polymer.

Example 4

In Example 3, 6 mmol of methylaluminoxane was used in place of 1 mmol of TIBA, and N, N-dimethylanilinium tetratetrakis (pentylfluorophenyl) borate was not used. Except for, the procedure was performed in the same manner as in Example 2. Table 1 shows the results.

Example 5

Example 3 was carried out in the same manner as in Example 3 except that toluene was used at 400 milliliters and that 1-octene 40 milliliter was not used. Table 1 shows the results.

Example 6

Example 4 was carried out in the same manner as in Example 4 except that toluene was used at 400 milliliters and that 1-octene 40 milliliter was not used. Table 1 shows the results. Table 1 1

〔note〕

TIBA: Triisobutyl aluminum

B-1: Tetrakis (pennyl fluorophenyl) borate N, N-dimethylaniline

M A 0: methyl aluminum oxane

A: [Ethylene bis (7- (4-methylindenyl))] zirconium chloride

Table 1 Table 2

* D S C, heating rate 10. Measured in second heat at C / min

* * 1 90. C, 2.16 kg of male toffee index

* * * 1 3 5 and measured in decal Example 7

[Ethylenebis (7- (4-t-butylindenyl))] zirconium dimethyl chloride (production of compound B)

The following compound group B, 1.1 g (3.0 millimoles) was dissolved in THF 50 milliliters, and then n-butyllithium 3.0 millimoles (1 Compound 6 B was added dropwise and stirred at room temperature for 1 hour.

Then, after distilling off the solvent, the residue was washed once with hexane 20 milliliters and dried to obtain a yellow powder. This solid was suspended in 20 milliliters of toluene, 0.7 g (3.0 millimoles) of zirconium tetrachloride was added at 120 ° C, and the mixture was stirred at room temperature for 12 hours and then the solvent was added. Was distilled off. The solid obtained was dried to give [ethylenebis (7- (4-1t-butylindenyl))] zirconium dichloride (compound B) as a yellow solid. Obtained. 'Η-NMR indicated that Compound B was a mixture of two isomers.

The resulting solid was extracted with hexane at 20 milliliters at room temperature, filtered, concentrated to 5 milliliters, and cooled to 120 ° C. 0.38 g of zirconium dichloride (compound (B11)), which is considered to be a meso form [ethylene (7- (4-t-butylindenyl))], was obtained as a yellow powder.

'H-NMR measurement of this product gave the following results. Ή - NMR (9 0 MH z , CDC 1 3, δ):. 1. 1 8 (1 8 H, s, t - Β u), 3. 2~3 6 (4 Η, m, - C Η 2 C Eta ₂ one), 6. 4 8, 6. 7 6, 7. 0 4~7. 2 5 (1 0 Η, C ρ ring, aromatic Eta)

Further, from the extraction residue, compound B12, which is considered to be a racemic body, was obtained as a yellow powder by extraction with dichloromethane 20 milliliters.

'H-NMR measurement of this product gave the following results. Ή - NMR (9 0 MH z , CDC 1 3, δ):. 1. 4 0 (1 8 Η, s, t - Β υ), 3. 0~3 5 (4 Η, m, one CH ₂ CH ₂ one), 4. 1 7 (2 H , m, C p rings), 6. 5~6. 8 (4 H, m, C p rings), 7. 4 0, 7. 5 8 (4 H, d, aromatic H)

From these, it is presumed that Compound B is a mixture of racemic body: meso body = 45:55.

Example 8

In a 1-litre crove, heated and dried under reduced pressure, at room temperature under nitrogen atmosphere, add 400 milliliters of toluene and 2 millimoles of methylaluminoxane, and raise the temperature of the solution to 30 ° C with stirring. After that, 2 micromoles of rac— [ethylenebis (7— (4—t-butylindenyl))] zirconium dichloride (compound (B12)) obtained in Example 7 was added. Was. 5 0 ^e C pro Pilet down continuously introduced while maintaining the 7 atm was 3 0 minutes polymerization.

After the reaction is completed, the reaction product is poured into a methanol-hydrochloric acid solution, stirred sufficiently, separated, washed thoroughly with methanol and dried, and then dried. 8 g were obtained. It had a melting point of 159 and a pentad-meso fraction CmnimnO of 90.2%. No peak of 2,1 insertion was observed from the NMR chart.

Note that the Ventatsu meso fraction [mmmm] is attributed to the pen mesomethod out of the total area of the nine signals appearing between 19 and 22 ppm out of ¹³ C of the volimer. It was measured as the ratio of the area occupied by the 1.545 ppm signal.

Example 9

Heated vacuum dried 1 liter autoclave at room temperature in a nitrogen atmosphere at room temperature for 360 tons of toluene, 40 milliliters of 1-octene and 3 millimoles of methylaluminoxane It was placed, after the 6 0 the temperature of the solution while擾柞, 6 0 ^e C in example 7 obtained in transition metal厲錯member (compound (B ll)) put 1 My Kuromoru, 8 0. The temperature was raised to C. At 80 ° C., polymerization was carried out for 10 minutes while continuously introducing ethylene and keeping the pressure at 8 atm.

After completion of the reaction, the reaction product was poured into a solution of methanol and monohydrochloric acid, and the mixture was sufficiently stirred.Then, the mixture was separated, washed sufficiently with methanol, and dried to obtain a polymer. . Table 2 shows the results of measuring the yield and characteristics of the obtained polymer.

Example 10

[Ethylene bis (7- (2,4-dimethylindenyl))] zirconium dimethyl chloride (Production of compound C) Compound Group C (12.6 g, 8.24 mmol) was dissolved in THF 60 milliliter, and then added to n-butyllithium 8.2 millimol (17.8 C). (6 M Z liter in hexane) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Compound group C 1

CHH

Then, after the solvent was distilled off, the residue was washed once with hexane 20 milliliters and dried to obtain a yellowish white powder. This solid was suspended in 70 milliliters of toluene, 1.9 g (8.2 millimoles) of zirconium tetrachloride was added at −20 ° C., the mixture was stirred at room temperature for 12 hours, and then the solvent was removed. Distilled off. The obtained solid was dried to give [ethylenebis (7- (2,4-dimethylindenyl))] zirconium dichloride (compound (C)) as a yellow solid. 'H-NMR indicated that Compound C was a mixture of two isomers. The resulting solid was extracted with 20 milliliters of hexane at room temperature, filtered, concentrated to 5 milliliters of filtrate, and cooled to 120 milliliters. 0.7 g of zirconium dichloride (compound (C 11)), which is considered to be a so-form [ethylenebis (7- (2,4-dimethylindenyl))], was obtained as a yellow powder.

'H-NMR measurement of this product gave the following results. Ή - NMR (9 0 MH z , CDC ", δ): 2. 3 0 (6 H, s, CH 3 -), 2. 3 4 (6 H, s, CH 3 I), 3.3 1 ( 4 H, m,-CH ₂ CH ₂ 1), 6.33 to 6.90 (8 H, m, C p-ring, aromatic H) Dichloromethane 20 milliliter from extraction residue As a result, compound C12 considered to be a racemic body was obtained as a yellow powder.

'Η-NMR measurement of this product gave the following results.

1 H - NR (9 0 MH z, CDC 1 3, 6): 2. 1 0 (6 H, s, CH 3 one), 2. 5 7 (6 H , s, CH 3 I), 2-9 0~ 3. 4 0 (4 H, m, - CH 2 CH 2 one), 4. 1 8 (2 H , d, C p rings), 6. 4 6 (2 H , d, C p rings) 6 9 ~ 7.15 (4 H, m, aromatic H)

Example 1 1

After dissolving 1.0 g (3.18 millimoles) of the compound group C used in Example 10 in 60 milliliters of ether, it was added to this mixture. At C, 3.2 millimoles of n-butyllithium (1.6 mol / liter of a hexane solution) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, the solvent was distilled off, and the residue was washed once with hexane 20 milliliters and dried to obtain an off-white powder. This solid was dissolved in 35 milliliters of THF and dried. C. Titanium trichloride.3 THF (1.2 g, 3.2 mmol) was added, and the mixture was stirred at room temperature for 12 hours. Then, silver chloride (1.0 g) was added, and the mixture was further stirred for 3 hours. After that, the solvent was distilled off, and the resulting solid was evaporated to dryness. Bis (7— (2,4-dimethylindenyl))] titanium dichloride

(Compound D) was obtained as a yellow solid.

The solid obtained was extracted with 20 milliliters of toluene at room temperature, filtered, concentrated to 5 milliliters, and then cooled to 20 milliliters to obtain a solid. [Ethylenebis (7- (2,4-dimethylindenyl))] titanium dichloride (compound (Dl1)) (0.25 g) was obtained as a yellow powder.

'H-NMR measurement of this product gave the following results.

Ή - NMR (9 0 MH z , CDC 1 3, δ): 2. 2 4 (6 H, s, CH 3 one), 2. 2 7 (6 H , s, CH 3 I), 3.0 7 ~ 3.38 (4 H, m,-CH a CH 2-), 6.3 4 ~ 7.2 0 (8 H, m, C p-ring, Hoka H)

Further, compound D12, which is considered to be a racemate, was obtained as a yellow powder from the extracted residue by extraction with hexane 20 milliliters.

'Η-NMR measurement of this product gave the following results. Ή - NMR (9 0 MH z , CDC 1 3, δ): 1. 9 5 (6 H, s, CH 3 one), 2. 5 3 (6 H , s, CH 3 -), 2. 8 4 ~ 3. 2 3. (4 H , S, - CH 2 CH 2 one), 3. 8 3 (2 H , S), 6. 5 7 (2 H, S), 6. 8 8~7 0 9 (4 H, m, C p-ring, aromatic H)

Example 1 2

The following compound E (1.82 g, 8.97 millimoles) was dissolved in 100 milliliters of THF, and 9.0 millimoles of n-butyllithium was added thereto at 178 ° C. (1.6 mol hexane solution) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Compound E 1

Then, after distilling off the solvent, the residue was washed once with 20 mil of hexane and dried to obtain an ocher powder. This solid was suspended in 35 milliliters of toluene, and 2.1 g (9.0 millimoles) of zirconium tetrachloride was added at 20 ° C, followed by stirring at room temperature for 12 hours, followed by removal of the solvent. Distilled off. The obtained solid was dried to give [ethylenebis (6- (2,3-dimethylindenyl))] zirconium dichloride (compound (E11)) as a yellow solid. The resulting solid was extracted with hexane at 20 milliliters at room temperature, filtered, concentrated to 5 milliliters, and cooled to 120 ° C. [Ethylenebis (6- (2,3-dimethylindenyl))] 0.9 mg of zirconium dichloride (compound (E11)) was obtained as a yellow powder.

'Η-NMR measurement of this product gave the following results. Ή - NMR (9 0 MH z , CDC 1 3, δ): 2. 2 2 (6 H, s, CH 3 one), 2. 2 8 (6 H , s, CH 3 -), 2 · 6 5 ~3, 2 5 (4 H, m, - CH 2 CH 2 one), 5. 8 8 (2 H , s), 6. 5 2 (2 H, s), 7. 0 7 (2 H, d ), 7.56 (2H, d) (Cp ring, aromatic H)

The following compound F12.75 g (6.27 millimoles) was dissolved in THF50 milliliters, and then n-butyllithium 6.3 milliliters was added thereto. The solution was added dropwise with 1.6 mol / liter of a hexane solution, and the mixture was stirred at room temperature for 1 hour. Compound F 1

Then, after the solvent was distilled off, the residue was washed once with hexane (20 milliliters) and dried to obtain a tan powder. This solid was suspended in 40 milliliters of toluene and added to the suspension. 1.6 g (2.3 mimol) of zirconium tetrachloride was added at C, and the mixture was stirred at room temperature for 12 hours, and then the solvent was distilled off. The obtained solid was dried to obtain [ethylenebis (6- (2-methyl-13-phenylindenyl))] zirconium dichloride (compound F11) as a yellow solid.

The resulting solid was extracted with 20 milliliters of hexane at room temperature, filtered, concentrated to 5 milliliters of filtrate, and cooled to 120 ° C. [Ethylenebis (6- (2-methyl-3-phenylenedenyl))] 1.3 mg of zirconium dichloride (compound (F11)) was obtained as a yellow powder.

The following results were obtained by measuring the NMR of this product. Ή - NMR (9 0 MH z , CDC 1 3, δ): 2. 3 2 (6 H, s, CH 3 -), 2. 6 5~ 3. 3 0 (4 H, m, - CH 2 CH ₂ —), 6.07 (2 H, s), 6.60 (2 H, s), 7.08 to 0.80 (18 H, m) (C p ring, aromatic H ) ' Example 14

Example 9 was carried out in the same manner as in Example 9 except that D11 was used instead of Catalyst B11. Table 2 shows the results.

Example 15

Example 9 was carried out in the same manner as in Example 9 except that E11 was used instead of the catalyst B11. Table 2 shows the results.

Example 16

Example 9 was carried out in the same manner as in Example 9 except that F11 was used instead of the catalyst B11. Table 2 shows the results.

Table 2 I

2 Table 1 2

* Measured in second heat at D S C, heating rate of 10'CZ

** 190, 2.16 kg melt index per index * * * 1 3 5 'C, measured in decalin

The transition metal compound of the present invention is a novel compound and is useful as a catalyst component for olefin polymerization. Further, the olefin polymer catalyst of the present invention has high activity, and by using the catalyst, an olefin polymer having a narrow molecular weight distribution and a relatively wide composition distribution can be efficiently obtained. In addition, since there is almost no heterogeneous bond due to 2,1-insertion in the polypropylene chain, a propylene polymer having a high melting point can be obtained. Industrial applicability

As described above, the transition metal compound of the present invention is useful as a component of an olefin polymerization catalyst. Further, the polymerization catalyst containing the transition metal compound is highly active, and gives an olefin-based polymer having a narrow molecular weight distribution and a relatively wide composition distribution, or a highly regular polypropylene. Can be. Further, by using this polymerization catalyst, an olefin homopolymer or a copolymer can be efficiently produced.

Claims

The scope of the claims

1. General formula (I)

(In the formula, M is a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanide series, X represents a ligand capable of bonding to M, and when there are a plurality of Xs, a plurality of Xs are represented by They may be the same or different, and may be crosslinked with an indenyl ring or Y. Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to an indenyl ring or X. A represents a crosslinking group, P represents an integer of 1 to 20, q represents an integer of 1 to 5, [(valency of M) 12], and r represents an integer of 0 to 3. R ^{1 to} R ⁸ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a heteroatom-containing group. They may be the same or different, or may form a ring with an adjacent group. Also, three R ^{4 's} may be the same or different, and three R ⁸ ' s may be the same or different. ]

A transition metal compound represented by

2. In the general formula (I), M is titanium, zirconium or Hough The transition metal compound according to claim 1, wherein the transition metal compound is selected from nickel.

3. (A) A catalyst for polymerization of olefins, comprising the transition metal compound according to claim 1 and an activation promoter.

4. Contains (A) the transition metal compound described in claim 1 and (B) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof. A catalyst for polymerization of olefins.

5 · The (B) component reacts with the (B-1) (A) component transition metal compound to form an ionic complex; (B-2) aluminoxane; 3) The catalyst for olefin polymerization according to claim 4, which is at least one kind selected from Louis acid.

6. The catalyst for polymerization of olefins according to claim 4, further comprising (C) an organic aluminum compound.

7. An olefin polymer obtained by using the catalyst for olefin polymerization according to any one of claims 3 to 6.

8. The olefins are homopolymerized in the presence of the catalyst for polymerization of olefins as defined in any one of claims 36, or the olefins and other olefins and other A method for producing an olefin polymer, comprising copolymerizing at least one of the above monomers.

9. The method for producing an olefin polymer according to claim 8, wherein the olefins are α-olefins having 2 to 20 carbon atoms.