JP2002167394A - Method for manufacturing organic transition metal compound, polymerization catalyst, and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel organic transition metal compound having a πcoordination compound as a ligand and useful as a catalyst component of a polymerization catalyst, and a polymerization catalyst therewith as a catalyst component. SOLUTION: This organic transition metal compound is expressed by the general formula: [(Z-A)n-D]mEaMXk-m-a (L)j (wherein, M is a transition metal of the group 3-11; D and E are respectively a πcoordination compound residue; A is a group bridging D and Z; X is a group forming a σ bond with M; L is a Lewis base; n and m are respectively 1 or 2; (a) and (j) are respectively 0 or 1; (k) is an oxidation number of M; k-m-a is an integer of 1 or more). The polymerization catalyst is composed of the combination of (A) the organic transition metal compound, (B) a compound producing an ionic compound by reactig with the component (A) of the organic transition metal compound, and on occasions (C) an organic alkyl metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organic transition metal compound, a polymerization catalyst and a method for producing a polymer.
More specifically, the present invention relates to a pyrazolyl-modified π
A novel organic transition metal compound having a coordinating compound as a ligand and useful as a catalyst component of a polymerization catalyst, and a olefin and an aromatic vinyl compound having a wide molecular weight distribution formed by using this compound as a catalyst component. Using a homogeneous and highly active polymerization catalyst to give a (co) polymer, and using this polymerization catalyst,
The present invention relates to a method for efficiently producing a (co) polymer of an olefin or an aromatic vinyl compound having a wide molecular weight distribution.

[0002]

2. Description of the Related Art Organometallic compounds having a π-coordinating compound having a charge of −1 as a ligand are effective as polymerization catalyst components, and various compounds have been used as polymerization catalysts.
It is known that various modifications of the π-coordinating compound can provide polymers having different molecular weights, copolymerizabilities, and stereoregularities. However, there is no known example in which an organometallic complex having a π-coordinating compound modified with a pyrazolyl group as a ligand is applied to a polymerization catalyst. It is generally known that when a conventional organometallic complex having a π-coordinating compound as a ligand is used as a polymerization catalyst, a polymer having a narrow molecular weight distribution and a uniform composition can be obtained. However, such a polymer has a problem that its moldability is poor as compared with a polymer having a wide molecular weight distribution and a non-uniform composition, which is obtained by a heterogeneous catalyst.

[0003]

Under such circumstances, the present invention provides a novel organic transition metal compound which has a π-coordinating compound as a ligand and is useful as a catalyst component of a polymerization catalyst. A homogeneous and highly active polymerization catalyst that gives a (co) polymer of olefins or aromatic vinyl compounds with a wide molecular weight distribution, using this as a catalyst component, and a molecular weight distribution of It is an object of the present invention to provide a method for efficiently producing a wide range of (co) polymers of olefins and aromatic vinyl compounds.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific structure in which a π-coordinating compound modified with a pyrazolyl group is used as a ligand is used. It has been found that the novel organic transition metal compound can achieve the object. The present invention has been completed based on such findings. That is, the present invention
(1) General formula (I) [(ZA) _n -D] _m E _a MX _kma (L) _j (I) wherein M is a transition metal of Groups 3 to 11 of the periodic table, D is -1
Π-coordinating compound residue having the following charge, Z is a pyrazolyl group or a substituted pyrazolyl group, A is a group that bridges D and Z, and E is-
A π-coordinating compound residue having a charge of 1, X represents a group forming a σ bond with M, and L represents a Lewis basic compound. n and m are each 1 or 2, a and j are each 0 or 1, k is an oxidation number of M, kma is an integer of 1 or more, and when n is 2, two (Z -A) may be the same or different. When m is 2, two [(Z-
A) _n -D] may be the same or different, or may be cross-linked. When a is 1, D and E, A and E, and Z and E may each be cross-linked. Good. D and X,
A and X, Z and X each may be cross-linked, and k-
When ma is 2 or more, a plurality of Xs may be the same or different. An organic transition metal compound represented by the formula:

(2) (A) an organic transition metal compound represented by the above general formula (I), and (B) a compound which reacts with the organic transition metal compound as the component (A) to form an ionic compound. And (C) a polymerization catalyst comprising a combination with an organometallic compound, and (3) a polymerization catalyst comprising polymerizing an olefin and / or an aromatic vinyl compound in the presence of the polymerization catalyst. And a method for producing a united product.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The organic transition metal compound of the present invention comprises
This is a novel compound having a structure represented by the general formula (I) [(ZA) _n -D] _m E _a MX _kma (L) _j (I). In the general formula (I), M represents a transition metal belonging to Groups 3 to 11, preferably Groups 4 to 6, of the periodic table, and specific examples thereof include titanium, zirconium, and hafnium.
D represents a π-coordinating compound residue having a charge of -1, and is preferably each of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, and substituted fluorenyl. Examples of the type of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroatom-containing hydrocarbon group having 3 to 10 carbon atoms, and the number of substituents is 0 to 4. . Specifically, examples of the alkyl group having 1 to 10 carbon atoms include groups such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, neopentyl, and octyl.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl, p-toluyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl,
Examples of each group include 2,6-diisopropyl-4-methylphenyl and naphthalenyl. Examples of the heteroatom-containing hydrocarbon group having 3 to 10 carbon atoms include a trimethylsilyl group and a trimethylsilylmethyl group.

Specific examples of the π-coordinating compound residue of D include cyclopentadienyl, indenyl, fluorenyl, methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl, and isopropylcyclopentadienyl. Enyl, butylcyclopentadienyl, tert-butylcyclopentadienyl, isobutylcyclopentadienyl, neopentycyclopentadienyl, octylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethyl Cyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, 1,2,3-trimethylcyclopentadienyl,
1,2,3,4-tetramethylcyclopentadienyl,
1-methyl-3-tert-butylcyclopentadienyl, phenylcyclopentadienyl, 1,3-diphenylcyclopentadienyl, 1-methyl-3-phenylcyclopentadienyl, trimethylsilylcyclopentadienyl, trimethylsilylmethyl Cyclopentadienyl, methylindenyl, phenylindenyl, trimethylsilylindenyl, trimethylsilylmethylindenyl, 2-methylindenyl, 2-phenylindenyl,
Tetrahydroindenyl, 4-phenylindenyl,
4,7-dimethylindenyl, 2,4,7-trimethylindenyl, 4,5-benzoindenyl, 5,6-benzoindenyl, 2,9-dimethylfluorenyl, 3,8
-Dimethylfluorenyl and the like.

Z represents a pyrazolyl group or a substituted pyrazolyl group. Examples of the type of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroatom-containing hydrocarbon group having 3 to 10 carbon atoms.
3. Specific examples include the substituents represented by D. Specific examples of the pyrazolyl group or substituted pyrazolyl group as Z include pyrazolyl, 3-methylpyrazolyl,
4-methylpyrazolyl, 5-methylpyrazolyl, 3,4
-Dimethylpyrazolyl, 3,5-dimethylpyrazolyl,
Examples of such groups include 4,5-dimethylpyrazolyl, 3,4,5-trimethylpyrazolyl, 3-isopropylpyrazolyl, and 3,5-diisopropylpyrazolyl. A is D
And a group bridging Z with, preferably a group having a carbon atom or a silicon atom in the main chain. Specifically, methylene, ethylene, ethylidene, propane-1,3-diyl, isopropylidene, butane-1,4-diyl, dimethylsilylene, diphenylsilylene, 2,2-dimethyl-2-silapropane-1,3- Each group such as diyl is exemplified. E represents a π-coordinating compound residue having a charge of -1, and preferably includes cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, and substituted fluorenyl groups. The number of substituents is 0-5. Examples of the type of the substituent and the specific examples of E are the same as the specific examples of the substituent and the π-coordinating compound residue described in the description of D, and pentamethylcyclopentadienyl, 1,2,3-trimethyl. Indenyl, 1
-Methylfluorenyl.

X is a group forming a σ bond with M. Preferred are a hydrogen atom, a halogen atom, an alkoxyl group, an aryloxy group, an amino group, an alkyl group or an aryl group, and specifically, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, furthermore, methoxy, ethoxy, Propoxy, isopropoxy, butoxy, tert-butoxy,
Phenoxy, p-methylphenoxy, pentafluorophenoxy, amino, dimethylamino, diethylamino,
Examples include diphenylamino, phenylmethylamino, bis (trimethylsilyl) amino, methyl, ethyl, propyl, isopropyl, butyl, bis (trimethylsilyl) methyl, phenyl, and p-methylphenyl.

L represents a Lewis basic compound, such as amines, ethers, phosphines, thioethers, esters, and nitriles. Specific examples of L include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine,
Methyldiphenylamine, pyridine, p-bromo-N,
Amines such as N-dimethylaniline; phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; nitriles such as acetonitrile and benzonitrile. Can be. n and m are 1 or 2, respectively;
a and j are each 0 or 1, k is the oxidation number of M, k-
ma represents an integer of 1 or more, and when n is 2, two (ZA) s may be the same or different. m
Is 2, the two [(ZA) _n -D] s may be the same or different, may be cross-linked,
Is 1, D and E, A and E, and Z and E may be crosslinked respectively. D and X, A and X, and Z and X may be cross-linked, respectively. When kma is 2 or more, a plurality of Xs may be the same or different.

Examples of the organic transition metal compound represented by the general formula (I) include (pentamethylcyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium dichloride and (pentamethylcyclopentadienyl) ( Pyrazolylethylcyclopentadienyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium diisopropoxide, (pentamethylcyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium chloride Hydride, (pentamethylcyclopentadienyl) (1,3-dimethylpyrazolylcyclopentadienyl) zirconium dichloride,
(Pentamethylcyclopentadienyl) (1,3-diisopropylpyrazolylethylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (pyrazolylethylindenyl) zirconium dichloride, (pentamethylcyclopentadienyl)
(Pyrazolylethylfluorenyl) zirconium dichloride, (cyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium dichloride, (indenyl) (pyrazolylethylcyclopentadienyl) zirconium dichloride, (fluorenyl) (pyrazolylethylcyclopentadiyl) (Enyl) zirconium dichloride, bis (pyrazolylethylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride, bis (1,3-diisopropylpyrazolylethylcyclopentadienyl) zirconium dichloride , (Pyrazolylethylcyclopentadienyl) zirconium trichloride, (1,3-dimethylpyrazolylethylcyclopentadienyl) Benzalkonium trichloride, (1,
3-dimethylpyrazolylethylcyclopentadienyl)
Zirconium triisopropoxide, (1,3-dimethylpyrazolylpropylcyclopentadienyl) zirconium trichloride, (1,3-dimethylpyrazolyldimethylsilylcyclopentadienyl) zirconium trichloride, and the like, and zirconium of these compounds is titanium And compounds substituted with hafnium.

The polymerization catalyst of the present invention comprises (A) an organic transition metal compound represented by the general formula (I) and (B) an ionic compound which reacts with the organic transition metal compound of the component (A). And optionally used (C)
It consists of a combination with an organometallic compound. In the polymerization catalyst of the present invention, the organic transition metal compound as the component (A) may be used alone or in a combination of two or more. On the other hand, as the compound which reacts with the organic transition metal compound of the component (A) as the component (B) to generate an ionic compound, (b-1) an oxygen-containing organic metal compound, and (b-2) A compound which reacts with a transition metal compound to form an ionic complex, (b-3) clay, clay mineral or an ion-exchange layered compound can be used. Among them, (b-1) the oxygen-containing organometallic compound is represented by the general formula (II) or the general formula (III)

[0013]

Embedded image

[Wherein R¹~ R⁷Is the number of carbon atoms independently
1 to 8 alkyl groups;¹~ G ^FiveAre each independently
13 shows a metal element of Group 13 of the periodic table. F to i are respectively
0 to 50, and (f + g) and (h + i)
Is 1 or more. The compound represented by is preferably used
You. In these general formulas (II) and (III), R¹~ R⁷But
Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group,
Chill group, n-propyl group, isopropyl group, various butyl groups
Group, various pentyl groups, various hexyl groups, various heptyl
Group, various octyl groups, and G¹~ G^FivePeriod represented by
As the Group 13 metal elements, boron, aluminum,
Gallium, indium, and thallium are mentioned. these
Among the metallic elements, boron and aluminum are particularly preferred.
Used. The values of f to i are 1 to 20,
Is preferably in the range of 1 to 5.

The oxygen-containing organometallic compounds represented by the general formulas (II) and (III) include, for example, tetramethyl dialumoxane, tetraisobutyl dialumoxane,
Examples include alumoxanes such as methylalumoxane, ethylalumoxane, butylalumoxane, and isobutylalumoxane, and boroxanes such as trimethylboroxine and methylboroxan. Of these, alumoxanes are preferred, and methylalumoxane and isobutylalumoxane are particularly preferably used. These alumoxanes may be modified with alcohols. Specific examples of alcohols used for denaturation include methanol, ethanol, propanol, butanol, triphenylmethanol, 2,6-dimethylphenol,
4,6-trimethylphenol, 2,6-diisopropylphenol, 2,6-diisopropyl-4-methylphenol, pentafluorophenol, 4-trifluoromethylphenol, 3,5-bis (trifluoromethyl) phenol, 1, 4-butanediol, catechol, trimethylsilanol, triphenylsilanol and the like can be mentioned.

On the other hand, (b-2) a compound which reacts with the organic transition metal compound to form an ionic complex includes:
A coordination complex compound comprising an anion and a cation having a plurality of groups bonded to a metal, or a Lewis acid is preferably used.
Examples of the coordination complex compound comprising an anion and a cation in which a plurality of groups are bonded to a metal include general formulas (IV) and (V) ([J ¹ -H] ^{c +} ) _d ([Q ¹ Y ¹ Y ^2. · · Y ^{p] _{(pq) -) e ··· (}} IV) ( [J ^{2] c} +) _d ^{([Q 2 Y 1 Y 2 ··· Y} p ] _{^{(pq) -) e ··· (}} V Wherein J ¹ is a Lewis base and J ² is Q ³ or R ⁸
R ⁹ Q ⁴ or R ¹⁰ ₃ C, wherein Q ¹ and Q ² are each a metal selected from Groups 5 to 15 of the periodic table, Q ³
Is a metal selected from Groups 1 and 8 to 12 of the periodic table; Q ⁴ is a metal selected from Groups 8 to 10 of the periodic table; Y ^{l to} Y ^p are each a hydrogen atom, dialkylamino Group, alkoxy group, aryloxy group, carbon number 1-2
0 alkyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, substituted alkyl group,
Indicates an organic metalloid group or a halogen atom. R ⁸ and R ⁹ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group, and R ¹⁰ represents an alkyl group. q is the valence of Q ¹ or Q ² and is an integer of 1 to 7, p is an integer of 2 to 8, and c is [J ¹
-H] and an integer of 1 to 7 in the valence of [J ² ], and d is 1
In the above integer, e is a value calculated by the equation [c × d / (p−q)]. ] Are preferably used.

The metals represented by Q ¹ and Q ² in the above general formulas (IV) and (V) are preferably boron, aluminum, silicon, phosphorus, arsenic and antimony, and the metals represented by Q ³ are silver, copper , sodium, lithium is preferred as the metal Q ⁴ represents, iron, cobalt, and nickel are preferable. Further, as specific examples of Y ^{1 to} Y ^p in the general formulas (IV) and (V), for example, a dialkylamino group is preferably a dimethylamino group or a diethylamino group, and an alkoxy group is preferably a methoxy group or an ethoxy group. Group, n-butoxy group and the like, and as the aryloxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group and the like are preferable. In addition, carbon number 1
Examples of the alkyl group of -20 are a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl group and the like are preferable. As the aryl group, alkylaryl group or arylalkyl group having 6 to 20 carbon atoms, phenyl group, p-tolyl group is preferable. Group, benzyl group, pentafluorophenyl group, 3,5-
Bis (trifluoromethyl) phenyl group, 4-tert
-Butylphenyl group, 2,6-dimethylphenyl group,
A 3,5-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group and the like are preferable.

The halogen atom is preferably a fluorine, chlorine, bromine or iodine atom, and the organic metalloid group is preferably a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, a diphenylboron group or the like. Is preferred. Preferred examples of the substituted cyclopentadienyl group represented by R ⁸ and R ⁹ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. In the present invention, specific examples of the anion having a plurality of groups bonded to a metal include B (C ₆ F ₅ ) ₄ ⁻ and B (C _{6
^{HF 4) 4 -, B (}} C 6 H 2 F 3) 4 -, B (C 6 H 3
F ₂ ) ₄ ⁻ , B (C ₆ H ₄ F) ₄ ⁻ , B [C ₆ (C
F ₃ ) F ₄ ] ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , FB (C ₆ F
^{_{5) 3 -, FB (C}} 10 F 7) 3 -, PF 6 -, P (C 6
^{_{F 5) 6 -, Al (}} C 6 F 5) 4 -, Al (C 6 H
F ₄ ) ₄ ⁻ , FAl (C ₆ F ₅ ) ₃ ⁻ , FAl (C ₁₀ F
₇ ) _3- ^{and the} like are preferred.

Further, as the metal cation, (C
_FiveH_Five)_TwoFe⁺, [[(CH_Three)_ThreeC] C _FiveH_Four]_TwoF
e⁺, [(CH_Three)_TwoC_FiveH_Three] Fe⁺, [(C
H_Three)_ThreeC_FiveH _Two]_TwoFe⁺, [(CH_Three)_FourC_FiveH]
_TwoFe⁺, [(CH_Three)_FiveC_Five]_TwoFe ⁺, Ag⁺, N
a⁺, Li⁺And the like. Ma
Other cations include pyridinium, 2,4
-Dinitro-N, N-diethylanilinium, diphenyl
Ruammonium, p-nitroanilinium, 2,5-di
Chloroanilinium, p-nitro-N, N-dimethyla
Nilinium, quinolinium, N, N-dimethylanilini
Nitrogen, N, N-diethylanilinium, etc.
Compound, triphenylcarbenium, tri (4-methyl
Enyl) carbenium, tri (4-methoxyphenyl)
Carbenium compounds such as carbenium, CH _ThreePH_Three
⁺, C_TwoH_FivePH_Three ⁺, C_ThreeH₇PH_Three ⁺, (CH_Three)
_TwoPH_Two ⁺, (C_TwoH_Five)_TwoPH_Two ⁺, (C_ThreeH₇)_Two
PH_Two ⁺, (CH_Three)_ThreePH⁺, (C_TwoH_Five)_ThreeP
H⁺, (C_ThreeH₇)_ThreePH⁺, (CF_Three)_ThreePH⁺,
(CH_Three)_FourP ⁺, (C_TwoH_Five)_FourP⁺, (C_ThreeH₇)
_FourP⁺Alkylphosphonium ions such as₆H
_FivePH_Three ⁺, (C₆H_Five)_TwoPH_Two ⁺, (C₆H_Five)_Three
PH⁺, (C₆H_Five)_FourP⁺, (C_TwoH_Five)_Two(C₆H
_Five) PH⁺, (CH_Three) (C₆H _Five) PH_Two ⁺, (CH
_Three)_Two(C₆H_Five) PH⁺, (C_TwoH_Five)_Two(C
₆H_Five) _TwoP⁺Such as arylphosphonium ion
Is mentioned.

Examples of the compound represented by the general formula (IV) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetrakis (pentafluorophenyl) ) Triethylammonium borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolium tetrakis (pentafluorophenyl) borate, tetrakis (Pentafluorophenyl) borate N,
N-dimethylanilinium, methyldiphenylammonium tetrakis (pentafluorophenyl) borate and the like are preferably used.

Further, the compound represented by the general formula (V) is
For example, ferrocenium tetraphenylborate,
Ferraceni thorax (pentafluorophenyl) borate
And di-tetrakis (pentafluorophenyl) borate
Methyl ferrocenium, tetrakis (pentafluorop
Enyl) decamethylferrocenium borate, tetrakis
(Pentafluorophenyl) acetylferrocenyl borate
And tetrakis (pentafluorophenyl) borate
Lumilferrocenium, tetrakis (pentafluorop
Enyl) cyanoferrocenium borate, tetraphenyl
Silver borate, tetrakis (pentafluorophenyl) borane
Silver, trityl tetraphenylborate, tetrakis (pe
(Nantafluorophenyl) trityl borate, hexafluoro
Silver arsenate, silver hexafluoroantimonate, tetraf
Silver fluoroborate and the like are preferably used. Furthermore, Louis
For example, B (C₆F_Five)_Three, B (C₆HF
_Four)_Three, B (C₆H_TwoF_Three)_Three, B (C₆H
_ThreeF_Two)_Three, B (C₆H_FourF)_Three, B (C₆H_Five)_Three,
BF_Three, B [C₆(CF_Three) F_Four]_Three, B (C_TenF₇)
_Three, FB (C ₆F_Five)_Two, PF_Five, P (C₆F_Five)_Five,
Al (C₆F_Five)_Three, Al (C₆HF _Four)_Three, Al (C
_TenF₇)_ThreeEtc. can also be used.

Next, as (b-3) clay, clay mineral or ion-exchange layered compound, the following compounds are preferably used. Clay or clay mineral Clay is an aggregate of fine hydrated silicate minerals,
A substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. The clay mineral refers to a hydrated silicate that is a main component of clay. These are not limited to natural products, and may be artificially synthesized. Ion-exchangeable layered compound The ion-exchanged layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable. Some clay minerals are ion-exchangeable layered compounds. For example, phyllosilicic acids are mentioned as clay minerals. The phyllosilicic acids include phyllosilicic acid and phyllosilicates. As phyllosilicates, natural products include montmorillonite, saponite, hectorite, illite belonging to mica, sericite, and mixed layer minerals of smectite and mica or mica and vermiculite, etc. Is mentioned.

Further, as synthetic products, tetrasilicic mica,
Laponite, smecton and the like. In addition, α-
Zr (HPO ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ , α-T
An ionic crystalline compound having a layered crystal structure that is not a clay mineral such as i (HPO ₄ ) ₂ and γ-Ti (HPO ₄ ) ₂ can be given. Clays and clay minerals that do not belong to the ion-exchangeable layered compound. Specific examples of the component (b-3) include clay called bentonite because of its low montmorillonite content, and Kibushi clay that contains many other components in montmorillonite. , Geilome clay, sepiolite exhibiting a fibrous form, palygorskite, and amorphous or low-crystalline allophane, imogolite, and the like.

In the present invention, (b-
The component (3) includes the component (A), the other component (b-1) and the component (b-
2) In contact with the component, the component (C) described below,
From the viewpoint of removing impurities from the clay mineral and the ion-exchangeable layered compound or changing the structure and function, it is also preferable to perform a chemical treatment. Here, the chemical treatment refers to either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the crystal structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic complex, and the like are formed, and the surface area, the interlayer distance, and the like can be changed. By replacing the exchangeable ions between layers with another bulky ion by utilizing ion exchangeability, an interlayer material having an enlarged interlayer can be obtained.

The above-mentioned component (b-3) may be used as it is, may be used by newly adding and adsorbing water, or may be used after being heated and dehydrated. The component (b-3) may be further treated with an organic aluminum compound and / or an organic silane compound. As the component (b-3), preferred are clay or clay mineral, and most preferred are phyllosilicates, among which smectite is preferred and montmorillonite is more preferred. And these (b-1) oxygen-containing organometallic compounds,
(B-2) a compound capable of forming an ionic complex by reacting with the organic transition metal compound represented by the general formula (I);
3) When a clay, a clay mineral or an ion-exchangeable layered compound is used as the component (B) of the catalyst, (b)
-1) Only one component may be used alone, or two or more types may be used in combination. In addition, the component (b-2) may be used alone or in a combination of two or more. In addition, the component (b-3) may be used alone or in a combination of two or more. Further, the component (b-1), the component (b-2) and the component (b-3) may be appropriately combined and used as the component (B).

Further, as the organometallic compound which is the component (C) used as required, the following general formulas (VI) and (VI)
^{I), (VIII) R 11} r Al (OR 12) s X 1 3-rs (VI) R 11 2 Mg (VII) R 11 2 Zn (VIII) [ wherein R ¹¹ and R ¹² are each independently X ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and X ¹ represents a hydrogen atom or a halogen atom. r is 0 <r ≦ 3, and s is 0 ≦ s <3. ] Are preferably used.
R ¹¹ or R ¹² in these general formulas (VI) to (VIII)
The hydrocarbon group represented by has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and particularly preferably an alkyl group. For example, those which are a methyl group, an ethyl group, a propyl group, an isopropyl group, various butyl groups and the like can be preferably mentioned. In the formula, r is preferably 2 or 3, and most preferably 3. Further, s is preferably 0 or 1.

The organic alkyl metal compounds represented by the general formulas (VI) to (VIII) include, for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutyl Aluminum, trialkylaluminum such as tri-tert-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride,
Dialkylaluminum halides such as di-n-butylaluminum chloride, diisobutylaluminum chloride, di-tert-butylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, diisobutylaluminum triphenylmethoxide Such as dialkyl aluminum alkoxide, dimethyl aluminum hydride, organic aluminum compounds such as dialkyl aluminum hydride such as diisobutyl aluminum hydride, dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dialkyl magnesium such as dibutyl magnesium, dimethyl zinc,
Examples include dialkyl zinc such as diethyl zinc, ethyl-n-propyl zinc, diisopropyl zinc and the like. Among these organometallic compounds, organoaluminum compounds, in particular,
Trialkyl aluminum is preferred. In the present invention, as the component (C), one kind of the organometallic compound may be used, or two or more kinds thereof may be used in combination.

Next, when preparing a catalyst using each of the above catalyst components, it is desirable to carry out the contacting operation in an atmosphere of an inert gas such as nitrogen gas. These catalyst components may be prepared in advance in a preparation device in a catalyst preparation tank and used directly for copolymerization. When preparing the catalyst in this polymerization reactor, it is desirable to carry out the polymerization at a temperature not higher than the polymerization temperature of the aromatic vinyl compound or the like, for example, at -30 to 200 ° C, preferably at 0 to 80 ° C. . And the mixing ratio of these components is
(B-1) With respect to the organic transition metal compound as the component (A),
The molar ratio of the oxygen-containing organometallic compound of the component is 1: 0.
1-1: 100000, preferably 1: 0.5-1:
It is better to be 10,000. The compound which forms an ionic complex by reacting with the organic transition metal compound as the component (b-2) is in a molar ratio of 1: 0.1 to 1: 1000, preferably 1: 1 to 1: 100. Is good. Also,
The mixing ratio of the clay, clay mineral, or ion-exchangeable layered compound of the component (b-3) is 0.1 to 1 as an addition amount of the component (A) per unit weight (g) of the component (b-3).
000 micromolar, preferably 1 to 200 micromolar. Further, the compounding ratio of the organometallic compound of the component (C) is 1: 1 to 1: 100,000, preferably, in a molar ratio with respect to the organic transition metal compound of the component (A).
1:10 to 1: 10000. The polymerization catalyst used in the present invention includes the components (A), (b-1), and (b) described above.
A solid catalyst in which at least one of the component -2) and the component (C) is supported on a particulate carrier may be used. Further, the polymerization catalyst includes a particulate carrier, a component (A), a component (b-1) (or a component (b-2)), and a polymer or copolymer produced by prepolymerization, and if necessary, (C ) Component.

[0029] Particulate support used for the production of a solid catalyst
The body is an inorganic or organic compound with a particle size of 10
~ 300 μm, preferably 20-200 μm granular
The chair is a finely divided solid. Of these, as inorganic carriers
Is preferably a porous oxide, specifically SiO 2_Two, Al
_TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, Ca
O, ZnO, BaO, ThO_TwoOr a mixture of these
Compound, for example SiO_Two-MgO, SiO_Two-Al
_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, S
iO_Two−Cr_TwoO_Three, SiO_Two-TiO_Two-MgO, etc.
Can be exemplified. Of these, SiO_Twoand
Al_TwoO_ThreeAt least one member selected from the group consisting of
It is preferable that the main component is a component. In addition, the above inorganic oxidation
A small amount of Na_TwoCO_Three, K_TwoCO_Three, CaCO_Three,
MgCO_Three, Na_TwoSO_Four, Al_Two(SO_Four)_Three, Ba
SO_Four, KNO_Three, Mg (NO_Three)_Two, Al (NO_Three)
_Three, Na _TwoO, K_TwoO, Li_TwoCarbonate such as O, sulfuric acid
Can contain salt, nitrate and oxide components
No.

The properties of such a fine particle carrier differ depending on the kind and the production method, but the specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g,
It is desirable that the pore volume is 0.3 to 2.5 cm ³ / g. The finely divided carrier may be 100 to 1000 as needed.
C., preferably at a temperature of 150 to 700 C. Further, the fine particle carrier has a particle size of 10 to 3
Granular or fine solid particles of an organic compound having a size of 00 μm can be mentioned. Such organic compounds include ethylene, propylene, 1-butene, 4-methyl-
Examples thereof include (co) polymers formed mainly of α-olefins having 2 to 14 carbon atoms such as 1-pentene, and polymers or copolymers formed mainly of vinylcyclohexane and styrene. . In the method for producing a polymer of the present invention, an olefin and / or an aromatic vinyl compound are polymerized in the presence of the above-mentioned polymerization catalyst to produce a (co) polymer. At this time, the polymerization reaction is carried out in the presence of a hydrocarbon such as butane, pentane, hexane, toluene, cyclohexane or a solvent such as liquefied α-olefin, or in the absence of a solvent. The polymerization temperature is not particularly limited, but is preferably −50 ° C. to 250 ° C.
And particularly preferably in the range of 0 ° C to 200 ° C. The pressure is not particularly limited, but is preferably from normal pressure to
The range is 20 MPa, particularly preferably normal pressure to 10 MPa.

In this polymerization reaction, silanes such as silane, phenyl silane, methyl silane, ethyl silane, butyl silane, octyl silane, diphenyl silane, dimethyl silane, diethyl silane, dibutyl silane, dioctyl silane and the like, hydrogen, etc. May be used. These chain transfer agents may be used alone or in combination of two or more. In addition, these chain transfer agents have the effect of improving the activity of the catalyst by adjusting the amount of use. The olefins used as monomers in the polymerization reaction include ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1- Hexene, 5-methyl-1-hexene, 3,3
-Dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene,
1,1-difluoroethylene, 3-fluoropropene,
Α-olefins such as trifluoroethylene and 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-
Examples include cyclic olefins such as dimethylnorbornene and 5-benzylnorbornene, and diolefins such as 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene. These olefins may be used alone or in combination of two or more.

On the other hand, aromatic vinyl compounds include styrene, p-methylstyrene, p-ethylstyrene,
Propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, alkyl styrenes such as m-ethyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,5-dimethyl styrene, p-methoxy styrene, o-methoxystyrene, alkoxystyrenes such as m-methoxystyrene,
p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene,
o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p
-Halogenated styrenes such as fluorostyrene,
-Phenylstyrene, p-trimethylsilylstyrene,
Vinyl benzoate, divinylbenzene and the like can be mentioned. These aromatic vinyl compounds may be used alone,
Two or more kinds may be used in combination. Moreover, you may use in combination with the said olefins.

[0033]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The synthesis reactions in Examples 1 to 5 were all performed using a Schlenk tube under a nitrogen stream. 3,5-Dimethylpyrazolylethyl tosylate and pentamethylcyclopentadienyl zirconium trichloride are each described in the literature [“Inorg.
Synth. 32, 85 pages (1998),
"Organometallics", Volume 1, 793
(1982)]. Pyrazolylethanol is described in the literature ["J. Chem. Soc."
2 (1960)], and pyrazolylethyl tosylate was synthesized using the same method as for 3,5-dimethylpyrazolylethyl tosylate. The analysis of the polymer obtained in each example was performed according to the following method. (1) Ethylene-styrene copolymer The styrene unit content in the ethylene-styrene copolymer was determined from the ¹³ C-NMR spectrum using the integrated value of each peak according to the following formula. Styrene unit content (mol%) = w / (t + u + v /
2 + w) × 100 where t, u, v, and w are 24.5 to 30.5 p, respectively.
pm, 33.5-35.0 ppm, 36.0-38.0
ppm, 40.0 to 48.5 ppm, and t
Is methylene carbon of ethylene, u is styrene-ethylene-
Methylene carbon of ethylene based on a hetero bond of styrene in styrene chain, v is methylene carbon of styrene in ethylene-styrene-ethylene chain, w is methine carbon of styrene in ethylene-styrene-ethylene chain and methine carbon of styrene in styrene-styrene chain And methylene carbon.

(2) Ethylene-octene copolymer The octene unit content in the ethylene-octene copolymer is as follows:
^{It was determined from the 13} C-NMR spectrum by the following formula using the integrated value of each peak. Octene unit content (mol%) = [x / ｛(y + z) /
2｝) × 100 where x, y, z are 32.20 ppm, 3
0.00 ppm, 30.51 ppm, x
Is assigned to the methylene carbon of octene, and y and z are assigned to the methylene carbon of ethylene. (3) Others GPC-FT / IR uses Shodex on GPC column.
UT806, FT / IR and Nicolet MAGNA-IR5
Using a 60FTIR system, 1,2,4-trichlorobenzene was used as a solvent, and the measurement was performed at 145 ° C. and a flow rate of 1.0 ml / min. For polyethylene and poly (ethylene-octene) copolymer, standard polyethylene conversion was used. For the poly (ethylene-styrene) copolymer, the weight average molecular weight was calculated as the standard polystyrene equivalent weight average molecular weight. The ¹³ C-NMR was measured at 130 ° C. using a mixed solvent of trichlorobenzene / deuterated benzene (3/1) using JSX-400 manufactured by JEOL Ltd.

Example 1 (1) Synthesis of pyrazolylethyl cyclopentadiene 7.80 g (29.3 mm) of pyrazolylethyl tosylate
ol) in 80 ml of a tetrahydrofuran (THF) solution was cooled to 0 ° C., and 200 ml of a THF solution of 5.80 g (65.8 mmol) of sodium cyclopentadienyl was added dropwise thereto. The reaction solution was raised to room temperature and stirred overnight. 50 ml of water and diethyl ether were added to the reaction mixture, and the organic layer was separated. The solvent was distilled off under reduced pressure, the residue was dissolved in a small amount of diethyl ether, and applied to an alumina column using a hexane / diethyl ether (1/1) developing solution. Collect the orange elution part,
The solvent was distilled off to obtain 2.70 g of pyrazolylethylcyclopentadiene (yield: 57%). (2) bis (pyrazolylethylcyclopentadienyl)
Synthesis of zirconium dichloride pyrazolylethylcyclopentadiene (7.49 mmol
l) and normal-butyllithium (7.49 mmol)
Was reacted at -78 ° C in 50 ml of tetrahydrofuran to prepare pyrazolylethylcyclopentadienyllithium. 0.875 g of zirconium tetrachloride suspended in 60 ml of toluene (3.
75 mmol) at -78 ° C. The reaction mixture is
After stirring overnight at room temperature, the solvent was distilled off under reduced pressure. After the residue was extracted with dichloromethane and the solvent was distilled off, the residue was washed with hexane / benzene (2/1) to give
1.296 g (yield 72%) of bis (pyrazolylethylcyclopentadienyl) zirconium dichloride was obtained.

Example 2 (1) Synthesis of 3,5-dimethylpyrazolylethylcyclopentadiene The procedure of Example 1 was repeated except that pyrazolylethyl tosylate was replaced by 3,5-dimethylpyrazolylethyl tosylate. Synthesized using a similar method. (2) Synthesis of bis (3,5-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride Instead of pyrazolylethylcyclopentadiene, 3,5
-Synthesis was performed using the same method as in (2) of Example 1 except that dimethylpyrazolylethylcyclopentadiene was used.

Example 3 Synthesis of (pentamethylcyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium dichloride pyrazolylethylcyclopentadiene (3.95 mmol)
l) and normal-butyllithium (3.96 mmol)
Was reacted at −78 ° C. in 40 ml of diethyl ether to prepare pyrazolylethylcyclopentadienyllithium. This suspension was suspended in 60 ml of toluene (pentamethylcyclopentadienyl).
1.315 g of zirconium trichloride (3.95 mm
ol) at -78 ° C. After stirring the reaction mixture at room temperature overnight, the solvent was distilled off under reduced pressure. After the residue was extracted with dichloromethane and the solvent was distilled off, the residue was crystallized from a diethyl ether / hexane solution to give
1.08 g (66% yield) of (pentamethylcyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium dichloride was obtained.

Example 4 Synthesis of (pentamethylcyclopentadienyl) (3,5-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride Instead of pyrazolylethylcyclopentadiene, 3,5
-Synthesis was performed in the same manner as in Example 3 except that dimethylpyrazolylethylcyclopentadiene was used.

Example 5 Synthesis of (3,5-dimethylpyrazolylethylcyclopentadienyl) titanium trichloride 3,5-dimethylpyrazolylethylcyclopentadiene and normal-butyllithium were prepared
The reaction was carried out at -78 ° C to prepare lithium 3,5-dimethylpyrazolylethylcyclopentadienyl. The reaction solution was cooled again to −78 ° C. in a dry ice-methanol bath, and trimethylsilyl chloride was added dropwise. The temperature was gradually raised to room temperature with stirring. The solvent was distilled off under reduced pressure, and extracted with hexane. The solvent was again distilled off under reduced pressure, and (3,
5-dimethylpyrazolylethyl) (trimethylsilyl)
Cyclopentadiene was obtained. Titanium tetrachloride was dissolved in dichloromethane and dissolved in dichloromethane (3,5-
Dimethylpyrazolylethyl) (trimethylsilyl) cyclopentadiene was added dropwise with stirring at room temperature. Thereafter, the resulting tan solid was collected by filtration to obtain (3,5-dimethylpyrazolylethylcyclopentadienyl) titanium trichloride. ¹ H NMR (CDCl ₃ ): 7.01 (m, 2H),
6.88 (m, 2H), 5.96 (s, 1H), 4.5
1 (m, 2H), 3.39 (m, 2H), 2.43
(S, 3H), 2.25 (s, 3H)

Example 6 360 ml of toluene and 1.0 ml of a 1.0 mol / l toluene solution of triisobutylaluminum were sequentially charged into an autoclave equipped with a catalyst introduction tube having an internal volume of 1.6 liters at 60 ° C. The temperature rose.
Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, a solution prepared by dissolving 10.0 micromoles of bis (3,5-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride and 10.0 millimoles of methylalumoxane in 40 milliliters of toluene was charged from the catalyst charging tube. . Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. A large amount of methanol was further added to the reaction product, followed by filtration, and the resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 0.66 g of polyethylene was obtained. GP
The weight average molecular weight measured by C-FT / IR is 56.7.
10,000, the molecular weight distribution [weight average molecular weight / number average molecular weight] is 2
It was 5.4.

Example 7 330 ml of toluene and 1-octene 30 were placed in an autoclave having a 1.6-liter internal volume equipped with a catalyst introduction tube.
Milliliter and 1.0 milliliter of a toluene solution of triisobutylaluminum at a concentration of 1.0 mol / liter were sequentially charged, and the temperature was raised to 50 ° C. Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, 10.0 micromoles of bis (3,5-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride and 10.
A solution in which 0 mmol of methylalumoxane was dissolved in 40 mL of toluene was charged. Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. The reaction product was further separated by filtration by adding a large amount of methanol, and the resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 0.45 g of a poly (ethylene-octene) copolymer was obtained.
^The 1-octene unit content determined by ¹³ C-NMR was 4.0.
Mole%, the weight average molecular weight measured by GPC-FT / IR was 3280,000, and the molecular weight distribution was 13.6.

Example 8 160 ml of toluene, 200 ml of styrene, and 1.0 ml of a 1.0 mol / l toluene solution of triisobutylaluminum were sequentially charged into an autoclave equipped with a catalyst introduction tube having an internal volume of 1.6 liter. Then, the temperature was raised to 50 ° C. Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, 10.0 micromoles of bis (3,5-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride, 10.0
A solution prepared by dissolving mmol of methylalumoxane in 40 ml of toluene was charged. Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. Reaction products include:
Further, a large amount of methanol was added and the mixture was separated by filtration, and the resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 0.27 g of a poly (ethylene-styrene) copolymer was obtained. ¹³
The styrene unit content determined by C-NMR was 37.5 mol%, the weight average molecular weight in terms of styrene measured by GPC-FT / IR was 2570,000, and the molecular weight distribution was 25.1.

Example 9 360 ml of toluene and 1.0 ml of a 1.0 mol / l toluene solution of triisobutylaluminum were sequentially charged into an autoclave equipped with a catalyst introduction tube having an internal volume of 1.6 liters at 50 ° C. The temperature rose.
Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, 10.0 micromoles of (pentamethylcyclopentadienyl) (3,5-dimethylpyrazolylethylcyclopentadienyl) zirconium dichloride,
A solution in which 0.0 mmol of methylalumoxane was dissolved in 40 mL of toluene was charged. Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. To the reaction product, a further large amount of methanol was added and separated by filtration,
The resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 16.7 g of polyethylene was obtained. GPC-FT / I
The weight average molecular weight measured by R was 51,000 and the molecular weight distribution was 19.6.

Example 10 360 ml of toluene and 1.0 ml of a 1.0 mol / l toluene solution of triisobutylaluminum were sequentially charged into an autoclave equipped with a 1.6-liter catalyst-introducing tube at 50 ° C. The temperature rose.
Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, 10.0 μmol of bis (pyrazolylethylcyclopentadienyl) zirconium dichloride,
A solution in which 0.0 mmol of methylalumoxane was dissolved in 40 mL of toluene was charged. Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. To the reaction product, a further large amount of methanol was added and separated by filtration,
The resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 0.26 g of polyethylene was obtained. GPC-FT / I
The weight average molecular weight measured by R was 326,000, and the molecular weight distribution was 15.9.

Example 11 360 ml of toluene and 1.0 ml of a 1.0 mol / l toluene solution of triisobutylaluminum were sequentially charged into an autoclave equipped with a catalyst introduction tube having an internal volume of 1.6 liter at 50 ° C. The temperature rose.
Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, a solution prepared by dissolving 10.0 micromoles of (pentamethylcyclopentadienyl) (pyrazolylethylcyclopentadienyl) zirconium dichloride and 10.0 millimoles of methylalumoxane in 40 milliliters of toluene was introduced from the catalyst introduction tube. I put it in. Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. A large amount of methanol was further added to the reaction product, followed by filtration, and the resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, polyethylene 1
0.2 g was obtained. The weight average molecular weight measured by GPC-FT / IR was 644,000, and the molecular weight distribution was 70.0.

Example 12 160 ml of toluene, 200 ml of styrene, and 1.0 ml of a 1.0 molar toluene solution of triisobutylaluminum were sequentially charged into an autoclave having a 1.6-liter internal volume equipped with a catalyst introduction tube.
The temperature was raised to 80 ° C. Then, ethylene was introduced into the autoclave so that the pressure became 0.3 MPa. Then, a solution prepared by dissolving 10.0 micromoles of (3,5-dimethylpyrazolylethylcyclopentadienyl) titanium trichloride and 10.0 millimoles of methylalumoxane in 40 milliliters of toluene was injected from the catalyst injection tube. did. Since the internal pressure of the autoclave decreases with the progress of the polymerization of ethylene, the polymerization reaction was carried out for 1 hour while continuously introducing ethylene so as to maintain the pressure of 0.3 MPa. Thereafter, the polymerization was stopped by adding methanol. A large amount of methanol was further added to the reaction product, followed by filtration, and the resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 0.8 g of an ethylene-styrene copolymer was obtained. ^The styrene content determined by ¹³ C-NMR was 89.9 mol%, the weight average molecular weight measured by GPC-FT / IR was 63,000, and the molecular weight distribution was 6.5.
Met.

[0047]

The organic transition metal compound of the present invention is a novel compound having a π-coordinating compound modified with a pyrazolyl group as a ligand, and is useful as a catalyst component of a polymerization catalyst. The polymerization catalyst of the present invention using this organic transition metal compound is homogeneous and highly active, can be used for polymerization of olefins and aromatic vinyl compounds, and has a wide molecular weight distribution. The polymer can be provided efficiently.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07F 7/28 C07F 7/28 FF Term (Reference) 4H049 VN05 VN06 VP01 VQ59 VR21 VR22 VR32 VR33 VU14 VW02 4H050 AA01 AA03 AB40 4J028 AA01A AB00A AB01A AC01A AC08A AC10A AC26A AC28A BA00A BA01A BA01B BA02B BB00A BB01A BB01B BB02B BC05B BC09B BC12A BC12B BC15B BC16B BC24B BC25A BC25B BC27B BC28A BC28B BC29A BC29B CA28A CA28B CA30A CA30B EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB11 EB12 EB15 EB17 EB18 EB21 ED08 ED09 GA01 GA06 4J128 AA01 AB00 AB01 AC01 AC08 AC10 AC26 AC28 AD00 AE00 BA00A BA01A BA01B BA02B BB00A BB01A BB01B BB02B BC05B BC09B BC12A BC12B BC15B BC16B BC24B BC25A BC25B BC27B30 BC28 BC28B28 BC28B30 BC28B28 EB15 EB17 EB18 EB21 ED08 ED09 GA01 GA06

Claims (4)

[Claims] 1. Formula (I) [(ZA) _n -D] _m E _a MX _kma (L) _j (I) wherein M is a transition of groups 3 to 11 of the periodic table. Metal, D is -1
Π-coordinating compound residue having the following charge, Z is a pyrazolyl group or a substituted pyrazolyl group, A is a group that bridges D and Z, and E is-
A π-coordinating compound residue having a charge of 1, X represents a group forming a σ bond with M, and L represents a Lewis basic compound. n and m are each 1 or 2, a and j are each 0 or 1, k is an oxidation number of M, kma is an integer of 1 or more, and when n is 2, two (Z -A) may be the same or different. When m is 2, two [(Z-
A) _n -D] may be the same or different, or may be cross-linked. When a is 1, D and E, A and E, and Z and E may each be cross-linked. Good. D and X,
A and X, Z and X each may be cross-linked, and k-
When ma is 2 or more, a plurality of Xs may be the same or different. ] The organic transition metal compound represented by these. (A) reacting the organic transition metal compound represented by the general formula (I) according to claim 1 with (B) the organic transition metal compound of the component (A) to form an ionic compound. A polymerization catalyst comprising a combination of a compound to be used and an organometallic compound (C) optionally used. 3. In the organic transition metal compound of the component (A), D and E in the general formula (I) each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, or a fluorenyl group. Or a substituted fluorenyl group, wherein A has a carbon atom or a silicon atom in the main chain, and X is a hydrogen atom, a halogen atom, an alkoxyl group, an aryloxy group, an amino group, an alkyl group or an aryl group. 2. The polymerization catalyst according to 2. 4. A method for producing a polymer, comprising polymerizing an olefin and / or an aromatic vinyl compound in the presence of the polymerization catalyst according to claim 2 or 3.