KR19980065371A - Method of producing polyethylene copolymer - Google Patents

Abstract

The present invention relates to a method for preparing an ethylene copolymer using a novel catalyst, which is expensive due to the use of a cation activator represented by the general formula M ^{n +} (X ⁻ ) _ng Z _g together with a conventional metalocene catalyst composition. Ethylene copolymers with high activity, narrow molecular weight distribution and narrow composition distribution can be produced without using aluminoxane. The composition prepared by the catalyst system of the present invention can produce a high yield of an ethylene copolymer having a sufficiently high molecular weight and excellent physical properties. Using this catalyst, a mixture of ethylene and an alpha olefin having 3 to 20 carbon atoms can be polymerized in a solution or a high pressure reactor at a temperature of -40 to 220 ° C. and a pressure of 1 to 180 atm to allow comonomer insertion up to 80% by weight. Do. Also, in the case of solution or high pressure reactor, there is no process restriction on the density of the polymer to be synthesized, so it is possible to synthesize a copolymer of a wide density range (0.86 to 0,96 g / cm 3) from VLDPE to HDPE, and the catalyst is added in a uniform state. It is possible to show the characteristics of the inherent homogeneous catalyst of the metalocene catalyst.

Description

Process for producing polyethylene copolymer

The present invention relates to a method for producing a copolymer of olefins such as ethylene using a novel catalyst for ethylene copolymerization, and more particularly to expensive aluminoxane (hereinafter abbreviated as MAO) or boron-based cocatalyst. It is possible to prepare an olefin compound such as ethylene-propylene rubber (EPR) and linear low density polyethylene (LLDPE), etc., which can produce an olefin copolymer having a sufficiently high molecular weight and excellent physical properties without using it. It is about.

The present inventors have proposed a novel catalyst for olefin polymerization and a method of polymerization of olefins using the same through Korean Patent Application No. 39309 of September 6, 1996. In the above application, the MAO cocatalyst is used by improving the need to use an expensive and excessive MAO, which is a problem in the conventional metalocene catalyst system, or to use an expensive Boron compound as a cocatalyst. However, the present invention provides a new technique for producing a high yield of an olefin homopolymer such as polyethylene by using a metalocene catalyst while having a sufficiently high molecular weight and excellent physical properties.

However, the above-mentioned Korean Patent Application No. 96-39309 relates only to the production of olefin homopolymers such as polyethylene and the like, and the copolymers of these olefins with other olefins such as propylene, comonomers such as styrene, diene or cycloolefins, Up to the technology of preparing the coalescence has not been tested.

The present invention further extends the technique of the above-described Korean Patent Application No. 96-39309 to a uniform composition of olefins such as ethylene and other olefins such as propylene, styrene, diene or cycloolefin up to 80% by weight in a uniform composition. It is possible to provide a method for obtaining a high molecular weight copolymer in a very high yield. These features are very advantageous industrially and are important as catalyst features.

Spectrum a) in the figure shows the DSC (Differential Scanning Calorimeter) spectrum of an ethylene / octene copolymer obtained using a metalocene catalyst (bis (n-butyl cyclopentadienyl) zirconium dichloride), and the spectrum b) is The spectrum of the polymer obtained using a Ziegler-Natta catalyst is shown.

In order to achieve the above object, the present invention uses an olefin copolymerization catalyst comprising a catalyst (A) composed of a transition metal complex, a component (B) composed of a cation activator, and a component (C) composed of an alkylating agent. Provided are methods for preparing ethylene / α-olefins including propylene, ethylene / 1-octene. The present invention also provides a process for producing ethylene / styrene, ethylene / diene or ethylene / cyclo olefins using the catalyst as described above.

The catalyst system used in the present invention is basically the same as the catalyst system disclosed in Korean Patent Application No. 96-39309, which is the preliminary application of the present inventors.

Component (A) constituting the catalyst system as described above is a metal belonging to group IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB on the periodic table of elements, C, Si, N, P, As, Sb, O, Compounds that form at least one bond with a functional group, including S, Se, F, Cl, Br, I, are compounds already known per se.

In addition, the component is a compound represented by the following structural formula, these are also compounds known per se.

_{^{M n + (X -) ng}} Z g

(Wherein n = 1, 2, 3 or 4, g is an integer 0 ≦ g <n, and M is IA, IIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, Or is a metal or organic substance belonging to IIB, and X is a compound consisting of an anion cluster containing one or more elements of O, S, N, F, Cl, Br, and I and having three or more elements. Is a compound consisting of an anion having at least 3 elements of H ^- or O, S, N, F, Cl, Br, I, and the number of elements is 3 or more. Compound.)

On the other hand, the component (C) is a metal belonging to IA, IIA, IIB, or IIIB on the periodic table of the elements and is an organometallic compound having a hydrocarbyl group such as alkyl, alkenyl, arylalkyl or allylalkyl having 1 to 20 carbon atoms These are also known compounds per se.

The characteristic of this invention is having these components (A), (B), and (C) mixed suitably, and using it for manufacture of an olefin copolymer. The components (B) and (C) are cocatalysts for activating component (A), which is a metalocene catalyst, and may be added in an amount sufficient to activate component (A). The addition amount of component (B) to component (A) is 1: 0.1-10 in molar concentration, Preferably it is 1: 1.

On the other hand, the addition amount of the component (C) with respect to the said component (A) is 1: 1-10,000 in molar concentration, Preferably it is 1: 100-2,000.

Transition metal complexes usable as component (A) in the present invention include, but are not limited to, dialkyl metalocenes represented by the above formula (I);

Bridge-bonded metalocenes represented by the formula R (CpRn) (CpR'm) MQp, wherein CpRn and CpR'm are substituted with one or more alkyl, phosphine, amine, alkyl ether, allyl ether, or An unsubstituted cyclopentadienyl, indenyl or fluorenyl group, R represents a bridge bond between the Cp rings, M is a transition metal of IVB or VB on the periodic table and Q is alkyl, allyl, allyl alkyl, amide, alkoxy, Group with halogen, sulfide, phosphine, where n, m, p are 0 ≦ n ≦ 4, 1 ≦ m ≦ 4 and 1 ≦ p ≦ 4, respectively);

And monocyclopentadienyl IVB transition metal catalysts having the general formula:

Wherein M represents zirconium, hafnium or titanium and has the highest oxidation number (+4, d ⁰ complex), (C ₅ H _5-yx R _x ) is a cyclopentadienyl compound, X is 0, Where 1, 2, 3, 4, 5 represents the number of substituents, R represents a C20 hydrocarbyl radical, and the hydrogen group is substituted with a halogen, amino, phosphido, alkoxy radical, or Lewis acid group or a radical having a basic functional group It can also be. (JR'z _-1-y ) is a hetero atom ligand, wherein J represents a compound having a coordination number of group VA of 3 or a compound of a coordination number of group VIA of 2 on the periodic table. Specifically, N, P, O, and S are represented, and preferably N is preferable. R 'represents a C20 hydrocarbyl radical at C1 and the hydrogen group may be substituted with a halogen, amino, phosphido, alkoxy radical, or Lewis acid group, or a radical having a basic functional group. z represents the coordination number of J and y is 0 or 1. Q represents halogen, hydride, substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, allyl oxide, amide, allylamide, phosphide, allyl phosphide.

Examples of the dialkyl metalocenes as described above include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl and bis (cyclopentadienyl) Zirconium diphenyl, bis (cyclopentadienyl) hafnium dimethyl and diphenyl, bis (cyclopentadienyl) titanium dinepentyl, bis (cyclopentadienyl) zirconium dinepentyl, bis (cyclopentadienyl) titanium di Benzyl, bis (cyclopentadienyl) vanadium dimethyl; As monoalkyl or monoallyl metalocene, bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium ethyl chloride, bis (cyclopentadienyl) titanium pentyl chloride, bis (cyclopentadiene) Nil) zirconium methyl chloride, bis (cyclopentadienyl) zirconium ethyl chloride, bis (cyclopentadienyl) zirconium phenyl chloride, bis (cyclopentadienyl) titanium methyl bromide, bis (cyclopentadienyl) Titanium methyl iodide, bis (cyclopentadienyl) titanium ethyl bromide, bis (cyclopentadienyl) titanium ethyl iodide, bis (cyclopentadienyl) titaniumphenyl bromide, bis (cyclopentadienyl) Titaniumphenyl iodide, bis (cyclopentadienyl) zirconium methyl bromide, bis (cyclopentadienyl) zirconium methyl bromide, bis (cyclopentadienyl) Zirconium methyl iodide, bis (cyclopentadienyl) zirconium ethyl bromide, bis (cyclopentadienyl) zirconium ethyl iodide, bis (cyclopentadienyl) zirconium phenyl bromide, bis (cyclopentadienyl) zirconium phenyl Iodide; As trialkyl metalocene, cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl titanium tri neopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium Trineopentyl, cyclopentadienyl hafnium trimethyl; Examples of the dihalide metalocene include bis (cyclopentadienyl) titanium dichloride and bis (cyclopentadienyl) zirconium dichloride.

On the other hand, examples of the above-described bridge-bonded metalocenes include dimethylsilyl bis (1-indenyl) zirconium dibromide, dimethylsilyl bis (1-indenyl) zirconium diethyl, and dimethylsilyl bis (1-indenyl) zirconium Dimethoxide, Dimethylsilyl bis (1-indenyl) zirconium dihydride, Dimethylsilyl bis (1-indenyl) zirconium chloride bromide, Dimethylsilyl bis (1-indenyl) zirconium chloride methoxide, Dimethylsilyl Bis (1-indenyl) zirconium chloride methyl, dimethylsilyl bis (1-indenyl) zirconium chloride hydride, dimethylsilyl (9-fluorenyl) (1-cyclpentadienyl) zirconium dichloride, dimethyl Cyryl (9-fluorenyl) (1-cyclentadienyl) zirconium dimethyl, dimethylsilyl (9-fluorenyl) (1-cyclentadienyl) zirconium diethoxide, dimethylsilyl bis (9-fluorenyl Zirconium Dichloride, Dimethylsilyl Bis (9-Fluorenyl) zirco Dimethyl, Dimethylsilyl bis (9-fluorenyl) zirconium diethoxide, Dimethylsilyl (9-fluorenyl) (1-cyclpentadienyl) zirconium diethoxide, dimethyldimethyl bis (1-cyclpentadienyl) Zirconium Dichloride, Dimethylsilyl Bis (1-cyclpentadienyl) zirconium dimethyl, Dimethylsilyl Bis (1-cyclpentadienyl) zirconium diethoxide, Dimethylsilyl Bis (1-indenyl) zirconium dichloride, dimethyl Cyryl bis (1-indenyl) zirconium dimethyl, dimethylsilyl bis (1-indenyl) zirconium diethoxide,

Dimethylsilyl (1-indenyl) (1-cyclpentadienyl) zirconium dichloride, dimethylsilyl (1-indenyl) (1-cyclpentadienyl) zirconium dimethyl, dimethylsilyl (1-indenyl) (1 Cyclopentadienyl) zirconium diethoxide, dimethylsilyl (1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilyl (1-indenyl) (9-fluorenyl) zirconium dichloride Dimethylsilyl (1-indenyl) (9-fluorenyl) zirconium dimethyl, dimethylsilyl (1-indenyl) (9-fluorenyl) zirconium diethoxide,

Dimethylsilyl (9-fluorenyl) (1-cyclpentadienyl) halfnium dichloride, dimethylsilyl (9-fluorenyl) (1-cyclpentadienyl) hafnium dimethyl, dimethylsilyl (9-fluorenyl ) (1-Cyclepentadienyl) hafnium diethoxide, dimethylsilyl bis (9-fluorenyl) hafnium dichloride, dimethylsilyl bis (9-fluorenyl) hafnium dimethyl, dimethylsilyl bis (9-fluore Nil) hafnium diethoxide, dimethylsilyl bis (1-cyclpentadienyl) hafnium dichloride,

Dimethylsilyl bis (1-cyclpentadienyl) halfnium dimethyl, dimethylsilyl bis (1-cyclpentadienyl) hafnium diethoxide,

Dimethylsilyl bis (1-indenyl) hafnium dichloride, dimethylsilyl bis (1-indenyl) hafnium dimethyl, dimethylsilyl bis (1-indenyl) hafnium diethoxide,

Dimethylsilyl (1-indenyl) (1-cyclpentadienyl) halfnium dichloride, dimethylsilyl (1-indenyl) (1-cyclpentadienyl) hafnium dimethyl, dimethylsilyl (1-indenyl) (1 Cyclpentadienyl) hafnium diethoxide,

Dimethylsilyl (1-indenyl) (9-fluorenyl) hafnium dichloride, dimethylsilyl (1-indenyl) (9-fluorenyl) hafnium dimethyl, dimethylsilyl (1-indenyl) (9-flu Orenyl) hafnium diethoxide, 2,2-propyl bis (1-indenyl) zirconium dibromide, 2,2-propyl bis (1-indenyl) zirconium diethyl, 2,2-propyl bis (1- Indenyl) zirconium dimethoxide, 2,2-propyl bis (1-indenyl) zirconium dihydride, 2,2-propyl bis (1-indenyl) zirconium chloride bromide, 2,2-propyl bis ( 1-indenyl) zirconium chloride methoxide, 2,2-propyl bis (1-indenyl) zirconium chloride methyl, 2,2-propyl bis (1-indenyl) zirconium chloride hydride, 2,2- Propyl Bis (trimethyl cyclopentadienyl) zirconium dichloride, 2,2-propyl bis (5-dimethylamino-1-indenyl) zirconium dichloride, 2,2-propyl bis (6-dipropylamino-1 Indenyl) Konium dichloride, 2,2-propyl bis (4,7-bis (dimethylamino) -1-indenyl) zirconium dichloride, 2,2-propyl bis (5-diphenylphosphino.-1- Yl) zirconium dichloride, 2,2-propyl (1-methylamino-9-fluorenyl) (1-cyclopentadienyl) zirconium dichloride, 2,2-propyl (4-butylthio-9- Fluorenyl) (1-cyclopentadienyl) zirconium dichloride, 2,2-propyl bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2-propyl Bis (4-methyl-1-indenyl) zirconium dichloride,

2,2-propyl bis (5-methyl-1-indenyl) zirconium dichloride, 2,2-propyl bis (6-methyl-1-indenyl) zirconium dichloride, 2,2-propyl bis (7 -Methyl-1-indenyl) zirconium dichloride, 2,2-propyl bis (5-methoxy-1-indenyl) zirconium dichloride, 2,2-propyl bis (4,7-dimethoxy-1 -Indenyl) zirconium dichloride, 2,2-propyl bis (2,3-dimethyl-1-indenyl) zirconium dichloride, 2,2-propyl bis (4,7-dimethyl-1-indenyl) Zirconium dichloride,

2,2-propyl (9-fluorenyl) (1-cyclpentadienyl) zirconium dichloride, 2,2-propyl (9-fluorenyl) (1-cyclpentadienyl) zirconium dimethyl, 2, 2-propyl (9-fluorenyl) (1-cyclpentadienyl) zirconium diethoxide, 2,2-propyl bis (9-fluorenyl) zirconium dichloride, 2,2-propyl bis (9- Fluorenyl) zirconium dimethyl, 2,2-propyl bis (9-fluorenyl) zirconium diethoxide,

2,2-propyl bis (1-indenyl) zirconium dichloride, 2,2-propyl bis (1-indenyl) zirconium dimethyl, 2,2-propyl bis (1-indenyl) zirconium diethoxide, 2 , 2-propyl (1-indenyl) (1-cyclpentadienyl) zirconium dichloride, 2,2-propyl (1-indenyl) (1-cyclpentadienyl) zirconium dimethyl, 2,2-propyl (1-indenyl) (1-cyclpentadienyl) zirconium diethoxide, 2,2-propyl (1-indenyl) (9-fluorenyl) zirconium dichloride, 2,2-propyl (1- Indenyl) (9-fluorenyl) zirconium dimethyl, 2,2-propyl (1-indenyl) (9-fluorenyl) zirconium diethoxide,

2,2-propyl (9-fluorenyl) (1-cyclpentadienyl) hafnium dichloride, 2,2-propyl (9-fluorenyl) (1-cyclpentadienyl) hafnium dimethyl, 2, 2-propyl (9-fluorenyl) (1-cyclpentadienyl) hafnium diethoxide, 2,2-propyl bis (9-fluorenyl) hafnium dichloride, 2,2-propyl bis (9- Fluorenyl) hafnium dimethyl, 2,2-propyl bis (9-fluorenyl) hafnium diethoxide, 2,2-propyl bis (1-cyclpentadienyl) hafnium dichloride, 2,2-propyl bis (1-cyclpentadienyl) hafnium dimethyl, 2,2-propyl bis (1-cyclpentadienyl) hafnium diethoxide,

2,2-propyl bis (1-indenyl) hafnium dichloride, 2,2-propyl bis (1-indenyl) hafnium dimethyl, 2,2-propyl bis (1-indenyl) hafnium diethoxide, 2 , 2-propyl (1-indenyl) (1-cyclpentadienyl) hafnium dimethyl, 2,2-propyl (1-indenyl) (1-cyclpentadienyl) hafnium diethoxide, 2,2-propyl (1-indenyl) (1-cyclpentadienyl) halfnium dichloride, 2,2-propyl (1-indenyl) (9-fluorenyl) hafnium dichloride, 2,2-propyl (1- Indenyl) (9-fluorenyl) hafnium dichloride, 2,2-propyl (1-indenyl) (9-fluorenyl) hafnium dimethyl, 2,2-propyl (1-indenyl) (9- Fluorenyl) hafnium diethoxide,

Diphenyl methyl bis (1-indenyl) zirconium dibromide, diphenyl methyl bis (1-indenyl) zirconium diethyl, diphenyl methyl bis (1-indenyl) zirconium dimethoxide, diphenylmethyl bis (1 Indenyl) zirconium dihydride, diphenyl methyl bis (1-indenyl) zirconium chloride bromide, diphenyl methyl bis (1-indenyl) zirconium chloride methoxide, diphenyl methyl bis (1-indenyl) Zirconium chloride methyl, diphenyl methyl bis (1-indenyl) zirconium chloride hydride,

Diphenyl methyl (9-fluorenyl) (1-cyclpentadienyl) zirconium dichloride, diphenylmethyl (9-fluorenyl) (1-cyclpentadienyl) zirconiumdimethyl, diphenyl methyl (9- Fluorenyl) (1-cyclpentadienyl) zirconium diethoxide,

Diphenyl methyl bis (9-fluorenyl) zirconium dichloride, diphenyl methyl bis (9-fluorenyl) zirconium dimethyl, diphenyl methyl bis (9-fluorenyl) zirconium diethoxide, diphenyl methyl bis (1-cyclpentadienyl) zirconium dichloride, diphenyl methyl bis (1-cyclpentadienyl) zirconium dimethyl, diphenyl methyl bis (1-cyclpentadienyl) zirconium diethoxide,

Diphenyl methyl bis (1-indenyl) zirconium dichloride, diphenyl methyl bis (1-indenyl) zirconium dimethyl, diphenyl methyl bis (1-indenyl) zirconium diethoxide, diphenylmethyl bis (1- Indenyl) zirconium dichloride, diphenyl methyl (1-indenyl) (1-cyclpentadienyl) zirconium dichloride, diphenyl methyl (1-indenyl) (1-cyclpentadienyl) zirconium dimethyl, Diphenyl methyl (1-indenyl) (1-cyclpentadienyl) zirconium diethoxide, diphenyl methyl (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenyl methyl (1-derin) Nil) (9-fluorenyl) zirconium dimethyl, diphenyl methyl (1-indenyl) (9-fluorenyl) zirconium diethoxide,

Diphenyl methyl (9-fluorenyl) (1-cyclpentadienyl) hafnium dichloride, diphenylmethyl (9-fluorenyl) (1-cyclpentadienyl) hafnium dimethyl, diphenyl methyl (9- Fluorenyl) (1-cyclpentadienyl) hafnium diethoxide, diphenyl methyl bis (9-fluorenyl) hafnium dichloride, diphenyl methyl bis (9-fluorenyl) hafnium dimethyl, diphenyl methyl Bis (9-fluorenyl) hafnium diethoxide,

Diphenyl methyl bis (1-cyclpentadienyl) hafnium dichloride, diphenyl methyl bis (1-cyclpentadienyl) hafnium dimethyl, diphenyl methyl bis (1-cyclpentadienyl) hafnium diethoxide, diphenyl Phenyl methyl bis (1-indenyl) hafnium dichloride, diphenyl methyl bis (1-indenyl) hafnium dimethyl, diphenyl methyl bis (1-indenyl) hafnium diethoxide,

Diphenyl methyl (1-indenyl) (1-cyclpentadienyl) hafnium dichloride, diphenyl methyl (1-indenyl) (1-cyclpentadienyl) hafnium dimethyl, diphenyl methyl (1-indenyl) (1-Cyclepentadienyl) hafnium diethoxide, diphenyl methyl (1-indenyl) (9-fluorenyl) hafnium dichloride, diphenyl methyl (1-indenyl) (9-fluorenyl Hafnium dimethyl, diphenyl methyl (1-indenyl) (9-fluorenyl) hafnium diethoxide,

Diphenyl Cyryl Bis (1-indenyl) zirconium dibromide, Diphenyl Cyryl Bis (1-indenyl) zirconium diethyl, Diphenyl Cyryl Bis (1-indenyl) zirconium dimethoxide, Diphenylsilyl bis (1 Indenyl) zirconium dihydride, diphenyl cyryl bis (1-indenyl) zirconium chloride bromide, diphenyl cyryl bis (1-indenyl) zirconium chloride methoxide, diphenyl cyryl bis (1-indenyl) Zirconium chloride methyl, diphenyl cyryl bis (1-indenyl) zirconium chloride hydride,

Diphenyl Cyryl (9-fluorenyl) (1-cyclentadienyl) zirconium dichloride, Diphenyl Cyryl (9-fluorenyl) (1-cyclentadienyl) zirconium dimethyl, diphenyl silyl (9- Fluorenyl) (1-cyclpentadienyl) zirconium diethoxide,

Diphenyl Cyryl (9-fluorenyl) zirconium dichloride, Diphenyl Cyryl (9-fluorenyl) zirconium dimethyl, Diphenyl Cyryl (9-fluorenyl) zirconium diethoxide, Diphenyl Cyryl (1-cycle) Pentadienyl) zirconium dichloride, diphenyl cyryl (1-cyclpentadienyl) zirconium dimethyl, diphenyl silyl (1-cyclpentadienyl) zirconium diethoxide,

Diphenyl silyl (1-indenyl) zirconium dichloride, diphenyl silyl (1-indenyl) zirconium dimethyl, diphenyl silyl (1-indenyl) zirconium diethoxide, diphenyl silyl (1-indenyl) ( 1-cyclic pentadienyl) zirconium dichloride, diphenyl cyryl (1-indenyl) (1-cyclpentadienyl) zirconium dimethyl, diphenyl cyryl (1-indenyl) (1-cyclpentadienyl) zirconium Diethoxide,

Diphenyl silyl (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenyl silyl (1-indenyl) (9-fluorenyl) zirconium dimethyl, diphenyl silyl (1-indenyl) ( 9-fluorenyl) zirconium diethoxide,

Diphenyl Cyryl (9-fluorenyl) (1-cyclpentadienyl) halfnium dichloride, Diphenyl Cyryl (9-fluorenyl) (1-cyclpentadienyl) hafnium dimethyl, diphenyl silyl (9- Fluorenyl) (1-cyclentadienyl) hafnium diethoxide, diphenyl cyryl bis (9-fluorenyl) hafnium dichloride, diphenyl cyryl bis (9-fluorenyl) hafnium dimethyl, diphenyl cyryl Bis (9-fluorenyl) hafnium diethoxide,

Diphenyl cyryl bis (1-cyclpentadienyl) hafnium dichloride, diphenyl cyryl bis (1-cyclpentadienyl) hafnium dimethyl, diphenyl cyryl bis (1-cyclpentadienyl) hafnium diethoxide, diphenyl Phenyl cyryl bis (1-indenyl) hafnium dichloride, diphenyl cyryl bis (1-indenyl) hafnium dimethyl, diphenyl cyryl bis (1-indenyl) hafnium diethoxide,

Diphenyl Cyryl Bis (1-indenyl) (1-cyclpentadienyl) halfnium dichloride, Diphenyl Cyryl Bis (1-indenyl) (1-cyclpentadienyl) hafnium dimethyl, diphenyl cyryl bis (1 Indenyl) (1-cyclpentadienyl) hafnium diethoxide,

Diphenyl Cyryl Bis (1-indenyl) (9-fluorenyl) halfnium dichloride, Diphenyl Cyrylbis (1-indenyl) (9-fluorenyl) hafnium dimethyl, diphenyl cyryl bis (1-densyl) Nil) (9-fluorenyl) hafnium diethoxide,

Ethylene bis (1-indenyl) zirconium dibromide, ethylene bis (1-indenyl) zirconium diethyl, ethylene bis (1-indenyl) zirconium dimethoxide, ethylene bis (1-indenyl) zirconium dihydride , Ethylene bis (1-indenyl) zirconium chloride bromide, ethylene bis (1-indenyl) zirconium chloride methoxide, ethylene bis (1-indenyl) zirconium chloride methyl, ethylene bis (1-indenyl) Zirconium chloride hydride,

Ethylene bis (trimethylcyclpentadienyl) zirconium dichloride, ethylene bis (5-dimethylamino-1-indenyl) zirconium dichloride, ethylene bis (6-dipropylamino-1-indenyl) zirconium dichloride , Ethylene bis (4,7-bis (dimethylamino) -1-indenyl) zirconium dichloride, ethylene bis (5-diphenylphosphino-1-indenyl) zirconium dichloride, ethylene (1-dimethylamino -9-fluorenyl) (1-cyclpentadienyl) zirconium dichloride, ethylene (4-butylthio-9-fluorenyl) (1-cyclpentadienyl) zirconium dichloride, ethylene bis (4 , 5,6,7-tetrahydro-1-indenyl) zirconium dichloride,

Ethylene bis (4-methyl-1-indenyl) zirconium dichloride, ethylene bis (5-methyl-1-indenyl) zirconium dichloride, ethylene bis (6-methyl-1-indenyl) zirconium dichloride , Ethylene bis (7-methyl-1-indenyl) zirconium dichloride, ethylene bis (5-methoxy-1-indenyl) zirconium dichloride, ethylene bis (4,7-methoxy-1-indenyl ) Zirconium dichloride, ethylene bis (2,3-methoxy-1-indenyl) zirconium dichloride, ethylene bis (4,7-methoxy-1-indenyl) zirconium dichloride,

Ethylene (9-fluorenyl) (1-cyclpentadienyl) zirconium dichloride, ethylene (9-fluorenyl) (1-cyclpentadienyl) zirconium dimethyl, ethylene (9-fluorenyl) (1 Cyclopentadienyl) zirconium diethoxide, ethylene bis (9-fluorenyl) zirconium dichloride, ethylene bis (9-fluorenyl) zirconium dimethyl, ethylene bis (9-fluorenyl) zirconium diethoxide , Ethylene bis (1-cyclpentadienyl) zirconium dichloride, ethylene bis (1-cyclpentadienyl) zirconium dimethyl, ethylene bis (1-cyclpentadienyl) zirconium diethoxide,

Ethylene bis (1-indenyl) zirconium dichloride, ethylene bis (1-indenyl) zirconium dimethyl, ethylene bis (1-indenyl) zirconium diethoxide, ethylene (1-indenyl) (1-cyclpentadiene Nil) zirconium dichloride, ethylene (1-indenyl) (1-cyclpentadienyl) zirconium dimethyl, ethylene (1-indenyl) (1-cyclpentadienyl) zirconium diethoxide,

Ethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (1-indenyl) (9-fluorenyl) zirconium dimethyl, ethylene (1-indenyl) (9-fluorenyl) Zirconium diethoxide, ethylene (9-fluorenyl) (1-cyclpentadienyl) hafnium dichloride, ethylene (9-fluorenyl) (1-cyclpentadienyl) hafnium dimethyl, ethylene (9-flu Orenyl) (1-cyclpentadienyl) hafnium diethoxide,

Ethylene bis (9-fluorenyl) hafnium dichloride, ethylene bis (9-fluorenyl) hafnium dimethyl, ethylene bis (9-fluorenyl) hafnium diethoxide, ethylene bis (1-cyclpentadienyl) Hafnium dichloride, ethylene bis (1-cyclpentadienyl) hafnium dimethyl, ethylene bis (1-cyclpentadienyl) hafnium diethoxide,

Ethylene bis (1-indenyl) hafnium dichloride, ethylene bis (1-indenyl) hafnium dimethyl, ethylene bis (1-indenyl) hafnium diethoxide, ethylene (1-indenyl) (1-cyclpentadier Nil) hafnium dichloride, ethylene (1-indenyl) (1-cyclpentadienyl) hafnium dimethyl, ethylene (1-indenyl) (1-cyclpentadienyl) hafnium diethoxide,

Ethylene (1-indenyl) (9-fluorenyl) hafnium dichloride, ethylene (1-indenyl) (9-fluorenyl) hafnium dimethyl, ethylene (1-indenyl) (9-fluorenyl) Hafnium diethoxide.

Examples of the monocyclopentadienyl metalocene include dimethylsilyltetramethyl cyclopentadienyl-tert-butylamido zirconium dichloride, dimethylsilyltetramethyl cyclopentadienyl-tert-butylamido hafnium dichloride, Dimethylsilyl tert-butyl cyclopentadienyl-tert-butylamido zirconium dichloride, dimethylsilyl tert-butyl cyclopentadienyl-tert-butylamido hafnium dichloride, dimethylsilyltrimethylsilyl cyclopentadienyl-tert -Butylamido zirconium dichloride, dimethylsilyltetramethyl cyclopentadienyl-phenylamido zirconium dichloride, dimethylsilyltetramethyl cyclopentadienyl-phenylamido hafnium dichloride, methylphenylsilyltetramethyl cyclopentadiene Nyl-tert-butylamido zirconium dichloride, methylphenylsilyltetramethyl cyclopentadienyl-tert-butylamido hafnium Dichlorolide, methylphenylsilyltetramethyl cyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethyl cyclopentadienyl-pn-phenylamido zirconium dichloride, dimethylsilyltetramethyl cyclopentadienyl-pn -Butylphenyl amido hafnium dichloride, etc. are mentioned.

In addition, the component (A) may be supported by the process restrictions and the following characteristics.

Since shape and particle size can be controlled, polymer having arbitrary shape and particle diameter can be obtained by using Reprica phenomenon.

② It is possible to increase the bulk density of the polymer by increasing the surface active species concentration.

③ The collision between active species is controlled, so that the activity is maintained for a long time and the thermal stability is also increased, which greatly improves the productivity.

(4) Vapor polymerization is also possible, which reduces manufacturing costs.

⑤ The long term storage of the catalyst is possible, so the polymerization operation is easy.

⑥ It is easy to remove the heat of polymerization by the action of carrier.

As described above, the metalocene catalyst may be used by being supported on silica, alumina, magnesium, or the like.

1) A method of forming a stable cationic complex on the surface of a carrier by applying metalocene to alumina and magnesium chloride having Lewis acid and then adding AlR ₃ .

2) Both of the methods of immobilizing and supporting MAO by using a surface hydroxyl group of silica or alumina and then alkylating by adding AlR ₃ by acting metalocene.

In addition, as a cation activator which can be used as a component (B) in this invention, both a perchlorate type and a chlorate type etc. can be used.

Examples of perchlorates include LiClO ₄ , Ca (ClO ₄ ) ₂ , Cd (ClO ₄ ) ₂ , Rb (ClO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , Pb (ClO ₄ ) ₂ , Sr (ClO ₄ ) ₂ , Zn (ClO ₄ ) ₂ , Cr (ClO ₄ ) ₃ , Mn (ClO ₄ ) ₂ , NaClO ₄ , AgClO ₄ , Fe (ClO ₄ ) ₂ , Ni (ClO ₄ ) ₂ , Cu (ClO ₄ ) ₂ , KClO ₄ , LiIO ₄ , Ca (IO ₄ ) ₂ , Cd (IO ₄ ) ₂ , Rb (IO ₄ ) ₂ , Mg (IO ₄ ) ₂ , Pb (IO ₄ ) ₂ , Sr (IO ₄ ) ₂ , Zn (IO ₄ ) ₂ , Cr (IO ₄ ) ₃ , Mn (IO ₄ ) ₂ , NaIO ₄ , AgIO ₄ , Fe (IO ₄ ) ₂ , Ni (IO ₄ ) ₂ , Cu (IO ₄ ) ₂ , KIO _{4, and the like} . Hydrates may also be used, and Mg (ClO ₄ ) ₂ and AgClO ₄ are most preferred.

In addition, as the chlorate, LiClO ₃ , Ca (ClO ₃ ) ₂ , Cd (ClO ₃ ) ₂ , Rb (ClO ₃ ) ₂ , Mg (ClO ₃ ) ₂ , Pb (ClO ₃ ) ₂ , Sr (ClO ₃ ) ₂ , Zn (ClO ₃ ) ₂ , Cr (ClO ₃ ) ₃ , Mn (ClO ₃ ) ₂ , NaClO ₃ , AgClO ₃ , Fe (ClO ₃ ) ₂ , Ni (ClO ₃ ) ₂ , Cu (ClO ₃ ) ₂ , KClO ₃ , LiIO ₃ , Ca (IO ₃ ) ₂ , Cd (IO ₃ ) ₂ , Rb (IO ₃ ) ₂ , Mg (IO ₃ ) ₂ , Pb (IO ₃ ) ₂ , Sr (IO ₃ ) ₂ , Zn (IO _{3) ) 2, Cr (IO 3)} 3, Mn (IO 3) 2, NaIO 3, AgIO 3, Fe (IO 3) 2, Ni (IO 3) 2, Cu (IO 3) 2, KIO 3 or the like of the compound Luggage can also be used.

That in addition to _{NH 4 · ClO 4, Ph 3} C · ClO 4, Cl 3 C · ClO 4, NF 4 · ClO 4, NBu 4 · ClO 4, NH 4 · IO 4, Ph 3 C · IO 4, Cl 3 C IO ₄ , NF ₄ , IO ₄ , NBu ₄ , IO ₄ and the like can also be used, and hydrates of these compounds can also be used.

As the component (C) of the present invention, any known alkylating agent may be used, but more effective alkylating agents include alkylaluminum, alkyl magnesium, alkyl zinc, and the like, and trimethylaluminum, triethylaluminum, triisobutylaluminum, Diethyl aluminum chloride, ethyl aluminum sesquichloride, and the like. Examples of the alkyl magnesium include butyloctyl magnesium, butyl ethyl magnesium, and dihexyl magnesium. Dialkyl zinc etc. are mentioned as alkyl zinc.

On the other hand, the catalyst composition of the present invention, provided that a homogeneous composition is obtained in the case of component (B) / component (A) <500 and converted to a heterogeneous system if component (B) / component (A)> 500 is described above. The components (A), (B) and (C) can be obtained by contacting in any order. Contact of each component can be performed by any method generally known. In general, the contact may be performed in the temperature range of 0-100 ° C., and the contact time is usually about 10 minutes to 5 hours. The contact of each component is carried out under stirring, and the order of contact of each component is the method of using the above components (A), (B) and (C) at the same time, after treating the components (A) and (B) The method of adding component (C), the treatment of component (A) and component (C), and the addition of component (B) can be used. The active point of the metalocene catalyst system is the method / sequence of contacting these components. As the environment changes, the molecular weight and molecular weight distribution of the resulting polymer may vary. It is preferable that the contact of each component is performed in the presence of a dispersant. Examples of the dispersant used include hydrocarbons, halogenated hydrocarbons, dialkyl siloxanes, and the like. Specific examples of the hydrocarbon include hexane, heptane, toluene, cyclohexane and the like, and specific examples of the halogenated hydrocarbon include n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, and the like of the dialkyl siloxane. Dimethyl polysiloxane, methyl-phenyl polysiloxane, etc. are mentioned as an example.

In the production of the ethylenic copolymer of the present invention, examples of the comonomer include linear or branched monoolefins having 3 to 20 carbon atoms, α-olefins substituted with aromatics, and diene compounds.

Specific examples of the α-olefins used include linear monoolefins such as propylene, butene-1, hexene-1, octene-1, nonene-1, decene-1, dodecene-1, hexadecene-1 and eicosene-1. And branched monoolefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, 2-ethylhexene-1, 2,2,4-trimethylpentene-1 and the like. And monoolefins substituted with aromatics such as styrene and alkyl substituted styrene.

Examples of the diene compound include linear or branched non-conjugated dienes having 6 to 20 carbon atoms, specifically 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7 Octadiene, 1,8-nonadiene, 1,9-decadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-dimethyl-4- t-butyl-2,6-heptadiene, 1,5,9-decatene, etc. are mentioned.

The catalyst according to the invention can be effectively used for ethylene / α-olefin copolymerization. As the polymerization method, any known polymerization method can be used, and examples thereof include solution polymerization, high temperature and high pressure polymerization, slurry polymerization, and gas phase polymerization. The polymerization temperature range is -40 to 220 ° C, preferably 10 ° C to 200 ° C, more preferably 40 ° C to 140 ° C.

Next, preferred embodiments of the present invention are described. However, these examples are only presented to aid the understanding of the present invention, and the present invention is not limited only to these examples.

Example

(Example 1)

(Production of Catalyst)

Into a fully dried Schlenk-type reactor on a magnetic stirrer (100 ml), a magnetic bar was placed, and 12.1 mg (0.03 mmol) of bis (n-butyl cyclopentadienyl) zirconium dichloride was added under a nitrogen atmosphere. 100 ml of toluene solvent dried through a distillation apparatus with sodium / benzophenone added to the reactor was stirred for two hours until the bis (n-butyl cyclopentadienyl) zirconium dichloride was sufficiently dissolved. Subsequently, 6.7 mg (0.03 mmol) of dried magnesium perchlorate [Mg (ClO ₄ ) ₂ ] was added dropwise under a nitrogen atmosphere, and the solution was stirred at room temperature under nitrogen for three hours. The solution (1) is obtained by reacting a homogeneous bis (n-butyl cyclopentadienyl) zirconium dichloride with Mg (ClO ₄ ) ₂ that is light yellow in color and completely dissolved in a solvent.

(Copolymerization of Ethylene / Propylene)

100 ml high pressure autoclave with magnetic bar was placed under nitrogen atmosphere, 50 ml of toluene, 1 ml (1 mmol) of triisobutyl aluminum, and 1 ml (0.03 × 10 ^-2 mmol- [Zr]) of the catalyst solution (1) prepared above. Put it in. Next, ethylene (0.089 mol) and propylene (0.089 mol) were metered in through a gas flow meter, and the reaction was started at 70 ° C. After a certain time of reaction, the unreacted monomer is removed, methanol is added to the resulting polymer to stop the reaction, and the product is placed in a large amount of methanol. After adding a small amount of hydrochloric acid, the mixture was stirred for 6 hours to remove catalyst residues. The polymer obtained was filtered and dried in a vacuum drier at 50 ° C. for 8 hours to give an ethylene / propylene copolymer of 4,500 kg-polymer / mol-Zr. Obtained with the activity of hr. The copolymer was analyzed by gel permeation chromatography (GPC, Waters 150CV) with 1,2,4-trichlorobenzene at 145 ° C. to obtain a molecular weight and molecular weight distribution of the copolymer. (Polystyrene-based Mn = 136,000, Mw = 462,000, Mw / Mn = 3.4)

(Comparative Example 1)

Except for using the prepared catalyst (1), only 46.6 mg (0.12 mmol) of bis (n-butyl cyclopentadienyl) zirconium dichloride and 1 ml (1 mmol) of triisobutyl aluminum were used without the cation activator under the same conditions. The polymerization was carried out in the same manner as in Example 1. As a result, a very small amount of polymer was obtained.

(Comparative Example 2)

The polymerization was carried out in the same manner as in Example 1, except that 2 mg (0.005 mmol) of the catalyst bis (n-butyl cyclopenta dienyl) zirconium dichloride was used in place of the above cation activator instead of 1 ml (3.2 mmol) of MAO. It was done. As a result, the ethylene / propylene copolymer was converted into 1,400 Kg-polymer / mol-Zr. Obtained with hr activity.

(Comparative Example 3)

1 mg (0.0025 mmol) of catalyst bis (n-butyl cyclopenta dienyl) zirconium dichloride was added to 1 ml (1 mmol) of Triisobutylaluminum and 2 mg (0.0025 mmol) of Dimethylanilinium Tetrakis (pentafluorophenyl) Boron instead of the above cation activator under the same conditions Polymerization was carried out in the same manner as in Example 1, except that it was used in order. As a result, an ethylene / propylene copolymer was obtained with an activity of 830 Kg-Polymer / mol-Zr.hr. As a result of GPC analysis of this polymer, the molecular weight and the molecular weight distribution were Mw = 220,000 and Mw / Mn = 4.4, respectively.

(Example 2-4)

As a metalocene catalyst (pentamethylcyclopentadienyl) zirconium trichloride (Example 2), ethylene bis (1-indenyl) zirconium dichloride (Example 3), dimethylsilyltetramethyl cyclopentadienyl-tert Ethylene / propylene was copolymerized in the same manner as in Example 1 except that butylamido titanium dichloride (CGC, Example 4) was used. The results are shown in Table 1.

TABLE 1

Example catalyst Activation (kg-polymer / mol-metal.time) _ Propylene Concentration (mol%) Tm (℃) ΔH (J / g) Mw Mw / Mn One (n-BuCp) ₂ ZrCl ₂ 4,500 8.0 105 83.7 462,000 3.4 2 Me ₅ CpZrCl ₃ 130 1.0 125 136.5 716,000 2.9 3 rac-Et (Ind) ₂ ZrCl ₂ 2,600 39.0 40 7.7 91,000 3.4 4 CGC 490 49.0 No peak － 288,000 3.3

Polymerization conditions: 100 ml autoclave, polymerization temperature; 70 ° C., ethylene = 0.089 mol,

[C ₂ ] / [C ₃ ] = 1, Cocatalyst: TIBA (1 ml, 1 M solution), Solvent: 50 ml of toluene,

Cation activator / Zr (mol / mol) = 1

(Example 5-7)

Copolymerization was carried out in the same manner as in Example 1, except that 1-octene was used instead of propylene as a comonomer using the catalyst system used in Examples 1, 3, and 4 above. Table 2 shows the results.

TABLE 2

Example catalyst Activation (kg-polymer / mol-metal.time) _ 1-octene concentration (mol%) Tm (℃) ΔH (J / g) Mw Mw / Mn Density (g / cm 3) 5 (n-BuCp) ₂ ZrCl ₂ 4,950 3.6 109 67.9 635,000 4.3 0.88 6 rac-Et (Ind) ₂ ZrCl ₂ 4,830 21.0 89 19.6 75,000 2.8 0.86 7 CGC 760 61.0 No peak － 250,000 3.2 －

Polymerization conditions: 100 ml autoclave, polymerization temperature; 70 ° C., ethylene = 0.089 mol, [C ₂ ] / [C ₈ ] = 1

Promoter: TIBA (1 ml, 1 M solution), solvent: 50 ml of toluene, cationic activator / Zr (mol / mol) = 1

(Comparative Example 4)

The polymerization was carried out in the same manner as in Example 5 except that 1 mg (0.0025 mmol) of the catalyst bis (n-butyl cyclopenta dienyl) zirconium dichloride was used in place of the above cation activator instead of 1 ml (3.2 mmol) of MAO. It was done. As a result, an ethylene / octene copolymer was obtained with an activity of 1,140 Kg-polymer / mol-Zr.hr.

(Comparative Example 5)

1 mg (0.0025 mmol) of catalyst bis (n-butyl cyclopenta dienyl) zirconium dichloride was added to 1 ml (1 mmol) of Triisobutylaluminum and 2 mg (0.0025 mmol) of Dimethylanilinium Tetrakis (pentafluorophenyl) Boron instead of the above cation activator under the same conditions. Polymerization was carried out in the same manner as in Example 5 except that it was used in sequence. As a result, an ethylene / octene copolymer was obtained with an activity of 1,160 Kg-Polymer / mol-Zr.hr. As a result of GPC analysis of this polymer, the molecular weight and the molecular weight distribution were Mw = 382,000 and Mw / Mn = 3.4, respectively.

(Example 8-10)

The polymerization was carried out in the same manner as in Example 1, except that the polymerization temperature was changed using the catalyst ethylene bis (1-indenyl) zirconium dichloride used in Example 3. Table 3 shows the results.

TABLE 3

Example Polymerization temperature Activation (kg-polymer / mol-metal.hours) Propylene Concentration (mol%) Tm (℃) ΔH (J / g) Mw Mw / Mn 3 70 2,600 39 40.0 7.7 91,000 3.4 8 107 21,500 － 104.7 12.7 83,000 3.1 9 160 78,100 － 111.0 20.6 53,000 3.2 10 180 85,400 26 114.3 19.6 51,000 3.6

Polymerization conditions: 100ml autoclave, ethylene = 0.089 mol, [C ₂ ] / [C ₃ ] = 1

Solvent: 50 ml of toluene,

Promoter: TIBA (1 ml, 1 M solution), Cationic activator / Zr (mol / mol) = 1

According to the present invention, it is possible to prepare an ethylene copolymer having high activity and narrow molecular weight distribution and composition distribution without using expensive aluminoxane. In addition, the composition prepared by the catalyst system of the present invention can produce a high yield of an ethylene copolymer having a sufficiently high molecular weight and excellent physical properties. According to the present invention, a mixture of ethylene and an alpha olefin having 3 to 20 carbon atoms can be polymerized in a solution or a high pressure reactor at a temperature of -40 to 220 ° C. and a pressure of 1 to 180 atm to allow comonomer insertion up to 80% by weight. . Also, in the case of solution or high pressure reactor, there is no process restriction on the density of the polymer to be synthesized, so it is possible to synthesize a copolymer of a wide density range (0.86 to 0,96 g / cm 3) from VLDPE to HDPE, and the catalyst is added in a uniform state. The effect which can show the characteristic of a metalocene catalyst original homogeneous catalyst is acquired.

Claims (17)

Copolymerization of ethylene and α-olefin in the presence of a catalyst formed by adding a component (B) consisting of a cation activator and a component (C) consisting of an alkylating agent as a cocatalyst to a known metallocene transition metal complex (A) as a transition metal complex Method for producing an olefin copolymer, characterized in that. The method according to claim 1, wherein the component (B) is a compound represented by the following structural formula. _{^{M n + (X -) ng}} Z g (Wherein n = 1, 2, 3 or 4, g is an integer, 0 ≦ g <n and M is a metal element belonging to IA, IIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB) Or an organic compound, X is a compound composed of anion clusters in which at least one element of F, Cl, Br, I is bonded to oxygen, and the number of elements is three or more, Z is H ^- or F, Cl, Br, one of them.) Characterized in that to the anions metallocene transition produce a cation of the metal to the metadata shown an olefin polymerization activity ^- of claim 2, wherein the component (B) reacts with the metallocene-transition metal complex (A) to the Meta the coordination bonding force is very weak X The manufacturing method to make. 4. A process according to claim 3 wherein component (B) is a compound wherein X is at least one perchlorate anion and the metal M is one of Li, Na, Ca, Mg, Ag. The method according to claim 4, wherein the component (B) is any one of LiClO ₄ , NaClO ₄ , Ca (ClO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , AgClO ₄ . The method according to claim 2, wherein the component (B) is a compound in which X is at least one perchlorate anion, and the organic compound M is a compound consisting of an organic material including one of C and N elements. The method of claim 6, wherein component (B) is any one of NH ₄ · ClO ₄ , Ph ₃ C · ClO ₄ , Cl ₃ C · ClO ₄ , NF ₄ · ClO ₄ , NBu ₄ · ClO ₄ , The manufacturing method to make. 2. The alkylating agent component (C) according to claim 1, wherein the alkylating agent component (C) is a metal belonging to IA, IIA, IIB, IIIB of the periodic table and has a hydrocarbyl group such as alkyl, alkenyl, arylalkyl or allylalkyl having 1 to 20 carbon atoms. Process for producing an organometallic compound. 9. The method according to claim 8, wherein the alkylating agent component (C) is any one of alkyl aluminum, alkyl magnesium and alkyl zinc. 10. The alkylating agent component (C) according to claim 9, wherein the alkylating agent component (C) is alkyl aluminum, alkyl magnesium, alkyl zinc or the like, and trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, butyl. It is any one of octyl magnesium, butyl ethyl magnesium, dihexyl magnesium, or diethyl zinc. A process according to claim 1, wherein said component (B) is added in a molar concentration ratio of 1: 0.1 to 10 and component (C) in a ratio of 1: 5,000 with respect to said component (A). 12. A process according to claim 11, wherein said component (B) is added in a molar concentration ratio of 1: 1 with respect to said component (A) and component (C) is added in a ratio of 1:10 to 2,000. The method of claim 1, wherein the α-olefin is a linear or branched mono-olefin or aromatic substituted with 3 to 20 carbon atoms, or a linear or branched non-conjugated diene having 6 to 20 carbon atoms. A manufacturing method characterized by the above-mentioned. The method of claim 13, wherein the α-olefin is propylene, butene-1, hexene-1, octene-1, nonene-1, decene-1, dodecene-1, hexadecene-1, eicosene-1 Characterized in the manufacturing method. The production process according to claim 13, wherein the aromatic α-olefin is styrene. The method of claim 13, wherein the diene is 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-dimethyl-4-t-butyl-2,6-heptadiene or 1,5,9-decatriene. 17. The polymerization method according to any one of claims 13 to 16, wherein the polymerization method is performed at any one of solution polymerization, high temperature and high pressure polymerization, slurry polymerization, or gas phase polymerization at a temperature of -40 to 220 ° C and a pressure of 1 to 180 atmospheres. A manufacturing method characterized by the above-mentioned.