JPH09278817A - Olefin polymerization catalyst and production of olefinic polymer therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalytic component usable as a substitute for aluminoxane to exhibit a high activity on the polymerization of an olefin, which can be synthesized under mild conditions and which has a high storability, and also to provide a process for producing an olefinic polymer therewith. SOLUTION: This catalyst comprises (A) a compound of a transition metal of the Groups 4 to 6 of the periodic table which comprises a cyclopentadienyl group, a crosslinked cyclopentadienyl group or a restrained geometric cyclopentadienyl group or a derivative thereof coordinated with a σ-ligand, (B) an organoaluminum compound of the formula: Rr AlT3-r (wherein R is a hydrocarbon group, T is a hydrogen, an alkoxyl group or a halogen, and r is an integer of 1 to 3), and (C) an aromatic compound having at lest two hydroxyl groups bonded to the aromtic ring. A process for producing an olefinic polymer in the presence of the catalyst is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art It is known that an olefin can be polymerized by using a catalyst composed of a metallocene compound and an aluminoxane (JP-A-58-19303). According to this method, the polymerization of olefin has obtained a very high polymerization activity per transition metal compound. However, the aluminoxane used here is an oligomer having a specific structure produced by adding water to trimethylaluminum as a condensing agent and hydrolyzing it, and the reaction between trimethylaluminum and water is extremely vigorous, and Very difficult to control.

Further, there is a problem in terms of safety and reaction controllability, for example, it is necessary to stop the reaction when the aluminoxane oligomer is formed to suppress the formation of a polymer having low polymerization activity. Furthermore, the aluminoxane oligomer thus obtained is extremely reactive and inactivated by the incorporation of a small amount of water, which makes it difficult to store for a long period of time. .

In order to solve these problems, a method of using a reaction product of a compound having a hydroxy group such as trialkylaluminum and sorbitol (JP-A-1-101303) or an organoaluminum compound and silane instead of aluminoxane. A method using a reaction product of a diol (Japanese Patent Laid-Open No. 22306/1990) is disclosed, but all of them have low polymerization activity and cannot be practically used.

[0005]

In view of the above problems, the present invention provides a catalyst component which exhibits high activity for olefin polymerization as an alternative to aluminoxane, can be synthesized under mild conditions, and has good storage stability. An object of the present invention is to provide a method for producing an olefin using

[0006]

As a result of intensive studies to achieve the above object, it was found that the catalyst component and the olefin production method using the catalyst component shown below can achieve the object. The present invention has been completed based on such findings. That is, the present invention provides the following manufacturing method. (1) (A) Cyclopentadienyl group, two bridged cyclopentadienyl groups, constrained geometry type cyclopentadienyl group or their derivatives and σ-ligand coordinate group 4 to 6 Transition metal compound of (B) the following general formula (1) R ¹ _r AlT _3-r (1) [wherein, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and T is a hydrogen atom. Represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is an integer of 1 to 3. ] An olefin polymerization catalyst comprising an organoaluminum compound represented by the following formula and (C) an aromatic compound having two or more hydroxy groups bonded to an aromatic ring. (2) The olefin system according to (1) above, wherein the aromatic compound having two or more hydroxy groups bonded to the aromatic ring of (C) is represented by the following general formula (2) or (3): Polymerization catalyst.

[0007]

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[0008]

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[Wherein, R^TwoIs carbonized water having 1 to 20 carbon atoms
Indicates either an elementary group or a halogen atom, and there are multiple
May be the same or different. R^ThreeAnd R^FourHas 1 carbon
~ 20 hydrocarbon groups, halogen atoms, phenyl groups or
Indicates one of the chlorhexyl groups, the same if multiple
But it may be different. Y is CHR^Five, CR^Five _Two, C =
O, NR^Five, PR^Five, R^FiveP = O, O, S, SiR^FiveR
⁶, CR^Five _TwoPhCR⁶ _Two, Cyclohexylidene or
Indicates either clopentylidene (R^Five, R⁶Is carbon
Number 1 to 20 hydrocarbons, Ph represents a phenyl group
You. ). f is an integer of 0 to 4, g is an integer of 2 to 6, h and
k is an integer of 0 to 4, i and j are integers of 1 to 5, and l is 0 to
Indicates an integer of 5. ] (3) Organoaluminum compound of (B) and aroma of (C)
Aromatic compounds having two or more hydroxy groups bonded to the ring
After reacting the product in advance, contact with the transition metal compound of (A)
The olefin-based polymerization according to the above (1) or (2)
Catalyst. (4) The olefin according to any one of (1) to (3) above.
Olef for polymerizing olefins using in-series polymerization catalysts
A method for producing a vinyl polymer.

[0010]

Embodiments of the present invention will be described in detail below. Among the olefin polymerization catalysts of the present invention, (A)
Is a cyclopentadienyl group, two bridged cyclopentadienyl groups, a constrained geometry type cyclopentadienyl group or a derivative thereof and a transition metal compound of Group 4 to 6 of the periodic table in which the σ ligand is coordinated. , Typically the following general formula (4)
(6) (C ₅ H _5-a R ⁷ _a ) M ¹ L ¹ L ² L ³ (4) Q ¹ _b (C ₅ H _5-bc R ⁸ _c ) (C ₅ H _5-bd R ⁹ _d ) M ¹ L ¹ L ²・ ・ ・ (5) Q ² (C ₅ H _4-e R ¹⁰ _e ) Z ¹ M ¹ L ¹ L ²・ ・ ・ (6) Periodic Table 4 ~ Group 6 transition metal compounds.

In the formula, M ¹ is a transition metal of Groups 4 to 6 of the periodic table, preferably titanium, zirconium or hafnium. Particularly preferred M is titanium.
_{(C 5 H 5-a R} 7 a), (C 5 H 5-bc R 8 c), (C
₅ H _5-bd R ⁹ _d ) and (C ₅ H _4-e R ¹⁰ _e ) are cyclopentadienyl groups or their derivatives, and R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ are each a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a hydrocarbon group. Is preferred. The hydrocarbon group preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. This hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and when there are a plurality of hydrocarbon groups, two of them are bonded to each other to form a part of the cyclopentadienyl group. It may form a ring structure. That is, these representative examples include a substituted or unsubstituted cyclopentadienyl group, an indenyl group,
A benzoindenyl group and a fluorenyl group. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms. The alkoxy group preferably has 1 to 12 carbon atoms. As the silicon-containing hydrocarbon group, SiR ¹¹ R ¹² R ¹³ (R ¹¹ , R ¹² , and R ¹³ are each a carbon number of 1 to 1).
20 hydrocarbon groups) and the like, and examples of the phosphorus-containing hydrocarbon group, the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group include PR ¹¹ R ¹² , NR ¹¹ R ¹² , BR ¹¹ R ^{12 and the} like. .

L¹, L^TwoAnd L^ThreeIs
The M¹Is a sigma ligand that coordinates to. With this σ ligand
For example, for example, R¹⁴, OR¹⁴, SR¹⁴, SO_ThreeR¹⁴,
NR ¹⁴R^Fifteen, PR¹⁴R^Fifteen, NO_Two, Halogen atom, 1-
Preference is given to pyrrolyl and 1-pyrrolidinyl.
it can. Where R¹⁴And R^FifteenIs carbonized with 1 to 20 carbon atoms
A silyl group containing a hydrogen group or a hydrocarbon group. And
At least one of the σ ligands is a halogen atom, OR¹⁴, N
R¹⁴R^FifteenOr PR¹⁴R^FifteenIt is preferred that The above
R¹⁴And R^FifteenIn, a hydrocarbon group having 1 to 20 carbon atoms
Are, for example, alkyl groups, cycloalkyl groups,
Group and aralkyl group. Also hydrocarbons
Examples of the silyl group containing a group include trimethylsilyl
Group, triphenylsilyl group and the like. Sa
In addition, the halogen atom includes fluorine, chlorine, bromine, and iodine.
I can mention the iodine.

Q ¹ represents two cyclopentadienyl groups or their derivatives (C ₅ H _5-bc R ⁸ _b ) and (C ₅ H _5-bd
R ⁹ _d ) is a linking group that crosslinks, Q ² is a cyclopentadienyl group or its derivative (C ₅ H _5-e R ¹⁰ _e ) and Z ¹
The bonding group which bridge | crosslinks a group is shown. Specific examples of Q ¹ and Q ² include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a cyclohexylene group, a cycloalkylene group or a lower alkyl of a side chain thereof. Alternatively, a phenyl substituent, a silylene group, a dimethylsilylene group, a methylphenylsilylene group, a diphenylsilylene group, a disilylene group, a silylene group such as a tetramethyldisilyne group, an oligosilylene group or a side chain lower alkyl or phenyl substituted product thereof, germanium, Examples thereof include a hydrocarbon group containing phosphorus, nitrogen, boron or aluminum (lower alkyl group, phenyl group, hydrocarbyloxy group, etc.). Among these, an alkylene group and a silylene group are preferable. b is 1 or 2.

Z ¹ is oxygen, sulfur, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, 1 to 40 carbon atoms,
Preferably 1-18 nitrogen-containing hydrocarbon group, 1-carbon
40, preferably 1-18 phosphorus-containing hydrocarbon radicals are represented. a is an integer of 0 to 5, c and d are integers of 0 to 4 when b = 1, respectively an integer of 0 to 3 when b = 2, and e is an integer of 0 to 4.

Examples of the transition metal compound represented by the general formula (4) include cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triethyl, cyclopentadienyl titanium tri (n-propyl), cyclopentadiene. Phenyl titanium triisopropyl, cyclopentadienyl titanium tri (n-butyl), cyclopentadienyl titanium triisobutyl, cyclopentadienyl titanium tri (sec-butyl), cyclopentadienyl titanium tri (t-butyl), methyl Cyclopentadienyl titanium trimethyl, 1,2-dimethylcyclopentadienyl titanium trimethyl, 1,2,4-trimethylcyclopentadienyl titanium trimethyl, 1,2,3,4-tetramethylcyclopentadienyl titanium trimethyl, Pentamethylcyclopenta Dienyl titanium trimethyl, pentamethylcyclopentadienyl titanium triethyl, pentamethylcyclopentadienyl titanium tri (n-propyl), pentamethylcyclopentadienyl titanium triisopropyl, pentamethylcyclopentadienyl titanium tri (n-butyl) ), Pentamethylcyclopentadienyl titanium triisobutyl, pentamethylcyclopentadienyl titanium tri (sec-butyl), pentamethylcyclopentadienyl titanium tri (t-butyl), cyclopentadienyl titanium trimethoxide, cyclo Pentadienyl titanium triethoxide, cyclopentadienyl titanium tri (n-propoxide), cyclopentadienyl titanium triisopropoxide, cyclopentadienyl titanium triphenoxide, methylcyclopeptide Tadienyl titanium trimethoxide, (n-butyl) cyclopentadienyl titanium trimethoxide, dimethylcyclopentadienyl titanium trimethoxide, dimethylcyclopentadienyl titanium triethoxide, dimethylcyclopentadienyl titanium tri (n -Propoxide), dimethylcyclopentadienyl titanium triisopropoxide, dimethyl cyclopentadienyl titanium triphenoxide, di (t
-Butyl) cyclopentadienyltitanium trimethoxide, di (t-butyl) cyclopentadienyltitanium triethoxide, di (t-butyl) cyclopentadienyltitanium tri (n-propoxide), di (t- Butyl) cyclopentadienyltitanium triisopropoxide, di (t
-Butyl) cyclopentadienyl titanium triphenoxide, bis (trimethylsilyl) cyclopentadienyl titanium trimethoxide, bis (trimethylsilyl) cyclopentadienyl titanium triethoxide, bis (trimethylsilyl) cyclopentadienyl titanium tri (n- Propoxide), bis (trimethylsilyl) cyclopentadienyl titanium triisopropoxide, bis (trimethylsilyl) cyclopentadienyl titanium triphenoxide, trimethylcyclopentadienyl titanium trimethoxide, trimethylcyclopentadienyl titanium triethoxide, Trimethylcyclopentadienyl titanium tri (n-propoxide), trimethylcyclopentadienyl titanium triisopropoxide, trimethylcyclopentadienyl titanium tri Phenoxide, triethylcyclopentadienyl titanium trimethoxide, [bis (dimethylsilyl), methyl] cyclopentadienyl titanium trimethoxide, [di (t-butyl, methyl)] cyclopentadienyl titanium triethoxide, tetra Methylcyclopentadienyl titanium trimethoxide, tetramethylcyclopentadienyl titanium triethoxide, tetramethylcyclopentadienyl titanium tri (n-propoxide), tetramethylcyclopentadienyl titanium triisopropoxide, tetramethyl Cyclopentadienyl titanium tri (n-butoxide), tetramethylcyclopentadienyl titanium triisobutoxide, tetramethylcyclopentadienyl titanium tri (sec-butoxide), tetramethylcyclopentadienyl tita Tri (t-butoxide), tetramethylcyclopentadienyl titanium triphenoxide, [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium trimethoxide, [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri Ethoxide, [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri (n-propoxide), [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium triisopropoxide, [tetramethyl, 4- Methoxyphenyl] cyclopentadienyl titanium triphenoxide,
[Tetramethyl, 4-methylphenyl] cyclopentadienyltitanium trimethoxide, [tetramethyl, 4-methylphenyl] cyclopentadienyltitanium triethoxide, [tetramethyl, 4-methylphenyl] cyclopentadienyltitanium Tri (n-propoxide), [tetramethyl, 4-methylphenyl] cyclopentadienyltitanium triisopropoxide, [tetramethyl, 4-methylphenyl] cyclopentadienyltitanium triphenoxide, [tetramethyl, benzyl] Cyclopentadienyl titanium trimethoxide, [tetramethyl, benzyl] cyclopentadienyl titanium triethoxide, [tetramethyl, benzyl] cyclopentadienyl titanium tri (n-propoxide), [tetramethyl, benzyl]
Cyclopentadienyl titanium triisopropoxide,
[Tetramethyl, benzyl] cyclopentadienyltitanium triphenoxide, [tetramethyl, 2-methoxyphenyl] cyclopentadienyltitanium trimethoxide,
[Tetramethyl, 2-methoxyphenyl] cyclopentadienyltitanium triethoxide, [tetramethyl, 2-methoxyphenyl]
[Methoxyphenyl] cyclopentadienyl titanium triphenoxide, [tetramethyl, ethyl] cyclopentadienyl titanium trimethoxide, [tetramethyl, ethyl] cyclopentadienyl titanium triethoxide, [tetramethyl, ethyl] cyclopentadiene Enyl titanium tri (n-propoxide), [tetramethyl, ethyl] cyclopentadienyl titanium triisopropoxide, [tetramethyl, ethyl] cyclopentadienyl titanium triphenoxide, [tetramethyl, n-butyl] cyclopenta Dienyl titanium trimethoxide, [tetramethyl, n
-Butyl] cyclopentadienyltitanium triethoxide, [tetramethyl, n-butyl] cyclopentadienyltitanium tri (n-propoxide), [tetramethyl,
[n-butyl] cyclopentadienyltitanium triisopropoxide, [tetramethyl, n-butyl] cyclopentadienyltitanium triphenoxide, [tetramethyl, phenyl] cyclopentadienyltitanium trimethoxide,
[Tetramethyl, phenyl] cyclopentadienyltitanium triethoxide, [tetramethyl, phenyl] cyclopentadienyltitanium triphenoxide, [tetramethyl, trimethylsilyl] cyclopentadienyltitanium trimethoxide, [tetramethyl, trimethylsilyl] Cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium triethoxide,
Pentamethylcyclopentadienyl titanium tri (n-propoxide), pentamethylcyclopentadienyl titanium triisopropoxide, pentamethylcyclopentadienyl titanium tri (n-butoxide), pentamethylcyclopentadienyl titanium triiso Butoxide, pentamethylcyclopentadienyl titanium tri (sec-butoxide), pentamethylcyclopentadienyl titanium tri (t-butoxide), pentamethylcyclopentadienyl titanium tri (cyclohexoxide), pentamethylcyclopentadienyl Titanium triphenoxide, cyclopentadienyl titanium tribenzyl, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl titanium trimethyl, indenyl titanium tribenzyl, cyclopen Dienyl titanium tri (methanesulfonyl), trimethyl cyclopentadienyl titanium (tri benzenesulfonyl) tetramethylcyclopentadienyl titanium tri (ethanesulfonyl), pentamethylcyclopentadienyl titanium tri (methanesulfonyl)
Cyclopentadienyl titanium tris (dimethylamide), trimethylcyclopentadienyl titanium tris (dimethylamide), pentamethylcyclopentadienyl titanium tris (dibenzylamide), pentamethylcyclopentadienyl titanium tris (dimethylamide),
Pentamethylcyclopentadienyltitanium tris (diethylamide), cyclopentadienyltitaniumtri (nitro), pentamethylcyclopentadienyltitaniumtri (nitro), etc. No.

Further, cyclopentadienyl titanium dimethyl monochloride, cyclopentadienyl titanium monoethyl dichloride, cyclopentadienyl titanium di (n
-Propyl) monochloride, cyclopentadienyl titanium diisopropyl monochloride, cyclopentadienyl titanium di (n-butyl) monochloride, cyclopentadienyl titanium diisobutyl monochloride, cyclopentadienyl titanium di (sec-butyl) mono Chloride, cyclopentadienyl titanium di (t-butyl) monochloride, 1,2-dimethylcyclopentadienyl titanium dimethyl monochloride, 1,2,4-trimethyl cyclopentadienyl titanium dimethyl monochloride, 1,2, 3,
4-tetramethylcyclopentadienyltitanium dimethyl monochloride, pentamethylcyclopentadienyl titanium dimethyl monochloride, cyclopentadienyl titanium monochlorodimethoxide, cyclopentadienyl titanium dichloromonomethoxide, cyclopentadienyl titanium dichloromono Ethoxide, cyclopentadienyltitanium monochlorodioxide (n-propoxide), cyclopentadienyltitanium monochlorodiisopropoxide, cyclopentadienyltitanium monochlorodiphenoxide, dimethylcyclopentadienyltitanium monochlorodimethoxide,
Dimethylcyclopentadienyl titanium monochlorodioxide, dimethylcyclopentadienyl titanium monochlorodioxide (n-propoxide), dimethylcyclopentadienyl titanium monochlorodiisopropoxide, dimethylcyclopentadienyl titanium monochlorodiphenoxide,
Di (t-butyl) cyclopentadienyltitanium monochlorodimethoxide, bis (trimethylsilyl) cyclopentadienyltitanium monochlorodimethoxide, trimethylcyclopentadienyltitanium monochlorodimethoxide,
Trimethylcyclopentadienyl titanium monochlorodimethoxide, triethylcyclopentadienyl titanium monochlorodimethoxide, [bis (dimethylsilyl), methyl] cyclopentadienyl titanium monochlorodimethoxide, tetramethylcyclopentadienyl titanium monochlorodimethoxide, tetra Methylcyclopentadienyltitanium dichloromonomethoxide, tetramethylcyclopentadienyltitanium monochloride (n-butoxide),
Tetramethylcyclopentadienyl titanium monochlorodiisobutoxide, tetramethylcyclopentadienyl titanium monochlorodioxide (sec-butoxide), tetramethylcyclopentadienyl titanium monochlorodioxide (t-butoxide), [tetramethyl, 4-methoxyphenyl Cyclopentadienyl titanium monochlorodimethoxide,
[Tetramethyl, 4-methylphenyl] cyclopentadienyltitanium monochlorodimethoxide, [tetramethyl, benzyl] cyclopentadienyltitanium monochlorodimethoxide, [tetramethyl, benzyl] cyclopentadienyltitanium monochlorodimethoxide, Methyl, 2-methoxyphenyl] cyclopentadienyltitanium monochlorodimethoxide, [tetramethyl, ethyl] cyclopentadienyltitanium monochlorodimethoxide, [tetramethyl, ethyl] cyclopentadienyltitanium monochlorodimethoxide, [tetramethyl , N-butyl] cyclopentadienyltitanium monochlorodiethoxide, [tetramethyl, n-butyl] cyclopentadienyltitanium monochlorodioxide (n-propoxide), [tetramethyl, n-butyl] ] Cyclopentadienyltitanium monochlorodiisopropoxide, [tetramethyl, phenyl] cyclopentadienyltitanium monochlorodimethoxide, [tetramethyl, trimethylsilyl] cyclopentadienyltitanium monochlorodimethoxide, pentamethylcyclopentadienyltitanium monochlorodioxide Dimethoxide,
Pentamethylcyclopentadienyltitanium dichloromonomethoxide, pentamethylcyclopentadienyltitanium monochlorodioxide, pentamethylcyclopentadienyltitanium monochlorodioxide (cyclohexoxide), pentamethylcyclopentadienyltitanium monochlorodiphenoxide, Indenyltitanium monochlorodimethoxide, cyclopentadienyltitanium monochlorodioxide (methanesulfonyl), pentamethylcyclopentadienyltitanium monochlorobis (diethylamide), pentamethylcyclopentadienyltitanium monochlorobis [di (n-butyl) amide] , Pentamethylcyclopentadienyltitanium dichloro (dimethylamide), pentamethylcyclopentadienyltitanium dichloro (diphenylamide),
Pentamethylcyclopentadienyl titanium dichloro (methylethylamide), pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilylamide), pentamethylcyclopentadienyl titanium dimethoxy (diphenylamide), pentamethylcyclopentadienyl titanium Monochlorobis (diethyl phosphide), pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) phosphide], pentamethylcyclopentadienyl titanium dichloro (dimethyl phosphide), pentamethylcyclopentadienyl titanium dimethoxy ( Dimethyl phosphide), pentamethylcyclopentadienyl titanium dichloro (diphenyl phosphide), pentamethylcyclopentadienyl titanium dichloro (methyl ethyl Fosufido), pentamethylcyclopentadienyl titanium dichloro (t-butyl trimethylsilyl phosphinothricin de), pentamethylcyclopentadienyl titanium dimethoxy (diphenyl phosphinate de), cyclopentadienyl titanium trichloride, n-
Butylcyclopentadienyltitanium trichloride, tetramethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trichloride,
Pentaethylcyclopentadienyltitanium trichloride, [tetramethyl, n-butyl] cyclopentadienyltitanium trichloride, tetraisopropylcyclopentadienyltitanium trichloride, tetraphenylcyclopentadienyltitanium trichloride, nobornacyclopenta Dienyl titanium trichloride, indenyl titanium trichloride, 4,5,6,7-tetrahydroindenyl titanium trichloride, [1,2,3-trimethyl, 4,
5,6,7-tetrahydro] indenyl titanium trichloride, [1,2,3,4,5,6,7-heptamethyl]
Indenyl titanium trichloride, pentamethylcyclopentadienyl titanium trifluoride, pentamethylcyclopentadienyl titanium tribromide, pentamethylcyclopentadienyl titanium triiodide and the like, and in addition to these compounds, titanium Instead, there may be mentioned corresponding compounds containing zirconium and hafnium. In the polymerization catalyst of the present invention, the transition metal compound of the component (A) may be used alone or in combination of two or more.

Examples of the transition metal compound represented by the general formula (5) include methylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium chlorohydride, ethylenebis (indenyl). Methyltitanium chloride, ethylenebis (indenyl) methoxychlorotitanium, ethylenebis (indenyl) titanium diethoxide, ethylenebis (indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylene Bis (2-methylindenyl) titanium dichloride,
Ethylenebis (2-ethylindenyl) titanium dichloride, ethylenebis (2,4-dimethylindenyl)
Titanium dichloride, ethylenebis (2-methyl-4)
-Trimethylsilylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl-5,6,7-trihydroindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3'-tert-butyl-
5'-methylcyclopentadienyl) titanium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2 -Methylindenyl) titanium dichloride,
Isopropylidene bis (indenyl) titanium dichloride, isopropylidene bis (2,4-dimethylindenyl) titanium dichloride, isopropylidene (2
4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride,
Isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) (3'-tert-butyl-
5'-methylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium dichloride,
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium chlorohydride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) dimethyltitanium, methylene (cyclopentadienyl) (3,4-Dimethylcyclopentadienyl) diphenyltitanium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropyl Ridene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) titanium Chloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (2-methylcyclopentadienyl)
(Fluorenyl) titanium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (3,3
4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride,
Ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium Dichloride,
Ethylene (2,5-diethylcyclopentadienyl)
(Fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, Cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (2,
A transition metal compound having two cyclopentadienyl groups or derivatives thereof bridged with an alkylene group such as 5-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis ( Indenyl) titanium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylene bis (2-methylindenyl) titanium dichloride, dimethylsilylene bis (2,4-dimethylindenyl) titanium Dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylene bis (indenyl) titanium dichloride, phenylmethylsilylene Bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, phenylmethylsilylene bis (2,4-dimethylindenyl)
Titanium dichloride, phenylmethylsilylene (2,
4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride,
Phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2,4,5-trimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilylene bis (2,4
-Dimethylindenyl) titanium dichloride, diphenylsilylenebis (indenyl) titanium dichloride, diphenylsilylenebis (2-methylindenyl)
Titanium dichloride, tetramethyldisilylenebis (indenyl) titanium dichloride, tetramethyldisilylenebis (cyclopentadienyl) titanium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) titanium dichloride,
Dimethylsilylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride,
Dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride,
Dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl)
Titanium dichloride, dimethyl silylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, dimethyl silylene (cyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethyl silylene (2 -Methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride,
Dimethylsilylene (2-ethylcyclopentadienyl)
(Fluorenyl) titanium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2,7-di-t
ert-butylfluorenyl) titanium dichloride,
Dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl)
Titanium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-
tert-butylfluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl)
(Octahydrofluorenyl) titanium dichloride,
Dimethylsilylene (dimethylcyclopentadienyl)
(Octahydrofluorenyl) titanium dichloride,
Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride and other silylene-bridged cyclopentadienyl groups or derivatives thereof 2
-Containing transition metal compounds, dimethylgermylene bis (indenyl) titanium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl) titanium dichloride, methylaluminene bis (indenyl) titanium dichloride, phenylamylenebis (indenyl) titanium dichloride , Phenylphosphylene bis (indenyl) titanium dichloride, ethylborene bis (indenyl) titanium dichloride, phenylamylene bis (indenyl) titanium dichloride, phenylamylene (cyclopentadienyl) (fluorenyl)
Transition metal compounds having two cyclopentadienyl groups or derivatives thereof bridged with a hydrocarbon group containing germanium such as titanium dichloride, aluminum, boron, phosphorus or nitrogen, (1,1′-dimethylsilylene) (2,
2'-isopropylidene) -bis (cyclopentadienyl) titanium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) -bis (cyclopentadienyl) titanium dichloride, (1,1) '-
Dimethylsilylene) (2,2'-isopropylidene)-
Bis (cyclopentadienyl) dimethyltitanium,
(1,1′-Dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) dibenzyltitanium, (1,1′-dimethylsilylene) (2,
2'-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) titanium, (1,1 '
-Dimethylsilylene) (2,2'-isopropylidene)
-Bis (cyclopentadienyl) bis (trimethylsilylmethyl) titanium, (1,2'-dimethylsilylene) (2,1'-ethylene) -bis (indenyl) titanium dichloride, (1,1'-dimethylsilylene)
(2,2'-ethylene) -bis (indenyl) titanium dichloride, (1,1'-ethylene) (2,2'-dimethylsilylene) -bis (indenyl) titanium dichloride, (1,1'-dimethylsilylene) (2,2'-
Cyclohexylidene) -bis (indenyl) titanium dichloride and other transition metal compounds having two cyclopentadienyl groups or their derivatives double-bridged with each other, and chlorine atoms of these compounds are bromine atoms, Examples thereof include iodine atoms, hydrogen atoms, methyl groups, phenyl groups, and the like, and those in which titanium, which is the central metal of the transition metal compound, is replaced with zirconium, hafnium, niobium, molybdenum, tungsten, or the like.

Examples of the transition metal compound represented by the general formula (6) include pentamethylcyclopentadienyl-bis (phenyl) aminotitanium dichloride, indenyl-bis (phenyl) aminotitanium dichloride and pentamethylcyclopenta. Dienyl-bis (trimethylsilyl) aminotitanium dichloride, pentamethylcyclopentadienylphenoxytitanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminotitanium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminotitanium dichloride, dimethylsilylene (Tetrahydroindenyl) [bis (trimethylsilyl) amino] titanium dichloride, dimethylgermylene (tetramethylcyclopentadienyl) Transition metal compounds having one cyclopentadienyl group such as phenylaminotitanium dichloride or a derivative thereof, and compounds in which chlorine atom of these compounds is replaced with bromine atom, iodine atom, hydrogen atom, methyl group, phenyl group, etc., Furthermore, the titanium, which is the central metal of the above transition metal compound, is replaced with zirconium, hafnium,
It may be replaced with niobium, molybdenum, or tungsten.

Among the olefin polymerization catalysts of the present invention,
The organoaluminum compound (B) is an organoaluminum compound represented by the following general formula (1) R ¹ _r AlT _{3 -r} (1). Where R ¹
Is a hydrocarbon group such as an alkyl group, an alkenyl group and an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12, T is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is Indicates an integer of 1 to 3.

Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-tert-aluminum.
Butyl aluminum, tridecyl aluminum such as tridecyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride, alkyl aluminum halides such as ethyl aluminum dichloride, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride, diethyl aluminum ethoxy And alkyl aluminum alkoxides such as dimethyl aluminum trimethyl siloxide and diethyl aluminum phenoxide. Of these, trialkylaluminum is preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. Among the olefin polymerization catalysts of the present invention, typical examples of the aromatic compound (C) having two or more hydroxy groups bonded to the aromatic ring are hydroquinones, bisphenols and their derivatives. Preferred are derivatives of hydroquinones and bisphenols represented by the general formulas (2) and (3). More preferred are biphenols in which 1 in the general formula (3) is 0, 1 and methylene bridged, ethylene bridged or isopropylidene bridged bisphenols.

[0021]

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[0022]

[Chemical 6]

Specific examples of the general formula (2) include 2-methylhydroquinone, 2,3-dimethylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and chlorohydroquinone. it can. Specific examples of the general formula (3) include 1,1'-biphenyl-4,4'-diol and 3,3 '
-Dimethyl- (1,1'-biphenyl) -4,4'-diol, 3,
3 ', 5,5'-Tetramethyl- (1,1'-biphenyl) -4,4'-diol, 3,3', 5,5'-Tetra-tert-butyl- (1,1'-biphenyl ) -4,4'-diol, 3,3'-difluoro- (1,1'-biphenyl) -4,4'-diol, 3,3 ', 5,5'-tetrafluoro- (1,1'-
Biphenyl) -4,4'-diol etc. can be mentioned.

As a specific example of the general formula (3), 4,4'-
Methylenebisphenol, 2,2'-methylenebis (4-methylphenol), 4,4'-methylenebis (2,6-dimethylphenol), 4,4'-methylenebis (3-nonylphenol), 2,2'-methylenebis ( 3-methyl-4,6-di-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-
Butylphenol), 4,4'-methylenebis (2,6-di-sec
-Butylphenol), 4,4'-methylenebis (2-fluorophenol), 2,2'-methylenebis (4-fluorophenol), 4,4'-methylenebis (2,6-dibromophenol)
, 4,4'-methylenebis (2,6-dimethylphenol),
2,2'-methylenebisphenol, 2,4'-methylenebisphenol, 4,4'-methylenebis [2- (2-propenyl) phenol], 4,4'-methylenebis (2-methylphenol)
, 2,2'-methylenebis (4,6-dimethylphenol),
Mention may be made of methylenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol). Also, mention should be made of ethylidene bisphenols such as 4,4'-ethylidene bisphenol, 2,2'-ethylidene bis (4-methylphenol) and 2,2'-ethylidene bis (4,6-di-tert-butylphenol). You can

Further, 2,2-bis (4-hydroxy-3-propenylphenyl) propane, 2,2-bis (4-hydroxy-3-)
Isopropylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-
Hydroxy-3-sec-butylphenyl) propane, 2,2-bis (2-hydroxy-5-sec-butylphenyl) propane,
2,2-bis (4-hydroxyphenol) propane (common name: B
is-A), 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-fluorophenyl) propane, 2,2-bis [5- (2-hydroxybiphenyl) )] Propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-di- (tert-butylphenyl) propane, 2,2-bis (3-cyclohexyl-4-
Hydroxyphenyl) propane, 2,2-bis (2-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (2-chloro-3-hydroxy-4-methylphenyl) propane, 2,
2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) ) Propylene bisphenols such as propane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane can be mentioned.

Further, 2,2-bis (4-hydroxyphenyl)
Butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 2,2- Bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4- Carbon such as (hydroxyphenyl) nonane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane Examples thereof include bisphenols crosslinked with a chain hydrocarbon group of several 4 or more.

Further, 1,1-bis (4-hydroxyphenyl)
Cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-tetr-butyl-4-hydroxyphenyl) Cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-
Bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxy-3-fluorophenyl) phenylmethane, 1,1-bis [3- (6-hydroxyphenyl) )] Ethylbenzene, 1,1-bis (4-hydroxy-3-methylphenyl) ethylbenzene, 2,2-bis (4-hydroxyphenyl) ethylbenzene, 4,4'-di-hydroxy-tetra-
Phenylmethane, 1,1-bis [3- (6-hydroxybiphenyl)] cyclohexane, 1,4-bis [2- (4,5-dihydroxyphenyl) propyl] benzene, 1,4-bis [2- (2 , 3,4-Trihydroxyphenyl) propyl] benzene, 1,4-bis [2
-(4-Hydroxy-3-methylphenyl) propyl] benzene, bisphenols crosslinked with a crosslinking group having a cyclic hydrocarbon group such as 9,9-bis (4-hydroxyphenyl) freon can be mentioned.

In addition, 4,4'-thio-bisphenol, 4,4'-dithio-bisphenol, 4,4'-thio-bis
(6-tert-butyl-m-cresol), 4,4'-thiobis (2
-Methyl-6-tert-butyl-phenol), 4,4'-dihydroxyamine, 4,4 '-(dimethylsilylene) bisphenol, 4,4'-oxyphenol, 4,4'-dihydroxybenzophenone, etc. You can

Further, as the above derivatives, hydroquinone sulfonic acid potassium salt, 1,7-di (4-hydroxy-phenyl-thio) -3,5-dioxy-heptane, 1,1,1-tris (2
-Methyl-1-hydroxyphenyl) ethane, (3,4-dihydroxy) bis (2,6-dimethyl-1-hydroxyphenyl) methane, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2- Cyclohexyl-5-methylphenol],
4,4 ', 4 "-Methylidene trisphenol, 1- [1,1-bis (4
-Hydroxyphenyl) ethyl] -4- [2- (4-hydroxyphenyl) propyl] benzene, 4,4 ', 4 "-ethylidenetrisphenol, 4,4'-[(4-hydroxyphenyl) methylene] bis [ 2-Methylphenol], 4,4 '-[(3,4-Di-hydroxyphenol) methylene] Bis [2-methylphenol], 2,6-bis [(2-hydroxy-5-methylphenyl)
Methyl] -4-methylphenol, 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol],
2,2-bis (4-hydroxyphenyl) propanoic acid, 1,1-bis (4-hydroxyphenyl) butyl acetate, 3,3-bis (3-
Methyl-4-hydroxyphenyl) -2-oxo-N-hydroindole, 4,4 '-[(4-fluorophenyl) methylene] bis
[2-Fluorophenol], 4,4 '-[(4-Fluorophenyl)
Methylene] bisphenol, 2,2 '-[(2-hydrophenyl) methylene] bis [3,5-dimethylphenol], 4,4'
-[(3-Hydrophenyl) methylene] bis [2,6-dimethylphenol], 2,2 '-[(4-hydrophenyl) methylene]
Bis [3,5-dimethylphenol], 4,4 '-[(2-hydrophenyl) methylene] Bis [2,4,6-trimethylphenol], 4,4'-(1-Methylethylene) bis [2 -Nitrophenol], 1,1,2,2-Tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,4-bis [bis (4-hydroxyphenyl) methyl] benzene, 4,4 '-(4 -Hydroxyphenylmethylene) bis [2-cyclohexyl-5-methylphenol], 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,4-bis [bis (3, 5-dimethyl-4
-Hydroxyphenyl) methyl] benzene, 4- [1- [4- (4
-Hydroxyphenyl) -4-methylcyclohexyl] -1-methyl-ethyl] phenol, 4- [1- [4- (4-hydroxy-3
-Methylphenyl) -4-methylhexyl-1-methylethyl] -2-methylphenol, 4- [1- [4- (4-hydroxy-3,5
-Dimethylphenyl) -4-methylhexyl-1-methylethyl] -2,6-dimethylphenol, [2-hydroxy-5-methyl] -1,3-benzenedimethanol,

[0030]

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[0031]

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[0032]

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And the like. The ratio of the component (A) and the component (B) used in the olefin-based polymerization catalyst of the present invention is such that the molar ratio of the organoaluminum compound (in terms of aluminum) of the component (B) / transition metal compound of the component (A) is It is usually selected in the range of 1 to 10,000. If this molar ratio is less than 1, the activity is not sufficiently exerted,
On the other hand, when it exceeds 10,000, the organoaluminum compound is wasted and a large amount remains in the resulting polymer. From the viewpoint of activity, economy, quality of the obtained polymer and the like, the preferable molar ratio is in the range of 10 to 5,000, and particularly preferably in the range of 20 to 2,000.

The concentration of the component (B) in the polymerization reaction field is preferably 3.5 mmol / liter or less. If the concentration of the component (B) is too high, the component (B) may not only be wasted but also its activity may be reduced. It is more preferably 2.5 mmol / liter.
The concentration of the component (B) in the polymerization field means the concentration per solvent in the solution polymerization method, slurry polymerization method and the like, and the concentration per reaction vessel in the gas phase polymerization method. Also,
The aromatic compound having two or more hydroxy groups bonded to the aromatic ring of the component (C) has a hydroxy group of the aromatic compound / the organoaluminum compound (aluminum conversion) molar ratio of the component (B) of 0.5 to 3. It is preferable to use it in the range of. If this molar ratio is less than 0.5, the activity and copolymerizability improving effect is insufficient, and if it exceeds 3, on the contrary, the activity and copolymerizability tend to decrease. From the viewpoint of activity and improvement of copolymerizability, a more preferable molar ratio is in the range of 1 to 3.

The order of contacting each catalyst component of the present invention is not particularly limited, but whether the component (A) is contacted after the component (B) and the component (C) are contacted is the aspect of the catalytic activity. Is preferred. The conditions for preliminarily contacting the component (B) and the component (C) are as follows: the component (B) and the component (C) are contacted in an inert solvent in an inert gas atmosphere such as argon or nitrogen. It is advisable to contact them in the temperature range of 78 to 100 ° C., preferably in the temperature range of −20 to 0 ° C. In addition, after contacting, if necessary, it is preferable to heat and destill within a temperature range of 80 to 100 ° C. Examples of the inert solvent include toluene, hexane, benzene, dichloromethane and heptane. The reaction time is usually 2 to 24.
Time.

In the olefin-based polymerization catalyst of the present invention, if desired, within the range where the object of the present invention is not impaired,
In addition to the components (A), (B) and (C),
Other catalyst components may be included. Also, if desired,
Each catalyst component may be brought into contact with an appropriate carrier to be supported on the carrier. Examples of the carrier include inorganic oxides such as silica and alumina, inorganic halides such as magnesium chloride, inorganic alkoxides such as diethoxymagnesium, and polymers such as polystyrene. In the method for producing an olefin-based polymer of the present invention, in the presence of the polymerization catalyst prepared as described above, homopolymerization of an olefin or co-polymerization of an olefin with another olefin and / or another polymerizable unsaturated compound is carried out. Polymerization takes place.

The olefin is not particularly limited and includes, for example, ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-.
1, nonene-1, decene-1, 4-phenylbutene-
1,6-phenylhexene-1,3-methylbutene-
1,4-methylpentene-1,3-methylpentene-
1,3-methylhexene-1,4-methylhexene-
1,5-methylhexene-1,3,3-dimethylpentene-1,3,4-dimethylpentene-1,4,4-dimethylpentene-1,3,5,5-trimethylhexene
1, α-olefins such as vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichlorobutene-1 Halogen-substituted α-
Olefins. Also, the other olefins described above may be appropriately selected from the above olefins. In the present invention, the above olefins may be used alone or in combination of two or more.

In the present invention, the other polymerizable unsaturated compound to be copolymerized with the olefin is, for example, cyclic olefin, cyclic diolefin, chain conjugated diolefin, chain non-conjugated diolefin, aromatic vinyl. A compound or the like can be used. Examples of the cyclic olefin include cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,5. 6-trimethylnorbornene, 5-
Examples thereof include phenyl norbornene and 5-benzyl norbornene, and examples of the cyclic diolefin include 5-ethylidene norbornene, 5-vinyl norbornene, dicyclopentadiene, norbornadiene and the like. Further, as the chain conjugated diolefin, for example, 1,3-
Examples of the chain-like non-conjugated diolefin include butadiene and isoprene.
-Methyl-1,4-hexadiene, 5-methyl-1,4
1,4-dienes such as hexadiene, 5-methyl-1,4-heptadiene, 1,5-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,5-hexadiene, 3,4 -Dimethyl-1,5-hexadiene,
1,5-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 1,5-octadiene, 5-methyl-1,5-octadiene, 6-
1,5-dienes such as methyl-1,5-octadiene,
1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 7-ethyl-1,6-octadiene, 1,6-nonadiene, 7-methyl-1,6- 1,6-dienes such as nonadiene and 4-methyl-1,6-nonadiene, 1,7-octadiene,
3-methyl-1,7-octadiene, 3-ethyl-1,
7-octadiene, 3,4-dimethyl-1,7-octadiene, 3,5-dimethyl-1,7-octadiene,
1,7-dienes such as 1,7-nonadiene and 8-methyl-1,7-nonadiene, and further 1,11-dodecadiene, 1,13-tetradecadiene and the like can be mentioned.

Further, examples of the aromatic vinyl compound include styrene and α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, pt-butylstyrene and p-phenylstyrene. Alkyl or aryl styrenes, p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene,
alkoxystyrenes such as pn-propoxystyrene and pn-butoxystyrene, p-chlorostyrene, p
Halogenated styrenes such as -bromostyrene and p-iodostyrene, p-trimethylsilylstyrene, m-trimethylsilylstyrene, o-trimethylsilylstyrene, p-dimethylphenylsilylstyrene, p-methyldiphenylsilylstyrene, p-triphenylsilylstyrene Alkyl- or aryl-group-containing silylstyrenes, such as p-dimethylchlorosilylstyrene, p-methyldichlorosilylstyrene, and p-trichlorosilylstyrene, halogen-containing silylstyrenes, p- (2-propenyl) styrene, m- (2-propenyl) styrene,
p- (3-butenyl) styrene, m- (3-butenyl)
Styrene, o- (3-butenyl) styrene, p- (3-
Alkenyl styrenes such as butenyl) -α-methylstyrene, vinyl biphenyls such as 4-vinylbiphenyl, 3-vinylbiphenyl and 2-vinylbiphenyl, 1- (4-vinylphenyl) naphthalene, 2- (3
Vinylphenylnaphthalenes such as -vinylphenyl) naphthalene, 1- (4-vinylphenyl) anthracene,
Vinylphenylanthracenes such as 2- (4-vinylphenyl) anthracene; vinylphenylphenanthrenes such as 1- (4-vinylphenyl) phenanthrene and 2- (4-vinylphenyl) phenanthrene; 1- (4-
Vinylphenyl) pyrene, 2- (4-vinylphenyl)
And vinylphenylpyrenes such as pyrene. In the present invention, the polymerizable unsaturated compound to be copolymerized with the olefin may be used alone or in combination of two or more kinds, or may be used in combination with the above-mentioned other α-olefin.

The polymerization method in the present invention is not particularly limited, and any polymerization method such as slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method and the like can be adopted. When a polymerization solvent is used, the solvent is, for example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms, an alicyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, specifically n. -Pentane, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.

The polymerization temperature is not particularly limited, but it is usually selected in the range of 0 to 350 ° C, preferably 20 to 250 ° C. On the other hand, the polymerization pressure is not particularly limited, but is usually 0 to 150 kg / cm ² G, preferably 0 to 10
It is selected in the range of 0 kg / cm ² G. The polymerization time is usually 5
It takes about 10 minutes to 10 minutes. As a method for controlling the molecular weight of the polymer, the type of each catalyst component, the amount used, the selection of the polymerization temperature,
Further, there is polymerization in the presence of hydrogen.

[0042]

[Example 1]

1. Reaction of organoaluminum compound with aromatic compound In a 300 ml glass container, bisphenol A [2,2-bis- (4-
Hydroxyphenyl) propane] 4.57 g (20 mmol) was added, and the interior was replaced with nitrogen, and dehydrated and purified toluene
100 ml was added. To this suspension, 10 ml of a toluene solution of trimethylaluminum (2 mol / l) was slowly added dropwise at room temperature, and the mixture was further stirred at room temperature for 3 hours to obtain a white suspension. This reaction product was confirmed by ¹ H-NMR analysis to be a 1: 1 condensate of trimethylaluminum and bisphenol A.

2. (Tertiary butylamide) dimethyl (η
Preparation of ⁵ -cyclopentadienyl) silane titanium dichloride (a) (chloro) (cyclopentadienyl) (dimethyl) silane 149 g (1.16 mmol) M in 750 ml diethyl ether
The solution of e ₂ SiCl ₂ was cooled to -78 ° C. Add to this solid sodium cyclopentadienide (30 g, 0.34 mo
l) was added from the powder addition funnel over 1.5 hr. The reaction mixture was heated to room temperature and stirred for 16 hr. The ether and some Me ₂ SiCl ₂ were distilled off, then residual ether, Me ₂ SiCl ₂ and product were removed from the NaCl formed during the reaction by vacuum distillation. The product was obtained in good yield as a pale yellow oil after fractional distillation. Mass spectrum: m / e = 158 (16%).

(B) (tertiary butylamide) (cyclopentadienyl) (dimethyl) silane 3.69 in 45 ml tetrahydrofuran (hereinafter THF).
2.00 g in a solution of g (50.4 mmol) tertiary butylamine
(12.6 mmol) (chloro) (cyclopentadienyl) (dimethyl) silane was added. A precipitate formed quickly. The slurry was stirred for a few days, then the amine hydrochloride was filtered off,
The solvent was then removed under reduced pressure to give the product as a very pale yellow oil. The yield was 2.07 g (yield 84%). Mass spectrum: m / e = 195 (6%). ¹ H and ¹³ C-
NMR shows the presence of some cyclopentadiene isomers.

(C) Dilithium (tertiary butylamide) (cyclopentadienyl) (dimethyl) silane 1.500 g (7.69 mmol) (tertiary butylamide) in 60 ml ether.
6.21 ml of 1.72 M (10.68 mmol) ether solution of methyllithium in (cyclopentadienyl) (dimethyl) silane
And then 1.81 ml of 2.6M (4.706 mmol) butyllithium in a mixed alkane solvent (total alkyl lithium 15.39 m
mol) was added slowly. The resulting slurry was stirred overnight, then filtered, washed with pentane and dried under reduced pressure to give the product as a white powder. Yield 1.36 g (85% yield)
Met. ^{According to 1} H-NMR (THF d-8),
δ 5.96 (t, 2H), 5.87 (t, 2H), 1.10 (s, 9H), 0.05 (s, 6
H). ¹³ C-NMR shows that according to (THF d-8), d 11
4, 105.2, 103.5, 52, 38.3, 7.3.

(D) (tertiary butylamide) dimethyl (η ⁵
-Cyclopentadienyl) silane titanium dichloride 0.700 g (3.38 mmol) of dilithium (tertiary butylamido) (cyclopentadienyl) (dimethyl) silane and 1.1
75 g of 28 g (3.38 mmol) TiCl ₄ · (THF) ₂
Were mixed in a flask containing 2 parts of toluene. The resulting yellow slurry turned mud reddish brown within a few hours. The reaction mixture was stirred for several days, then the red solution was filtered and the solvent was removed under reduced pressure. The crystalline material formed was slurried with pentane and filtered to remove soluble red impurities from the brown product. Yield 0.537 g (Yield = 51%). ¹ H
According to NMR (C ₆ D ₆ ), δ 6.60 (t, 2H), 6.07
(t, 2H), 1.38 (s, 9H), 0.18 (s, 6H). ¹³ C-NMR (C ₆
According to D ₆ ), δ 126.3, 125.6, 110.0, 63.7, 3
2.2, -0.2.

3. Copolymerization of ethylene and 1-octene After replacing the dry 1 liter polymerization reactor with stirrer with dry nitrogen, dry toluene 480 ml and 1-octene
20 ml was added. Next, 0.5 mmol of triisobutylaluminum and 0.5 mmol of the compound obtained in [Example 1] -1 in terms of aluminum atom were added, and the temperature was raised to 80 ° C.
[Example 1] 0.2 µmol of the compound obtained in -2 was introduced at the same time with ethylene gas, and polymerization was carried out at 80 ° C for 60 minutes while maintaining the ethylene partial pressure at 4 kg / cm ² G. After the completion of the polymerization, the polymerization was stopped by introducing methanol into the polymerization vessel. The contents of the polymerization reactor were poured into a large amount of a methanol-hydrochloric acid mixed solution to deash. The polymerization product was filtered off and dried under reduced pressure at 80 ° C. for 4 hours to obtain 4.0 g of an ethylene-1-octene copolymer. The polymerization activity was 41 kg / g-Ti. [Η] of the obtained copolymer was 6.52 dl / g, melting point Tm was 60.5 ° C, and density was
It was 0.8737 g / cc.

[Comparative Example 1] In [Example 1] -3,
[Example 1] -3, except that trimethylaluminum was used instead of the compound obtained in -1.
Polymerization was carried out in the same manner as above, but no copolymer was obtained. [Comparative Example 2] A reaction mixture was obtained in the same manner as in [Example 1] -1, except that 1.2 g (6.7 mmol) of glucose was used instead of bisphenol A in [Example 1] -1.
Polymerization was carried out in the same manner as in [Example 1] -3 except that the compound obtained above was used instead of the compound obtained in [Example 1] -1. However, no polymer was obtained.

Example 2 In Example 1, bisphenol A was replaced by 2,6-dimethylbisA (2,2-bis (4-hydroxy-2,6-dimethylphenyl) propane) instead of bisphenol A.
A reaction mixture was obtained in the same manner as in [Example 1] -1 except that 5.12 g (20 mmol) was added (white slurry). Further, in [Example 1] -3, polymerization was performed in the same manner as in [Example 1] -3 except that the compound obtained above was used instead of the compound obtained in [Example 1] -1. As a result, 5.3 g of an ethylene-1-octene copolymer was obtained. Activity is 55 kg / g-Ti, [η] is 7.14 dl / g, Tm is 61.6 ℃,
The density was 0.8749 g / cc.

[Example 3] In [Example 1] -1, instead of bisphenol A, [2,2-bis (4-hydroxy-
2,6-Di-tert-butylphenyl) methane] 8.5 g (20 mmo
A reaction mixture was obtained in the same manner as in [Example 1] -1, except that 1) was used (homogeneous solution). In addition, [Example 1] -3
In the above, polymerization was carried out in the same manner as in [Example 1] -3 except that 0.05 mmol of the compound obtained above was used instead of the compound obtained in [Example 1] -1, and ethylene-1 3.9 g of octene copolymer was obtained. 41 kg / activity
g-Ti, [η] 7.02 dl / g, Tm 60.1 ℃, density 0.8754
was g / cc

[0051]

INDUSTRIAL APPLICABILITY The present invention shows a catalyst component having high activity as an alternative to aluminoxane for the polymerization of olefins, which can be synthesized under mild conditions, and has good storage stability, and a process for producing olefins using the same. Can be provided.

Claims (4)

[Claims] 1. Periodic table 4 in which (A) a cyclopentadienyl group, two bridged cyclopentadienyl groups, a constrained geometric cyclopentadienyl group or a derivative thereof and a σ ligand are coordinated. Group 6 transition metal compound, (B) General formula (1) R ¹ _r AlT _{3 -r} (1) [wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and T is A hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or a halogen atom is shown, and r is an integer of 1 to 3. ] An olefin polymerization catalyst comprising an organoaluminum compound represented by the following formula and (C) an aromatic compound having two or more hydroxy groups bonded to an aromatic ring. 2. A hydroxy group bonded to the aromatic ring of (C)
An aromatic compound having two or more of the following general formula (2) or
The olefin according to claim 1, which is represented by (3)
System polymerization catalyst. [Chemical 1]Embedded image[Wherein, R^TwoIs a hydrocarbon group having 1 to 20 carbon atoms or halo
Indicates one of the gen atoms.
May be. R^ThreeAnd R^FourIs carbonized with 1 to 20 carbon atoms
Hydrogen group, halogen atom, phenyl group or cyclohexyl
Indicates any of the groups, and if there are more than one
Good. Y is CHR^Five, CR^Five _Two, C = O, NR^Five,
PR^Five, R^FiveP = O, O, S, SiR^FiveR⁶, CR^Five _Two
PhCR⁶ _Two, Cyclohexylidene or cyclopentyl
Indicates either den (R^Five, R⁶Has 1 to 20 carbon atoms
Hydrocarbon and Ph represent a phenyl group. ). f is 0-4
, G is an integer of 2 to 6, h and k are integers of 0 to 4,
i and j show the integer of 1-5, l shows the integer of 0-5. ] 3. An organoaluminum compound of (B) and an aromatic compound of (C) having two or more hydroxy groups bonded to an aromatic ring are previously reacted with each other, and then contacted with a transition metal compound of (A). Item 3. The olefin polymerization catalyst according to Item 1 or 2. 4. A method for producing an olefin-based polymer, wherein an olefin is polymerized using the olefin-based polymerization catalyst according to any one of claims 1 to 3.