JPH0995510A - Production of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a polyolefin whereby the control of the molecular weight of the formed polymer is possible. SOLUTION: An olefin is polymerized in a vapor phase in the reaction system in which a saturated hydrocarbon compound or an aromatic hydrocarbon compound exists in the presence of a catalyst prepared by bringing a compound represented by the formula: Me<1> R<1> 1 (OR<2> )q X<1> 4-p-q [wherein R<1> and R<2> are each a hydrocarbon group; X<1> is a halogen or hydrogen; Me<1> is Zr, Ti or Hf; 0<=p<=4; 0<=p<=4: and 0<=p+q<=4], a compound represented by the formula: Me<2> R<3> m (OR<4> )n X<2> z-m-n (wherein R<3> and R<4> are each a hydrocarbon; X<2> is a halogen or hydrogen; Me<2> is an element of group I, III or III; (z) is the valence of Me<2> ; 0<m<=z; 0<=n<=z; and 0<m+n<=z), an organic cyclic compound having two or more conjugated double bonds and a modified organic aluminum compound containing an Al-O-Al bond into contact with each other.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a polyolefin. More specifically, the present invention relates to a method for producing a polyolefin capable of controlling the molecular weight of a polymer produced in a gas phase polymerization method by completely different means from conventional methods.

[0002]

2. Description of the Related Art In producing a polyolefin, particularly an ethylene polymer or an ethylene / α-olefin copolymer, it is important to control the molecular weight of the polymer in order to widen the product grade range. It is a problem. As a method of adjusting the molecular weight of the polymer, a method of adjusting the concentration of hydrogen stuck in the polymerization reaction system,
Alternatively, a method of controlling the polymerization temperature or the polymerization pressure is generally known. An object of the present invention is to provide a method for producing a polyolefin, which employs a completely different method for controlling the molecular weight of a polymer.

[0003]

One of the methods for producing a polyolefin according to the present invention is (1) a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq , , R ¹ and R ² individually have 1 to 1 carbon atoms.
24 hydrocarbon groups, X ¹ is a halogen atom or a hydrogen atom, Me ¹ is Zr, Ti or Hf, and p and q
Are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4, respectively. (2) A compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn , [wherein R ³ and R ⁴ are individually a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom, M
e ² is a Group I to III element of the periodic table, z is the valence of Me ² , and m and n are 0 <m ≦ z and 0 ≦ n ≦ z, respectively.
And 0 <m + n ≦ z] (3) A cyclic organic compound having two or more conjugated double bonds,
And (4) a saturated hydrocarbon compound when polymerizing or copolymerizing olefins in a substantially gas phase in the presence of a catalyst obtained by bringing modified organoaluminum compounds containing an Al—O—Al bond into contact with each other. And at least one liquid and / or gaseous hydrocarbon compound selected from aromatic hydrocarbon compounds are allowed to coexist in the reaction system, and the type and / or amount of the hydrocarbon compound is selected. Another method for producing a polyolefin according to the present invention is (1) a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq , wherein [wherein R ¹ and R ² are Individually a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a halogen atom or a hydrogen atom, M
e ¹ represents Zr, Ti or Hf, and p and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4 and 0 ≦ p + q ≦ 4, respectively. (2) General formula Me ² R ³ _m (OR ⁴ ) a compound represented by _n X ² _zmn [wherein R ³ and R ⁴ are independently a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom, M 2
e ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n are 0 <m ≦ z and 0 ≦ n ≦ z, respectively.
And 0 <m + n ≦ z] (3) Cyclic organic compound having two or more conjugated double bonds, (4) Modified organoaluminum compound containing Al—O—Al bond, and (5) Inorganic compound When a olefin is polymerized or copolymerized in a substantially gas phase in the presence of a catalyst obtained by bringing a carrier and / or a particulate polymer carrier into contact with each other, it is selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound. It is characterized in that at least one liquid and / or gaseous hydrocarbon compound described above is allowed to coexist in the reaction system, and the type and / or amount of the hydrocarbon compound is selected. According to the method of the present invention, in the case of producing an olefin polymer, a polymer having a high molecular weight and a relatively wide molecular weight distribution can be produced in a high yield, and in the case of producing an olefin copolymer. As a result, a copolymer having a narrow composition distribution can be produced in high yield. Further, according to the present invention, it is possible to obtain an olefin polymer and a copolymer having good particle properties. Then, in the method of the present invention, the molecular weight of the product can be adjusted by appropriately selecting the type and / or the amount of the specific hydrocarbon compound coexisting in the polymerization reaction system.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION First, the catalyst used in the present invention will be described. The catalyst used in the present invention is a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq (component (1)), a general formula Me ² R ³ _m (OR ⁴ ) _n. A compound represented by X ² _zmn (component (2)), a cyclic organic compound having two or more conjugated double bonds (component (3)), and a modified organoaluminum compound containing an Al—O—Al bond (component ( 4)),
The above-mentioned four components are brought into contact with each other, or the five components obtained by adding the inorganic compound carrier and / or the particulate polymer carrier (component (5)) to the above-mentioned four components are brought into contact with each other. .

The component (1) is represented by the following general formula (1). General formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq (1) In the general formula (1), R ¹ and R ² are each independently a carbon number of 1
-24, preferably 1-12, more preferably 1-8
Represents a hydrocarbon group. Examples of the hydrocarbon group that R ¹ and R ² can independently take include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, Alkyl groups such as isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group; alkenyl groups such as vinyl group, allyl group; phenyl group, tolyl group, xylyl group, mesityl group, Aryl groups such as indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group,
Examples thereof include aralkyl groups such as phenylbutyl group, phenylpropyl group, and neophyll group. These hydrocarbon groups may have a branched chain. X ¹ is a halogen atom of fluorine, iodine, chlorine and bromine or a hydrogen atom. Me ¹ represents Zr, Ti or Hf,
Zr is preferred. p and q are 0 ≦ p ≦
4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4, preferably 0
It is an integer that satisfies the range of <p + q ≦ 4.

The compound represented by the general formula (1) is
One kind or a mixture of two or more kinds can be used as the component (1) of the present invention. When specific examples of the compound represented by the general formula (1) are described, tetramethylzirconium,
Tetraethylzirconium, tetrapropylzirconium, tetra-n-butylzirconium, tetrapentylzirconium, tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetraallylzirconium, tetraneofilzirconium,
Tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium, tetratolyloxyzirconium, tetrabenzyloxyzirconium, tetraallyloxyzirconium, tetraneofiloxyzirconium, trimethylmonochlorozirconium, Triethyl monochloro zirconium, tripropyl monochloro zirconium, tri n-butyl monochloro zirconium, tripentyl monochloro zirconium, triphenyl monochloro zirconium, tritolyl monochloro zirconium, tribenzyl monochloro zirconium, triallyl monochloro zirconium, trineophyll monochloro zirconium Dimethyl zirconium dichloride, diethyl dichloro zirconium, dipropyl zirconium dichloride, di-n- butyl zirconium dichloride, dipentyl dichloro zirconium, diphenyl zirconium dichloride, ditolyl zirconium dichloride, dibenzyl zirconium dichloride, diallyl dichloro zirconium,
Dineofildichlorozirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, monopropyltrichlorozirconium, mono-n-butyltrichlorozirconium, monopentyltrichlorozirconium, monophenyltrichlorozirconium,
Monotolyltrichlorozirconium, monobenzyltrichlorozirconium, monoallyltrichlorozirconium, mononeophyltrichlorozirconium, tetrachlorozirconium, trimethoxymonochlorozirconium, dimethoxydichlorozirconium, monomethoxytrichlorozirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, mono Ethoxytrichlorozirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, monopropoxytrichlorozirconium, tri-n-butoxymonochlorozirconium, di-n-butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tripentyloxymonochlorozirconium, dipentyloxydichlorozirconium. Zirconium, monopentyloxytrichlorozirconium, triphenoxymonochlorozirconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium, tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tribenzyloxymonochlorozirconium, dibenzyloxy. Dichlorozirconium, monobenzyloxytrichlorozirconium, triallyloxymonochlorozirconium, diallyloxydichlorozirconium, monoallyloxytrichlorozirconium, trineophyloxymonochlorozirconium, dineofiloxydichlorozirconium, mononeophylloxytrichlorozirconium, tetrabromozil Ni, trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tri-n-butylmonobromozirconium, tripentylmonobromozirconium, triphenylmonobromozirconium, tritolylmonobromozirconium, tribenzylmonobromozirconium, tri Allyl monobromozirconium, trineofil monobromozirconium, dimethyldibromozirconium, diethyldibromozirconium, dipropyldibromozirconium, di-n-butyldibromozirconium, dipentyldibromozirconium, diphenyldibromozirconium, ditolyldibromozirconium, dibenzyldibromozirconium, Diallyldibromozirconium, Dineofildibromo Zirconium, monomethyltribromozirconium, monoethyltribromozirconium, monopropyltribromozirconium, mono-n-butyltribromozirconium, monopentyltribromozirconium,
Monophenyltribromozirconium, monotolyltribromozirconium, monobenzyltribromozirconium, monoallyltribromozirconium, mononeophyltribromozirconium, trimethoxymonobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymono Bromozirconium, diethoxydibromozirconium,
Triethoxytribromozirconium, tripropoxymonobromozirconium, dipropoxydibromozirconium, monopropoxytribromozirconium, tri-n-butoxymonobromozirconium, di-n-butoxydibromozirconium, mono-n-butoxytribromozirconium, tripentyloxymonomono Bromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tritolyloxymonobromozirconium, ditolyloxydibromozirconium, monotolyloxytribromo Zirconium, tribenzyloxymonobromozirconium, dibenzyloxy Dibromo zirconium, mono-benzyloxy tribromo zirconium, triallyl oxy mono bromo zirconium, di-allyloxy-dibromo zirconium, monoallyl oxy tribromo zirconium,
Trineophylloxy monobromozirconium, Dyneofiloxy dibromozirconium, Mononeophylloxy tribromozirconium, Tetraiodozirconium, Trimethylmonoiodozirconium, Triethylmonoiodozirconium, Tripropylmonoiodozirconium, Tri-n-butylmonoiodozirconium , Tripentyl monoiodo zirconium, triphenyl monoiodo zirconium, tritolyl monoiodo zirconium, tribenzyl monoiodo zirconium, triallyl monoiodo zirconium, trineophyll monoiodo zirconium, dimethyldiiodo zirconium, diethyl diiodo zirconium, dipropyl di Iodozirconium, di-n-butyldiiodozirconium, dipentyldiiodozirconium Diphenyl diiodo zirconium, ditolyl diiodo zirconium, dibenzyl diiodo zirconium, diallyl diiodo zirconium, dineofil diiodo zirconium, monomethyl triiodo zirconium, monoethyl triiodo zirconium, monopropyl triiodo zirconium, mono n-butyl tri Iodozirconium, monopentyl triiodozirconium, monophenyltriiodozirconium, monotolyltriiodozirconium, monobenzyltriiodozirconium, tetraiodozirconium, trimethoxymonoiodozirconium, dimethoxydiiodozirconium, monomethoxytriiodozirconium, triethoxy Monoiodozirconium, diethoxydiiodozirconium, monoethoxytriiododi Conium, tripropoxymonoiodozirconium, dipropoxydiiodozirconium, monopropoxytriiodozirconium, tri-n-butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-butoxytriiodozirconium, tripentyloxymonoiodozirconium , Dipentyloxydiiodozirconium, monopentyloxytriiodozirconium, triphenoxymonoiodozirconium, diphenoxydiiodozirconium, monophenoxytriiodozirconium, tritolyloxymonoiodozirconium, ditolyloxydiiodozirconium, monotolyloxytriiodine Iodozirconium, tribenzyloxymonoiodozirconium, dibenzyloxydiiodozirconium, molybdenum Nobenzyloxytriiodozirconium, triallyloxymonoiodozirconium, diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineophylloxymonoiodozirconium, dineofiloxydiiodozirconium, mononeophylloxytriiodozirconium , Tribenzylmonomethoxyzirconium, tribenzylmonoethoxyzirconium, tribenzylmonopropoxyzirconium, tribenzylmonobutoxyzirconium, tribenzylmonopentyloxyzirconium, tribenzylmonophenoxyzirconium, tribenzylmonotolyloxyzirconium, tribenzylmonobenzyloxy Zirconium, tribenzyl monoallyloxy zirconium, tribenzyl mono Ofiloxyzirconium, dibenzyldimethoxyzirconium, dibenzyldiethoxyzirconium, dibenzyldipropoxyzirconium, dibenzyldibutoxyzirconium, dibenzyldipentyloxyzirconium, dibenzyldiphenoxyzirconium, dibenzylditolyloxyzirconium, dibenzyldibenzyl Oxyzirconium, dibenzyldiallyloxyzirconium, dibenzyldineophyloxyzirconium, monobenzyltrimethoxyzirconium, monobenzyltriethoxyzirconium, monobenzyltripropoxyzirconium, monobenzyltributoxyzirconium, monobenzyltripentyloxyzirconium, monobenzyl Triphenoxyzirconium, monobenzyltritolyl oki Zirconium, monobenzyltribenzyloxyzirconium, monobenzyltriallyloxyzirconium, monobenzyltrineophyloxyzirconium, trineophile monomethoxyzirconium, trineophile monoethoxyzirconium, trineophile monopropoxyzirconium, trineophile monobutoxy Zirconium, trineophyll monophenoxy zirconium, dineofil dimethoxy zirconium, dineofil diethoxy zirconium, dineofil dipropoxy zirconium, dineofil dibutoxy zirconium, dineofil diphenoxy zirconium, mononeophyll trimethoxy zirconium, Mononeophyll triethoxy zirconium, mononeophyll tripropoxy zirconium, mononeoff Filamentoxy zirconium, mononeophyl triphenoxy zirconium, zirconium tetrahydride, zirconium monohydride trimethoxide, zirconium monohydride triethoxide, zirconium monohydride tripropoxide, zirconium monohydride tributoxide, zirconium dihydride dimethoxide. , Zirconium dihydride diethoxide, zirconium dihydride dipropoxide, zirconium dihydride dibutoxide, zirconium trihydride monomethoxide, zirconium trihydride monoethoxide, zirconium trihydride monopropoxide, zirconium trihydride monobutoxide Side, zirconium mono high Ride trichloride, zirconium monohydride tribromide, zirconium monohydride triiodide, zirconium monohydride trifluoride, zirconium dihydride dichloride, zirconium dihydride dibromide, zirconium dihydride difluoride, zirconium dihydride difluoride, zirconium trioxide Hydride Monochloride, Zirconium Trihydride Monobromide, Zirconium Trihydride Monoiodide, Zirconium Trihydride Monofluoride, Zirconium Monohydride Trimethyl, Zirconium Monohydride Tribenzyl, Zirconium Monohydride Triphenyl, Zirconium Dihydride Dimethyl, Di Konium dihydride dibenzyl, zirconium dihydride diphenyl, zirconium trihydride monomethyl, zirconium trihydride monobenzyl, zirconium trihydride monophenyl, zirconium monohydride dimethoxide monochloride, zirconium monohydride dietoxide monochloride, zirconium monohydride Dipropoxide monochloride, zirconium monohydride dibutoxide monochloride, zirconium dihydride monomethoxide monochloride, zirconium dihydride monoethoxide monochloride, zirconium dihydride monopropoxide monochloride, zirconium dihydride monobutoxide Monochrome ride, J Ruconium Monohydride Dimethoxide Monomethyl, Zirconium Monohydride Diethoxide Monobenzyl, Zirconium Monohydride Dipropoxide Monophenyl, Zirconium Dihydride Monomethoxide Monomethyl, Zirconium Dihydride Monoethoxide Monobenzyl, Zirconium Dihydride Monopropoxide Side monophenyl,
Zirconium monohydride monomethoxide monochloride monobenzyl, zirconium monohydride monomethoxide monochloride monophenyl, zirconium monohydride monomethoxide monochloride monomethyl,

Tetramethyl titanium, tetraethyl titanium, tetrapropyl titanium, tetra n-butyl titanium, tetrapentyl titanium, tetraphenyl titanium, tetratolyl titanium, tetrabenzyl titanium, tetraallyl titanium, tetra neophyll titanium, tetramethoxy titanium, tetra Ethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrabenzyloxytitanium, tetraallyloxytitanium, tetraneophylloxytitanium, trimethylmonochlorotitanium, triethylmonochlorotitanium, tri Propyl monochlorotitanium, tri-n- Till monochlorotitanium, tribenzyl monochlorotitanium, dimethyldichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, mono-n-butyltrichlorotitanium, monobenzyltrichlorotitanium, Tetrachlorotitanium, trimethoxymonochlorotitanium, dimethoxydichlorotitanium, monomethoxytrichlorotitanium, triethoxymonochlorotitanium, ethoxydichlorotitanium, monoethoxytrichlorotitanium,
Tripropoxymonochlorotitanium, dipropoxydichlorotitanium, monopropoxytrichlorotitanium, tri-n-butoxymonochlorotitanium, di-n-butoxydichlorotitanium, mono-n-butoxytrichlorotitanium, tripentyloxymonochlorotitanium, dipentyloxydichlorotitanium, monopentyloxy Trichlorotitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tritolyloxymonochlorotitanium, ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium, monobenzyl Oxytrichlorotitanium, tetra Lomotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyl Dibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-butyltribromotitanium, monobenzyltribromotitanium, tetrabromotitanium, trimethoxymonobromotitanium, dimethoxydibromotitanium, trimethoxytribromotitanium, triethoxy Monobromotitanium, diethoxydibromotitanium, monoethoxytribromotitanium, tripro Xyloxymonobromotitanium, dipropoxydibromotitanium, monopropoxytribromotitanium, tri-n-butoxymonobromotitanium, di-n-butoxydibromotitanium, mono-n-butoxytribromotitanium, tripentyloxymonobromotitanium, dipentyloxydibromotitanium , Monopentyloxytribromotitanium, triphenoxymonobromotitanium, diphenoxydibromotitanium, monophenoxytribromotitanium, tritolyloxymonobromotitanium,
Ditryloxydibromotitanium, monotolyloxytribromotitanium, tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium, monobenzyloxytribromotitanium, tetraiodotitanium, trimethylmonoiodotitanium, triethylmonoiodotitanium, tripropylmonotitanium Iodotitanium, tri-n-butylmonoiodotitanium, tribenzylmonoiodotitanium, dimethyldiiodotitanium, diethyldiiodotitanium, di-n-butyldiiodotitanium, dibenzyldiiodotitanium, monomethyltriiodotitanium, monoethyltriiodo Titanium, mono-n-butyltriiodotitanium, monobenzyltriiodotitanium, tetraiodotitanium, trimethoxy Monoiodotitanium, dimethoxydiiodotitanium, monomethoxytriiodotitanium, triethoxymonoiodotitanium, diethoxydiiodotitanium, monoethoxytriiodotitanium, tripropoxymonoiodotitanium, dipropoxydiiodotitanium, monopropoxytriiodotitanium , Tri-n-butoxymonoiodotitanium, di-n
-Butoxydiiodotitanium, mono-n-butoxytriiodotitanium, tripentyloxymonoiodotitanium, dipentyloxydiiodotitanium, monopentyloxytriiodotitanium, triphenoxymonoiodotitanium, diphenoxydiiodotitanium, monophenoxytriiodo Titanium, tritolyloxymonoiodotitanium, ditolyloxydiiodotitanium, monotolyloxytriiodotitanium,
Tribenzyloxymonoiodotitanium, dibenzyloxydiiodotitanium, monobenzyloxytriiodotitanium, tribenzylmonomethoxytitanium, tribenzylmonoethoxytitanium, tribenzylmonopropoxytitanium, tribenzylmonobutoxytitanium, tribenzylmonophenoxytitanium , Dibenzyldimethoxytitanium, dibenzyldiethoxytitanium, dibenzyldipropoxytitanium, dibenzyldibutoxytitanium, dibenzyldiphenoxytitanium, monobenzyltrimethoxytitanium, monobenzyltriethoxytitanium, monobenzyltripropoxytitanium, monobenzyl Tributoxy Titanium, Monobenzyl Triphenoxy Titanium, Trineofil Mono Toxitanium, Trineophyll monoethoxytitanium, Trineophyll monopropoxytitanium, Trineophyll monobutoxytitanium, Trineophyll monophenoxytitanium, Dineofil dimethoxytitanium, Dineofil diethoxytitanium, Dineofil dipropoxytitanium , Dineofildibutoxytitanium, Dineofil diphenoxytitanium, Mononeophyltrimethoxytitanium, Mononeophile triethoxytitanium,
Mononeophyll tripropoxytitanium, mononeophyll tributoxytitanium, mononeophyll triphenoxytitanium,

Tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrapentyl hafnium, tetraphenyl hafnium, tetratolyl hafnium, tetrabenzyl hafnium, tetraallyl hafnium, tetraneophyll hafnium, tetramethoxy hafnium, tetra Ethoxyhafnium, tetrapropoxyhafnium, tetrabutoxyhafnium, tetrapentyloxyhafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrabenzyloxyhafnium, tetraallyloxyhafnium, tetraneophyloxyhafnium, trimethylmonochlorohafnium, triethylmonochlorohafnium, tri Propyl monochlorohafnium, tri n- Till monochlorohafnium, tribenzyl monochlorohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium, Tetrachlorohafnium, trimethoxymonochlorohafnium, dimethoxydichlorohafnium, monomethoxytrichlorohafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium, monoethoxytrichlorohafnium, tripropoxymonochlorohafnium, dipropoxydichlorohafnium, monopropoxytrichlorohafnium, trin -Butoxy Monochrome Chloride, di-n
-Butoxydichlorohafnium, mono-n-butoxytrichlorohafnium, tripentyloxymonochlorohafnium, dipentyloxydichlorohafnium, monopentyloxytrichlorohafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tritolyloxymonochlorohafnium, Ditolyloxydichlorohafnium, monotolyloxytrichlorohafnium,
Tribenzyloxy monochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, tetrabromohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, tri-n-butylmonobromohafnium, tribenzylmonobromo Hafnium, dimethyldibromohafnium, diethyldibromohafnium, di-n-butyldibromohafnium, dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribromohafnium, monobenzyltribromohafnium, tetrabromohafnium , Trimethoxymonobromohafnium, dimethoxydibromohafnium, monomethoxytrib Mohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, tripropoxymonobromohafnium, dipropoxydibromohafnium, monopropoxytribromohafnium, tri-n-butoxymonobromohafnium, di-n-butoxydibromohafnium , Mono-n-butoxytribromohafnium, tripentyloxymonobromohafnium, dipentyloxydibromohafnium, monopentyloxytribromohafnium, triphenoxymonobromohafnium, diethoxydibromohafnium, monophenoxytribromohafnium, tritolyloxymonobromo hafnium,
Ditolyloxydibromohafnium, monotolyloxytribromohafnium, tribenzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, tetraiodohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmono Iodohafnium, tri-n-butylmonoiodohafnium, tribenzylmonoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium, di-n-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodo Hafnium, mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium, trimethoxy Monoiodohafnium, dimethoxydiiodohafnium, monomethoxytriiodohafnium, triethoxymonoiodohafnium, diethoxydiiodohafnium, monoethoxytriiodohafnium, tripropoxymonoiodohafnium, dipropoxydiiodohafnium, monopropoxytriiodohafnium , Tri-n-butoxymonoiodohafnium, di-n
-Butoxydiiodohafnium, mono-n-butoxytriiodohafnium, tripentyloxymonoiodohafnium, dipentyloxydiiodohafnium, monopentyloxytriiodohafnium, triphenoxymonoiodohafnium, diphenoxydiiodohafnium, monophenoxytriiodo Hafnium, tritolyloxymonoiodohafnium, ditolyloxydiiodohafnium, monotolyloxytriiodohafnium,
Tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodohafnium, tribenzylmonomethoxyhafnium, tribenzylmonoethoxyhafnium, tribenzylmonopropoxyhafnium, tribenzylmonobutoxyhafnium, tribenzylmonophenoxyhafnium , Dibenzyldimethoxyhafnium, dibenzyldiethoxyhafnium, dibenzyldipropoxyhafnium, dibenzyldibutoxyhafnium, dibenzyldiphenoxyhafnium, monobenzyltrimethoxyhafnium, monobenzyltriethoxyhafnium, monobenzyltripropoxyhafnium, monobenzyl Tributoxy hafnium, monobenzyl triphenoxy hafnium, trineophyll mono Toxihafnium, Trineophyll monoethoxy hafnium, Trineophyll monopropoxy hafnium, Trineofil monobutoxy hafnium, Trineophyll monophenoxy hafnium, Dineofil dimethoxy hafnium, Dineofil diethoxy hafnium, Dineofil dipropoxy hafnium , Dineofildibutoxyhafnium, Dineofildiphenoxyhafnium, Mononeophile trimethoxyhafnium, Mononeophile triethoxyhafnium,
Examples include mononeophyll tripropoxy hafnium, mononeophyll tributoxy hafnium, and mononeophyll triphenoxy hafnium. In each of the above-exemplified compounds, R ¹ and R ² in the general formula (1) are linear (normal), but these are iso-,
Structural isomers that are sec-, tert-, and neo-
Of course, it can be used as the component (1).

Among the compounds exemplified above as specific examples, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrabutoxytitanium and tetrabutoxyhafnium are preferable. Particularly preferably, the general formula Zr (O) such as tetraethoxyzirconium, tetrapropoxyzirconium and tetrabutoxyzirconium is used.
R) ₄ is a compound represented by [R = alkyl group].

The component (2) is represented by the following general formula (2). Me ² R ³ _m (OR ⁴ ) _n X ² _zmn (2) In the general formula (2), Me ² is I to III of the periodic table.
Indicates any of the group elements, including lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. In particular III
The tribe is desirable. R ³ and R ⁴ are independently C 1-24,
It is preferably 1 to 12, more preferably 1 to 8 hydrocarbon groups. Hydrocarbon groups that R ³ and R ⁴ can independently take include a methyl group, an ethyl group, a propyl group,
Isopropyl group, cyclopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group,
Alkyl groups such as neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; alkenyl groups such as vinyl group, allyl group, phenyl group, tolyl group, xylyl group, Examples thereof include aryl groups such as mesityl group, indenyl group, and naphthyl group; aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, and neofil group. These hydrocarbon groups may have a branched chain. X ² represents a halogen atom such as fluorine, iodine, chlorine, bromine or a hydrogen atom,
When X ² is a hydrogen atom, Me ² is a Group III element of the periodic table exemplified by boron, aluminum and the like. z is M
represents the valence of e ² , and m and n are 0 ≦ m ≦ z, 0 ≦ n ≦ z
, 0 <m + n ≦ z.

The compound represented by the general formula (2) is No. 1
One kind or a mixture of two or more kinds can be used as the component (2) of the present invention. Specific examples of the compound represented by the general formula (2) are methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, butyl lithium, t-butyl lithium, pentyl lithium,
Octyl lithium, phenyl lithium, benzyl lithium, dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-t-butyl magnesium, dipentyl magnesium, dioctyl magnesium, diphenyl magnesium, dibenzyl magnesium, methyl magnesium chloride, Ethyl magnesium chloride, propyl magnesium chloride, isopropyl magnesium chloride, butyl magnesium chloride, t-butyl magnesium chloride, pentyl magnesium chloride, octyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, methyl magnesium Iodide, ethylmagnesium bromide, ethylmagnesium iodide, propyl bromide, propyl magnesium iodide, isopropyl magnesium bromide,
Isopropyl magnesium iodide, butyl magnesium bromide, butyl magnesium iodide,
t-butyl magnesium bromide, t-butyl magnesium iodide, pentyl magnesium bromide, pentyl magnesium iodide, octyl magnesium bromide, octyl magnesium iodide, phenyl magnesium bromide, phenyl magnesium iodide, benzyl magnesium bromide, benzyl magnesium iodide, dimethyl Zinc, diethyl zinc, dipropyl zinc, diisopropyl zinc, di-n-butyl zinc, di-t-butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, dibenzyl zinc, trimethylboron, triethylboron, tripropylboron, triisopropylboron, tributyl Boron, tri-t-butylboron, tripentylboron, trioctylboron, triphe Ruborone, tribenzylboron, trimethylaluminum, triethylaluminum, diethylaluminium chloride, diethylaluminum bromide, diethylaluminum fluoride, diethylaluminium iodide, ethylaluminum dichloride, ethylaluminium dibromide, ethylaluminium difluoride, ethylaluminium diiodide. , Tripropyl aluminum, dipropyl aluminum chloride, dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide, propyl aluminum dichloride, propyl aluminum dibromide, propyl aluminum difluoride, propyl aluminum diiodide, triisopropyl Luminium, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride, diisopropyl aluminum iodide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, propyl aluminum sesquichloride, propyl aluminum sesquibromide, butyl aluminum sesquichloride, butyl aluminum sesquibromide, Isopropyl aluminum dichloride, isopropyl aluminum dibromide, isopropyl aluminum difluoride, isopropyl aluminum diiodide, tributyl aluminum, dibutyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum fluoride, Dibutyl aluminum iodide, butyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum difluoride, butyl aluminum diiodide, tri sec-
Butyl aluminum, disec-butyl aluminum chloride, disec-butyl aluminum bromide,
Disec-butylaluminum fluoride, disec
-Butyl aluminum iodide, sec-butyl aluminum dichloride, sec-butyl aluminum dibromide, sec-butyl aluminum difluoride, sec-butyl aluminum diiodide, tri-tert-butyl aluminum, di-tert-butyl aluminum chloride, di-tert -Butyl aluminum bromide, di-tert-butyl aluminum fluoride, di-tert-butyl aluminum iodide, tert-butyl aluminum dichloride, te
rt-Butyl aluminum dibromide, tert-butyl aluminum difluoride, tert-butyl aluminum diiodide, triisobutyl aluminum, diisobutyl aluminum chloride, diisobutyl aluminum bromide, diisobutyl aluminum fluoride, diisobutyl aluminum iodide, isobutyl aluminum dichloride, isobutyl Aluminum dibromide, isobutyl aluminum difluoride, isobutyl aluminum diiodide, trihexyl aluminum, dihexyl aluminum chloride, dihexyl aluminum bromide, dihexyl aluminum fluoride, dihexyl aluminum iodide, hexyl aluminum dichloride, hexyl aluminum Mudibromide, hexyl aluminum difluoride, hexyl aluminum diiodide, tripentyl aluminum, dipentyl aluminum chloride, dipentyl aluminum bromide, dipentyl aluminum fluoride, dipentyl aluminum iodide, pentyl aluminum dichloride, pentyl aluminum dibromide, pentyl aluminum difluoride Ride and pentyl aluminum diiodide, methyl aluminum methoxide,
Methyl aluminum ethoxide, methyl aluminum propoxide, methyl aluminum butoxide, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, ethyl aluminum methoxide, ethyl aluminum ethoxide, ethyl aluminum propoxide, ethyl aluminum Butoxide, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, propyl aluminum methoxide, propyl aluminum ethoxide, propyl aluminum propoxide, propyl aluminum butoxide, dipropyl aluminum methoxide, dipropyl aluminum ethoxide. , Dipropyl aluminum propoxide, dipropyl aluminum butoxide, butyl aluminum methoxide, butyl aluminum ethoxide, butyl aluminum propoxide, butyl aluminum butoxide, dibutyl aluminum methoxide, dibutyl aluminum ethoxide, dibutyl aluminum propoxide, dibutyl aluminum butoxide , Dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride,
Diisopropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, methyl aluminum dihydride, ethyl aluminum dihydride, propyl aluminum dihydride, isopropyl aluminum dihydride, butyl aluminum dihydride, isobutyl aluminum dihydride, Examples include hexyl aluminum dihydride, cyclohexyl aluminum dihydride, dimethylboron hydride, diethylboron hydride, methylboron dihydride, ethylboron dihydride and the like.

Among the above compounds, the component (2)
Preferred compounds include trimethylaluminum,
Triethyl aluminum, diethyl aluminum chloride, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, tri-sec-butyl aluminum, tri-tert-butyl aluminum, triisobutyl aluminum, trihexyl aluminum,
Examples include tripentyl aluminum, diisobutyl aluminum hydride, and tridecyl aluminum.

The component (3) of the present invention is a compound which is cyclic and has two or more conjugated double bonds, and one or more of the compounds can be used as the component (3). Examples of the compound that can be used as the component (3) include: 1 or 2 or more carbon rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds, A cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms, wherein the cyclic hydrocarbon compound has 1 to 6 hydrocarbon groups (typically an alkyl group or aralkyl having 1 to 12 carbon atoms) A cyclic hydrocarbon compound partially substituted with a group), having 1 or 2 or more carbocycles having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds, An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12, hydrogen of the above cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon groups. Organosilicon compound having a cyclic hydrocarbon group, Alkali metal salts of the compound shown (sodium or lithium salt), and the like. Among these compounds, those having a cyclopentadiene structure in the molecule are preferable.

One of the cyclic hydrocarbon compounds suitable as the component (3) is represented by the following general formula (3).

Embedded image [In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ^{9 each} independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and any two of the hydrocarbon groups jointly form cyclic carbon atoms. Hydrogen radicals can be formed. ] The hydrocarbon group represented by the general formula (3) includes methyl, ethyl,
It includes an alkyl group such as propyl, butyl, t-butyl, hexyl and octyl, an aryl group such as phenyl, an alkoxy group such as methoxy, ethoxy and propoxy, an aryloxy group such as phenoxy and an aralkyl group such as benzyl. When any two hydrocarbon groups of the general formula (3) cooperate to form a cyclic hydrocarbon group, the skeleton thereof includes cycloheptatriene, aryl and condensed rings thereof. Among the cyclic hydrocarbon compounds represented by the general formula (3), preferred examples include cyclopentadiene, indene, azulene, and the like, as well as alkyl, aryl, aralkyl, alkoxy or aryloxy having 1 to 10 carbon atoms. There are various derivatives substituted with. The cyclic hydrocarbon compound of the general formula (3) is
Alkylene group (its carbon number is usually 2 to 8, preferably 2)
Compounds bonded (crosslinked) via 3 to 3) are also suitably used as the component (3) of the present invention.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula (4). (Cp) _r SiR ¹⁰ _s X ³ _4-rs wherein Cp represents the cyclic hydrocarbon group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R ¹⁰ Is a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, t
-Alkyl groups such as butyl group, pentyl group, hexyl group, octyl group; alkenyl groups such as vinyl group, allyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; phenyl group, tolyl group, xylyl An aryl group such as a group; an aryloxy group such as a phenoxy group; a hydrocarbon having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, as exemplified by an aralkyl group such as a benzyl group, a phenethyl group, a styryl group, and a neofil group. Indicates a residue or hydrogen. This hydrocarbon residue does not necessarily have to be linear (normal), but branched (iso-, se).
c-, tert-, neo-, etc.). X ³ represents a halogen atom such as fluorine, iodine, chlorine or bromine, and r and s are 0 <r ≦ 4 and 0 ≦ s ≦ 3.
And preferably 1 ≦ r + s ≦ 4.

The organic cyclic hydrocarbon compounds usable as the component (3) of the present invention include the following compounds. Cyclopentadiene, methylcyclopentadiene,
Ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene,
Substituted cyclopentadiene such as 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-
Methylindene, 4,7-dimethylindene, 4,5,
A substituted indene such as 6,7-tetrahydroindene,
Substituted cycloheptatriene such as cycloheptatriene and methylcycloheptatriene, substituted cyclooctatetraene such as cyclooctatetraene and methylcyclooctatetraene, and substituted fluorene such as azulene, methylazulene, ethylazulene, fluorene and methylfluorene A cyclopolyene having 7 to 24 carbon atoms or a substituted cyclopolyene,

Monocyclopentadienylsilane, dicyclopentadienylsilane, tricyclopentadienylsilane, tetracyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclo Pentadienyldimethylsilane, Monocyclopentadienyldiethylsilane, Monocyclopentadienyltrimethylsilane, Monocyclopentadienyltriethylsilane, Monocyclopentadienylmonomethoxysilane, Monocyclopentadienylmonoethoxysilane, Monocyclo Pentadienylmonophenoxysilane, Monocyclopentadienylmonomethylmonochlorosilane, Monocyclopentadienylmonoethylmonochlorosilane, Monocyclopentadienylmonomethyldichlorosilane Silane, monocyclopentadienyl monoethyldichlorosilane, monocyclopentadienyl trichlorosilane, dicyclopentadienyl monomethylsilane, dicyclopentadienyl monoethylsilane, dicyclopentadienyl dimethylsilane, dicyclopentadienyl Diethylsilane, dicyclopentadienylmethylethylsilane, dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane,
Dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane, dicyclopentadienylmethylchlorosilane, dicyclopentadienylethylchlorosilane, dicyclopentadienyldichlorosilane, dicyclopentadienylmonomethoxysilane, Dicyclopentadienyl monoethoxysilane, Dicyclopentadienyl monomethoxy monochlorosilane, Dicyclopentadienyl monoethoxy monochlorosilane, Tricyclopentadienyl monomethylsilane, Tricyclopentadienyl monoethylsilane, Tricyclopentadiene Ethyl monomethoxysilane, tricyclopentadienyl monoethoxysilane, tricyclopentadienyl monochlorosilane, 3-methylcyclopentadienylsilane, bis-3-methylcyclo 1,3-dimethylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane,

Monoindenylsilane, diindenylsilane, triindenylsilane, tetraindenylsilane,
Monoindenyl monomethylsilane, monoindenyl monoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane , Monoindenyl monophenoxysilane, monoindenyl monomethyl monochlorosilane, monoindenyl monoethyl monochlorosilane, monoindenyl monomethyl dichlorosilane, monoindenyl monoethyl dichlorosilane, monoindenyl trichlorosilane, diindenyl monomethylsilane, Diindenylmonoethylsilane, diindenyldimethylsilane, diindenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, Indenyl ethylpropyl silane,
Diindenyldiephenylsilane, diindenylphenylmethylsilane, diindenylmethylchlorosilane, diindenylethylchlorosilane, diindenyldichlorosilane, diindenylmonomethoxysilane, diindenylmonoethoxysilane, diindenylmonosilane Methoxymonochlorosilane, diindenylmonoethoxymonochlorosilane, triindenylmonomethylsilane, triindenylmonoethylsilane, triindenylmonomethoxysilane, triindenylmonoethoxysilane, triindenylmonochlorosilane, 3-methylindenyl Silane, bis-3-methylindenylsilane, 3-methylindenylmethylsilane, 1,2-dimethylindenylsilane,
1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, pentamethylindenylsilane, and the like. Preferred are cyclopentadiene, substituted cyclopentadiene, indene, substituted indene and the like.

Further, any one of the above-mentioned compounds may be an alkylene group (the carbon number of which is usually 2-8, preferably 2
Compounds bound via 3) can also be used as component (3) of the present invention, such compounds include, for example, bisindenylethane, bis (4,5,6,7-tetrahydro-1- Indenyl) ethane, 1,3-propanedienylbisindene, 1,3-propanedienylbis (4
5,6,7-Tetrahydro) indene, propylylene bis (1-indene), isopropylylene (1-indenyl) cyclopentadiene, diphenylmethylene (9-
Fluorenyl) cyclopentadiene, isopropylidenecyclopentadienyl-1-fluorene and the like.

The component (4) of the present invention contains 1 to 10 in the molecule.
It is a modified organoaluminum compound having 0, preferably 1 to 50 Al-O-Al bonds. Such a modified organoaluminum compound is usually a reaction product obtained by reacting an organoaluminum compound and water in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include aliphatic hydrocarbons (eg, pentane, hexane, heptane, etc.), alicyclic hydrocarbons (eg, cyclohexane, methylcyclohexane, etc.) and aromatic hydrocarbons (eg, benzene, toluene, xylene). Etc.) can be used, but it is preferable to use an aliphatic hydrocarbon or an aromatic hydrocarbon. The organoaluminum compound used for preparing the modified organoaluminum compound has the following general formula (5):
Can be shown as ^{_{R 11 t AlX 4 3-t}} (5) [ wherein, R ¹¹ is 1 to 18 carbon atoms, preferably 1 to 12 alkyl group, an alkenyl group, an aryl group, a hydrocarbon group, an aralkyl group, X ⁴ Represents a hydrogen atom or a halogen atom, and t represents an integer of 1 ≦ t ≦ 3.] Of these, trialkylaluminum is preferable. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable. The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is 0.25 / 1 to 1.2 / 1.
In particular, it is preferably 0.5 / 1 to 1/1, and the reaction temperature is usually -70 to 100 ° C, preferably -20 to 20 ° C. The reaction time is usually 5 minutes to 24 hours, preferably 10
It is selected in the range of minutes to 5 hours. As water required for the reaction, so-called water can be used, and also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can be used. Incidentally, among the modified organoaluminum compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxane, and particularly methylaluminoxane (or one substantially consisting of methylaluminoxane) is Suitable as component (4). As a matter of course, as the component (4) of the present invention, two or more kinds of the above modified organoaluminum compounds may be used in combination, and the modified organoaluminum compound may be dissolved or dispersed in the above-mentioned inert hydrocarbon solvent. You may use what was made into the solution.

As the component (5) of the present invention, an inorganic carrier and / or a particulate polymer carrier is used. The inorganic carrier may be in any shape such as powder, granules, flakes, foil or fibrous as long as it retains its original shape in the step of preparing the catalyst of the present invention. The maximum diameter is usually 5
Those in the range of 200 μm, preferably 10 to 150 μm are suitable. The inorganic carrier is preferably porous, and usually has a surface area of 30 to 1000 m ² /
g, the pore volume is in the range of 0.1 to ³ cm ³ / g. As the inorganic carrier of the present invention, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used, and these are usually in the air at 200 to 900 ° C. or in nitrogen, argon, etc. It is used by firing in an inert gas. Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like. As the metal oxide, Group I to Group V of the periodic table
Examples thereof include single oxides or complex oxides of elements selected from Group III, such as SiO ₂ , Al ₂ O ₃ , MgO and Ca.
O, B ₂ O ₃ , TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , Al ₂ O ₃ ·
MgO, Al ₂ O ₃ · CaO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃
・ MgO ・ CaO, Al ₂ O ₃・ MgO ・ SiO ₂ , Al ₂ O
₃・ CuO, Al ₂ O ₃・ Fe ₂ O ₃ , Al ₂ O ₃・ NiO, S
Examples thereof include various natural or synthetic multiple oxides such as iO ₂ .MgO. Here, the above formula does not represent a molecular formula but represents only the composition, and the structure and component ratio of the multiple oxide used in the present invention are not particularly limited. Further, the metal oxide used in the present invention may absorb a small amount of water and may contain a small amount of impurities. As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples thereof include magnesium carbonate, calcium carbonate and barium carbonate. Examples of the carbonaceous material include carbon black and activated carbon. Any of the above inorganic carriers can be preferably used in the present invention, but the use of metal oxide, silica, alumina and the like is particularly preferable.

As the particle polymer carrier, either a thermoplastic resin or a thermosetting resin can be used as long as it does not melt and remains solid during catalyst preparation and polymerization reaction. Is usually 5 to 2000 μm, preferably 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction, and can be arbitrarily selected from low molecular weight to ultra high molecular weight. It can be used.
When specific examples of the particle polymer carrier are enumerated, various polyolefins (preferably carbon) represented by particulate ethylene polymers, ethylene / α-olefin copolymers, propylene polymers or copolymers, poly-1-butene and the like are preferable. Number 2
12), polyester, polyamide, polyvinyl chloride,
Examples include polymethyl methacrylate, polymethyl acrylate, polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and particulate polymer carrier can be used as they are as the component (5) of the present invention. Prior to their use, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-n-aluminum. An organoaluminum compound such as hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylmonoethoxyaluminum, or a modified organoaluminum compound containing an Al-O-Al bond (this compound was exemplified in the aforementioned component (4)) It is the same as the compound) or a pretreatment consisting of contact with a silane compound or the like. Speaking of inorganic carriers, alcohol, active hydrogen-containing compounds such as aldehydes, esters, electron-donating compounds such as ethers, tetraalkoxysilicates, trialkoxyaluminum, alkoxide machine-containing compounds such as transition metal tetraalkoxides, etc., A method of contacting in advance and then using it as the component (5) is also preferably used. Examples of the contact treatment method include aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene and ethylbenzene, heptane, hexane, decane, dodecane and cyclohexane, usually in an inert atmosphere such as nitrogen or argon. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually 5 to 12) such as
A method of bringing the carrier into contact with the pretreatment compound with or without stirring is included. This contact is usually -100
C. to 200.degree. C., preferably -50.degree. C. to 100.degree. C., for 30 minutes to 50 hours, preferably 1 hour to 24 hours. The contact reaction is preferably carried out in a solvent in which the pretreatment compound is soluble, that is, an aromatic hydrocarbon (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene and ethylbenzene. In this case, after the contact reaction, the solvent can be directly used for the preparation of the contact component of the present invention without removing the solvent. Further, in the contact reaction product, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or sparingly soluble (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, decane, dodecane, cyclohexane). Such as aliphatic or alicyclic hydrocarbon) to precipitate component (5) as a solid component and dry it, or part or all of aromatic hydrocarbon which is a solvent solution at the time of pretreatment, After removal by means such as drying, the component (5) can be taken out as a solid component. The ratio of the inorganic carrier and / or the particulate polymer carrier to be subjected to the pretreatment and the pretreatment compound is not particularly limited as long as the object of the present invention is not impaired, but usually 1 to 10000 mmol per 100 g of the carrier, It is preferably selected within the range of 5 to 1500 mmol (however, in the modified aluminum compound, the Al atom concentration).

As described above, the olefin polymerization catalyst of the present invention comprises contacting the component (1), the component (2), the component (3), the component (4), and optionally the component (5) with each other. The contact order of these components is not particularly limited. For example, in the case of contacting the components (1) to (4) to obtain the catalyst of the present invention, <1> a method of simultaneously adding the components (1), (2), (3) and (4). <2> Contact the components (1), (2), and (3) at the same time,
Next, a method of contacting the component (4). (Hereinafter, the case of simultaneous contact is represented by {}, and the case of sequential contact is represented by →. For example, in the case of <2>, {(1) (2) (3)} → (4) is displayed. ) <3> {(1) (2) (4)} → (3) <4> {(1) (3) (4)} → (2) <5> {(2) (3) (4) } → (1) <6> {(1) (2)} → {(3) (4)} <7> {(1) (3)} → {(2) (4)} <8> {( 1) (4)} → {(2) (3)} <9> {(1) (2)} → (3) → (4) <10> {(1) (2)} → (4) → (3) <11> {(1) (3)} → (2) → (4) <12> {(1) (3)} → (4) → (2) <13> {(1) (4 )} → (2) → (3) <14> {(1) (4)} → (3) → (2) <15> {(2) (3)} → (1) → (4) <16 > {(2) (3)} → (4) → (1) <17> {(2) (4)} → (1) → (3) <18> {(2) (4)} → (3) → (1) <19> {(3) (4)} → (1) → (2) <20> {(3) (4)} → (2) → (1) <21> (3) → ((1) (2)} → (4) <22> (4 ) → ((1) (2)} → (3) <23> (2) → ((1) (3)} → (4) <24> (4) → ((1) (3)} → ( 2) <25> (2) → {(1) (4)} → (3) <26> (3) → {(1) (4)} → (2) <27> (1) → {(2 ) (3)} → (4) <28> (4) → {(2) (3)} → (1) <29> (1) → {(2) (4)} → (3) <30> (3) → {(2) (4)} → (1) <31> (1) → {(3) (4)} → (2) <32> (2) → {(3) (4)} → Examples include contact sequence such as (1), among which <1>2><5><7><11><15><23><27> While it is also arbitrary preferably .4 component contact method employed, usually in an inert atmosphere such as nitrogen or argon,
In the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene and xylene, usually -100 ° C to 2
Component (1), component (2), component (3) and component (4) at a temperature of 00 ° C, preferably -50 ° C to 150 ° C.
Is used for 5 minutes to 250 hours, preferably 30 minutes to 24 hours. When each component is contacted in an inert hydrocarbon solvent, the produced catalyst may be directly subjected to polymerization in a solution state after completion of all contact reactions, or if possible, precipitation, drying, etc. By means of
After being once taken out as a solid catalyst component, it may be used for polymerization. Of course, the contact reaction of each component may be performed multiple times.

When the catalyst of the present invention is obtained by contacting the components (1) to (5), the components (1) to (32) may be contacted in the order of <33> to <32>.
A method of preparing the reaction product of (4) and contacting it with the component (5). ({(1) (2) (3) (4)} →
(5)) <34> (5) → (4) → {(1) (2) (3)} <35> (5) → (4) → {(1) (2)} → (3 ) <36> (5) → (4) → {(1) (3)} → (2) <37> (5) → (4) → {(2) (3)} → (1) <38> (5) → (4) → (3) → {(1) (2)} <39> (5) → (4) → (2) → {(1) (3)} <40> (5) → (4) → (1) → {(2) (3)} <41> (5) → (4) → (1) → (2) → (3) <42> (5) → (4) → ( 1) → (3) → (2) <43> (5) → (4) → (2) → (3) → (1) <44> (5) → (4) → (2) → (1) → (3) <45> (5) → (4) → (3) → (1) → (2) <46> (5) → (4) → (3) → (2) → (1) <47 > (5) → (1) → {(2) (3) (4)} <48> (5) → (1) → { 2) (3)} → (4) <49> (5) → (1) → {(2) (4)} → (3) <50> (5) → (1) → {(3) (4 )} → (2) <51> (5) → (1) → (4) → {(2) (3)} <52> (5) → (1) → (3) → {(2) (4 )} <53> (5) → (1) → (2) → {(3) (4)} <54> (5) → (1) → (2) → (3) → (4) <55> (5) → (1) → (2) → (4) → (3) <56> (5) → (1) → (3) → (2) → (4) <57> (5) → (1 ) → (3) → (4) → (2) <58> (5) → (1) → (4) → (2) → (3) <59> (5) → (1) → (4) → (3) → (2) <60> (5) → (2) → {(1) (3) (4)} <61> (5) → (3) → {(1) (2) (4) } Etc. can be adopted. In these contact sequences, <3
3><34><47> are preferably used. Ingredient (1) ~
The contact of (5) is generally carried out in an inert atmosphere such as nitrogen or argon, in general, an aromatic hydrocarbon such as benzene, toluene, xylene and ethylbenzene, an aliphatic such as heptane, hexane, decane, dodecane, cyclohexane or an alicyclic ring. It is carried out with or without stirring in the presence of a liquid inert hydrocarbon such as a group hydrocarbon. In particular, it is preferable to carry out in a solvent in which the components (1) to (4) are soluble, that is, in an aromatic hydrocarbon such as benzene, toluene, xylene, and ethylbenzene. This contact is usually -100 ~
5 at a temperature of 200 ° C, preferably -50 to 150 ° C
It is desirable to carry out the treatment for minutes to 250 hours, preferably 30 minutes to 24 hours. Upon contacting the components (1) to (5), as described above, an aromatic hydrocarbon solvent in which a certain component is soluble and an aliphatic or alicyclic hydrocarbon in which a certain component is insoluble or sparingly soluble. Although any solvent can be used, it is particularly preferable to use an aromatic hydrocarbon in which the components (1) to (4) are soluble as a solvent. Then, in the case of carrying out the stepwise contact reaction of each component, without removing any of the soluble aromatic hydrocarbon solvent used in the previous stage,
This may be used as it is as a solvent for the subsequent catalytic reaction.
In addition, after the first-stage catalytic reaction using a soluble solvent, a liquid inert hydrocarbon in which a certain component is insoluble or sparingly soluble (for example, an aliphatic or alicyclic hydrocarbon such as pentane, hexane, decane, dodecane, cyclohexane). ) Is added and the desired product is removed as a solid, then the subsequent catalytic reaction of the desired product can be carried out using any of the inert hydrocarbon solvents described above. In the present invention, the contact reaction of each component may be carried out multiple times.

Components (1) to (1) for preparing the catalyst of the present invention
The ratio of (4) or components (1) to (5) to be used is such that the component (2) is usually 0.01 to 1 with respect to 1 mol of the component (1).
000 mol, preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol, and component (3) is usually 0.01 to 1000 mol, preferably 0.1 to 100 mol, more preferably In the range of 0.5 to 50 mol, the component (4) is usually 1 to 10,000 mol, preferably 5-1.
It is used in an amount of 000 mol, more preferably 10 to 500 mol. When component (5) is used in combination, the proportion of component (1) used is usually 5 mmol or less, preferably 0.0001 to 5 mmol, and preferably 0.001 to 0. It is desirable that the proportion is 5 mmol, more preferably 0.01 to 0.1 mmol.
The catalyst of the present invention obtained by bringing the components (1) to (4) or the components (1) to (5) into contact with each other is a halogen having a C—X bond (X: halogen such as fluorine), if desired. It may be used in combination with a compounded hydrocarbon compound, a halogenated oxygen-containing compound, a halogen / carbon compound or a sulfide, and a borane or a borate which does not correspond to the component (2).

In the polymerization method of the present invention, olefins are polymerized or co-polymerized in the presence of the above catalyst in the presence of one or more hydrocarbon compounds selected from saturated hydrocarbon compounds and aromatic hydrocarbon compounds. The hydrocarbon compound to be polymerized but coexisting in the polymerization reaction system is at room temperature (usually
Use liquid or gas at atmospheric pressure (about 25 ° C). The present invention is characterized in that the molecular weight of the produced polymer can be changed by the presence or absence of the hydrocarbon compound or the increase or decrease of the amount of the hydrocarbon compound. The saturated hydrocarbon compound that is involved in controlling the molecular weight usually has 1 to 2 carbon atoms.
4, preferably a chain hydrocarbon having 1 to 12 carbon atoms (whether linear or branched) and cyclic hydrocarbon, and the aromatic compound is usually It has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms. Specifically, methane, ethane, propane, n
-Butane, isobutane, 2,2 dimethylpropane, n-
Pentane, isopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2
-Dimethylbutane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethyl Pentane, 3,3-dimethylpentane, 2,2,3-
Trimethylbutane, cycloheptane, methylcyclohexane, ethylcyclopentane, n-octane, 2-methylheptane, 3-methylheptane, 2,2-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3, 4-dimethylhexane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane,
Cyclooctane, ethylcyclohexane, n-nonane,
Saturated aliphatic or alicyclic hydrocarbons such as n-decane, cyclodecane, n-undecane, n-dodecane, n-tridecane, n-tetradecane and n-pentadecane, and aromatics such as ethylbenzene, toluene, xylene and mesitylene. Hydrocarbons are used for molecular weight control purposes. Among them, it is preferable to use methane, ethane, propane, 2,2-dimethylpropane, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, cyclooctane, n-decane, toluene, xylene and the like. . These compounds can be used as a mixture of two or more kinds. The amount of hydrocarbon used to control the molecular weight is 0.001 with respect to 1 g of the catalyst.
To 100 mol, preferably 0.005 to 50 mol, and more preferably 0.01 to 10 mol.

In the method of the present invention, olefins are homopolymerized or copolymerized. The olefins referred to in the present invention include α-olefins, cyclic olefins, dienes and trienes. α-olefins include
Those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms are included,
Specific examples include ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1 and the like. α
-Olefins can be homopolymerized and 2
It is also possible to copolymerize more than one type of α-olefin,
The copolymerization may be any of alternating copolymerization, random copolymerization and block copolymerization. For the copolymerization of α-olefins, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, such as ethylene and 3 to 1 carbon atoms are used.
When 2, 2, preferably 3-8 α-olefins are copolymerized, propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1,
Probylene and hexene-1, propylene and octene-1
And propylene and a carbon number of 3 to 12, preferably 3
The case of copolymerizing with .alpha.-olefin of .about.8 is included.
When copolymerizing ethylene or propylene with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of the total monomers,
Generally, in the case of ethylene copolymer, 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol%
In the propylene copolymer, 1 to 90 mol%, preferably 5 to 90 mol%, more preferably 10
It is selected in the range of up to 70 mol%. As the cyclic olefin, those having 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms can be used in the present invention, and examples thereof include cyclopentene, cyclobutene, cyclopentene, cyclohexene,
3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5
-Methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-
Dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, ethylidene norbornene and the like are included. The cyclic olefin is usually copolymerized with the above-mentioned α-olefin, and in this case, the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. It is in the range of%. Dienes and trienes that can be used as raw material monomers have 4 carbon atoms.
26, preferably 6 to 26 polyenes. Specifically, butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene. , 1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-
1,5-heptadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-octadiene, 2,
Examples thereof include 3 dimethyl butadiene, ethylidene norbornene, dicyclopentadiene, isoprene, 1,3,7-octatriene, and 1,5,9-decatriene.
When a chain diene or triene is used as a monomer in the present invention, it is usually copolymerized with the above-mentioned α-olefin, but the content of the chain diene and / or triene in the copolymer is , Generally in the range of 0.1 to 50 mol%, preferably 0.2 to 10 mol%.

The polymerization reaction of the present invention can be carried out in a substantially gas phase state and in a state where oxygen, water and the like are substantially cut off. The polymerization conditions are temperature 20 to 200 ° C., preferably 50 to 120 ° C., pressure and atmospheric pressure to 70 kg / cm ² G, preferably atmospheric pressure to 20 kg / cm ² G, and polymerization time is 5 minutes to 20 hours. It is usual that 30 minutes to 10 hours are preferably adopted. Further, the saturated hydrocarbon and / or aromatic hydrocarbon added to the reaction system for the purpose of controlling the molecular weight may be in a gaseous state or a liquid state under the polymerization reaction conditions. In some cases it may be desirable to have them dispersed in the reactants. The molecular weight of the produced polymer is controlled by supplying an appropriate amount of a saturated hydrocarbon compound and / or an aromatic hydrocarbon compound to the reactor before and / or after the initiation of the polymerization reaction. The method of supplying to the reactor is, prior to the supply of the catalyst,
A method of entraining with a scavenger supplied to remove impurities in the reactor, a method of entraining with a raw material monomer,
Alternatively, it may be supplied by any method, and it may be introduced into the reactor together with both the scavenger and the raw material monomer. Further, even after the polymerization is substantially started, it is accompanied by an inert gas and / or olefins,
It is also possible to feed to the reactor. As the scavenger, organoaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, the above-mentioned modified organoaluminum compound, and modified organoaluminum containing a branched alkyl can be used. Further, one of the features of the present invention is that the molecular weight of the produced polymer can be adjusted by allowing a saturated hydrocarbon and / or an aromatic hydrocarbon to coexist in the reaction system. , This means that the polymerization conditions (temperature,
It does not mean that the present invention excludes the use of means for controlling the molecular weight of the produced polymer by adjusting the pressure, the amount of catalyst used, the hydrogen partial pressure, etc.). Furthermore, the present invention can be applied to a multi-stage polymerization method using two or more reaction stages under different polymerization conditions without any trouble.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods. Melt Flow Rate (MFR) ASTM D 1238-57T 190 ° C, 2.16
It was measured based on kg load. It was calculated by number average molecular weight (Mn) gel permeation chromatography (manufactured by Waters, model type 150-C type) using orthodichlorobenzene as a solvent and a measurement temperature of 135 ° C. Example 1 (A) Preparation of catalyst Under a nitrogen atmosphere, 10 ml of purified toluene was added to a 100 ml three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube, and then 0.11 g of tetrapropoxyzirconium.
1,2,2-bisindenylethane (0.1 g) and triisobutylaluminum (0.7 g) were added, and the mixture was stirred and reacted for 2 hours under heated reflux conditions. Next, a toluene solution of methylaluminoxane (made by Schering Co., concentration 3.1 mmo
11 ml of 1 Al / ml) was added, and the mixture was reacted with stirring at room temperature for 1 hour. (B) Polymerization A 3 L capacity stainless steel autoclave equipped with a stirrer was replaced with nitrogen, 200 g of sea sand heat-treated with acid and heat-treated at 300 ° C. was introduced therein, and sufficiently dried at 80 ° C. under reduced pressure. Next, 2 ml of the above catalyst solution was added, then 3.9 ml (30 mmol) of hexane was added, and ethylene and 1-butene (butene / ethylene = 0.
The total pressure is 9 Kgf while continuously supplying the mixed gas of 2).
/ Cm ² G, and polymerization was carried out at 80 ° C for 2 hours.
Catalyst efficiency is 134 kg / g Zr, MFR is 4.5 g
/ 10 min, Mn was 39800. Example 2 In Example 1, the amount of hexane supplied during the polymerization was 1.
Polymerization was performed in the same manner as in Example 1 except that the amount was changed to 3 ml (10 mmol). The catalyst efficiency was 130 kg / gZr, MFR was 3.5 g / 10 min, and Mn was 47200. Comparative Example 1 The procedure of Example 1 was repeated, except that hexane was not supplied during the polymerization. Catalyst efficiency is 1
32 kg / g Zr, MFR is 3.0 g / 10 min, M
n was 52300. Example 3 (A) Preparation of solid catalyst Under a nitrogen atmosphere, 100 ml of purified toluene in a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube.
2.0 g of tetrapropoxy zirconium
And 1.9 g of methylcyclopentadiene and 2.1 g of triethylaluminum were added, and the mixture was reacted with stirring under heating and refluxing conditions for 2 hours. Next, a toluene solution of methylaluminoxane (made by Schering, concentration 3.1 mmol Al / m
l) 195 ml was added, and the mixture was reacted with stirring at room temperature for 1 hour.
Under a nitrogen atmosphere, in a 1 L three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube, 150 g of silica (Fuji-Davison # 952) preliminarily calcined at 500 ° C. for 7 hours was put, and the flask was heated to 150 ° C. for 1 hour. It was dried under reduced pressure. After completion of the drying, the flask was cooled to room temperature, the catalyst component solution obtained above was added thereto, and the reaction was carried out at room temperature for 1 hour. Then, the flask is heated to 40 ° C.,
The resulting slurry solution was dried under reduced pressure for 60 minutes to remove the solvent, thereby obtaining 201 g of a solid catalyst having good fluidity. (B) Polymerization After the autoclave made of stainless steel with a stirrer and having a capacity of 3 L was replaced with nitrogen, the inside of the autoclave was heated to 75 ° C.
The temperature was raised to. Then, in order to perform scavenging in the polymerization system, a toluene diluted solution of triethylaluminum (1 mm
hexane / 3.9)
Add ml (30 mmol) and add ethylene and butene-1.
Mixed gas (butene-1 / ethylene molar ratio 0.15) so as to be 8 Kgf / cm ² G, 100 mg (Zr = 0.27 mg) of the solid catalyst obtained above was supplied to start polymerization, Polymerization was carried out for 2 hours while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05) while maintaining the total pressure at 9 Kgf / cm ² G. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 45 g of a white polymer.
At this time, the catalyst efficiency was 166 Kg / gZr. The MFR of this white polymer was measured and found to be 1.2 g /
It was 10 min and Mn was 67300. Example 4 The amount of solid catalyst used in Example 3 was 107 mg (Z
r = 0.29 mg) and the amount of hexane added was 1.3.
The experiment was performed in the same manner as in Example 3 except that the amount was changed to ml (10 mmol). After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 48 g of a white polymer. The catalyst efficiency was 166 Kg / gZr. When the MFR of this white polymer was measured, it was 0.97 g / 10min and Mn was 70800. Example 5 In Example 3, the amount of solid catalyst used was 98 mg (Z
r = 0.27 mg) and the amount of hexane added is 0.2
An experiment was conducted in the same manner as in Example 3 except that the amount was 6 ml (2 mmol). After the completion of the polymerization, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 46 g of a white polymer. The catalyst efficiency was 170 Kg / gZr. When the MFR of this white polymer was measured, it was 0.90 g / 10min and Mn was 72300. Comparative Example 2 The amount of solid catalyst used in Example 3 was 111 mg (Z
The experiment was performed in the same manner as in Example 3 except that r = 0.30 mg) and no hydrocarbon component was added. After the completion of polymerization, discharge excess gas, cool and take out the contents,
50 g of white polymer was obtained. Catalyst efficiency is 167 Kg / g
It was Zr. When the MFR of this white polymer was measured, it was 0.85 g / 10 min, and Mn was 7530.
It was 0. Example 6 (A) Preparation of solid catalyst Under a nitrogen atmosphere, 100 ml of purified toluene in a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube.
2.0 g of tetrapropoxy zirconium
And 5.6 g of indene and 9.2 g of triisobutylaluminum are added, and the mixture is reacted under stirring under heating and refluxing for 2 hours.
A transition metal catalyst component was prepared. Next, a toluene solution of methylaluminoxane (made by Schering, concentration 3.1m)
195 ml of (molAl / ml) was added, and the mixture was reacted with stirring at room temperature for 1 hour. Under a nitrogen atmosphere, a 1 L three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube was preheated to 500 ° C.
Silica (Fuji Devison # 95 # 95)
2) 150 g was added, the flask was heated to 150 ° C., and dried under reduced pressure for 1 hour. After the completion of drying, the flask was cooled to room temperature, the catalyst component solution obtained above was added, and the mixture was reacted at room temperature for 1 hour. Next, the flask is heated to 40 ° C., and the obtained slurry solution is dried under reduced pressure for 60 minutes to remove the solvent, whereby the solid catalyst 19 having good fluidity is obtained.
9 g were obtained. (B) Polymerization After the autoclave made of stainless steel with a stirrer and having a capacity of 3 L was replaced with nitrogen, the inside of the autoclave was heated to 75 ° C.
The temperature was raised to. Then, in order to perform scavenging in the polymerization system, a toluene diluted solution of triethylaluminum (1 mm
ol / ml) and added 10 ml of solid catalyst.
6 mg (Zr = 0.29 mg) was supplied. Next, 5.4 ml (50 mmol) of cyclohexane was mixed with a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.
15) Initiated polymerization with 9 Kgf / cm ² G. After the initiation of the polymerization, while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.05), the total pressure was maintained at 9 Kgf / cm ² G and the polymerization was carried out for 2 hours. .. After the completion of the polymerization, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 43 g of a white polymer.
At this time, the catalyst efficiency was 148 Kg / gZr. When the MFR of this white polymer was measured, it was 8.5 g /
It was 10 min and Mn was 36500. Example 7 In Example 6, the amount of solid catalyst used was 111 mg.
An experiment was performed in the same manner as in Example 6 except that (Zr = 0.30 mg) and methylcyclopentane (5.6 ml, 50 mmol) were added. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 45 g of a white polymer. The catalyst efficiency was 150 Kg / gZr. When the MFR of this white polymer was measured, it was 8.3 g / 10.
min and Mn was 36900. Example 8 In Example 6, the amount of solid catalyst used was 95 mg (Z
r = 0.26 mg) and isobutane 2.9 g (50
The experiment was performed in the same manner as in Example 6 except that the addition was performed. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 40 g of a white polymer. Catalyst efficiency is 1
It was 55 Kg / gZr. MFR of this white polymer
Was measured to be 8.6 g / 10 min, and Mn
Was 36200. Example 9 The amount of solid catalyst used in Example 6 was 110 mg.
(Zr = 0.30 mg) and 1.2 g of isobutane
An experiment was conducted in the same manner as in Example 6 except that (20 mmol) was added. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 48 g of a white polymer. The catalyst efficiency was 160 Kg / gZr. When the MFR of this white polymer was measured, it was 7.2 g / 10 min and Mn was 37,700. Comparative Example 3 The amount of solid catalyst used in Example 6 was 111 mg (Z
The experiment was performed in the same manner as in Example 6 except that r = 0.30 mg) and no hydrocarbon component was added. After completion of the polymerization, discharge excess gas, cool and take out the contents,
47 g of white polymer was obtained. Catalyst efficiency is 156Kg / g
It was Zr. When the MFR of this white polymer was measured, it was 6.5 g / 10 min, and Mn was 38300.
Met. Example 10 (A) Preparation of solid catalyst Under a nitrogen atmosphere, 100 ml of purified toluene in a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube.
Then, 2.3 g of tetrabutoxyzirconium, 3.2 g of cyclopentadiene and 13.1 g of triethylaluminum were added, and the mixture was stirred and heated under a reflux condition for 2 hours. Next, a toluene solution of methylaluminoxane (Schelling Co., concentration 3.1 mmol Al / ml) 1
95 ml was added, and the mixture was reacted with stirring at room temperature for 1 hour. Attached electromagnetic induction stirrer and cooling pipe under nitrogen atmosphere 1
Into an L three-necked flask, 150 g of alumina which had been preliminarily calcined at 500 ° C. for 7 hours was put, the flask was heated to 150 ° C. and dried under reduced pressure for 1 hour. After the drying is completed, the flask is cooled to room temperature, the above catalyst component solution is added, and the mixture is allowed to stand at room temperature
Allowed to react for hours. Next, the flask is heated to 40 ° C., and the obtained slurry solution is dried under reduced pressure for 60 minutes to remove the solvent, thereby obtaining 190 g of a solid catalyst having good fluidity.
I got (B) Polymerization After the autoclave made of stainless steel with a stirrer and having a capacity of 3 L was replaced with nitrogen, the inside of the autoclave was heated to 75 ° C.
The temperature was raised to. Then, in order to perform scavenging in the polymerization system, a toluene diluted solution of triethylaluminum (1 mm
ol / ml) and added 10 ml of solid catalyst.
6 mg (Zr = 0.29 mg) was supplied. Then, 3.9 ml (30 mmol) of n-hexane was mixed with a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.1.
5) Coupling polymerization was started with 9 Kgf / cm ² G. After the initiation of the polymerization, while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.05), the total pressure was maintained at 9 Kgf / cm ² G and the polymerization was carried out for 2 hours. .. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 41 g of a white polymer. The catalyst efficiency at this time was 141 Kg / gZr. When the MFR of this white polymer was measured, it was 4.3 g / 10.
min and Mn was 41200. Comparative Example 4 The amount of the solid catalyst used in Example 10 was 111 mg.
An experiment was conducted in the same manner as in Example 10 except that (Zr = 0.30 mg) and no hydrocarbon component was added. After the polymerization was completed, the excess gas was discharged and the contents were taken out by cooling to obtain 41 g of a white polymer. Catalyst efficiency is 138K
It was g / gZr. When the MFR of this white polymer was measured, it was 3.1 g / 10 min, and Mn was 51.
It was 200. Example 11 (A) Preparation of solid catalyst Under nitrogen atmosphere, 100 ml of purified toluene in a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube.
2.0 g of tetrapropoxy zirconium
And 1.9 g of methylcyclopentadiene and 2.1 g of triethylaluminum were added, and the mixture was stirred and reacted for 2 hours under the condition of heating under reflux. Next, a toluene solution of methylaluminoxane (made by Schering, concentration 3.1 mmol Al / m
l) 195 ml was added, and the mixture was reacted with stirring at room temperature for 1 hour.
Under a nitrogen atmosphere, styrene-divinylbenzene copolymer beads (manufactured by Organo) 1 that had been sufficiently dried in a 1 L three-necked flask equipped with an electromagnetic induction stirrer and a cooling tube 1
50 g was charged, the flask was heated to 90 ° C., and dried under reduced pressure for 1 hour. After completion of the drying, the flask was cooled to room temperature, the catalyst component solution obtained above was added thereto, and the reaction was carried out at room temperature for 1 hour. Next, the flask is heated to 40 ° C., and the obtained slurry solution is dried under reduced pressure for 60 minutes to remove the solvent, whereby the solid catalyst 201 having good fluidity is obtained.
g was obtained. (B) Polymerization After the autoclave made of stainless steel with a stirrer and having a capacity of 3 L was replaced with nitrogen, the inside of the autoclave was heated to 75 ° C.
The temperature was raised to. Then, in order to perform scavenging in the polymerization system, a toluene diluted solution of triethylaluminum (1 mm
ol / ml) and added 10 ml of solid catalyst.
6 mg (Zr = 0.29 mg) was supplied. Next, 0.5 L (22 mmol) of ethane was mixed with 9 K of a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.15).
Infiltration polymerization was initiated with gf / cm ² G. After initiation of polymerization, a mixed gas of ethylene and butene-1 (butene-1
/ Ethylene molar ratio of 0.05) was continuously supplied while maintaining the total pressure at 9 Kgf / cm ² G to carry out polymerization for 2 hours. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 38 g of a white polymer. At this time, the catalyst efficiency was 130 Kg / gZr. When the MFR of this white polymer was measured, it was 1.03 g / 10 min.
And Mn was 69500. Comparative Example 5 The amount of solid catalyst used in Example 11 was 98 mg (Z
The experiment was performed in the same manner as in Example 11 except that r = 0.27 mg) and ethane was not added. After polymerization,
Excess gas was discharged, cooled and the contents were taken out to obtain 36 g of white polymer. The catalyst efficiency is 132Kg / gZr
Met. When the MFR of this white polymer was measured, it was 0.90 g / 10 min, and Mn was 72,300.
Met. Example 12 (A) Preparation of solid catalyst It was prepared in the same manner as in Example 6. (B) Polymerization Using a stainless steel autoclave equipped with a stirrer in a gas phase polymerization apparatus, a loop was formed by a blower, a flow rate controller and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water into a jacket. The solid catalyst obtained in (A) was placed in an autoclave adjusted to 60 ° C.
0 mg / h and 80 ml / h of hexane (0.6 mo
1 / h) and each gas was supplied while controlling the butene-1 / ethylene molar ratio in the autoclave gas phase to be 0.25, and the total pressure was 8 Kgf / cm.
While maintaining ² G, the gas in the system was circulated by a blower, and the produced polymer was intermittently withdrawn to carry out continuous polymerization for 10 hours. The catalyst efficiency is 70 kg / gZr, M
FR is 6.2 g / 10 min and Mn is 38500.
Met. Example 13 In Example 12, the amount of hexane supplied during the polymerization was 8
Polymerization was performed in the same manner as in Example 12 except that the amount was changed to ml / h (0.06 mol / h). Catalyst efficiency is 72 kg / g
Zr, MFR was 5.3 g / 10 min and Mn was 39800. Comparative Example 6 The same polymerization as in Example 12 was carried out except that hexane was not supplied during the polymerization. The catalyst efficiency is 71 kg / gZr and the MFR is 3.3 g / 10 mi.
n and Mn was 50100.

[Brief description of drawings]

FIG. 1 is a flow sheet showing the steps for preparing a polymerization catalyst of the present invention.

Claims (2)

[Claims] 1. A general formula Me ¹ R ¹ _p (OR ² ) _q X
A compound represented by ¹ _4-pq , wherein R ¹ and R ² are independently a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a halogen atom or a hydrogen atom, and Me ¹ is Zr, Ti or Hf, p and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦, respectively.
p + q ≦ 4] (2) A compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn , wherein R ³ and R ⁴ are independently a hydrocarbon having 1 to 24 carbon atoms. Group, X ² is a halogen atom or a hydrogen atom, M
e ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n are 0 <m ≦ z and 0 ≦ n ≦ z, respectively.
And 0 <m + n ≦ z] (3) A cyclic organic compound having two or more conjugated double bonds,
And (4) a saturated hydrocarbon compound when polymerizing or copolymerizing olefins in a substantially gas phase in the presence of a catalyst obtained by bringing modified organoaluminum compounds containing an Al—O—Al bond into contact with each other. And at least one liquid and / or gaseous hydrocarbon compound selected from aromatic hydrocarbon compounds are allowed to coexist in the reaction system, and the type and / or amount of the hydrocarbon compound is selected to produce a molecular weight of the produced polyolefin. The method for producing a polyolefin is characterized in that: (1) General formula Me ¹ R ¹ _p (OR ² ) _q X ¹
A compound represented by _4-pq , wherein R ¹ and R ² are independently a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a halogen atom or a hydrogen atom, and Me ¹ is Zr, Ti or Hf. Indicates
p and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p +, respectively.
q ≦ 4] (2) A compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn , wherein R ³ and R ⁴ are independently a hydrocarbon having 1 to 24 carbon atoms. Group, X ² is a halogen atom or a hydrogen atom, M
e ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n are 0 <m ≦ z and 0 ≦ n ≦ z, respectively.
And 0 <m + n ≦ z] (3) Cyclic organic compound having two or more conjugated double bonds, (4) Modified organoaluminum compound containing Al—O—Al bond, and (5) Inorganic compound When a olefin is polymerized or copolymerized in a substantially gas phase in the presence of a catalyst obtained by bringing a carrier and / or a particulate polymer carrier into contact with each other, it is selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound. Characterized in that the molecular weight of the produced polyolefin is adjusted by allowing at least one liquid and / or gaseous hydrocarbon compound present in the reaction system to coexist in the reaction system and selecting the type and / or amount of the hydrocarbon compound. Method for producing polyolefin.