JPH04218507A - Solid titanium catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for polymerizing olefins - Google Patents

Abstract

PURPOSE:A solid titanium catalyst component for olefin polymerization capable of producing an olefinic polymer or a copolymer having more excellent stereoregularity than conventional one, the catalyst for the polymerization of an olefin, and a method for polymerizing the olefin with the catalyst. CONSTITUTION:The solid titanium catalyst component contains titanium, magnesium, a halogen, and a compound containing two or more ether bonds through plural atoms, and is produced by bringing the following components into contact with each other. (a) A liquid magnesium compound without reducing ability, (b) a compound having two or more ether bonds through plural atoms, (c) a liquid titanium compound and, if necessary, (d) a precipitating agent, provided that at least one of the components is a halogen-containing compound. The catalyst for the polymerization of the olefin contains the above solid titanium catalyst component. The polymerization method of the olefin comprises the polymerization or copolymerization of the olefin in the presence of the above catalyst.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to solid catalyst components, catalysts, and polymerization methods for producing homopolymers of ethylene and α-olefins, or copolymers thereof.

0002

Technical Background of the Invention Conventionally, active magnesium halide has been used as a catalyst for producing olefin polymers such as ethylene, α-olefin homopolymers, or ethylene/α-olefin copolymers. Catalysts containing supported titanium compounds are known.

[0003] Such an olefin polymerization catalyst (hereinafter referred to as
As the polymerization catalyst (sometimes used to include a copolymerization catalyst), there are known catalysts comprising a solid titanium catalyst component comprising magnesium, titanium, halogen, and an electron donor, and an organometallic compound.

This catalyst has high activity in the polymerization or copolymerization (hereinafter, "polymerization" may include copolymerization) of α-olefins such as propylene and butene-1, as well as in the polymerization of ethylene. The stereospecificity of the polymer (hereinafter, the term "polymer" may include copolymers) is also high.

Among these catalysts, in particular, a solid titanium catalyst component supported with an electron donor selected from carboxylic acid esters, of which phthalate esters are a typical example, and an aluminum-alkyl compound as a co-catalyst component are used. It is known that excellent performance is exhibited when a silicon compound having at least one Si-OR (wherein R is a hydrocarbon group) is used.

The present inventors conducted research with the aim of obtaining an olefin polymerization catalyst with even better polymerization activity and stereoregularity, and found that two atoms exist as electron donors via multiple atoms. It has been discovered that a solid titanium catalyst component using a compound having an ether bond as described above and a catalyst using a compound having two or more ether bonds as an electron donor achieve the object, and in order to complete the present invention. It's arrived.

[0007] A solid component containing magnesium, titanium, a halogen atom, and an electron donor is added to the benzene ring.
When using a catalyst system consisting of a combination of a solid catalyst component obtained by contacting an alkoxy group-containing aromatic compound substituted with ~6 alkoxy groups and an organoaluminum compound, it is possible to form a polymer with low stereoregularity. It has been found that it can be manufactured (see Japanese Patent Application Laid-open No. 1-236203).

[0008]

[Object of the invention] The present invention has been made in view of the current situation, and is a method for producing a catalyst that can obtain an olefin (co)polymer having high catalytic activity and high stereospecificity. The object of the present invention is to provide a solid titanium catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for polymerizing olefins.

[0009]

Summary of the Invention The solid titanium catalyst component for olefin polymerization according to the present invention comprises: (a) a liquid magnesium compound without reducing ability; (b) two or more ether bonds existing through a plurality of atoms. (c) a titanium compound in a liquid state, and optionally (
d) Titanium, magnesium, halogen and the above obtained by contacting a precipitation agent (at least one of component (a), component (b), component (c) and component (d) contains a halogen-containing compound) Contains compounds with two or more ether bonds.

According to the solid titanium catalyst component for olefin polymerization according to the present invention, since a compound having two or more ether bonds as described above is used as an electron donor, additional electrons are added during polymerization. Donor (herein:
To obtain a catalyst for olefin polymerization that can produce a polymer with high activity and high stereospecificity without using an electron donor (which does not include a compound having two ether bonds as described above unless otherwise specified). is possible.

Furthermore, according to the solid titanium catalyst component according to the present invention, by further using a compound having two or more ether bonds or a specific electron donor during polymerization, a polymer with even higher stereoregularity can be obtained. It is possible to obtain an olefin polymerization catalyst that can produce.

[0012] The first olefin polymerization catalyst according to the present invention comprises [Ia] (a) a magnesium compound in a liquid state that does not have reducing ability; (b) two or more ether bonds existing through a plurality of atoms; (c) a titanium compound in a liquid state, and optionally (
d) Obtained by contacting a precipitating agent (at least one of component (a), component (b), component (c) and component (d) contains a halogen-containing compound), titanium, magnesium, halogen and [II] An organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table. It is a feature.

[0013] Furthermore, the first olefin polymerization method according to the present invention includes ethylene and/or α-olefin,
It is characterized by polymerization or copolymerization using the above-mentioned olefin polymerization catalyst.

According to the first olefin polymerization catalyst and the first olefin polymerization method according to the present invention, the organometallic compound catalyst component [II] is used together with the first solid titanium catalyst component [Ia] according to the present invention. When used, it is possible to not only perform a polymerization reaction efficiently due to high catalytic activity, but also to obtain a polymer with high stereospecificity.

Further, the first olefin polymerization catalyst and the first olefin polymerization method according to the present invention contain, in addition to the above two components, the organometallic compound catalyst component [II] as well as the above compound having two or more ether bonds. Alternatively, by using a catalyst containing a specific electron donor (f), a polymer with even higher stereoregularity can be obtained.

[0016] The second olefin polymerization catalyst according to the present invention comprises [Ib] (a) a liquid magnesium compound having no reducing ability, (c) a liquid titanium compound, (e) an electron donor, and If necessary, titanium is obtained by contacting with (d) a precipitating agent (at least one of component (a), component (c), component (e), and component (d) contains a halogen-containing compound). , magnesium, halogen, and the electron donor (e); [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table;
III] An ether compound having two or more ether bonds existing through a plurality of atoms.

[0017] Furthermore, the second olefin polymerization method according to the present invention includes ethylene and/or α-olefin,
It is characterized by polymerization or copolymerization using the above-mentioned olefin polymerization catalyst.

According to the second olefin polymerization catalyst and second olefin polymerization method according to the present invention, in addition to the solid titanium catalyst component [Ib], the organometallic compound catalyst component [II] and the two or more ethers By using the compound [III] having a bond, not only the catalyst activity is high and the polymerization reaction can be carried out efficiently, but also a polymer with high stereospecificity can be obtained.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The solid catalyst component for olefin polymerization, the catalyst for olefin polymerization, and the olefin polymerization method according to the present invention will be explained in detail below.

The solid titanium catalyst component [I] for olefin polymerization according to the present invention includes (a) a liquid magnesium compound having no reducing ability, (b) two or more ethers present via a plurality of atoms. a compound having a bond, (c) a titanium compound in a liquid state, and optionally (
d) Obtained by contacting with a precipitating agent (at least one of component (a), component (b), component (c), and component (d) contains a halogen-containing compound).

The first olefin polymerization catalyst according to the present invention comprises such a solid titanium catalyst component [Ia]
Contains. Further, the second olefin polymerization catalyst according to the present invention comprises (a) a liquid magnesium compound having no reducing ability, (c) a liquid titanium compound, (e) an electron donor, and, if necessary, (d) Obtained by contacting a precipitating agent (at least one of component (a), component (c), component (e) and component (d) contains a halogen-containing compound), titanium, magnesium, halogen and a solid titanium catalyst component containing the electron donor (e).

[0022] Such a solid titanium catalyst component [Ia]
The magnesium compound without reducing ability used in the preparation of [IIb] may be derived from a magnesium compound having reducing ability. in particular,
Magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; phenoxychloride Allyloxymagnesium halides such as magnesium, methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, octoxymagnesium, 2-ethylhexoxymagnesium; aryloxymagnesiums such as phenoxymagnesium, dimethylphenoxymagnesium Roxymagnesium; magnesium laurate,
Examples include magnesium carboxylates such as magnesium stearate, inorganic acid salts such as magnesium carbonate, magnesium borate, and magnesium silicate; however, the magnesium compounds include complex compounds with other metals,
It may be a composite compound or a mixture with other metal compounds. Furthermore, a mixture of two or more of these compounds may be used. Among these are magnesium halides,
Especially preferred is magnesium chloride. Further, the magnesium compound having no reducing ability may be derived from another substance.

In the present invention, when such a magnesium compound is a solid, it is dissolved in a solvent capable of solubilizing the magnesium compound to form a liquid magnesium compound (a) having no reducing ability. use Further, when the magnesium compound is a liquid, it can be used as it is as the magnesium compound (a) which does not have a reducing ability in a liquid state, but it can be used by dissolving it in a solvent having an ability to solubilize a magnesium compound.

As such a solvent, for example, a titanate ester can be used, and an electron donor (g) such as an alcohol, an aldehyde, an amine, a carboxylic acid, or a metal acid ester other than titanium can be used. These compounds may be used alone or in combination of two or more.

Examples of titanate esters include methyl orthotitanate, ethyl orthotitanate, n-orthotitanate,
Propyl, i-propyl orthotitanate, n-butyl orthotitanate, i-butyl orthotitanate, n-amyl orthotitanate, 2-ethylhexyl orthotitanate,
Orthotitanate esters such as n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate, n-butyl polytitanate, polytitanium Examples include polytitanate esters such as i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate, and cyclohexyl polytitanate.

Specific examples of alcohols capable of solubilizing magnesium compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl carbitol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, and n-heptanol. -octanol,
2-ethylhexanol, decanol, dodecanol,
Aliphatic alcohols such as tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol, alicyclic alcohols such as cyclohexanol, methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol, α , aromatic alcohols such as α-dimethylbenzyl alcohol, and aliphatic alcohols containing alkoxy groups such as n-butyl cellosolve and 1-butoxy-2-propanol.

Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid, 2-ethylhexanoic acid, undecylenic acid, undecanoic acid, nonylic acid, and octanoic acid. Examples of the aldehyde include aldehydes having 7 or more carbon atoms, such as capric aldehyde, 2-ethylhexylaldehyde, caprylic aldehyde, and undecylic aldehyde.

Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecylamine, and 2-ethylhexylamine.

Examples of the metal acid ester include zirconium tetraalkoxides such as zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrabutoxide, and zirconium tetrapropoxide.

These titanate esters and electron donors (g) can be used together with inert solvents, and examples of such inert solvents include propane, butane, pentane, hexane, heptane, and octane. , aliphatic hydrocarbons such as decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene;
Examples include halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

Furthermore, in the liquid obtained by dissolving the magnesium compound (b) in such a solvent capable of solubilizing the magnesium compound, the magnesium compound is contained in an amount of 0.1 to 20 mol/liter based on the solvent. , preferably 0.
It is used in an amount of 5 to 5 mol/liter.

In the first solid titanium catalyst component [Ia] according to the present invention, in addition to the above-mentioned liquid magnesium compound (a), two or more ether bonds exist through a plurality of atoms. A compound (b) having the following is used.

The solid titanium catalyst component [Ib] contained in the second olefin polymerization catalyst according to the present invention is an electron donor (e) other than the compound (b) having two or more ether bonds. is used.

Solid titanium catalyst component [Ia
The compound having two or more ether bonds used in the preparation of Among these compounds, a relatively bulky substituent is bonded to the atom between the ether bonds, and the atoms between two or more ether bonds contain multiple carbon atoms. Compounds are preferred.

Examples of the compound (b) having two or more ether bonds include the following formula:

0036
]

[Chemical formula 3]

(In the formula, n is an integer of 2≦n≦10, and R1 to R26 are at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon. is a substituent having an arbitrary R1
~R26, preferably R1 to R20, may jointly form a ring other than a benzene ring, and the main chain may contain atoms other than carbon, and the main chain may include, Atoms other than carbon may be included. ) can be mentioned.

Compounds having two or more ether bonds as described above include 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-(p-t-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane , 2,2-dipropyl-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, 2,2-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-benzyl-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-bis(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, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,3 -diisoneopentyloxyethane, 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-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-methoxy Methyl-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, tris(p-methoxyphenyl)phosphine, methylphenylbis(methoxymethyl)silane, diphenylbis(methoxymethyl)silane, methylcyclohexylbis(methoxymethyl)silane, di-t-butylbis(methoxy Examples include methyl) silane, cyclohexyl-t-butylbis(methoxymethyl)silane, and i-propyl-t-butylbis(methoxymethyl)silane.

Among these, 1,3-diethers are preferred, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,
3-dimethoxypropane, 2,2-dicyclohexyl-
1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane are preferred.

The solid titanium catalyst component [Ib] contained in the second olefin polymerization catalyst according to the present invention contains an electron donor (
e). Such an electron donor (
Examples of e) include organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, aldehydes, tertiary amines, phosphorous esters, phosphoric esters, phosphoric acid amides,
Examples include carboxylic acid amides and nitriles; specifically, ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, and benzoquinone; acetaldehyde, propionaldehyde, octylaldehyde, and benzaldehyde. , tolualdehyde, naphthaldehyde and other aldehydes with 2 to 15 carbon atoms; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, chloro Methyl acetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoic acid Benzyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate,
Organic acid esters with 2 to 18 carbon atoms such as ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, etc. 2 to 15 acid halides; methyl ether, ethyl ether, isopropyl ether,
2-2 carbon atoms such as butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc.
0 ethers; acid amides such as acetic acid N,N-dimethylamide, benzoic acid N,N-diethylamide, and toluic acid N,N-dimethylamide; trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, etc. tertiary amines;
Examples include nitriles such as acetonitrile, benzonitrile, and trinitrile, and among these, aromatic carboxylic acid esters are preferred. Two or more of these compounds can be used in combination.

Furthermore, as the organic acid ester, polyvalent carboxylic acid esters can be mentioned as particularly preferable examples, and such polyvalent carboxylic acid esters have the following general formula:

[0042]

[C4]

(However, R1 is a substituted or unsubstituted hydrocarbon group, R2, R5, and R6 are hydrogen or a substituted or unsubstituted hydrocarbon group, and R3 and R4 are hydrogen or a substituted or unsubstituted hydrocarbon group. and preferably at least one of them is a substituted or unsubstituted hydrocarbon group, and R3
and R4 may be connected to each other, and the hydrocarbon group R1
The substituent when ~R6 is substituted includes a heteroatom such as N, O, S, etc., for example, C-O-C, COOR, CO
Examples include compounds having a skeleton represented by (having groups such as OH, OH, SO3H, -C-N-C-, and NH2).

Specific examples of such polyhydric carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, and isopropyl succinate. Diethyl malonate, butyl diethyl malonate, phenyl diethyl malonate, diethyl diethyl malonate, dibutyl diethyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, butyl dibutyl maleate, butyl diethyl maleate, β-methyl Aliphatic polycarboxylic acid esters such as diisopropyl glutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconate, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate,
Alicyclic polycarboxylic acid esters such as diethyl nazic acid, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethylisobutyl phthalate, di-n-propyl phthalate, phthalate Diisopropyl, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate,
Di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitic acid Preferred examples include aromatic polycarboxylic acid esters such as dibutyl, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid. In addition, other examples of polyvalent carboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n sebacate, etc.
-octyl, esters of long chain dicarboxylic acids such as di-2-ethylhexyl sebacate, and the like. Among these compounds, it is preferable to use carboxylic esters, and it is particularly preferable to use polyhydric carboxylic esters, especially phthalic esters.

[0045] These electron donors (a) do not necessarily need to be used as starting materials, but can also be generated during the process of preparing the solid titanium catalyst component [Ib]. Further, the solid titanium catalyst component [Ib] may be prepared by contacting the above-mentioned metal magnesium or organomagnesium compound, halogen-containing compound, and liquid titanium compound with the above-mentioned carrier compound.

Solid titanium catalyst component according to the present invention [Ia
] and the liquid titanium compound (c) used for preparing the solid titanium catalyst component [Ib], for example, Ti(OR)gX4-g (R is a hydrocarbon group, X is a halogen atom, 0≦g< Examples include tetravalent halogen-containing titanium compounds represented by 4). More specifically, T
Tetrahalogenated titanium such as iCl4, TiBr4, TiI4; Trihalogenated alkoxytitanium such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(On-C4H9)Cl3, Ti(OC2H5)Br3, Ti(OisoC4H9)Br3 ; Dihalogenated alkoxy titanium such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(On-C4H9)2Cl2, Ti(OC2H5)2Br2; Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(On-C4H9) )3Cl, Ti(OC2H5)3Br; Ti(OCH3)4, Ti(OC2H5)4, Ti(On-C4H9)4 Ti(Oiso-C4H9)4 Ti(O-2-ethylhexyl) Examples include tetraalkoxytitaniums such as 4 and the like.

Among these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon.

[0048] Examples of the precipitation agent (d) used as necessary in the synthesis of solid titanium catalysts [Ia] and [Ib] in the present invention include silicon compounds. Such a silicon compound has the general formula SiXmR
q4-m (X is halogen, R is an alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, m is 1 to 4
is a real number. ) can be mentioned. As the halogen-containing silicon compound represented by the above formula, a halogen-containing silicon compound in which R1 is an alkyl group, a cycloalkyl group, an aryl group, or a general formula

[0049]

[C5]

A silicon-based polymer compound represented by the following can be exemplified. Specifically, the compound represented by the general formula SiXnRq4-n includes tetrahalosilane represented by the general formula SiX4 (in the above formula, n=0), specifically, tetrahalosilane includes tetrachlorosilane, Tetrabromosilane, tetraiodosilane, tetrafluorosilane, trichlorobromosilane, trichloroiodosilane, trichlorofluorosilane, dichlordibromosilane, dichlordiiodosilane, dichlordifluorosilane, chlortribromosilane, chlortriiodosilane , chlortrifluorosilane, bromotriiodosilane, bromotrifluorosilane, dibromdiiodosilane, dibromdifluorosilane, tribromyodosilane, tribromfluorosilane, iodotrifluorosilane, diiododifluorosilane, Triiodofluorosilane can be exemplified, and among these, tetrachlorosilane, tetrabromosilane, trichlorobromosilane, dichlorodibromosilane, and chlorotribromosilane are preferred, and the most suitable one is tetrachlorosilane.

Further, as the halogen-containing silicon compound, compounds represented by the general formula R1SiX3 (n=1 in the above formula), such as methyltrichlorosilane, ethyltrichlorosilane, n- and i-propyltrichlorosilane, n-, i -, sec- and tert-butyltrichlorosilane, n- and i-amyltrichlorosilane,
Saturated alkyl groups having up to 16 carbon atoms such as n-hexyltrichlorosilane, n-heptyltrichlorosilane, n-octyltrichlorosilane, n-dodecyltrichlorosilane, n-tetradecyltrichlorosilane, n-hexadecyltrichlorosilane, etc. Alkyltrichlorosilane containing; unsaturated alkyltrichlorosilane containing an unsaturated alkyl group having 1 to 4 carbon atoms such as vinyltrichlorosilane, isobutenyltrichlorosilane; chloromethyltrichlorosilane, dichloromethyltrichlorosilane, trichloromethyltrichlor Silane, (2-chloroethyl)
Trichlorosilane, (1,2-dibromoethyl)trichlorosilane, trifluoromethyltrichlorosilane, (
haloalkyl or unsaturated haloalkyltrichlorosilanes such as vinyl-1-chloro)trichlorosilane; saturated or unsaturated cycloalkyltrichlorosilanes such as cyclopropyltrichlorosilane, cyclopentyltrichlorosilane, cyclohexenyltrichlorosilane, 3-cyclohexenyltrichlorosilane; Aryl or aralkyltrichlorosilanes such as phenyltrichlorosilane, 2-, 3- and 4-tolyltrichlorosilane, benzyltrichlorosilane; methyldifluorochlorosilane, methylfluorodichlorosilane, ethyldifluorochlorosilane, ethylfluorodichlorosilane ,
n- and i-propyldifluorochlorosilane, n-
Butyldifluorochlorosilane, n-butylfluorodichlorosilane; alkyl such as phenyldifluorochlorosilane, methyldichlorobromosilane, ethyldichlorobromosilane, methyldichloroiodosilane, (trifluoromethyl)difluorobromosilane, etc. or haloalkyl mixed trihalosilanes, etc. Dialkyldihalosilanes represented by the general formula R12SiX2 (in the above formula, n=2), such as dimethyldichlorosilane, diethyldichlorosilane, di-n- and -i-
Propyldichlorosilane, di-n-, -i-, -sec
- and -tert-butyldichlorosilane, di-n-
and -i-amyldichlorosilane, di-n-hexyldichlorosilane, di-n-heptyldichlorosilane, di-n-octyldichlorosilane; dicycloalkyldihalosilanes, such as dicyclopentyldichlorosilane,
Dicyclohexyldichlorosilane, dicyclohexyldibromosilane, dicyclohexyldiiodosilane, dicyclohexyldifluorosilane; diaryl or dialkyldihalosilanes, such as diphenyldichlorosilane, di-2-, -3- or -4-tolyldichlorosilane , dibenzyldichlorosilane, etc.: Trialkylhalosilanes represented by the general formula R13SiX (in the above formula, n=3), such as trimethylchlorosilane, triethylchlorosilane, tri(n- and i-propyl)chlorosilane, tri( n- and i-butyl)
Chlorsilane, tri(n-hexyl)chlorosilane, tri(n-heptyl)chlorosilane, tri(n-octyl)chlorosilane, dimethyl(ethyl)chlorosilane, methyl(diethyl)chlorosilane; triaryl or trialkylhalosilanes, such as triphenylchlor Examples include silane, tri(2-, 3- or 4-tolyl)chlorosilane, tribenzylchlorosilane, and the like.

Among these, silicon tetrachloride and mono-, di- and trichlorosilanes in which R3 is methyl, ethyl and phenyl are preferred. Examples of silicon-based polymer compounds include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, and cyclohexylhydropolysiloxane. These compounds can also be used in combination. Among these compounds, silicon tetrachloride and methylhydropolysiloxane are particularly preferred. There are no particular limitations on the degree of polymerization of the silicon-based polymer compound, but in practice, it is preferably about 10 centistokes to 100 centistokes. Further, although the terminal structure does not have a large effect on the catalytic performance, it is desirable that the terminal structure is blocked with an inert group.

Another example is the organometallic compound [II] described below. Such a precipitating agent (d) may not be used if the other components have a function as a precipitating agent.

As explained above, in the preparation of the solid titanium catalyst component [Ia] according to the present invention, the above-mentioned liquid magnesium compound (a) and a compound having two or more ether bonds (b) are used. , a titanium compound (c) and a precipitating agent (d) used as necessary are used, but in addition to these compounds, other carrier compounds, the above electron donor (e) and a halogen-containing compound, etc. are used,
These compounds may be brought into contact.

Further, in the preparation of the solid titanium catalyst component [Ib] contained in the second olefin polymerization catalyst according to the present invention, the liquid magnesium compound (a) as described above and the electron donor (e ), the titanium compound (c), and the precipitating agent (d) used as necessary, other carrier compounds, halogen-containing compounds, etc. may be used, and these compounds may be brought into contact with each other.

As such a carrier compound, Al2O
3, SiO2, B2O3, MgO, CaO, TiO2,
Metal oxides such as ZnO, ZnO2, SnO2, BaO, and ThO, resins such as styrene-divinylbenzene copolymer, and the like are used. Among these, Al2O3, SiO2
, styrene-divinylbenzene copolymer is preferred.

In addition to the above-mentioned halogen-containing silicon compounds, examples of halogen-containing compounds include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1
-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1
-pentanol, 6-chloro-1-hexanol, 3-
Chlor-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m,o
,p)-Chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-(m,o)-cresol, 6-chloro-(m,o)-cresol, 4-chloro-3,5-dimethylphenol, chlorhydroquinone , 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m,o,p)-chlorophenol, p-chloro-
α-Methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo- 2-butanol, 2-bromo-p-cresol, 1-
Bromo-2-naphthol, 6-bromo-2-naphthol, (m,o,p)-bromophenol, 4-bromoresorcin, (m,o,p)-fluorophenol, p-iodophenol: 2,2 -dichloroethanol, 2,3-
Dichloro-1-propanol, 1,3-dichloro-2-
Propanol, 3-chloro-1-(α-chloromethyl-
1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol , 1,1,1-trichloro-2-propanol, β, β, β-trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,
6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-trifluoroethanol , α, α,
α-Trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A, tetrabromobisphenol A, 2,
2,3,3-tetrafluoro-1-propanol, 2,
Examples include halogen-containing alcohols such as 3,5,6-tetrafluorophenol and tetrafluororesorcin.

Other examples of halogen-containing compounds include: halogen in elemental state: for example, chlorine, bromine, hydrogen iodohalide: for example, hydrogen chloride, hydrogen bromide and hydrogen iodide; haloalkanes: for example, carbon tetrachloride, chloroform, Ethane dichloride, ethane tetrachloride, methylene chloride, trichloride, methyl chloride, ethyl chloride, chloride-
n-Butyl, -n-octyl chloride Nonmetal oxyhalides: e.g. sulfuryl chloride, thionyl chloride, nitrosyl chloride, phosphorus oxychloride, phosgene Nonmetal halides: e.g. phosphorus trichloride, phosphorus pentachloride metal and ammonium halogens Compounds: Examples include aluminum chloride and ammonium chloride.

Solid titanium catalyst component [Ia
] Examples of the electron donor used in the solid titanium catalyst [Ib] include the electron donor (e) used in the solid titanium catalyst [Ib], and these electron donors (e) do not necessarily need to be used as a starting material. There is no solid titanium catalyst component [I
a] It can also be generated during the preparation process.

Solid titanium catalyst component [Ia
] is a liquid magnesium compound (a) without reducing ability as described above, a compound (b) having two or more ether bonds, a liquid titanium compound (c), and as necessary as described above. It is prepared by contacting a precipitating agent (d) with a carrier compound, an electron donor (e), and a halogen-containing compound.

[0061] Such a solid titanium catalyst component [Ia]
There is no particular restriction on the preparation method, but for example, (1
) Magnesium compound that does not have reducing ability in liquid state (a
) and a liquid titanium compound (c) in the presence of a compound (b) having two or more ether bonds to precipitate a solid titanium complex, (2) a method of precipitating a solid titanium composite with a magnesium compound (a) Titanium compound (c)
A method of precipitating a solid titanium complex by reacting the above-mentioned compound (b) having two or more ethers in the presence of the electron donor (e), (3) using the magnesium compound (a) as a precipitating agent. (d), the resulting precipitate is reacted with a compound (b) having two or more ether bonds, a titanium compound (c), and optionally an electron donor (e), A method for obtaining a solid titanium composite, (4) After bringing the magnesium compound (a) into contact with the precipitating agent (d), the obtained precipitate is combined with a halogen-containing compound having two or more ether bonds. Compound (b);
titanium compound (c) and, if necessary, an electron donor (e)
(5) A method of further reacting the reaction products obtained in (1), (2), (3), and (4) with a titanium compound (c). ,
(6) A method of further reacting the reaction products obtained in (1), (2), (3), and (4) with a compound (b) having an ether bond and a titanium compound (c), (7) ( Examples include a method in which the reaction products obtained in steps 1) to (6) are further reacted with the compound (b) having an ether bond.

When producing solid titanium catalyst component [Ia] by such a method, components (a), (b), (
The amount of c) and (d) to be used varies depending on the type, contact conditions, contact order, etc., but the amount of compound having two or more ether bonds ( b) is about 0.01 mole to about 5
The titanium compound (c) in liquid state is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol. It will be done. Further, the precipitating agent (d) may be used in an amount sufficient to form a solid product, but is 0.1 mol to 1 mol per 1 mol of the liquid magnesium compound (a).
000 mol, particularly preferably from 1 mol to about 200 mol.

The temperature at which these components (a), (b), (c) and (d) are brought into contact is usually -70°C to 20°C.
The temperature is 0°C, preferably 10°C to 150°C. The solid titanium catalyst component [Ia] thus obtained contains titanium, magnesium and halogen, and a compound (b) having two or more ether bonds existing through at least two atoms. ing.

Further, in the solid titanium catalyst component [Ia], the halogen/titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and the compound having two or more ether bonds/titanium (molar ratio) is 2 to 100, preferably 4 to 90. ratio) is 0.01 to 10
0, preferably 0.2 to 10, and the magnesium/titanium (atomic ratio) is preferably 2 to 100, preferably 4 to 50.

In preparing the solid titanium catalyst component [Ib] contained in the second olefin polymerization catalyst according to the present invention,
In addition to the above-mentioned magnesium compound (a), electron donor (e), titanium compound (c), and optionally used precipitation agent (d), the above-mentioned carrier compound and halogen-containing compound, etc. These compounds are brought into contact with each other.

[0066] Such a solid titanium catalyst component [Ib]
There is no particular restriction on the preparation method, but for example, (1
) Magnesium compound that does not have reducing ability in liquid state (a
) and a liquid titanium compound (c) as an electron donor (e)
A method in which a solid titanium complex is precipitated by reaction in the presence of an electron donor (e ) and the titanium compound (c) to obtain a solid titanium composite. containing compound, titanium compound (c), and electron donor (e
), (4) A method of further reacting the reaction products obtained in (1), (2), and (3) with a titanium compound (c), (5) )(
1) A method in which the reaction products obtained in (2) and (3) are further reacted with an electron donor (e) and a titanium compound (c), (6) a method in which the reaction products obtained in (1) to (5) are further reacted. Examples include a method in which the reaction product is further reacted with an electron donor (e).

When producing solid titanium catalyst component [Ib] by such a method, components (a), (e), (
The amounts of c) and (d) to be used vary depending on the type, contact conditions, contact order, etc., but the amount of electron donor (e) is approximately 0.0% per 1 mole of magnesium compound (a).
The titanium compound (c) in a liquid state is used in an amount of 0.01 mol to about 5 mol, particularly preferably about 0.1 mol to about 1 mol.
is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol. In addition, precipitation agent (d)
may be in an amount sufficient to form a solid product, but for 1 mole of liquid magnesium compound (a),
It is used in amounts of 0.1 mol to 1000 mol, particularly preferably 1 mol to about 200 mol.

The temperature at which these components (a), (e), (c) and (d) are brought into contact is usually -70°C to 20°C.
The temperature is 0°C, preferably 10°C to 150°C. The solid titanium catalyst component [Ib] thus obtained contains titanium, magnesium and halogen, and the electron donor (e
).

In the solid titanium catalyst component [Ib], the halogen/titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and the electron donor (e)/titanium (molar ratio) is , 0.01-100, preferably 0.2
~10, and the magnesium/titanium (atomic ratio) is 2
-100, preferably 4-50.

The catalyst for olefin polymerization according to the present invention comprises the thus obtained solid titanium catalyst component [Ia] and an organic metal containing a metal selected from Groups I to III of the Periodic Table. It contains a compound catalyst component [II].

FIG. 1 shows an explanatory diagram of the preparation process of the olefin polymerization catalyst according to the present invention. As such an organometallic compound catalyst component [II], for example, an organoaluminum compound, a complex alkylated product of a group I metal and aluminum, an organometallic compound of a group II metal, etc. can be used.

Examples of organic aluminum compounds include RanAlX3-n (wherein Ra is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, and n
is 1 to 3).

In the above formula, Ra is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group. , isobutyl group,
These include pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

[0074] Specifically, the following compounds are used as such organoaluminum compounds. Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum. Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide.

Alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide and the like.

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide.

Alkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride. In addition, as an organoaluminum compound, RanAlY3-n (in the formula, Ra is the same as above, Y is -ORb group, -OSi Rc3 group, -O
AlRd2 group, -NRe2 group, -SiRf3 group or -N(Rg)AlRh2 group, n is 1 to 2
, Rb, Rc, Rd and Rh are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., and Re is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group. etc., where Rf and Rg are a methyl group, an ethyl group, etc.) can also be used.

[0079] As such an organoaluminum compound, specifically, the following compounds are used. (i) RanAl(ORb)3-n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc., (ii) RanAl(OSiRc3)3-n Et2A
l(OSiMe3) (iso-Bu)2Al(OSiMe3)(iso-B
u) 2Al(OSiEt3) etc., (iii) RanA
l(OARd2)3-n Et2AlOAlEt2 (iso-Bu)2AlOAl(iso-Bu)2, etc., (iv) RanAl(NRe2)3-n Me2Al
NEt2 Et2AlNHMe Me2AlNHEt Et2AlN(Me3Si)2 (iso-Bu)2AlN(Me3Si)2 etc., (
v) RanAl(SiRf3)3-n (iso-Bu
)2AlSiMe3 etc., (vi) RanAl(N(R
g) AlRh2)3-nEt2AlN(Me)AlE
t2 (iso-Bu)2AlN(Et)Al(iso-B
u) 2 etc.

[0080] Examples of the above organoaluminum compounds include Ra3Al, RanAl(ORb)3-n, Ra
An organoaluminum compound represented by nAl(OAlRd2)3-n can be cited as a suitable example.

The complex alkylated product of Group I metal and aluminum has the general formula M1AlRj4 (where M1 is Li, Na, or K, and Rj has 1 carbon number).
-15 hydrocarbon groups), specifically, LiAl(C2H5)4, LiAl(
Examples include C7H15)4.

The organometallic compound of Group II metal has the general formula R1R2M2 (where Rk and Rl have 1 to 1 carbon atoms).
15 hydrocarbon groups or halogens, which may be the same or different from each other, except when both are halogens. M2 is Mg, Zn, or Cd), and specific examples include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like.

Two or more of these compounds can also be used in combination. Further, the above-mentioned compound (b) having two or more ether bonds and the electron donor (f) may be brought into contact with the organometallic compound catalyst component [II], if necessary. As such an electron donor (f), the above-mentioned electron donor (e) and an organosilicon compound can be used. Among these, compounds (b) having two or more ether bonds and organosilicon compounds are preferred.

Such an organosilicon compound can be represented by the following general formula. RnSi(OR')4-n [wherein R and R' are hydrocarbon groups, 0<n<4
Specifically, the organosilicon compounds represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxysilane. Silane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o
-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltri Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane Ethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2
- norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane,
Dimethyltetraethoxydisiloxane; cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis (2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, Cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Among these, ethyltriethoxysilane, n-
Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethyl Methoxysilane and the like are preferably used.

In addition to these organosilicon compounds, examples of electron donors (f) that can be used include nitrogen-containing compounds, other oxygen-containing compounds, and phosphorus-containing compounds.

[0087] As such a nitrogen-containing compound, specifically, the following compounds can be used.

[0088]

[C6]

[0089]

[C7]

2,6-substituted piperidines such as:

00
91]

[Chemical formula 8]

2,5-substituted piperidines such as: N,N
,N',N'-tetramethylmethylenediamine, N,N
,N',N'-tetraethylmethylenediamine and other substituted methylene diamines; and substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzy-2-phenylimidazolidine.

[0093] As the phosphorus-containing compound, specifically, the following phosphite esters can be used. Phosphite esters such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, and diethylphenyl phosphite.

Further, as the oxygen-containing compound, the following compounds can be used.

[0095]

[Chemical formula 9]

2,6-substituted tetrahydropyrans such as:

[0097]

[Chemical formula 10]

2,5-substituted tetrahydropyrans such as [0098] The second olefin polymerization catalyst according to the present invention comprises a solid titanium catalyst component [Ib] and an organometallic compound catalyst component [II] as described above, and two or more ethers present via a plurality of atoms. Compound [II
I ].

FIG. 2 shows an explanatory diagram of the preparation process of the second olefin polymerization catalyst according to the present invention. Examples of such organometallic compound catalyst component [II] include organoaluminum compounds similar to those used in the preparation of the first olefin polymerization catalyst according to the present invention, complex alkyl compounds of Group I metal and aluminum, Examples include organometallic compounds of group II metals.

[0100] As the compound [III] having two or more ether bonds as described above, the same two or more ether bonds as used in the preparation of the first solid titanium catalyst component [Ia] according to the present invention can be used. A compound (b) having an ether bond is used.

Further, the second olefin polymerization catalyst according to the present invention may contain an electron donor in addition to the compound [III] having two or more ether bonds,
As such an electron donor, for example, the electron donor (f) used as necessary in the preparation of the first olefin polymerization catalyst according to the present invention can be used.

[0102] In the first olefin polymerization method according to the present invention, olefins are polymerized using the first olefin polymerization catalyst according to the present invention. Moreover, the second according to the present invention
In the method for polymerizing olefins, the second olefin polymerization catalyst according to the present invention is used to polymerize olefins.

[0103] In the first and second olefin polymerization methods according to the present invention, it is preferable to prepolymerize α-olefin in the olefin polymerization catalyst. This prepolymerization is carried out in an amount of 0.1 to 1000 g per 1 g of olefin polymerization catalyst.
Preferably 0.3-500g, particularly preferably 1-20g
This is done by prepolymerizing the α-olefin in an amount of 0 g.

[0104] In the prepolymerization, a catalyst can be used at a higher concentration than the catalyst concentration in the system in the main polymerization.
The concentration of the solid titanium catalyst component [Ia] or [Ib] in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, especially about 0.01 to 50 mmol, in terms of titanium atoms per liter of liquid medium. Preferably 0.1
It is desirable to set it as the range of 20 mmol.

[0105] The amount of organometallic compound catalyst component [II] is:
The amount of the solid titanium catalyst component [Ia] or [Ib] may be such that 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is produced per 1 g of the solid titanium catalyst component [Ia] or [Ib]. Usually about 0.1 to 300 mol, preferably about 0.5 to 1 mol per mol of titanium atom in Ib]
00 mol, particularly preferably 1 to 50 mol.

In the prepolymerization, the above-mentioned compound (b) or electron donor (e) having two or more ether bonds can be used as necessary, and in this case, these components (b),
(e) is a solid titanium catalyst component [Ia] or [Ib
0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol per mol of titanium atom in ]
Used in molar amounts.

Prepolymerization can be carried out under mild conditions by adding the olefin and the catalyst components described above to an inert hydrocarbon medium. Specifically, the inert hydrocarbon medium used at this time includes propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene;
Examples include halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. When an inert hydrocarbon medium is used in this way, it is preferable to carry out the prepolymerization in a batch manner. On the other hand, prepolymerization can be carried out using the olefin itself as a solvent, or it can be carried out in a state substantially free of solvent. In this case, it is preferable to carry out the prepolymerization continuously.

[0108] Even if the olefin used in the prepolymerization is the same as the olefin used in the main polymerization described later,
They may be different, and specifically, propylene is preferred.

[0109] The reaction temperature during prepolymerization is usually about -20
It is desirable that the temperature range is from about -20 to +100°C, preferably from about -20 to +80°C, and more preferably from 0 to +40°C. In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight regulator has an intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135°C of about 0.2 dl/g or more, preferably about 0.5 to 10 dl/g. It is desirable to use the amount such that As mentioned above, the prepolymerization is carried out at a rate of about 0.1 to 1 per 1 g of solid titanium catalyst component [I].
000 g, preferably about 0.3 to 500 g, particularly preferably 1 to 200 g, of polymer. If the amount of prepolymerization is too large, the production efficiency of the olefin polymer may decrease.

Prepolymerization can be carried out batchwise or continuously. Olefins that can be used in this polymerization include ethylene and carbon atoms of 3 to 20.
α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1
-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

In the polymerization method of the present invention, these olefins can be used alone or in combination. Furthermore, aromatic vinyl compounds such as styrene and allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5 ,8-dimethano-
Cyclic olefins such as 1,2,3,4,4a,5,8,8a-octahydronaphthalene, 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-
Compounds with polyunsaturated bonds such as conjugated dienes and non-conjugated dienes such as dienes such as decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene and butadiene are used as raw materials for polymerization. It can also be used as

In the present invention, polymerization can be carried out by either liquid phase polymerization methods such as solution polymerization or suspension polymerization, or gas phase polymerization methods. When the main polymerization takes the reaction form of liquid phase polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can also be used.

[0113] In the polymerization method of the present invention, the solid titanium catalyst component [Ia] or [Ib] is usually in an amount of about 0.001 to 1 Ti atoms per liter of polymerization volume.
It is used in an amount of 0.5 mmol, preferably about 0.005-0.1 mmol. Also, organometallic compound [II]
is used in an amount such that the amount of metal atoms is usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atoms in the prepolymerized catalyst component in the polymerization system.

Furthermore, in the second polymerization method according to the present invention, the compound having two or more ether bonds (b
) is usually about 0.001 mol to 10 mol, preferably 0.01 mol to 10 mol, per 1 mol of metal atoms of component [II].
It is used in an amount of 2 moles.

[0115] If hydrogen is used during main polymerization, the molecular weight of the resulting polymer can be adjusted, and the melt flow can be adjusted.
A polymer with a high rate is obtained. In the present invention, the olefin polymerization temperature is usually about 20 to 200°C, preferably about 50 to 150°C, and the pressure is usually normal pressure to 10°C.
It is set to 0 kg/cm2, preferably about 2 to 50 kg/cm2. In the polymerization method of the present invention, polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be a homopolymer, a random copolymer, a block copolymer, or the like. When olefin polymerization, particularly propylene polymerization, is carried out using the above catalyst for olefin polymerization, the isotactic index (II) shown by the boiling heptane extraction residue is 70% or more, preferably 85% or more, particularly preferably 95%. The above propylene polymer is obtained. At this time, the stereoregularity can be easily controlled by adjusting the amount of the compound having two or more ether bonds or the electron donor.

[0117] Furthermore, the molecular weight distribution index Mw/Mn value measured using GPC (gel permeation chromatography) is smaller than that of polymers obtained by conventional methods, and is generally 5 or less. A polymer is obtained.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above-mentioned components.

[0119]

Effects of the Invention The first solid titanium catalyst component for olefin polymerization according to the present invention comprises: (a) a liquid magnesium compound having no reducing ability; (b) two or more atoms present through a plurality of atoms; (c) a titanium compound in a liquid state, and optionally (
d) Obtained by contacting a precipitating agent (at least one of component (a), component (b), component (c) and component (d) contains a halogen-containing compound), titanium, magnesium, halogen and Contains a compound having two or more of the above ether bonds.

Therefore, according to this solid titanium catalyst component, it is possible to obtain a catalyst for olefin polymerization that has high catalytic activity and high stereospecificity of the obtained polymer without using an electron donor during polymerization. A catalyst for olefin polymerization that is capable of producing a polymer with even higher catalytic activity and higher stereospecificity by using a compound having two or more ether bonds and other electron donors during polymerization. can be manufactured.

The first olefin polymerization catalyst according to the present invention comprises the solid titanium catalyst component [Ia] and an organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table. [II], and the first olefin polymerization method according to the present invention comprises polymerizing or copolymerizing a monomer selected from ethylene and α-olefin using the above-mentioned olefin polymerization catalyst. are doing. Therefore, according to the first olefin polymerization catalyst and the first olefin polymerization method of the present invention, it is possible to obtain a polymer with high catalytic activity and efficient polymerization reaction, as well as high stereospecificity.

[0122] The second olefin polymerization catalyst according to the present invention comprises (a) a liquid magnesium compound having no reducing ability, (c) a liquid titanium compound, (e) an electron donor, and, if necessary, (d) is obtained by contacting with a precipitating agent (at least one of component (a), component (c), component (e), and component (d) contains a halogen-containing compound), titanium, magnesium, A solid titanium catalyst component [Ib] containing a halogen and the electron donor (e), and an organometallic compound catalyst component [Ib] containing a metal selected from Groups I to III of the periodic table.
I] and a compound [III] having two or more ether bonds existing through a plurality of atoms, and the first olefin polymerization method according to the present invention comprises ethylene and α-olefin. Monomers selected from the following are polymerized or copolymerized using the above-mentioned olefin polymerization catalyst. Therefore, according to the second olefin polymerization catalyst and polymerization method according to the present invention, it is possible to obtain a polymer with high catalytic activity and efficient polymerization reaction, as well as high stereospecificity.

[0123]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

[0124]

[Example 1] [Preparation of solid titanium catalyst component (A)] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were added to 130 ml of
After performing a heating reaction at ℃ for 2 hours to obtain a homogeneous solution, 21.3 g of phthalic anhydride was added to this solution, and further 13 g of phthalic anhydride was added.
Stirring and mixing were performed at 0° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution obtained in this way to room temperature, 75 ml of this homogeneous solution was added to -20°C.
The entire amount was added dropwise over 1 hour to 200 ml of titanium tetrachloride held at . After charging, the temperature of this liquid mixture was raised to 110°C over 4 hours, and when it reached 110°C, 2-isopropyl-2-isopentyl-1,3-
4.79 ml of dimethoxypropane (IPAMP) was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After the 2-hour reaction was completed, the solid portion was collected by hot filtration, and after resuspending this solid portion in 275 ml of titanium tetrachloride, the heating reaction was performed again at 110° C. for 2 hours. After the reaction was completed, the solid portion was again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component (A) prepared by the above operations was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.3% by weight of titanium and 63% by weight of chlorine.
, magnesium 22% by weight and IPAMP 9.8
% by weight. [Polymerization] 750 ml of purified hexane was charged into an autoclave with an internal volume of 2 liters, and 0.75 mmol of triisobutylaluminum and the titanium catalyst component (A) were added at 40° C. in a propylene atmosphere to 0.75 mmol in terms of titanium atoms.
0075 mmol-Ti was charged.

After heating to 60°C, 150 ml of hydrogen was introduced, the temperature was raised to 70°C, and propylene polymerization was carried out at this temperature for 2 hours. The pressure during polymerization was maintained at 7 kg/cm2G. After the polymerization was completed, the slurry containing the produced solid was filtered and separated into a white powder and a liquid phase. The yield of white powdery polymer after drying was 377.2 g, the extraction residue with boiling heptane was 96.83%, the MFR was 1.4 dg/min, and the apparent bulk specific gravity was 0.44 g/ml. On the other hand, 3.3 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 50,700 g-pp/mmol-Ti, and the overall II (t.I.I.) was 96.0%.

[0126]

[Example 2] In [Polymerization] of Example 1, triethylaluminum was used instead of triisobutylaluminum, and 2-isopropyl-2-
Isopentyl-1,3-dimethoxypropane (IPA
Propylene polymerization was carried out in the same manner as in Example 1 except that 0.075 mmol of MP) was added.

[0127] The results are shown in Table 1. The Mw/Mn value determined by gel permeation chromatography (GPC) was 4.76.

[0128]

[Example 3] [Preparation of solid titanium catalyst component (B)] In the preparation of the solid titanium catalyst component of Example 1, IPAM
5. Diisobutyl phthalate (DIBP) instead of S.
A solid titanium catalyst component (B) was prepared in the same manner as in Example 1 except that 22 g was used. Its composition is 2.4% titanium, 20% magnesium, 60% chlorine, DIB
P was 13.0%. [Polymerization] 0.015% of solid titanium catalyst component (B)
Propylene polymerization was carried out in the same manner as in Example 2 except that 200 ml of mmol-Ti hydrogen was used.

[0129] The results are shown in Table 1. Mw/Mn is 4.3
It was 1.

[0130]

[Comparative Example 1] [Polymerization] Solid titanium catalyst component (B)
using 0.0075 mmol-Ti and cyclohexylmethyldimethoxysilane (CMM) instead of IPAMP.
Propylene polymerization was carried out in the same manner as in Example 2 except that S) was used.

[0131] The results are shown in Table 1. Note that Mw/Mn is 4
．． It was 31.

[0132]

Example 4 [Preparation of solid titanium catalyst component (C)] In a reactor, 30 ml of purified decane, 4.8 g of anhydrous magnesium chloride, 17 g of n-butyl orthotitanate, and 19.9 g of 2-ethyl-1-hexanol. 5 g were mixed and heated to 130° C. for 1 hour while stirring to dissolve and form a uniform solution. The solution was brought to room temperature, 3.2 g of methyl p-toluate was added, and then heated at 70°C for 1 hour, followed by dropwise addition of 52 g of silicon tetrachloride over 2.5 hours with stirring to precipitate a solid. The mixture was further heated to 70°C for 1 hour. The solid was separated from the solvent and washed with purified hexane to yield a solid product. The entire amount of the solid product was mixed with 50 ml of titanium tetrachloride dissolved in 50 ml of 1,2-dichloroethane, then 2.57 ml of IPAMP was added, the reaction was carried out at 100°C for 2 hours with stirring, and then the liquid was dissolved at the same temperature. Remove the phase by decantation and add 1 and 2
-50 ml of dichloroethane and 50 ml of titanium tetrachloride
was added, stirred at 100°C for 2 hours, and washed with purified hexane to obtain a solid titanium catalyst component (C).

Composition: 1.7% titanium, 18% magnesium
%, chlorine 57%, and IPAMP 17.4%. Note that all reactions were performed under a nitrogen stream. [Polymerization] In Example 2, solid titanium catalyst component (
Using 0.015 mmol of (C) instead of A), IP
Propylene polymerization was carried out in the same manner as in Example 2, except that CMMS was used instead of AMP and 200 ml of hydrogen was used.

[0134] The results are shown in Table 2.

[0135]

[Example 5] In Example 2 [Polymerization], 0.015 mmol of (C) was added in place of the solid titanium catalyst component (A).
Propylene was polymerized in the same manner as in Example 2, except that 200 ml of hydrogen was used.

[0136] The results are shown in Table 2.

[0137]

[Comparative Example 2] [Preparation of solid titanium catalyst component (D)] In the preparation of the solid titanium catalyst component (D) in Example 4, IPA
A solid titanium catalyst component (D) was prepared in the same manner as in Example 1 except that diisobutyl phthalate (DIBP) was used in an equimolar amount as IPAMP instead of MP. Its composition is 4.7% titanium, 13% magnesium, and 5% chlorine.
2%, and DIBP 19.8%. [Polymerization] Propylene was polymerized in the same manner as in Example 4, except that the solid titanium catalyst component (D) was used.

[0138] The results are shown in Table 2.

[0139]

Example 6 [Preparation of solid titanium catalyst component (E)] 75 ml of purified heptane, 37.5 ml of titanium tetrabutoxide, and 5 g of anhydrous magnesium chloride are added to a reactor. Thereafter, the temperature of the flask is raised to 90° C., and the magnesium chloride is completely dissolved over a period of 2 hours.

[0140]Subsequently, with stirring, 52 g of silicon tetrachloride
(0.31 mol) was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further heated to 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to give a solid product. Transfer the total amount of the solid product to 50 ml of 1,2-dichloroethane.
50 ml of titanium tetrachloride dissolved in I
Add 2.57 ml of PAMP and add 100 ml of PAMP while stirring.
After reacting at ℃ for 2 hours, the liquid phase was removed by decantation at the same temperature, and 50 ml of 1,2-dichloroethane and 50 ml of titanium tetrachloride were added again.
The mixture was stirred at ℃ for 2 hours and washed with purified hexane to obtain a solid titanium catalyst component (E).

Composition: 1.7% titanium, 18% magnesium
%, chlorine 57%, and IPAMP 6.62%. [Polymerization] Propylene was polymerized in the same manner as in Example 4, except that the solid titanium catalyst component (E) was used.

[0142] The results are shown in Table 2.

[0143]

[Example 7] [Preparation of solid titanium catalyst component (F)] In a reactor, 30 ml of purified decane, 4.8 g (0.5 mol) of anhydrous magnesium chloride, orthotitanic acid n
17 g of -butyl and 19.5 g of 2-ethyl-1-hexanol were mixed and heated to 130° C. for 1 hour with stirring to dissolve and form a uniform solution. The solution was cooled to 40°C and the methyl hydrogen polysiloxane 7.5
ml, the magnesium chloride complex is precipitated. After washing this with purified heptane, 100 ml of silicon tetrachloride and 1.82 ml of IPAMP were added.
Hold at 0°C for 2 hours. After this, it was washed with purified heptane, and 100 ml of titanium tetrachloride was added and heated at 110°C for 2 hours.
Hold time. This was filtered at 110°C and washed with purified heptane to obtain a solid titanium catalyst component (F).

The composition was 1.4% by weight of titanium, 18% of magnesium, 54% of chlorine, and 23.3% of IPAMP.

[0145]

[Table 1]

[0146]

[Table 2]

[0147]

[Example 8] "Preparation of solid titanium catalyst component (F)" In a reactor, 30 ml of purified decane, 4.8 g (0.5 mmol) of anhydrous magnesium chloride, orthotitanic acid n
-butyl 17g and 2-ethylhexanol 19.5g
g were mixed and heated at 130° C. for 1 hour while stirring to dissolve and form a uniform solution. The solution is cooled to room temperature and the magnesium chloride complex is precipitated by adding 7.5 ml of methylhydrogenpolysiloxane. After washing this with purified n-hexane, silicon tetrachloride 100
ml and 1.82 ml of IPAMP were added and kept at 50°C for 2 hours. The obtained solid was filtered and washed with purified n-hexane, and then 100 ml of titanium tetrachloride was added and held at 110°C for 2 hours, filtered at 110°C, and further 100 ml of titanium tetrachloride was added and held at 110°C for 2 hours. do. This was filtered at 110°C and washed with purified n-hexane to obtain a solid titanium catalyst component (F).

The composition was 1.4% titanium, 18% magnesium, 54% chlorine, and 23.3% IPAMP. "Polymerization" Polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component (F) was used. The results are shown in Table 3.

[0149]

Example 9 Polymerization was carried out in the same manner as in Example 5 except that a solid titanium catalyst component (F) was used. The results are shown in Table 3.

[0150]

Example 10 Polymerization was carried out in the same manner as in Example 4 except that a solid titanium catalyst component (F) was used. The results are shown in Table 3.

[0151]

[Comparative Example 3] “Preparation of solid titanium catalyst component (G)” I
A solid titanium catalyst component was prepared in the same manner as in Example 8 except that 1.7 ml of DIBP was used instead of PAMP.

The composition was 7.8% titanium, 9.1% magnesium, 45% chlorine, and 33.6% DIBP. "Polymerization" Polymerization was carried out in the same manner as in Example 4 except that the solid titanium catalyst component (H) was used. The results are shown in Table 3.

[0153]

[Table 3]

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 2 is an explanatory diagram of the preparation process of the olefin polymerization catalyst according to the present invention.

Claims (15)

[Claims] Claim 1: (a) a magnesium compound in a liquid state without reducing ability; (b) a compound having two or more ether bonds existing through multiple atoms; (c) a titanium compound in a liquid state; as needed(
d) Titanium, magnesium, halogen and the above obtained by contacting a precipitation agent (at least one of component (a), component (b), component (c) and component (d) contains a halogen-containing compound) A solid titanium catalyst component for olefin polymerization, comprising a compound having two or more ether bonds. 2. The solid titanium catalyst component for olefin polymerization according to claim 1, wherein the component (a) is a liquid magnesium compound consisting of a titanate ester and a magnesium compound. 3. The solid titanium for olefin polymerization according to claim 1, wherein the component (a) is a liquid magnesium compound comprising an electron donor (g) and a magnesium compound. Catalyst component. 4. The solid titanium catalyst component for olefin polymerization according to claim 1, wherein the component (a) comprises an inert solvent and a magnesium compound. 5. The solid form for olefin polymerization according to claim 1, wherein the component (b) is a compound having two or more ether bonds existing through a plurality of carbon atoms. Titanium catalyst component. 6. The component (b) has the following formula: [Formula 1] (where n is an integer of 2≦n≦10,
R26 is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon, and any R1 to R26 jointly represent a ring other than a benzene ring. 6. The solid titanium catalyst component for olefin polymerization according to claim 5, wherein the solid titanium catalyst component for olefin polymerization is represented by the following formula. [Ia] (a) A magnesium compound without reducing ability in a liquid state, (b) An ether compound having two or more ether bonds existing through a plurality of atoms, (c) A magnesium compound in a liquid state that has two or more ether bonds. titanium compounds, and if necessary (
d) Obtained by contacting a precipitating agent (at least one of component (a), component (b), component (c) and component (d) contains a halogen-containing compound), titanium, magnesium, halogen and [II] An organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table. Characteristic catalyst for olefin polymerization. 8. A method for polymerizing olefins, which comprises polymerizing ethylene and/or α-olefin using the olefin polymerization catalyst according to claim 7. [Ib] (a) a liquid magnesium compound without reducing ability, (c) a liquid titanium compound, (e) an electron donor, and optionally (d) a precipitation agent ( However, at least one of component (a), component (c), component (e), and component (d) contains a halogen-containing compound), and contains titanium, magnesium, halogen, and the above electron donor. a solid titanium catalyst component; [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table;
] An olefin polymerization catalyst characterized by comprising an ether compound having two or more ether bonds existing through a plurality of atoms. 10. The solid titanium catalyst component for olefin polymerization according to claim 9, wherein the component (a) is a liquid magnesium compound consisting of a titanate ester and a magnesium compound. 11. The catalyst for olefin polymerization according to claim 9, wherein the component (a) is a liquid magnesium compound comprising an electron donor (g) and a magnesium compound. 12. The catalyst for olefin polymerization according to claim 9, wherein the component (a) comprises an inert solvent and a magnesium compound. 13. The olefin polymerization according to claim 9, wherein the compound having two or more ether bonds is a compound having two or more ether bonds existing through a plurality of carbon atoms. Catalyst for use. 14. The compound having two or more ether bonds has the following formula:
R26 is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon, and any R1 to R26 jointly represent a ring other than a benzene ring. 14. The catalyst for olefin polymerization according to claim 13, wherein the catalyst is represented by the following formula: the main chain may contain atoms other than carbon. 15. A method for polymerizing olefins, which comprises polymerizing ethylene and/or α-olefin using the olefin polymerization catalyst according to claim 9.