JPH11217407A - Catalyst for olefin polymerization and manufacture of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin having a wide molecular weight distribution in a low molecular weight range and an excellent moldability and rigidity by employing a solid titanium catalyst component comprising Mg, Ti, a halogen and a polycarboxylic ester or a polyether, an organoaluminum compound and a certain trimethoxy silane compound. SOLUTION: 1 mol of a halogen-containing magnesium compound, 0.01-1,000 mol of a tetravalent titanium compound, 0.01-10 mol of a polycarboxylic ester or a polyether and optionally an electron donor are contacted at from -70 to 200 deg.C to obtain a solid titanium catalyst component. A catalyst for olefin polymerization is obtained from the catalyst component, an organoaluminum compound and a trimethoxy silane represented by the formula: RSi(OCH3 )3 (wherein R is a 1-10C alkyl group). Olefins are polymerized in the presence of the catalyst to obtain a polyolefin having a MFR of 50-300 g/10 min (230 deg.C, 2.16 kg) and a molecular weight distribution (Mw/Mn) of 6 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst capable of producing a polyolefin excellent in moldability and rigidity, particularly having a wide molecular weight distribution at a low molecular weight, and a method for producing a polyolefin using the olefin polymerization catalyst.

[0002]

BACKGROUND OF THE INVENTION As a catalyst for polyolefin production, a Ziegler-Natta catalyst comprising a titanium catalyst component and an organoaluminum compound has been widely used. In particular, a carrier-supported solid titanium catalyst component has been used as the titanium catalyst component. It is known that a catalyst containing the compound exhibits high polymerization activity. Particularly, a catalyst containing a magnesium chloride-supported titanium catalyst component among solid titanium catalyst components exhibits high polymerization activity and can produce a polyolefin having high stereoregularity when an olefin such as propylene is polymerized. Known as a catalyst.

Various studies have been conducted on a catalyst containing such a solid titanium catalyst component in order to improve the polymerization activity and obtain a polyolefin having desired characteristics.
For example, as a component when preparing a solid titanium catalyst component,
Alternatively, it has been proposed to use various electron donors when forming an olefin polymerization catalyst from a solid titanium catalyst component and an organoaluminum compound.

[0004] The applicant of the present invention has also disclosed in Japanese Patent Application Laid-Open No. 58-83006 that a highly stereoregular polyolefin can be produced in a high yield and that the particle size, particle size distribution, particle properties and bulk specific gravity are excellent. As a polyolefin production catalyst, a solid titanium catalyst component containing at least a carboxylic acid ester as an internal donor (internal electron donor) and an organoaluminum compound, and Si—O—C or Si as an external donor (external electron donor) An olefin polymerization catalyst comprising an -silicon compound having an -NC bond has been proposed. Si—O as such an electron donor
Specific examples of the organosilicon compound having a -C bond include tetraethoxysilane, phenyltriethoxysilane,
An alkoxysilane such as diphenyldimethoxysilane is used.

[0005] Among such alkoxysilanes, cyclopentyl, substituted cyclopentyl, cyclopentenyl, substituted cyclopentenyl, cyclopentadienyl, substituted cyclopentadienyl represented by dicyclopentyldimethoxysilane, etc. Group or S
An olefin polymerization catalyst using dimethoxysilane having two hydrocarbon groups in which the carbon adjacent to i is a secondary or tertiary carbon as an electron donor has also been proposed.

In order to improve the moldability of the above-mentioned polyolefins, especially polypropylene, the melt flow rate (MFR) may be increased. Usually, a high molecular weight regulator such as hydrogen is used in the polymerization of olefins to increase the MFR. That is, a low molecular weight polyolefin is produced.

It is known that the rigidity of polypropylene may be increased by increasing the molecular weight distribution (Mw / Mn). However, when a low molecular weight polypropylene is produced, the molecular weight distribution is usually narrow and the mechanical strength such as rigidity is low. It tends to decrease. For this reason, propylene is polymerized in multiple stages and the MFR
For example, a process for producing polypropylene having high rigidity and low rigidity and a process for producing polypropylene having high molecular weight and high rigidity are carried out to improve the moldability and rigidity of polypropylene.

For this reason, there has been a demand for a catalyst capable of obtaining a polyolefin, particularly polypropylene, having a high MFR and a wide molecular weight distribution and excellent moldability. The present inventor has continued research on such an olefin polymerization catalyst, and found that, together with the solid titanium catalyst component and the organoaluminum compound, among the organosilicon compounds as the external electron donor, in particular, alkyltrimethoxysilane was used. The formed olefin polymerization catalyst has an MFR of 50.
When a low molecular weight polyolefin having a molecular weight of up to 300 g / 10 min is produced, a polyolefin having a wide molecular weight distribution of Mw / Mn of 6 or more can be obtained, and the polyolefin is produced with excellent polymerization activity by one-stage polymerization of the olefin. To complete the present invention.

[0009]

An object of the present invention is to provide an olefin polymerization catalyst capable of producing a highly stereoregular polyolefin having a high molecular weight distribution at a low molecular weight and having excellent moldability and rigidity with high polymerization activity.
And a method for producing a polyolefin using the olefin polymerization catalyst.

[0010]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
Melt flow rate (MFR: ASTM D1238;
A catalyst for producing a polyolefin having a molecular weight distribution (Mw / Mn) of 6 or more at 230 ° C. under a load of 2.16 kg) of 50 to 300 g / 10 min. And a solid titanium catalyst component containing a polycarboxylic acid ester or polyether, (B) an organoaluminum compound, and (C) RS
i (OCH ₃ ) _{3 wherein} R is an alkyl group having 1 to 10 carbon atoms.

The olefin polymerization catalyst comprises: [I] the olefin polymerization catalyst comprising (A) the above-mentioned solid titanium catalyst component, (B) an organoaluminum compound and, if necessary, (D) an electron donor. And a prepolymerized catalyst obtained by prepolymerizing an olefin, and [II] the organosilane compound (C).
And [III] an organoaluminum compound (B) if necessary.

The electron donor (D) at the time of the prepolymerization may be the above-mentioned organic silane compound (C). In the method for producing a polyolefin according to the present invention, the olefin is polymerized or copolymerized in one step in the presence of the olefin polymerization catalyst as described above, and a melt flow rate (MFR: ASTM D
1238; 230 ° C, under a load of 2.16 kg) 50 to 30
A polyolefin having 0 g / 10 min and a molecular weight distribution (Mw / Mn) of 6 or more is obtained.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" is not limited to homopolymer but also copolymer. Is sometimes used in a sense that also includes

First, the solid titanium catalyst component (A) used in forming the olefin polymerization catalyst according to the present invention will be described. The solid titanium catalyst component used in the present invention contains at least magnesium, titanium, halogen, and a polycarboxylic acid ester or polyether as essential components. The solid titanium catalyst component is
The preparation method is not limited as long as these components are contained, and (a-1) a magnesium compound, (a-2) a titanium compound and (a-3) a polycarboxylic acid ester or polyether can be prepared by various methods. Can be prepared by contact with The components used when preparing the solid titanium catalyst component are shown below. (A-1) Magnesium compound In the present invention, examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Examples of the magnesium compound having a reducing ability include an organic magnesium compound represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
20 to 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different. X is a halogen.

Specific examples of such an organomagnesium compound having a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, and the like.
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium; alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halide, butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium, and other butyl magnesium hydrides.

Specific examples of the magnesium compound having no reducing ability include halogen such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, and isopropoxy magnesium chloride. Alkoxy magnesium halides such as butoxymagnesium chloride, octoxymagnesium chloride, allyoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride, ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxy Alkoxy magnesium such as magnesium,
Examples include allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium carboxylate such as magnesium laurate and magnesium stearate. In addition, magnesium metal and magnesium hydride can be used.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

The above-mentioned magnesium compound having a reducing ability and the magnesium compound having no reducing ability form complex compounds and complex compounds with other metals such as aluminum, zinc, boron, beryllium, sodium and potassium. Or a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more of the above compounds may be used in combination.

As the magnesium compound used for preparing the solid titanium catalyst component, any magnesium compound other than those described above can be used. However, in the finally obtained solid titanium catalyst component, a magnesium compound containing halogen is present. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with a halogen-containing compound during the preparation.

Of these, magnesium compounds having no reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferred.

In the present invention, when preparing a solid titanium catalyst component, the magnesium compound (a-
1) is preferably used in a liquid state. When the magnesium compound is a solid among the above magnesium compounds, the magnesium compound can be made into a liquid state by using the electron donor (a-4).

As the electron donor (a-4), alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like described later as the electron donor (a-6) can be used. Can be used.

Further, metal acid esters such as tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium can also be used. .

Of these, alcohols and metal acid esters are particularly preferably used. The reaction between the solid magnesium compound and the electron donor (a-4) is performed by bringing the solid magnesium compound into contact with the electron donor (a-4),
The method of heating as needed is common. This contact is usually performed at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.

The above reaction is carried out in a hydrocarbon solvent (a-5).
It may be performed in any coexistence. With such hydrocarbon solvents
Specifically, pentane, hexane, heptane,
Octane, decane, dodecane, tetradecane, kerosene, etc.
Aliphatic hydrocarbons, cyclopentane, methylcyclopente
Tan, cyclohexane, methylcyclohexane, cyclo
Alicyclic hydrocarbons such as octane and cyclohexene,
Dichloroethane, dichloropropane, trichloroethylene
Halogenated hydrocarbons such as
Aromatic hydrocarbons such as benzene, toluene, xylene, etc.
Is used. (A-2) Titanium compound In the present invention, the titanium compound (a-2) is a liquid titanium
Compounds are preferred, especially tetravalent titanium compounds
Used. As such a tetravalent titanium compound,
The compound represented by the following formula can be mentioned.

[0028] During _{Ti (OR) g X 4-} g formulas, R is a hydrocarbon group, X is a halogen atom, a 0 ≦ g ≦ 4. Specific examples of such a compound include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (O
_{C 2 H 5) Cl 3,} Ti (On-C 4 H 9) Cl 3, Ti (OC
_{2 H 5) Br 3, Ti} (O-iso-C 4 H 9) trihalide, alkoxy titanium such as _{Br 3, Ti (OCH 3)} 2 C
l ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ C
_{l 2, Ti (OC 2 H} 5) 2 Br 2 dihalogenated dialkoxy titanium, such _{as, Ti (OCH 3) 3 Cl} , Ti (OC 2
_{H 5) 3 Cl, Ti (} On-C 4 H 9) 3 Cl, Ti (OC 2 H
₅₎ monohalogenated trialkoxy titanium such as ₃ Br,
Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C _{4
H 9) 4, Ti (O} -iso-C 4 H 9) 4, etc. tetraalkoxy titanium such as Ti (O-2-ethylhexyl) _4.

Of these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds can be used in combination of two or more. The above titanium compound may be used after being diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon. (A-3) Polyvalent carboxylic acid ester or polyether In preparing the solid titanium catalyst component, a polyvalent carboxylic acid ester or polyether is used as an electron donor.

The polycarboxylic acid ester is represented by the following general formula, for example.

[0031]

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In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted hydrocarbon group. Or an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. Also R
³ and R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, etc.
O-C, COOR, COOH, OH, SO 3 H, -C-
With N-C-, a group such as NH _2.

Specific examples of such polycarboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, and isopropyl malonate. Diethyl acrylate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, β-methyl glutar Aliphatic polycarboxylates such as diisopropyl acrylate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexane Diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate, alicyclic polycarboxylic acid esters such as diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and heterogeneous substances such as 3,4-furandicarboxylic acid Cyclic polycarboxylic acid esters and the like.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Long chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate can also be mentioned.

Of these, phthalic esters are particularly preferred. These may be used in combination of two or more.
As the polyether, a polyether compound having two or more ether bonds existing through a plurality of atoms can be used.

Examples of the polyether include carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur, and compounds in which two or more kinds of atoms are present between ether bonds. Among these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in an atom existing between two or more ether bonds is preferable. For example, a compound represented by the following formula: Polyethers are preferred.

[0037]

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(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and arbitrary R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and atoms other than carbon may be contained in the main chain. As the polyether as described above, specifically, 2-
(2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2- Cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- ( 2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl)- 1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1 , 3-Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3 -Dimethoxypropane,
2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-
Dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-
Methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2
-Isopropyl-1,3-dimethoxypropane, 2-methyl-2-
Phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-
Cyclohexylethyl) -1,3-dimethoxypropane, 2-
Methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-
Dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-
Diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-
1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-
Butyl-1,3-dimethoxypropane, 2,2-di-s-butyl-1,3
-Dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2 -Phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl- 2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane,
2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl 2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3 -Diphenyl-1,4-
Diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3 -Screw (p-
Chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p
-Fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-
Dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-
Methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diiso Neopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-
1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,5] undecane, 3,7-
Dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1 1,1-Dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl 2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-
1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-
1,3-dimethoxycyclohexane, 2-cyclohexyl-2-
Methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl -1,3-diethoxycyclohexane, 2-cyclohexyl-
2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-
Isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2- Isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane and the like.

As polyethers, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis ( Methoxymethyl) silane, cyclohexyl-t-butylbis (methoxymethyl)
Silane, i-propyl-t-butylbis (methoxymethyl)
Silane and the like can also be mentioned.

Among these, 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, -Isopropyl-2-isopentyl-1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl)-
1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-s-
Butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-
Dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane and the like are preferably used. These may be used in combination of two or more.

In preparing the solid titanium catalyst component, both the above-mentioned polyvalent carboxylic acid ester and polyether may be used, and other electron donors may be used together with the polyvalent carboxylic acid ester or polyether. (A-6) can be used. Particularly, in the present invention, it is preferable to use a polycarboxylic acid ester.

Examples of the other electron donor (a-6) include alcohols, phenols, ketones, aldehydes, and the like.
Carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, ammonia,
An amine, a nitrile, an isocyanate, a nitrogen-containing cyclic compound, an oxygen-containing cyclic compound, or the like can be used. More specifically, methanol, ethanol, propanol,
Alcohols having 1 to 18 carbon atoms such as butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, and isopropylbenzyl alcohol; C1 to C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol; phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and lower alkyl groups such as naphthol. Phenols having good C20 to C20, acetone,
C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; and C2 to C15 such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.
Aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, crotonic acid Ethyl, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-
Organic acid esters having 2 to 18 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate, and 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride
Acid halides, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether and the like having 2 to 20 carbon atoms, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide , Toluic acid
Acid amides such as N, N-dimethylamide, methylamine,
Ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine,
Amines such as tribenzylamine, tetramethylenediamine, hexamethylenediamine, nitriles such as acetonitrile, benzonitrile and trinitrile, acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride, pyrrole, methylpyrrole and dimethylpyrrole Pyrroles such as pyrroline; pyrrolidine; indole; pyridine;
Methylpyridine, ethylpyridine, propylpyridine,
Pyridines such as dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, and isoquinolines; tetrahydrofuran; 1,4-dineol; And cyclic oxygen-containing compounds such as cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and ditetropyran.

Further, as the electron donor (a-6), an organic silane compound, water or an anionic, cationic or nonionic surfactant as described later can be used as a catalyst component.

These electron donors (a-6) can be used in combination of two or more. Preparation of Solid Titanium Catalyst Component (A) In preparing the solid titanium catalyst component, in addition to the above compounds, an organic compound or an inorganic compound containing silicon, phosphorus, aluminum or the like used as a carrier and a reaction aid, etc. A compound or the like may be used.

As such a carrier, Al ₂ O ₃ , Si
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Sn
Resins such as O ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are exemplified. Among them, Al ₂ O ₃ , SiO ₂ and styrene-divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (A) includes the magnesium compound (a-1) and the titanium compound (a-
2) and a polyvalent carboxylic acid ester or polyether (a-3), and can be prepared by any method including a known method. The preparation method is not particularly limited. In the present invention, it is preferable that the magnesium compound (a-1), the liquid titanium compound (a-2) and the polycarboxylic acid ester or polyether (a-3) in a liquid state are brought into contact with each other.

When the compounds (a-1) to (a-3) are brought into contact with each other to prepare a solid titanium catalyst component, a hydrocarbon can be used if necessary. The same hydrocarbon solvents as those described when liquefying the compound (a-1) can be used.

Hereinafter, a specific method for preparing a solid titanium catalyst component will be briefly described with reference to several examples. In the following method, as the organoaluminum compound, those described below as the organoaluminum compound (B) are used.

(1) Magnesium compound, electron donor (a-
4) and a liquid state magnesium compound (a-1) composed of a hydrocarbon solvent is contact-reacted with an organoaluminum compound to precipitate a solid, or is contacted with a titanium compound (a-2) during precipitation. .

In this process, the polycarboxylic acid ester or polyether (a-3) (hereinafter referred to as electron donor (a-3)
) Is contacted with the contact product at least once. (2) A titanium compound (a-2) and an electron donor (a-3) are contact-reacted with a contact product of an inorganic carrier and an organomagnesium compound (a-1).

At this time, a contact product of the inorganic carrier and the organomagnesium compound (a-1) may be reacted in advance with a halogen-containing compound and / or an organoaluminum compound. (3) From a mixture of a magnesium compound, an electron donor (a-4), a magnesium compound in a liquid state (a-1) optionally containing a hydrocarbon solvent and an inorganic carrier or an organic carrier, a magnesium compound A supported inorganic or organic carrier is prepared, and then a titanium compound (a-
2) Make contact.

In this step, the electron donor (a-3) is brought into contact with the contact product at least once. (4) Magnesium compound (a-1), titanium compound (a-
2) Contacting the electron donor (a-3) with a solution containing an electron donor (a-4), and optionally a hydrocarbon solvent, an inorganic carrier or an organic carrier, and the electron donor (a-3).

(5) The liquid state organomagnesium compound (a
-1) is contacted with a halogen-containing titanium compound (a-2) and an electron donor (a-3). (6) After contacting the liquid state organomagnesium compound (a-1) with a halogen-containing compound, the titanium compound (a-
2) Make contact.

In this step, the electron donor (a-3) is used at least once. (7) An alkoxy group-containing magnesium compound (a-1) is converted into a halogen-containing titanium compound (a-2) and an electron donor (a-
Contact reaction with 3).

(8) A liquid magnesium compound (a-1) comprising an alkoxy group-containing magnesium compound and an electron donor (a-4) is converted into a titanium compound (a-2) and an electron donor (a-3). ) And contact reaction.

(9) A magnesium compound (a-1) in a liquid state comprising an alkoxy group-containing magnesium compound and an electron donor (a-4) is brought into contact with an organoaluminum compound, and then a titanium compound (a-2) And contact reaction.

In this step, the electron donor (a-3) is brought into contact with the contact product at least once. (10) Liquid magnesium compound having no reducing ability (a-
1) is brought into contact with the titanium compound (a-2) in the presence or absence of the electron donor (a-3).

In this step, the electron donor (a-3) is brought into contact with the contact product at least once. (11) The reaction product obtained in (1) to (10) is further contacted with a titanium compound (a-2).

(12) The reaction products obtained in (1) to (11)
Further, the electron donor (a-3) and the titanium compound (a-2) are brought into contact with each other. The contact of each component as described above is usually performed at -70 ° C to 200 ° C.
C, preferably at a temperature of -50C to 150C, more preferably -30C to 130C.

The amount of each component used in preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally. For example, per mole of magnesium compound, a polycarboxylic acid ester or polyether (a-
3) is used in an amount of 0.01 to 10 mol, preferably 0.1 to 5 mol, and the titanium compound (a-2) in a liquid state is used in an amount of 0.01 to 10 mol.
It can be used in an amount of 00 mol, preferably 0.1 to 200 mol.

In the present invention, the solid titanium catalyst component thus obtained is preferably washed with a hydrocarbon solvent at 0 to 150 ° C. As the hydrocarbon solvent, the hydrocarbon solvent (a-5) as described above for liquefying the magnesium compound can be used, and among these, an aliphatic hydrocarbon solvent or a halogen-free aromatic solvent is used. A group hydrocarbon solvent is preferably used.

When washing the solid titanium catalyst component,
The hydrocarbon solvent is usually from 10 to 500 per gram of the solid.
It can be used in an amount of about ml. The solid titanium catalyst component (A) thus obtained contains magnesium, titanium, halogen and a polycarboxylic acid ester or polyether, and contains 0.1 to 10% by weight, preferably 0.1 to 10% by weight of titanium. 2 to 7.0% by weight, magnesium and halogen in a total amount of 95 to 30% by weight, and the polycarboxylic acid ester or polyether is 0.5 to 30% by weight.
It is desirable to contain it in an amount of% by weight. (B) Organoaluminum Compound In the present invention, the organoaluminum compound used for forming the olefin polymerization catalyst is represented by, for example, the following formula.

[0063] In R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X
Is halogen or hydrogen, and n is 1 to 3. ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group and isobutyl group. Pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl, and the like. Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and alkenylaluminum such as isoprenylaluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride Alkylaluminum sesquihalide such as Romido, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

Further, examples of the organoaluminum compound include compounds represented by the following formula. In R ^a _n AlY _3-n the above formulas, R ^a is as defined above, Y is -OR ^b
Group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
A SiR ^f ₃ group or a —N (R ^g ) AlR ^h ₂ group, n is 1-2, and R ^b , R ^c , R ^d and ^Rh are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, A cyclohexyl group, a phenyl group or the like, and ^Re is hydrogen, a methyl group,
Examples include an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, and the like.

Specific examples of such an organoaluminum compound include the following compounds. _{^{(i) R a n Al (}} OR b) 3-n dimethyl aluminum methoxide, diethyl aluminum ethoxide, and diisobutyl Al um _{^{methoxide, (ii) R a n Al}} (OSiR c) 3-n Et 2 Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OS
_{iMe 3), (iso-Bu} ) such as _{2 Al (OSiEt 3), (} iii) R a n Al (OAlR d 2) 3-n E 2 AlOAlEt 2, (iso-Bu) 2 AlOAl (iso-
Bu) _{2, ^{etc., (iv) R a n Al}} (NR e 2) 3-n Me 2 AlNEt 2, Et 2 AlNHMe, Me 2 AlNH
Et, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ Al
Such as N (Me ₃ Si) ₂ , (v) R ^a _n 1 (SiR ^f ₃ ) _{3 -n} (iso-Bu) ₂ AlSiMe _3, etc., (vi) R ^a _n Al [N (R ^g ) -AlR ^h _{2] 3-n Et 2 AlN} (Me) -AlEt 2 (iso-Bu) 2 AlN
(Et) Al (iso-Bu) _{2 and the} like.

Further, similar compounds, for example, organic aluminum compounds in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be mentioned. More specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C
_{4 H 9) 2 AlOAl (C} 4 H 9) 2, (C 2 H 5) 2 AlN
(C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and the like, and aluminoxanes such as methylaluminoxane.

Among the above-mentioned organoaluminum compounds, R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n , R ^a _n Al
An organic aluminum compound represented by (OAlR ^d ₂ ) _3-n is preferably used.

Further, as the organoaluminum compound, a complex alkylated compound represented by the following general formula can also be used. M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms) Specifically, LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 and the like.

These compounds can be used in combination of two or more kinds. (C) Organosilane Compound In the present invention, when preparing an olefin polymerization catalyst,
Along with the solid titanium catalyst component (A) and organoaluminum compound (B) as described above, RSi (OCH ₃ ) ₃
[Where R is an alkyl group having 1 to 10 carbon atoms].

Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, (n-, i-) propyl,
(N-, i-, t-, sec-) butyl, pentyl, hexyl, heptyl, (n-, i-) octyl, nonyl, decyl and the like.

Specific examples of such an organic silane compound include methyltrimethoxysilane, ethyltrimethoxysilane, (n-, i-) propyltrimethoxysilane, (n-, i-, t, sec-). Butyltrimethoxysilane,
Pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, (n-, i-) octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane and the like can be mentioned.

Of these, n-propyltrimethoxysilane is particularly preferably used. Olefin polymerization catalyst The olefin polymerization catalyst according to the present invention is formed from (A) the solid titanium catalyst component, (B) an organoaluminum compound, and (C) alkyltrimethoxysilane, and When a polyolefin having a molecular weight is produced, a polyolefin having a wide molecular weight distribution can be obtained. Specifically, the melt flow rate (MFR: ASTM)
D1238; 230 ° C, under a load of 2.16 kg) 50 to 3
A polyolefin having a molecular weight distribution (Mw / Mn) of 6 or more at 00 g / 10 min can be obtained.

FIG. 1 shows a process for preparing an olefin polymerization catalyst and a process for producing a polyolefin according to the present invention. In the present invention, a prepolymerized catalyst [I] can be formed by preliminarily (co) polymerizing an olefin with the above catalyst component, and specifically, [I] the solid titanium catalyst component (A) described above. And (B) an organoaluminum compound and, if necessary, (D) an electron donor.
An olefin polymerization catalyst can also be formed from a prepolymerized catalyst obtained by prepolymerizing an olefin, [II] alkyltrimethoxysilane, and [III] an organoaluminum compound as required.

This alkyltrimethoxysilane [II]
Are the same as those exemplified as the alkyltrimethoxysilane (C), and the organoaluminum compound [III]
Is the same as that exemplified as the organoaluminum compound (B). The electron donor and the organoaluminum compound may be the same compound or different compounds at the time of prepolymerization and main polymerization.

At the time of the prepolymerization, an electron donor (D) can be used if necessary.
Specifically, the above-mentioned (C) alkyltrimethoxysilane can be used, and other electron donors can also be used.

Other electron donors include, for example, the aforementioned polyether compounds, 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, Nitrogen-containing electrons such as substituted methylenediamines such as N, N, N ', N'-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine Donors, phosphites such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite, etc. Oxygen-containing electron donors such as phosphorus-containing electron donors, 2,6-substituted tetrahydropyrans, and 2,5-substituted tetrahydropyrans may also be used. Can, it is also possible to further use of the organic silane compound other than the above (C) Other electron donor. As other organic silane compounds, specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t- -Amylmethyldiethoxysilane,
Diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bism-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, vinyl Trimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n -
Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane,
Examples include vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, ethyl silicate, butyl silicate, and the like.

As another organic silane compound, an organic silane compound having a bulky group represented by the following formula (2) can also be mentioned. During _{^{R a n Si (OR b)}} 4-n ... (2) ( wherein, n is 1, 2 or 3, when n is 1, R ^a is an secondary or tertiary hydrocarbon group , N is 2
Or when 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When (4-n) is 2 or 3, OR ^b may be the same or different. The compound represented by the formula (2) does not include alkyltrimethoxysilane (C).

In the organosilane compound having a bulky group represented by the formula (2), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a substituent And hydrocarbon groups in which the carbon adjacent to Si is secondary or tertiary.

Specific examples include dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane, and the like. Can be

These may be used in combination of two or more.
Examples of olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-methyl-1-pentene.
Ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1
-Hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Two or more α-olefins are included. Further, other vinyl compounds and polyene compounds as described later can also be used at the time of preliminary polymerization. These may be used in combination of two or more.

The α-olefin used in the prepolymerization is
It may be the same as or different from the α-olefin used in the main polymerization described below. In the present invention, there is no particular limitation on the method of performing the prepolymerization, for example, olefins, polyene compound can be performed in a liquid state,
Further, the reaction can be carried out in the presence of an inert solvent, and furthermore, can be carried out under gas phase conditions. Of these, it is preferable to add olefins and various catalyst components to the inert solvent in the presence of an inert solvent, and to carry out prepolymerization under relatively mild conditions. At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium, or may be carried out under a condition in which the prepolymer is not dissolved, but it is preferably carried out under a condition in which the prepolymer is not dissolved.

The prepolymerization is usually carried out at about -20 to + 100 ° C.
Preferably about -20 to 80 ° C, more preferably -10.
It is desirable to carry out at a temperature of + 40 ° C. The pre-polymerization is
It can be performed in any of a batch system, a semi-continuous system, and a continuous system.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. Although the concentration of the catalyst component in the prepolymerization varies depending on the type of the catalyst component, the concentration of the solid titanium catalyst component (A) is as follows.
Usually about 0.001 to 5000 mmol, preferably about 0.01 to 5000 mmol, in terms of titanium atom, per liter of polymerization volume.
It is desirable that the amount be 1000 mmol, particularly preferably 0.1 to 500 mmol.

The organoaluminum compound (B) is usually used in an amount of about 0.1 to 0.1 mol per mol of titanium in the solid titanium catalyst component.
It can be used in an amount of 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol.

In the prepolymerization, the electron donor (D)
Is usually 0.01 to 50 mol, preferably 0.05 to 30 mol, per mol of titanium atom in the solid titanium catalyst component (A).
Moles, more preferably 0.1 to 10 moles, if necessary.

At the time of prepolymerization, a molecular weight regulator such as hydrogen can be used. In the above prepolymerization, 0.01 to 2 per gram of the solid titanium catalyst component (A) is used.
000 g, preferably from 0.03 to 1000 g, more preferably from 0.05 to 200 g of the preliminary (co) polymer can be produced.

When the prepolymerized catalyst is obtained in a suspended state, in the subsequent (main) polymerization, the prepolymerized catalyst can be used as it is in a suspended state, or the prepolymerized catalyst formed from the suspension can be used. The polymerization catalyst can be used separately.

The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization in addition to the above components. Olefin Polymerization Method In the olefin polymerization method according to the present invention, the olefin polymerization catalyst comprising (A) a solid titanium catalyst component, (B) an organoaluminum compound and (C) alkyltrimethoxysilane, or [ I] a pre-polymerization catalyst,
An olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising [II] alkyltrimethoxysilane and, if necessary, [III] an organoaluminum compound.

The olefin to be polymerized in the present invention includes:
Specific examples include α-olefins having 2 or more carbon atoms as shown in the preliminary polymerization. Furthermore, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-Cycloolefins such as octahydronaphthalene, styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalenes, allyltoluenes, allylbenzene, vinyl Vinyl compounds such as cyclopentane, vinylcyclohexane, vinylcycloheptane, and allyltrialkylsilanes can also be used.

The olefin may be homopolymerized, or two or more olefins may be copolymerized. Of these, ethylene, propylene, 1-butene, 3-methyl-1-
Butene, 3-methyl-1-pentene, 4-methyl-1-pentene,
Vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene and the like are preferably used. In particular, it is preferable to polymerize propylene.

Further, a small amount of a diene compound may be copolymerized with an olefin. As such a diene compound, specifically, 1,3-butadiene, 1,3-pentadiene,
1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6 -Butyl-1,6-
Octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,
6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,
6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,
Examples include 6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. They are,
Two or more kinds may be used in combination.

In the present invention, a low molecular weight polyolefin having a melt flow rate (MFR) of 50 to 300 g / 10 min is produced by polymerizing or copolymerizing the above olefin in one step. Has a molecular weight distribution (Mw / Mn) of 6 or more,
It is preferably 6 to 30, more preferably 7 to 25, more preferably 7 to 20, and particularly preferably 7.5 to 20.

The amount of the n-decane-soluble component (t-DS) at 23 ° C. of the polyolefin is 0 to 5% by weight, preferably 0 to 2% by weight.
It is desirable that

In the present invention, it is preferable to obtain polypropylene as the above-mentioned polyolefin, particularly by polymerization of propylene. The stereoregularity index (II) obtained as the boiling heptane extraction residual ratio is 94% by weight or more. Preferably, it is 96% by weight or more.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. When the polymerization takes a reaction form of slurry polymerization, the above-mentioned inert organic solvent can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can be used.

In the polymerization, the solid titanium catalyst component (A) or the prepolymerized catalyst [I] is usually used in an amount of about 0.001 to 1 in terms of titanium atom per liter of polymerization volume.
It can be used in an amount of 00 mmol, preferably about 0.005 to 20 mmol.

The organoaluminum compound (B) (or [III]) has a metal atom in the compound (B) of usually about 1 to 2000 mol per mol of titanium atom in the polymerization system.
Preferably, it can be used in an amount of about 2 to 500 mol.

When the prepolymerized catalyst [I] is used, the organoaluminum compound [III] may not be used in some cases. The alkyltrimethoxysilane (C) (or [II]) is usually used in an amount of about 0.001 mol to 10 mol per 1 mol of the metal atom of the organoaluminum compound (B).
Preferably, it can be used in an amount of 0.01 mol to 5 mol.

In the olefin polymerization method according to the present invention,
Although it depends on the type of olefin and the type of polymerization,
The polymerization is usually carried out at about 20 to 300 ° C, preferably about 50 to 1 ° C.
The reaction is carried out at a temperature of 50 ° C. and a pressure of from normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² .

The polyolefin melt flow rate can be adjusted by allowing hydrogen and the like to coexist during the polymerization. In the polymerization method of the present invention, the polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system.

[0101]

According to the present invention in which the above-mentioned specific alkyltrimethoxysilane is used as an external electron donor, a highly stereoregular polyolefin having a low molecular weight, a wide molecular weight distribution, and excellent moldability and rigidity can be obtained. It can be obtained by one-stage polymerization with polymerization activity.

[0102]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

In the following Examples and Comparative Examples, the boiling heptane extraction residue ratio (t-II), which is an index of stereoregularity of polyolefin, was determined by soxhlet extraction of boiling polyheptane with boiling heptane until the residue remained constant. .

The amount of the n-decane-soluble component (t-DS) of the polyolefin at 23 ° C. was measured as follows. In a 1 liter flask, 3 g of sample (polyolefin), 20 mg of 2,
6-di-tert-butyl-4-methylphenol, 500 ml of n-
Add decane and heat at 145 ° C to dissolve. Cool to 23 ° C. over 8 hours after dissolution and maintain at 23 ° C. for 8 hours. The precipitated solid and an n-decane solution containing the dissolved polymer are separated by filtration through a glass filter. The liquid phase is dried at 150 ° C. under reduced pressure until a constant weight is obtained, and its weight is measured. The obtained polymer dissolution amount is calculated as a percentage with respect to the weight of the sample, and is defined as the amount of a 23 ° C. decane-soluble component of polypropylene.

The melt flow rate of the polyolefin (M
FR) is 230 ° C. according to ASTM D1238,
It was measured under a 2.16 kg load. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyolefin were determined by GPC.

[0106]

Example 1 [Preparation of solid titanium catalyst component] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added to this solution, and further dissolved by stirring and mixing at 130 ° C. for 1 hour.

After the thus obtained homogeneous solution was cooled to room temperature, 30 ml of this homogeneous solution was dropped into 80 ml of titanium tetrachloride (TiCl ₄ ) maintained at -20 ° C. over 1 hour. .

The temperature of the resulting mixture was raised to 11 over 4 hours.
The temperature was raised to 0 ° C., and when the temperature reached 110 ° C., 2.1 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred and maintained at the same temperature for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
After resuspending this solid portion in 110 ml TiCl ₄ ,
The resulting suspension was heated again at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component obtained as described above was stored as a hexane slurry. A portion of the solid titanium catalyst component hexane slurry was collected and dried, and the composition of the catalyst component was analyzed.

As the solid titanium catalyst component, titanium was 2.2.
19.0% by weight of magnesium, 59.0% by weight of chlorine
% Of DIBP and 19.8% by weight of DIBP. [Polymerization] 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and the autoclave was heated at 60 ° C. under a propylene atmosphere.
0.4 mmol of triethylaluminum, 0.4 mmol of n-propyltrimethoxysilane and 0.008 mmol of the solid titanium catalyst component obtained above were charged in terms of titanium atoms.

After introducing 1000 ml of hydrogen and raising the temperature to 70 ° C., the temperature was maintained for 1 hour to polymerize propylene. During the polymerization, the pressure was kept at 5 kg / cm ² G. After completion of the polymerization, the slurry containing the produced polymer (solid) was filtered to separate into a white powder and a liquid phase.

The yield of the polymer obtained in the form of a white powder was 3
0.3 g. The boiling heptane extraction residual ratio of the powdery polymer was 97.3% by weight, and the amount of n-decane soluble components at 23 ° C. was 0.93% by weight. Melt flow rate (MF
R) was 67 g / 10 min, and the molecular weight distribution Mw / Mn measured by GPC was 8.0.

The liquid phase was concentrated to obtain 0.3 g of a solvent-soluble polymer. Therefore, the activity is 3830 g / mmol-Ti,
1460 g / g-cat, the boiling heptane extraction residual ratio (t-II) of the whole propylene polymer was 96.3% by weight, and the amount of n-decane soluble component (t-DS) at 23 ° C. was 1.90% by weight. %Met.

The results are shown in Table 1.

[0116]

Comparative Example 1 In Example 1, except that the amount of hydrogen charged during the polymerization was changed from 1000 ml to 100 ml,
Polymerization of propylene was carried out in the same manner as in Example 1. Table 1 shows the results.

[0117]

Comparative Example 2 Propylene was polymerized in the same manner as in Example 1 except that dicyclopentyldimethoxysilane was used instead of n-propyltrimethoxysilane. Table 1 shows the results.

[0118]

[Table 1]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of a process for preparing an olefin polymerization catalyst according to the present invention and a process for producing a polyolefin.

Claims (3)

[Claims] (A) magnesium, titanium, halogen,
And a solid titanium catalyst component containing a polycarboxylic acid ester or polyether, (B) an organoaluminum compound, and (C) RSi (OCH ₃ ) _{3 wherein} R is an alkyl group having 1 to 10 carbon atoms. And a melt flow rate (MFR: ASTM D1238;
An olefin polymerization catalyst for producing a polyolefin having a molecular weight distribution (Mw / Mn) of 6 to 30 g at 230 ° C under a load of 2.16 kg) of 50 to 300 g / 10 min. 2. (I) (A) a solid titanium catalyst component containing magnesium, titanium, halogen, and a polycarboxylic acid ester or polyether; (B) an organoaluminum compound; ) An olefin polymerization catalyst comprising an electron donor, a prepolymerized catalyst in which an olefin is prepolymerized, and [II] R
A trimethoxysilane compound represented by Si (OCH ₃ ) _{3 wherein} R is an alkyl group having 1 to 10 carbon atoms;
[III] An organoaluminum compound, if necessary, having a melt flow rate (MFR: ASTM D123)
8; 230 ° C, under a load of 2.16 kg) 50 to 300 g / 1
An olefin polymerization catalyst for producing a polyolefin having 0 minutes and a molecular weight distribution (Mw / Mn) of 6 or more. 3. An olefin is polymerized or copolymerized in one step in the presence of the olefin polymerization catalyst according to claim 1 or 2, and a melt flow rate (MFR: ASTM D1238;
A method for producing a polyolefin, characterized in that a polyolefin having a molecular weight distribution (Mw / Mn) of 6 or more at 230 ° C. under a load of 2.16 kg) is 50 to 300 g / 10 min.