US 5,409,874 AGrant

Catalyst for Olefin Polymerization, Process for the Polymerization of Olefin, and Transition Metal Compound Employable for the Catalyst

Issue Date:1995-04-25

•15 Claims

•3 Drawing Sheets

Abstract

The catalyst for olefin polymerization of the present invention contains R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m M(SO.sub.3 R.sup.4) (M=Zr, Ti or Hf; R.sup.1-3 =a group having a cyclopentadienyl skeleton) as a catalyst component of a transition metal compound. According to the catalyst of the invention, an olefin polymer having excellent particle properties can be prepared with high polymerization activities, and further a copolymer having a narrow composition distribution can be prepared when two or more monomers are copolymerized. Of the above-mentioned transition metal compounds, a compound represented by the following formula is a novel compound unknown so far and shows excellent catalytic properties. ##STR1## (Cp=a group having a cyclopentadienyl skeleton, X=SO.sub.3 R, a halogen atom, R, OR, NR.sub.n, S(O).sub.q R, SiR.sub.3 or P(O).sub.q R.sub.3, n=1, 2 or 3; q=0, 1 or 2)

Metadata

Assignee

Mitsui Petrochemical Industries, Ltd.

Inventors

Junichi Imuta
Junji Saito
Takashi Ueda
Teruaki Mukaiyama

Application Information

Application Number:US 9010157

Filing Date:1992-06-19

Priority Date:1991-06-20

Art Unit:116

Classifications

IPC:

B01J 3100C08F 460

Field of Search:

502103;108;117

Patent Drawings (3 sheets)

Description

FIELD OF THE INVENTION

The present invention relates to a catalyst for olefin polymerization and a process for the polymerization of olefin using the catalyst, more particularly to a catalyst for olefin polymerization capable of producing an olefin polymer excellent in particle properties with a high polymerization activity and a process for the polymerization of olefin using the catalyst.

Moreover, the invention relates to a novel transition metal compound preferably used for the above catalyst for olefin polymerization.

BACKGROUND OF THE INVENTION

For preparing .alpha.-olefin polymers, there have been heretofore known processes for copolymerizing ethylene and .alpha.-olefin in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound.

The ethylene/.alpha.-olefin copolymers obtained by using a titanium catalyst generally have a wide molecular-weight distribution and a wide composition distribution, and are deteriorated in transparency, anti-surface stickiness and mechanical and physical properties. On the other hand, the ethylene/.alpha.-olefin copolymers obtained by using a vanadium catalyst have a molecular-weight distribution and a composition distribution both narrower than those obtained using the titanium catalyst, and they are relatively improved in the transparency, anti-surface stickiness and mechanical and physical properties. However, those properties are still insufficient for various use applications requiring high properties. Hence, now required are catalysts capable of producing .alpha.-olefin polymers, particularly ethylene/.alpha.-olefin copolymers, much more improved in those properties.

There has recently been developed a new Ziegler type catalyst for olefin polymerization comprising a zirconium compound and an aluminoxane. For example, processes for the preparation of ethylene/.alpha.-olefin copolymers using this new Ziegler type catalyst have been proposed in Japanese Patent Provisional Publications, No. 58(1983)-19309, No. 60(1985)-35005, No. 60(1985)-35006, No. 60(1985)-35007, No. 60(1985)-35008, etc.

The catalysts composed of a transition metal compound and an aluminoxane proposed in the prior art are excellent in polymerization activities, especially ethylene polymerization activities, as compared with catalysts having been known prior to the appearance of these catalysts which are composed of a transition metal compound and an organoaluminum compound. However, most of the catalysts are soluble in the reaction system, and in most cases the processes for the preparation are limited to a solution polymerization system. In addition, the catalysts have such a problem that, when the manufacture of a polymer having a high molecular weight is tried, the productivity of a polymer is lowered due to a marked increase in the viscosity of the polymer-containing solution.

On the other hand, polymerization of olefin has been tried in a suspension polymerization system or a gas phase polymerization system by using catalysts in which at least one of the transition metal compound component and the aluminoxane component described above is supported on a porous inorganic oxide carrier such as silica, alumina and silica-alumina.

For example, the aforementioned Japanese Patent Provisional Publications No. 60(1985)-35006, No. 60(1985)-35007 and No. 60(1985)-35008 disclose that there can be used catalysts in which a transition metal compound and an aluminoxane are supported on silica, alumina, silica-alumina, etc.

Further, the above publications and Japanese Patent Provisional Publications No. 61(1986)-130314 and No. 2(1990)-41303 disclose that a catalyst system in which a metallocene compound of a transition metal compound having, as a ligand, a pentadienyl group (e.g., cyclopentadienyl group), an alkyl group and/or a halogen atom is combined with aluminoxane has a high activity for olefin polymerization and can produce a polymer of excellent properties.

Furthermore, Japanese Patent Provisional Publications No. 60(1985)-106808 and No. 60(1985)-106809 disclose a process for the preparation of a composition composed of an ethylene polymer and a filler. This process comprises polymerizing ethylene or copolymerizing ethylene and .alpha.-olefin in the presence of an organoaluminum compound and a filler having an affinity for polyolefin, and a product prepared by pre-contacting a highly activated catalyst component containing a hydrocarbon-soluble titanium compound and/or a zirconium compound with a filler.

Japanese Patent Provisional Publication No.. 61(1986)-31404 discloses a process for polymerizing ethylene or copolymerizing ethylene and .alpha.-olefin in the presence of a mixed catalyst composed of a transition metal compound and a product obtained by a reaction of trialkylaluminum and water in the presence of silicon dioxide or aluminum oxide.

Furthermore, Japanese Patent Provisional Publications No. 61(1986)-108610 and No. 61(1986)-296008 discloses a process for polymerizing olefin in the presence of a catalyst in which a transition metal compound such as metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide.

However, in the case of polymerizing or copolymerizing olefin in a suspension or gas phase using such a solid catalyst component supported on a carrier as described in the above-mentioned publications, the polymerization activities are markedly lower as compared with the above-described solution polymerization.

In "Journal of Organometallic Chemistry", 363 (1989), C12 to C14 are disclosed Cp.sub.2 Zr (CF.sub.3 SO.sub.3).sub.2 (THF) and [Cp.sub.2 Zr(CF.sub.3 SO.sub.3)(bipy)].sup.+ CF.sub.3 SO.sub.3.sup.-, but these two compounds are lower in olefin polymerization activities as compared with the above-mentioned cyclopentadienyl compound. Moreover, they show markedly low olefin polymerization activities when a concentration of aluminoxane is low.

Under these circumstances, earnestly desired is a novel transition metal compound capable of being a catalyst component for olefin polymerization which shows high activities for olefin polymerization and produces an olefin polymer having excellent properties.

OBJECT OF THE INVENTION

The present invention is intended to solve such problems associated with the prior art technique as described above, and an object of the invention is to provide a catalyst for olefin polymerization capable of producing an olefin polymer of excellent particle properties with high polymerization activities and also capable of producing a copolymer having a narrow composition distribution when monomers of two or more kinds are copolymerized.

A second object of the invention is to provide a process for polymerizing olefin using the above-mentioned catalyst having excellent properties.

A third object of the invention is to provide a novel transition metal compound preferably used as a component of the above-mentioned catalyst for olefin polymerization.

SUMMARY OF THE INVENTION

The first catalyst for olefin polymerization according to the invention comprises [A] a catalyst component of a transition metal compound having a transition metal atom in Group IVB of the periodic table, a ligand containing a --SO.sub.3 R group wherein R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, and a ligand having a cyclopentadienyl skeleton, and [B] an organoaluminum oxy-compound.

The second catalyst for olefin polymerization according to the invention comprises the component [A], the compound [B] and an organoaluminum compound [C].

The third catalyst for olefin polymerization according to the invention comprises a particulate carrier, the component [A] and the compound [B], said component [A] and said compound [B] being supported on the particulate carrier.

The fourth catalyst for olefin polymerization according to the invention comprises a solid catalyst component and the compound [C], wherein the solid catalyst component comprises a particulate carrier, the component [A] and the compound [B], said component [A] and said compound [B] being supported on the particulate carrier.

The fifth catalyst for olefin polymerization according to the invention comprises a particulate carrier, the component [A], the compound [B] and an olefin polymer prepared by prepolymerization.

The sixth catalyst for olefin polymerization according to the invention comprises a particulate carrier, the component [A], the compound [B], the compound [C] and an olefin polymer prepared by prepolymerization.

The process for the polymerization of olefin according to the invention comprises polymerizing or copolymerizing olefin in the presence of the above-mentioned catalyst for olefin polymerization.

The novel transition metal compound according to the invention is represented by the following formula: ##STR2## wherein M is a transition metal in Group IVB of the periodic table, each of Cp.sup.1 and Cp.sup.2 is a group having a cyclopentadienyl skeleton, said group having a cyclopentadienyl skeleton may have a substituent group, Cp.sup.1 and Cp.sup.2 may be linked to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, X is SO.sub.3 R, a halogen atom, R, OR, NR.sub.n, S(O).sub.q R, SiR.sub.3 or P(O).sub.q R.sub.3, n is 1, 2 or 3, and q is 0, 1 or 2.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 3 illustrate steps of a process for the preparation of the catalyst for olefin polymerization according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The catalyst for olefin polymerization, the process for the polymerization of olefin using the catalyst and the novel transition metal compound, according to the invention, are described below in detail.

In the invention, the meaning of the term "polymerization" may include not only homopolymerization but also copolymerization, and the meaning of the term "polymer" may include not only homopolymer but also copolymer.

The first and second catalysts for olefin polymerization according to the invention are illustrated below.

The catalyst component [A] used for the first and second catalysts for olefin polymerization according to the invention is a compound of a transition metal in Group IVB of the periodic table which contains a ligand containing a --SO.sub.3 R group wherein R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, and a ligand having a cyclopentadienyl skeleton. In concrete, the catalyst component [A] is for example a transition metal compound represented by the following formula [I].

In the formula [I], M is a transition metal in Group IVB of the periodic table, R.sup.1 is a group having a cyclopentadienyl skeleton, and this group having a cyclopentadienyl skeleton may have a substituent group. Each of R.sup.2 and R.sup.3 is a group having a cyclopentadienyl skeleton (may have a substituent group), SO.sub.3 R.sup.4, a halogen atom, R.sup.4, OR.sup.4, NR.sup.4.sub.n, S(O).sub.q R.sup.4 SiR.sup.4.sub.3 or P(O).sub.q R.sup.4.sub.3, wherein R.sup.4 is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group. Two of R.sup.1, R.sup.2 and R.sup.3 may be linked to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. k is a number satisfying the conditions of k.gtoreq.1 and k+l+m =3, n is 1, 2 or 3, and q is 0, 1 or 2.

In the formula [I], M is a transition metal in Group IVB of the periodic table, and preferably M is zirconium, titanium or hafnium.

Examples of the groups having a cyclopentadienyl skeleton include cyclopentadienyl group; alkyl-substituted cyclopentadienyl group such as methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group and pentamethylcyclopentadienyl group; indenyl group; and fluorenyl group.

Of these, preferred are alkyl-substituted cyclopentadienyl group and indenyl group.

Examples of the alkylene groups include ethylene group and propylene group, examples of the substituted alkylene groups include isopropylidene group and diphenylmethylene group, and an example of the substituted silylene group is dimethylsilylene group. Further, examples of the alkyl groups include methyl group, ethyl group, propyl group, isopropyl group and butyl group, and examples of the aryl groups include phenyl group and tolyl group. Halogen is fluorine, chlorine, bromine or iodine.

Concrete examples of the transition metal compounds represented by the formula [I] are given below.

Bis(cyclopentadienyl)-zirconium (IV)-bis(methanesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-bis(p-toluenesulfonate)

Bis(cyclopentadienyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-bis(benzenesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-bis(2,4,6-trimethylbenzenesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-bis(2,4,6-triisopropylbenzenesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-bis(pentafluorobenzenesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-(benzenesulfonate) monochloride,

Bis(cyclopentadienyl)-zirconium (IV)-(2,4,6-trimethylbenzenesulfonate) monochloride,

Bis(cyclopentadienyl)-zirconium (IV)-(2,4,6-triisopropylbenzenesulfonate) monochloride,

Bis(cyclopentadienyl)-zirconium (IV)-(pentafluorobenzenesulfonate) monochloride,

Bis(cyclopentadienyl)-zirconium (IV)-(etoxy) (trifluoromethanesulfonate),

Bis(methylcyclopentadienyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Bis(methylcyclopentadienyl)-zirconium (IV)-trifluoromethanesulfonate monochloride,

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-(trifluoromethanesulfonate) monochloride,

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-bis(benzenesulfonate),

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-bis(p-toluenesulfonate),

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-bis(2,4,6-trimethylbenzenesulfonate),

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-bis-(2,4,6-triisopropylbenzenesulfonate),

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-bis (pentafluorobenzenesulfonate),

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-(benzenesulfonate) monochloride,

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-(2,4,6-trimethylbenzenesulfonate) monochloride,

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-(2,4,6-triisopropylbenzenesulfonate) monochloride,

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-(pentafluorobenzenesulfonate) monochloride,

Bis(1,3-dimethylcyclopentadienyl)-zirconium (IV)-(trifluoromethanesulfonate) dimethylamide,

Bis(1,3,5-trimethylcyclopentadienyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Bis(1,3,5-trimethylcyclopentadienyl)-zirconium (IV)-trifluoromethanesulfonate monochloride,

Ethylenebis(indenyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(methanesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(p-toluenesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(p-chlorobenzenesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monochloride,

Ethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monobromide,

Ethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monofluoride,

Ethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monoiodide,

Ethylenebis(indenyl)-zirconium (IV)-methanesulfonate monochloride,

Ethylenebis(indenyl)-zirconium (IV)-p-toluenesulfonate monochloride,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)methyl,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)methyl,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)phenyl,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)phenyl,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)methoxy,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)methoxy,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate) dimethylamide,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)dimethylamide,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)methylmercapto,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)methylmercapto,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)thiophenyl,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)thiophenyl,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)methylsulfone,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)methylsulfone,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)methylsulfoxide,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)methylsulfoxide,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)trimehylsilyl,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)trimethylsilyl,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)trimethylphosphine,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)trimethylphosphine,

Ethylenebis(indenyl)-zirconium (IV)-(trifluoromethanesulfonate)triphenylphosphine,

Ethylenebis(indenyl)-zirconium (IV)-(methanesulfonate)triphenylphosphine,

Ethylenebis(indenyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(benzenesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(2,4,6-trimethylbenzenesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(2,4,6-triisopropylbenzenesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-bis(pentafluorobenzenesulfonate),

Ethylenebis(indenyl)-zirconium (IV)-(benzenesulfonate)monochloride,

Ethylenebis(indenyl)-zirconium (IV)-(2,4,6-trimethylbenzenesulfonate)monochloride,

Ethylenebis(indenyl)-zirconium (IV)-(2,4,6-triisopropylbenzenesulfonate)monochloride,

Ethylenebis(indenyl)-zirconium (IV)-(pentafluorobenzenesulfonate)monochloride,

Ethylenebis(indenyl)-hafnium (IV)-bis(trifluoromethanesulfonate),

Ethylenebis(indenyl)-hafnium (IV)-bis(methanesulfonate),

Ethylenebis(indenyl)-hafnium (IV)-bis(p-toluenesulfonate),

Ethylenebis(indenyl)-hafnium (IV)-bis(p-chlorobenzenesulfonate),

Ethylenebis(indenyl)-hafnium (IV)-trifluoromethanesulfonate monochloride,

Ethylenebis(indenyl)-hafnium (IV)-trifluoromethanesulfonate monobromide,

Ethylenebis(indenyl)-hafnium (IV)-trifluoromethanesulfonate monofluoride,

Ethylenebis(indenyl)-hafnium (IV)-trifluoromethanesulfonate monoiodide,

Ethylenebis(indenyl)-hafnium (IV)-methanesulfonate monochloride,

Ethylenebis(indenyl)-hafnium (IV)-p-toluenesulfonate monochloride,

Ethylenebis(indenyl)-titanium (IV)-bis(trifluoromethanesulfonate),

Ethylenebis(indenyl)-titanium (IV)-bis(methanesulfonate),

Ethylenebis(indenyl)-titanium (IV)-bis(p-toluenesulfonate),

Ethylenebis(indenyl)-titanium (IV)-bis(p-chlorobenzenesulfonate),

Ethylenebis(indenyl)-titanium (IV)-trifluoromethanesulfonate monochloride,

Ethylenebis(indenyl)-titanium (IV)-trifluoromethanesulfonate monobromide,

Ethylenebis(indenyl)-titanium (IV)-trifluoromethanesulfonate monofluoride,

Ethylenebis(indenyl)-titanium (IV)-trifluoromethanesulfonate monoiodide,

Ethylenebis(indenyl)-titanium (IV)-methanesulfonate monochloride,

Ethylenebis(indenyl)-titanium (IV)-p-toluenesulfonate monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(methanesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(p-toluenesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(p-chlorobenzenesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monobromide,

Dimethylsilylbis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monofluoride,

Dimethylsilylbis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monoiodide,

Dimethylsilylbis(indenyl)-zirconium (IV)-methanesulfonate monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-p-toluenesulfonate monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(benzenesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(2,4,6-trimethylbenzenesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(2,4,6-triisopropylbenzenesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-bis(pentafluorobenzenesulfonate),

Dimethylsilylbis(indenyl)-zirconium (IV)-(benzenesulfonate) monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-(2,4,6-trimethylbenzenesulfonate) monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-(2,4,6-triisopropylbenzenesulfonate) monochloride,

Dimethylsilylbis(indenyl)-zirconium (IV)-(pentafluorobenzenesulfonate) monochloride,

Diphenylmethylenebis(indenyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Diphenylmethylenebis(indenyl)-zirconium (IV)-bis(methanesulfonate),

Diphenylmethylenebis(indenyl)-zirconium (IV)-bis(p-toluenesulfonate),

Diphenylmethylenebis(indenyl)-zirconium (IV)-bis(p-chlorobenzenesulfonate),

Diphenylmethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monochloride,

Diphenylmethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monobromide,

Diphenylmethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monofluoride,

Diphenylmethylenebis(indenyl)-zirconium (IV)-trifluoromethanesulfonate monoiodide,

Diphenylmethylenebis(indenyl)-zirconium (IV)-methanesulfonate monochloride,

Diphenylmethylenebis(indenyl)-zirconium (IV)-p-toluenesulfonate monochloride,

Diphenylsilylbis(indenyl)-zirconium (IV)-bis(benzenesulfonate),

Diphenylsilylbis(indenyl)-zirconium (IV)-bis(2,4,6-trimethylbenzenesulfonate),

Diphenylsilylbis(indenyl)-zirconium (IV)-bis(2,4,6-triisopropylbenzenesulfonate),

Diphenylsilylbis(indenyl)-zirconium (IV)-bis(pentafluorobenzenesulfonate),

Diphenylsilylbis(indenyl)-zirconium (IV)-(benzenesulfonate) monochloride,

Diphenylsilylbis(indenyl)-zirconium (IV)-(2,4,6-trimethylbenzenesulfonate) monochloride,

Diphenylsilylbis(indenyl)-zirconium (IV)-(2,4,6-triisopropylbenzenesulfonate) monochloride, and

Diphenylsilylbis(indenyl)-zirconium (IV)-(pentafluorobenzenesulfonate) monochloride.

Such transition metal compounds can be prepared from a compound represented by the following formula [II] and a sulfonic acid derivative represented by the following formula [III].

In the formula [II], M is a transition metal in Group IVB of the periodic table, R.sup.1 is a group having a cyclopentadienyl skeleton, and this group having a cyclopentadienyl skeleton may have a substituent group. Each of R.sup.2 and R.sup.3 is a group having a cyclopentadienyl skeleton (may have a substituent group), SO.sub.3 R.sup.4, a halogen atom, R.sup.4, OR.sup.4, NR.sup.4.sub.n, S(O).sub.q R.sup.4, SiR.sup.4.sub.3 or P(O).sub.q R.sup.4.sub.3, wherein R.sup.4 is an alkyl group, an alkyl group substituted with a halogen atom or an alkyl group, an aryl group or an aryl group substituted with a halogen atom or an alkyl group. Two of R.sup.1, R.sup.2 and R.sup.3 may be linked to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. k is a number satisfying the conditions of k.gtoreq.1 and k+l+m =3, n is 1, 2 or 3, and q is 0, 1 or 2. X is halogen.

In the formula [III], R.sup.4 is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group. Y is an Ag, alkali metal (e.g., Na and K) or an ammonium group (e.g., triethyl ammonium and tri(n-octyl)ammonium).

The preparation of the transition metal compounds from the compound represented by the formula [II] and the sulfonic acid derivative represented by the formula [III] is carried out in accordance with the following reaction formula.

The reaction conditions in this reaction varies depending upon the composition of the aimed compound [I], but the compound [III] is generally used in an amount of 1-10 times by mol, preferably 1-3 times by mole, of the amount of the compound [II]. The reaction temperature is generally in the range of -20.degree. to 180.degree. C., preferably 0 to 130.degree. C., and the reaction period is generally in the range of 0.5 to 48 hours, preferably 2 to 12 hours.

Suitable solvents used in this reaction include aliphatic hydrocarbons such as hexane and decane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride; and ketones such as acetone and methyl isobutyl ketone; and acetonitrile. Of these, toluene and xylene are particularly preferred. Such hydrocarbon solvent as mentioned above is used generally in an amount of 1-1,000 times, preferably 50-500 times, of the amount of the compound [II].

The catalyst component [B] used in the invention may be aluminoxane hitherto known or such benzene-insoluble organoaluminum oxy compounds.

The known aluminoxane may be prepared, for example, by the following methods.

(1) A method wherein suspensions of compounds containing adsorbed water or salts containing water of crystallization, for example, magnesiumchloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate and ceriun (I) chloride hydrate, in hydrocarbon solvents are allowed to react with an organoaluminum compound such as trialkylaluminum, and the desired aluminoxane is recovered as a hydrocarbon solution containing the same.

(2) A method wherein an organoaluminum compound such as trialkylaluminum is treated directly with water, ice or water vapor in such solvent as benzene, toluene, ethyl ether or tetrahydrofuran, and the desired aluminoxane is recovered as a hydrocarbon solution containing the same.

(3) A method wherein an organoaluminum compound such as trialkylaluminum is allowed to react with an organotin oxide in a solvent such as decane, benzene or toluene.

The aluminoxane as illustrated above may contain small amounts of organometallic components. From the above-mentioned solution containing aluminoxane as recovered, the solvent or unaltered organoaluminum compound is removed by distillation, and the remaining aluminoxane may dissolved again in a solvent.

The organoaluminum compound used in preparing the above-mentioned solution of aluminoxane includes concretely

trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylalminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum,

tricycloalkylaluminum such as tricyclohexylaluminum or tricyclooctylaluminum;

dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide or diisobutylaluminum chloride;

dialkylaluminum hydride such as diethylaluminum hydride or diisobutylaluminum hydride;

dialkylaluminum alkoxide such as dimethylaluminum methoxide or diethylaluminum ethoxide; and

dialkylaluminum aryloxide such as diethylaluminum phenoxide.

Of these solvents as exemplified above, particularly preferred is trialkylaluminum.

Furthermore, there may also be used as the organoaluminum compound isoprenylaluminum represented by the general formula

wherein x, y and z are each a positive number, and z.gtoreq.2x.

The organoaluminum compounds mentioned above may be used either singly or in combination.

Solvents used in the solutions of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and gas oil; or haloganated hydrocarbons such as halides, particularly chloride and bromides, of the above-mentioned aromatic, aliphatic and alicyclic hydrocarbons. In addition thereto, there may also be used ethers other than ethyl ether and tetrahydrofurano Of these solvents as exemplified above, particularly preferred are aromatic hydrocarbons.

The benzene-insoluble organoaluminum oxy-compound may be obtained by a process comprising bringing a solution of an aluminoxane into contact with water or an active hydrogen containing-compound or a process comprising bringing such an organoaluminum as described above into contact with water, directly.

In the first process for obtaining the benzene-insoluble organoaluminum oxy compound, the solution of the aluminoxane is brought into contact with water or the active hydrogen containing-compound.

Examples of the active hydrogen-containing compound include

alcohols such as methanol, ethanol, n-propanol and isopropanol;

diols such as ethylene glycol and hydroquinone; and

organic acids such as acetic acid and propionic acid.

Of these compounds, preferred are alcohols and diols, and particulaly preferred are alcohols.

Water or the active hydrogen containing compound with which the solution of an aluminoxane is brought into contact may be used as a solution or a dispersions in a hydrocarbon solvent such as benzene, toluene and hexane, in an ether solvent such as tetrahydrofuran or in an amine solvent such as triethylamine, or may be used in the form of vapor or solid. The water with which the solution of an aluminoxane is brought into contact may be water of crystallization of a salt such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate and cerous chloride, or adsorbed water adsorbed to an inorganic compound such as silica, alumina and aluminum hydroxide or a polymer.

Reaction of an aluminoxane in a solution with water or an active hydrogen-containing compound is carried out usually in a solvent.

The solvent includes the solvents described above, for example, the hydrocarbon solvents such as aromatic hydrocarbons; aliphatic hydrocarbons and alicyclic hydrocarbons, petroleum fractions, halogenated hydrocarbons and ethers. Of these solvents as exemplified above, particularly preferred are aromatic hydrocarbons.

In the reaction as mentioned above, water or the active hydrogen-containing compound is used in an amount of 0.1-5 moles, preferably 0.2-3 moles based on 1 gram atom of Al present in the solution of an aluminoxane. The concentration in terms of aluminum atom in the reaction system is normally 1.times.10.sup.-3 -5 gram atom/l, preferably 1.times.10.sup.-2-3 gram atom/l, and the concentration of water in the reaction system is normally 2.times.10.sup.-4 -5 mol/l, preferably 2.times.10.sup.-3 -3 mol/l.

The solution of an aluminoxane may be brought into contact with water or the active hydrogen-containing compound, for example, by the following procedures.

(1) A procedure which comprises bringing the solution of an aluminoxane into contact with a hydrocarbon solvent containing water or the active hydrogen-containing compound.

(2) A procedure which comprises blowing steam or the vapor of the active hydrogen-containing compound into the solution of an aluminoxane, thereby bringing the aluminoxane into contact with the steam or vapor.

(3) A procedure which comprises bringing the solution of an aluminoxane into contact directly with water, ice or the active hydrogen-containing compound.

(4) A procedure which comprises mixing the solution of an aluminoxane with a suspension of an adsorbed water-containing compound or a water of crystallization-containing compound in hydrocarbon, or with a suspension of a compound, to which the active hydrogen-containing compound is adsorbed, in hydrocarbon, thereby bringing the aluminoxane into contact with the adsorbed water or water of crystallization.

The solution of an aluminoxane may contain other components so long as they do not exert adverse effects on the reaction of the aluminoxane with water or the active hydrogen-containing compound.

The above-mentioned reaction of an aluminoxane in a solution with water or the active hydrogen-containing compound is carried out at a temperature of usually -50.degree. to 150.degree. C., preferably 0.degree. to 120.degree. C., more preferably 20.degree. to 100.degree. C. The reaction time employed is usually 0.5 to 300 hours, preferably about 1 to 150 hours, though said reaction time varies largely depending upon the reaction temperature used.

In the second process for obtaining the benzene insoluble organoaluminum oxy-compound, such an organoaluminum as described above is brought into contact with water directly.

In this case, water is used in such an amount that the organoaluminum atoms dissolved in the reaction system are not greater than 20% based on the total organoaluminum atoms

Water with which the organoaluminum compound is brought into contact may be used as a solution or dispersion in a hydrocarbon solvent such as benzene, toluene and hexane, an ether solvent such as tetrahydrofuran or an amine solvent such as triethylamine, or may be used in the form of steam or ice. The water with which the organoaluminum compound is brought into contact may be water of crystallization of a salt such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate and cerous chloride, or adsorbed water adsorbed to an inorganic compound such as silica, alumina and aluminum hydroxide or a polymer.

Reaction of the organoaluminum compound with water is carried out usually in a solvent, for example, hydrocarbon solvents or halogenated hydrocarbon solvents described above. Of these solvents, particularly preferred is aromatic hydrocarbons.

The concentration of the organoaluminum compound in the reaction system in terms of aluminum atom is desirably 1.times.10.sup.-3 -5 gram atom/l, preferably 1.times.10.sup.-2 -3 gram atom/l, and the concentration of water in the reaction system is desirably 1.times.10.sup.-3 -5 mol/l, preferably 1.times.10.sup.-2 -3 mol/l. In the reaction mentioned above, the organoaluminum atoms dissolved in the reaction system are not greater than 20%, preferably not greater than 10%, more preferably 0 to 5% based on the total organoaluminum atoms.

The organoaluminum compound may be brought into contact with water, for example, by the following procedures.

(1) A procedure which comprises bringing the hydrocarbon solution of the organoaluminum into contact with a hydrocarbon solvent containing water.

(2) A procedure which comprises blowing steam into the hydrocarbon solution of the organoaluminum, etc., thereby bringing the organoaluminum into contact with the steam.

(3) A procedure which comprises mixing the hydrocarbon solution of the organoaluminum with a suspension of an adsorbed water-containing compound or a water of crystallization-containing compound in hydrocarbon, thereby bringing the organoaluminum into contact with the adsorbed water or water of crystallization.

(4) A procedure which comprises bringing the hydrocarbon solution of the organoaluminum into contact directly with ice.

The hydrocarbon solution of the organoaluminum as described above may contain other components so long as they do not exert adverse effects on the reaction of the organoaluminum with water.

The above-mentioned reaction of the organoaluminum with water is carried out at a temperature of usually -100.degree. to 150.degree. C., preferably -70.degree. to 100.degree. C., more preferably at -50.degree. to 80.degree. C. The reaction time employed is usually 1 to 200 hours, preferably 2 to 100 hours, though the reaction time varies largely depending upon the reaction temperature.

The benzene-insoluble organoaluminum oxy-compounds used in the invention contain an Al component soluble in benzene at 60.degree. C. in an amount of not greater than 10%, preferably not greater than 5%, particularly preferably not greater than 2% in terms of Al atom, and they are insoluble or sparingly soluble in benzene. Solubility in benzene of such organoaluminum oxy-compounds as mentioned above is obtained by suspending in 100 ml of benzene the organoaluminum oxy-compound in an amount corresponding to 100 mg atoms in terms of Al, mixing the resulting suspension at 60.degree. C. for 6 hours with stirring, filtering the resulting mixture with a G-5 glass filter equipped with a jacket kept at 60.degree. C. washing 4 times the solid portion separated on the filter with 50 ml of benzene at 60.degree. C. and measuring the amount (x mmole) of Al atoms present in the whole filtrate.

When the benzene-insoluble organoaluminum oxo-compounds as described above of the present invention are analyzed by infrared spectrophotometry (IR), a ratio (D.sub.1260/ D.sub.1220) of an absorbance (D.sub.1260) at about 1260 cm.sup.-1 to an absorbance (D.sub.1220) at about 1220 cm.sup.-1 is preferably not greater than 0.09, more preferably not greater than 0.08, particularly preferably in the range of 0.04 to 0.07.

Infrared spectrophotometric analysis of the organoaluminum oxy-compounds is carried out in the following manner.

First, the organoaluminum oxy-compound is ground, together with nujol, in an agate mortar in a nitrogen box to form paste. Next, the paste-like sample thus obtained is held between KBr plates, and IR spectrum is measured in a nitrogen atmosphere by means of IR-810 manufactured by Nippon Bunko K.K. From the thus obtained IR spectrum, a D.sub.1260 /D.sub.1220 ratio is sought, and a value of said ratio is obtained in the following manner.

(a) A line connecting a maximum point at about 1280 cm.sup.-1 and a maximum point at about 1240 cm.sup.-1 is taken as a base line L.sub.1.

(b) A transmittance (T %) of an absorption minimum point at about 1260 cm.sup.-1 and a transmittance (T.sub.0 %) of a point of intersection formed by a vertical line from said absorption minimum point to a wave number axis (abscissa) and said base line L.sub.1 are read, and an absorbance (D.sub.1260 =log T.sub.0 /T) is calculated.

(c) Similarly, a line connecting maximum points at about 1280 cm.sup.-1 and at about 1180 cm.sup.-1 is taken as a base line L.sub.2.

(d) A transmittance (T' %) of an absorption minimum point at about 1220 cm.sup.-1 and a transmittance (T'.sub.0 %) of a point of intersection formed by a vertical line from said absorption minimum point to a wave number axis (abscissa) and said base line L.sub.2 are read, and an absorbance (D.sub.1220 =log T'.sub.0 /T') is calculated.

(e) From these values as obtained above, a D.sub.1260 /D.sub.1220 ratio is calculated.

The benzene-soluble organoaluminum oxy-compound has a D.sub.1260 /D.sub.1220 value of about 0.10 to 0.13, and thus the benzene-insoluble organoaluminum oxy-compound of the present invention obviously differ from the known benzene-soluble organoaluminum oxy-compound on the value of D.sub.1260 /D.sub.1220.

The benzene-insoluble organoaluminum oxy-compounds as described above are presumed to have an alkyloxyaluminum unit represented by the formula [V] ##STR3##

In the above-mentioned alkyloxyaluminum unit (i) represented by the formula [V] of the benzene-insoluble organoaluminum oxy-compounds used in the invention, R.sup.5 includes hydorocarbon groups having 1-9 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl and cyclooctyl. Of these hydrocarbon groups exemplified above, preferred are methyl and ethyl, and particularly preferred is methyl. In the benzene-insoluble organoaluminum oxy-compounds, one or more kinds of the above-mentioned alkyloxyaluminum units (i) represented by the above formula [V] may be contained.

In addition to the alkyloxyaluminum unit of the formula [V], one or more kinds of an alkyloxyaluminum unit (ii) represented by the following formula [VI] may be contained. ##STR4## wherein R.sup.6 is a hydrocarbon group of 10 to 12 carbon atoms, a alkoxy group of 1-12 carbon atoms, aryloxy group of 6-20 carbon atoms, hydroxyl group, halogen or hydrogen.

In this case, the organoaluminum oxy-compounds desirably contain the alkyloxyaluminum unit (i) and the alkyloxyaluminum unit (ii) so that the alkyloxyaluminum unit (i) is in a proportion of not less than 30 mol %, preferably not less than 50 mol %, particularly preferably not less than 70 mol %.

The catalyst component [C] used in the second catalyst of the present invention are represented by the formula:

wherein R.sup.7 is hydrocarbon of 1-12 carbon atoms, X is halogen or hydrogen, and n is 1-3.

In the above-mentioned formula [VII], R.sup.7 is hydrocarbon of 1-12 carbon atoms, for example, alkyl, cycloalkyl or aryl, including concretely methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl, etc.

The organoaluminum compounds of the formula R.sup.7.sub.n AlX.sub.3-n include, in concrete, such compounds as mentioned below.

Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, etc;

alkenylaluminum such as isoprenylaluminum, etc;

dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, etc;

alkylaluminum sesquihalides such as methylalulminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, etc;

alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide, etc, and

alkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride.

As the catalyst component [C], there may also be used a compound represented by the following formula:

in the formula [VIII]R.sup.7 is as defined above, Y is --OR.sup.8, --OSiR.sup.9.sub.3, --OAlR.sup.10.sub.2, --NR.sup.11.sub.2, --SiR.sup.12.sub.3) or --N(R.sup.13)AlR.sup.14.sub.2, n is 1-2 and R.sup.8, R.sup.9, R.sup.10 and R.sup.14 are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc; R.sup.11 is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc; and R.sup.12 and R.sup.13 are each methyl, ethyl, etc.

The organoaluminum compounds of the formula R.sup.7.sub.n AlY.sub.3-n [VIII] include, in concrete, such compounds as mentioned below.

(i) Compounds of the formula R.sup.7.sub.n Al(OR.sup.8).sub.3-n such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc;

(ii) Compounds of the formula R.sup.7.sub.n Al(OSiR.sup.9.sub.3).sub.3-n such as (C.sub.2 H.sub.5).sub.2 AlOSi(CH.sub.3).sub.3, (iso-C.sub.4 H.sub.9).sub.2 AlOSi(CH.sub.3).sub.3, (iso-C.sub.4 H.sub.9).sub.2 AlOSi(C.sub.2 H.sub.5).sub.3, etc;

(iii) Compounds of the formula R.sub.7 nAl(OAlR.sup.10 2).sub.3-n such as (C.sub.2 H.sub.5).sub.2 AlOAl(C.sub.2 H.sub.5).sub.2, (iso-C.sub.4 H.sub.9).sub.2 AlOAl (iso-C.sub.4 H.sub.9).sub.2, etc.;

(iv) Compounds of the formula R.sub.7 nAl(NR.sup.11.sub.2).sub.3-n such as (CH.sub.3).sub.2 AlN(C.sub.2 H.sub.5).sub.2, (C.sub.2 H.sub.5).sub.2 AlNHCH.sub.3, (CH.sub.3).sub.2 AlNH(C.sub.2 H.sub.5); (C.sub.2 H.sub.5).sub.2 AlN(Si(CH.sub.3).sub.3).sub.2, (iso-C.sub.4 H.sub.9).sub.2 AlN(Si(CH.sub.3).sub.3).sub.2, etc;

(v) Compounds of the formula R.sub.7 nAl(SiR.sup.12.sub.3).sub.3-n such as (iso-C.sub.4 H.sub.9).sub.2 AlSi(CH.sub.3).sub.3, etc; and

(vi) Compounds of the formula ##STR5## such as ##STR6##

Of the organoaluminum compounds as exemplified in the fromulas [VII] and [VIII], preferred are those having the formulas

and particularly preferred are those having the above-mentioned formulas in which R.sup.7 is isoalkyl and n is 2. These organoaluminum compounds may also be used in combination of two or more.

In the invention, water may be used as a catalyst component in addition to the above-mentioned catalyst components [A], [B] and [C]. Examples of water employable in the invention include water dissolved in the later-described polymerization solvent, adsorbed-water or water of crystallization contained in a compound or a salt useed for preparing the catalyst component [B].

The first catalyst for olefin polymerization according to the invention can be prepared by mixing the catalyst components [A] and [B] and if desired water as a catalyst component in an inert hydrocarbon solvent or an olefin medium.

The order of mixing each components is optional, but it is preferred that the organoaluminum oxy-compound [B] is mixed with water and then to the resulting mixture is added the transition metal compound [A].

The second catalyst for olefin polymerization according to the invention can be prepared by mixing the catalyst components [A], [B] and [C] and if desired water as a catalyst component in an inert solvent or an olefin medium.

The order of mixing each components is optional, but it is preferred that the organoaluminum oxy-compound [B] is mixed with the organoaluminum compound [C] and then to the resulting mixture is added the transition metal compound [A].

FIG. 1 illustrates steps of a process for preparing the first and second catalysts for olefin polymerization according to the invention.

In the mixing of the above-mentioned components, an atomic ratio of aluminum contained in the catalyst component [B] to the transition metal contained in the catalyst component [A] (Al/transition metal) is generally in the range of 10 to 10,000, preferably 20 to 5,000, and a concentration of the component [A] is generally in the range of about 10.sup.-8 to 10.sup.-1 mol/l, preferably 10.sup.-7 to 5.times.10.sup.-2 mol/l.

In the second catalyst for olefin polymerization according to the invention, an atomic ratio of aluminum atom (Alc) contained in the catalyst component [C] to aluminum atom (AlB) contained in the catalyst component [B] (AlC/AlB) is generally in the range of 0.02 to 20, preferably 0.2 to 10.

In the case of using water as a catalyst component, a molar ratio of aluminum atom (AlB) contained in the catalyst component [B] to water (H.sub.2 O) is generally in the range of 0.5 to 50, preferably 1 to 40.

The above-mentioned each components may be mixed with each other in a polymerizer, or a mixture of those components having been prepared in advance may be introduced into the polymerizer. When those components are in advance mixed with each other, the mixing temperature is generally in the range of -50.degree. to 150.degree. C., preferably -20.degree. to 1.20.degree. C., and the contact period is in the range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The temperature may be varied during the mixing procedure.

Concrete examples of the inert hydrocarbon solvents used for preparing the catalysts for olefin polymerization according to the invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopenpane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; and mixtures thereof.

Next, the third and fourth catalysts for olefin polymerization according to the invention are illustrated below.

The third catalyst for olefin polymerization according to the invention comprises a particulate carrier, [A] a catalyst component of a transition metal compound having a transition metal atom in Group IVB of the periodic table, a ligand containing a -SO.sub.3 R group wherein R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, and a ligand having a cyclopentadienyl skeleton and [B] an organoaluminum oxy-compound, the transition metal compound [A] and the organoaluminum oxy-compound [B] being supported on the particulate carrier.

The fourth catalyst for olefin polymerization according to the invention comprises a solid catalyst component and [C] an organoaluminum compound, wherein the solid catalyst component comprises a particulate carrier, [A] a catalyst component of a transition metal compound having a transition metal atom in Group IVB of the periodic table, a ligand containing a -SO.sub.3 .sup.R group wherein R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, and a ligand having a cyclopentadienyl skeleton and [B] an organoaluminum oxy-compound, the transition metal compound [A] and the organoaluminum oxy-compound [B] being supported on the particulate carrier.

The carrier employable in the invention is a solid inorganic or organic compound in granules or fine particles having a particle size of 10 to 300 .mu.m, preferably 20 to 200 .mu.m. Of these carriers, porous oxides are preferable as inorganic compound carriers. Concrete examples of the porous oxides include SiO.sub.2, Al.sub.2 O.sub.3, MgO, ZrO.sub.2, TiO.sub.2, B.sub.2 O.sub.3, CaO, ZnO, BaO, ThO.sub.2, or a mixture of these compounds such as SiO.sub.2 -MgO, SiO.sub.2 -Al.sub.2 O.sub.3, SiO.sub.2 -TiO.sub.2, SiO.sub.2 -V.sub.2 O.sub.5, SiO.sub.2 -Cr.sub.2 O.sub.3 and SiO.sub.2 -TiO.sub.2 -MgO. Of these carriers, preferred are those comprising at least one compound selected from the group consisting of SiO.sub.2 and Al.sub.2 O.sub.3 as a major component.

Furthermore, the above-mentioned inorganic compounds may also contain a small amount of a carbonate, a sulfate, a nitrate and an oxide such as Na.sub.2 CO.sub.3, K.sub.2 CO.sub.3, CaCO.sub.3, MgCO.sub.3, Na.sub.2 SO.sub.4, Al.sub.2 (SO.sub.4).sub.3, BaSO.sub.4, KNO.sub.3, Mg(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, Na.sub.2 O, K.sub.2 O and LiO.sub.2.

Moreover, there can be used organic compounds in granular solid or fine solid particles each having a particle size of 10 to 300 .mu.m as carriers in the present invention. Examples of these organic compounds include (co)polymers containing, as the main component, an .alpha.-olefin of 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene and 4-methyl-1-pentene; polymers or copolymers containing, as the main component, vinylcyclohexane or styrene; and ring opening polymers of norbornene.

The particulate carriers may contain hydroxyl group or water, and in this case, the amount of the surface hydroxyl group is not less than 1.0 wt. %, preferably in the range of 1.5 to 4.0 wt. %, more preferably 2.0 to 3.5 wt. %, and the amount of water is not less than 1.0 wt. %, preferably in the range of 1.2 to 20 wt. %, more preferably 1.4 to 15 wt. %. The water contained in the particulate carrier means water adsorbed on the surface of the particulate carrier.

The amount of the surface hydroxyl group contained in the particulate carrier can be determined in the following manner. That is, the carrier is dried at 200.degree. C. under a normal pressure in a stream of nitrogen, and the obtained weight of the carrier is set to X (g). Further, the carrier is fired at 1,000.degree. C. for 20 hours to give a fired product in which the surface hydroxyl group have vanished, and the obtained weight of the carrier is set to Y (g) . Thus obtained X and Y are introduced into the following formula to obtain the weight of the surface hydroxyl group.

The weight of water contained in the particulate carrier can be weighed by means of a heat loss process. In the invention, weight loss of carrier after drying at 200.degree. C. for 4 hours in a stream of a dry gas such as dry air or dry nitrogen is a weight of adsorbed water.

If the particulate carrier containing adsorbed water and surface hydroxyl group of specific weight is used, there can be obtained a solid catalyst for olefin polymerization capable of producing an olefin polymer having excellent particle properties with high polymerization activities.

Examples of the transition metal compound [A] used in the third and fourth catalysts for olefin polymerization according to the invention are the aforementioned transition metal compounds [A] used in the first and second catalysts for olefin polymerization.

Likewise, examples of the organoaluminum oxy-compound [B] used in the third and fourth catalysts for olefin polymerization are the aforementioned organoaluminum oxy-compounds [B] used in the first and second catalysts for olefin polymerization.

Further, examples of the organoaluminum compound [C] used in the fourth catalyst for olefin polymerization are the aforementioned organoaluminum compound [C] used in the second catalyst for olefin polymerization.

In the third and fourth Catalysts, such water as described with respect to the first and second catalysts can be also employed in addition to the above-mentioned catalyst components.

The third catalyst for olefin polymerization according to the invention can be prepared by mixing and contacting the particulate carrier and the catalyst components [A] and [B] and if desired water with each other in an inert hydrocarbon solvent or an olefin medium. The component [C] may be further added after the mixing procedure to prepare the fourth catalyst of the invention.

The order of adding each components is optional, but it is preferable that the particulate carrier and the organoaluminum oxy-compound [B] are mixed and brought into contact with each other, and then the transition metal compound [A] is brought into contact, and thereafter if desired water is brought into contact with the resulting mixture. Otherwise, a mixture of the organoaluminum oxy-compound [B] and the transition metal compound [A] is mixed and brought into contact with the particulate carrier, and then if desired, water is brought into contact with the resulting mixture. Alternatively, the particulate carrier, the organoaluminum oxy-compound [B] and water are mixed and brought into contact with each other, and then the transition metal compound [A] is brought into contact with the resulting mixture.

FIG. 2 illustrates steps of a process for preparing the third and fourth catalysts for olefin polymerization according to the invention.

In the mixing of the above-mentioned components, the catalyst component [A] is generally used in an amount of 10.sup.-5 to 5.times.10.sup.-3 mol, preferably 5.times.10.sup.-5 to 10.sup.-3 mol, per 1 g of the particulate carrier, and a concentration of the component [A] is generally in the range of about 10.sup.-4 to 2.times.10.sup.-2 mol/l, preferably 2.times.10.sup.-4 to 10.sup.-2 mol/l. An atomic ratio of aluminum contained in the catalyst component [B] to the transition metal contained in the catalyst component [A] (Al/transition metal) is generally in the range of 10 to 3,000, preferably 20 to 2,000.

The temperature in the above mixing procedure is generally in the range of -50.degree. to 150.degree. C., preferably 20.degree. to 120.degree. C. and the contact period is in the range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The temperature may be varied during the mixing procedure.

The fourth catalyst for olefin polymerization according to the invention comprises the above-mentioned third catalyst and the organoaluminum compound [C]. The organoaluminum compound [C] is used generally in an amount of not more than 500 mol, preferably in the range of 5 to 200 mol, per 1 gram atom of the transition metal atom.

The catalysts for olefin polymerization according to the invention may contain other additives which are useful for olefin polymerization in addition to the above components.

As the inert hydrocarbon medium employable for preparing the third and fourth catalysts for olefin polymerization according to the invention, there can be exemplified the similar media to those used for preparing the aforementioned first and second catalysts.

Next, the fifth and sixth catalysts for olefin polymerization according to the invention are described below.

The fifth catalyst for olefin polymerization according to the invention comprises a particulate carrier, [A] a catalyst component of a transition metal compound having a transition metal atom in Group IVB of the periodic table, a ligand containing a --SO.sub.3 R group wherein R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, and a ligand having a cyclopentadienyl skeleton, [B] an organoaluminum oxy-compound, and an olefin polymer prepared by prepolymerization.

The sixth catalyst for olefin polymerization according to the invention comprises a particulate carrier, [A] a catalyst component of a transition metal compound having a transition metal atom in Group IVB of the periodic table, a ligand containing a --SO.sub.3 R group wherein R is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, and a ligand having a cyclopentadienyl skeleton, [B] an organoaluminum oxy-compound, [C] an organoaluminum compound, and an olefin polymer prepared by prepolymerization.

The particulate carrier, the transition metal compound [A], the organoaluminum oxy-compound [B] and the organoaluminum compound [C] used in the above catalysts for olefin polymerization are similar to those described before. Water can be also employed for these fifth and sixth catalysts.

These fifth catalyst for olefin polymerization according to the invention can be prepared by mixing and contacting the particulate carrier, the component [A] and the component [B] and if desired water with each other in an inert hydrocarbon solvent or an olefin medium to give a solid catalyst, and then prepolymerizing a small amount of olefin with the solid catalyst.

The component [C] can be also added after the mixing procedure.

The sixth catalyst for olefin polymerization according to the invention comprises the above-mentioned fifth catalyst and the organoaluminum compound [C].

The order of adding each components is optional, but it is preferable that the particulate carrier and the organoaluminum oxy-compound [B] are mixed and brought into contact with each other, and then the transition metal compound [A] is brought into contact, and thereafter if desired, water is brought into contact with the resulting mixture. Otherwise, a mixture of the organoaluminum oxy-compound [B] and the transition metal compound [A] is mixed and brought into contact with the particulate carrier, and then if desired water is brought into contact with the resulting mixture. Alternatively, the particulate carrier, the organoaluminum oxy-compound [B] and water are mixed and brought into contact with each other, and then the transition metal compound [A] is brought into contact with the resulting mixture.

FIG. 3 illustrates steps of a process for preparing the fifth and sixth catalysts for olefin polymerization according to the invention.

In the mixing of the above-mentioned components, the catalyst component [A] is generally used in an amount of 10.sup.-5 to 5.times.10.sup.-3 mol, preferably 5.times.10.sup.-5 to 10.sup.-3 mol, per 1 g of the particulate carrier, and a concentration of the component A] is generally in the range of about 10.sup.-4 to 2.times.10.sup.-2 mol/l, preferably 2.times.10.sup.-4 to 10.sup.-2 mol/l. An atomic ratio of aluminum contained in the catalyst component [B] to the transition metal contained in the catalyst component [A] (Al/transition metal) is generally in the range of 10 to 3,000, preferably 20 to 2,000.

In the case of using water as a catalyst component, a molar ratio of aluminum atom (Al.sub.B) contained in the catalyst component [B] to water (H.sub.2 O) is generally in the range of 0.5 to 50, preferably 1 to 40.

The temperature in the above mixing procedure is generally in the range of -50.degree. to 150.degree. C. preferably -20.degree. to 120.degree. C. and the contact period is in the range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The temperature may be varied during the mixing procedure.

The fifth catalyst for olefin polymerization according to the invention can be prepared by prepolymerizing olefin in the presence of the above-mentioned each components. In the prepolymerization, the catalyst component [A] is used in an amount of 10.sup.-5 to 2.times.10.sup.-2 mol/l, preferably 5.times.10.sup.-5 to 10.sup.-2 mol/l, the prepolymerization temperature is generally in the range of -20.degree. to 80.degree. C. preferably 0.degree. to 50.degree. C. and the prepolymerization period is generally in the range of 0.5 to 100 hours, preferably 1 to 50 hours.

The olefin used in the prepolymerization is selected form olefins used for polymerization, but preferred are the same monomer as that for polymerization or a mixture of said monomer and .alpha.-olefin.

In the catalyst for olefin polymerization obtained as above, the transition metal atom is supported on the particulate carrier in an amount of about 5.times.10.sup.-6 to 10.sup.-3 g atom, preferably 10.sup.-5 to 3.times.10.sup.-4 g atom, per 1 g of the particulate carrier, and the aluminum atom is supported on the particulate carrier in an amount of about 10.sup.-3 to 10.sup.-1 g atom, preferably 2.times.10.sup.-3 to 5.times.10.sup.-2 g atom, per 1 g of the particulate carrier. Further, the weight of the polymer prepared by the prepolymerization is in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, more preferably 1 to 100 g, based on 1 g of the particulate carrier.

The sixth catalyst for olefin polymerization according to the invention comprises the above-mentioned fifth catalyst and the organoaluminum compound [C] . The organoaluminum compound [C] is used generally in an amount of not more than 500 mol, preferably in the range of 5 to 200 mol, per 1 gram atom of the transition metal atom.

The catalysts for olefin polymerization according to the invention may contain other additives which are useful for olefin polymerization in addition to the above components.

As the inert hydrocarbon medium employable for preparing the fifth and sixth catalysts for olefin polymerization according to the invention, there can be exemplified the similar media to those used for preparing the aforementioned first and second catalysts.

The polymerization process of the invention is described below.

In the invention, olefin is polymerized in the presence of the above-mentioned catalysts for olefin polymerization.

The polymerization of olefin can be carried out in any process of liquid phase polymerization (e.g., suspension polymerization and solution polymerization) and gas phase polymerization. In the liquid phase polymerization, the same inert hydrocarbon solvent as that used for the preparation of the catalysts can be employed, or olefin per se can be employed as the solvent.

When the polymerization of olefin is conducted using the third or fourth catalyst for olefin polymerization according to the invention, the catalyst component [A] is used in an amount generally 10.sup.-8 to 10.sup.-1 g atom/l, preferably 10.sup.-7 to 5.times.10.sup.-2 g atom/l, in terms of a concentration of the transition metal atom in the polymerization reaction system. In this polymerization, aluminoxane may be employed, if desired.

In the case of conducting the polymerization of olefin using the catalysts containing a prepolymerized olefin, as in the case of the fifth and sixth catalysts of the invention, the transition metal compound of the catalyst component [A] is used generally in an amount of 10.sup.-8 to 10.sup.-3 g atom, preferably 10.sup.-7 to 10.sup.-4 g atom, in terms of transition metal atom, per 1 liter of polymerization volume. In this polymerization, an organoaluminum compound or aluminoxane may be employed, if desired. Examples of the organoaluminum compounds used herein are the similar compounds to the aforementioned catalyst component [C]. The amount thereof preferably is in the range of 0 to 500 mol per 1 gram atom of the transition metal atom.

The temperature for olefin polymerization is generally in the range of -50.degree. to 100.degree. C. preferably 0.degree. to 90.degree. C. in the case of slurry polymerization; it is generally in the range of 0.degree. to 250.degree. C., preferably 20.degree. to 200..degree. C., in the case of solution polymerization; and it is generally in the range of 0.degree. to 120.degree. C. , preferably 20.degree. to 100.degree. C., in the case of gas phase polymerization. The polymerization pressure is generally in the range of a normal pressure to 100 kg/cm.sup.2, preferably a normal pressure to 50 kg/cm.sup.2. The polymerization reaction may be performed by any of a batch process, a semi-continuous process and a continuous process. Further, it is also possible to perform the polymerization in two or more stages different in the reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing water to exist in the polymerization system or by varying the polymerization temperature.

Examples of the olefins which can be polymerized by using the catalysts for olefin polymerization include ethylene and .alpha.-olefins of 3-20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; and cycloolefins of 3-20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Also employable are styrene, vinylcyclohexane, diene, etc.

The present inventors have energetically studied on development of the novel catalysts as mentioned above, and on this way, we have developed a novel transition metal compound employable as the catalyst component [A] of the invention. If this novel transition metal compound is used as the component [A], a catalyst having high catalytic activities for olefin polymerization can be obtained.

The novel transition metal compound is described in more detail below.

This novel transition metal compound of the invention is represented by the following formula [IX]. ##STR7##

In the formula [IX], M is a transition metal in Group IVB of the periodic table, each of Cp.sup.1 and Cp.sup.2 is a group having a cyclopentadienyl skeleton, said group having a cyclopentadienyl skeleton may have a substituent group, Cp.sup.1 and Cp.sup.2 may be linked to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, R.sup.1 is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group, X is --SO.sub.3 R.sup.1, a halogen atom, R.sup.1, OR.sup.1, NR.sup.1.sub.n, S(O).sub.q R.sup.1, SiR.sup.1.sub.3 or P(O).sub.q R.sup.1.sub.3, n is 1, 2 or 3 and q is 0,1 or 2. Preferably, X is --SO.sup.3 R.sup.1, --OR, --NR.sup.1.sub.n or a halogen atom.

M in the formula [IX] is a transition metal in Group IVB of the periodic table, and in concrete it is zirconium, titanium or hafnium.

Examples of the group having a cyclopentadienyl skeleton include cyclopentadienyl group; alkyl-substituted cyclopentadienyl group such as methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group and pentamethylcyclopentadienyl group; indenyl group; and fluorenyl group. Of these, preferred are alkyl-substituted cyclopentadienyl group and indenyl group.

Examples of the alkylene group include ethylene group and propylene group.

Examples of the substituted alkylene group include isopropylidene group and diphenylmethylene group, and an example of the substituted silylene group is dimethylsilylene group.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group and butyl group, and examples of the aryl group include phenyl group and tolyl group.

The halogen is fluorine, chlorine, bromine or iodine.

The transition metal compound represented by the formula [IX] is very stable, and when used as a catalyst for olefin polymerization with an organoaluminum oxy-compound, it shows high activities for olefin polymerization.

Concrete examples of the transition metal compounds represented by the formula [IX] are given below.

Bis(cyclopentadienyl)-zirconium (IV)-bis(methanesulfonate),

Bis(cyclopentadienyl)-zirconium (IV) -bis(p-toluenesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-bis(trifluoromethanesulfonate),

Bis(cyclopentadienyl)-zirconium (IV)-trifluoromethanesulfonate monochloride,