JPH04218509A - Preliminary polymerization catalyst, catalyst and method for polymerization olefin - Google Patents

Abstract

PURPOSE:A preliminary polymerization catalyst capable of producing olefinic polymers having more excellent stereoregularity than conventional polymers in a high polymerization activity. CONSTITUTION:The first preliminary polymerization catalyst is produced by preliminarily polymerizing an olefin in the presence of an olefin polymerization catalyst formed from (A1) a solid titanium catalyst component containing magnesium, titanium, a halogen and a compound having two or more ether bonds through plural atoms and (B) an organometallic compound catalyst component containing a metal selected from the groups I, II and II metals in the periodic table. The first catalyst for the polymerization of the olefins contains the preliminary polymerization catalyst. The method for polymerization the olefins comprises the polymerization or copolymerization of the olefins in the presence of the above-mentioned catalyst.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a prepolymerization catalyst, a catalyst, and a polymerization method for producing homopolymers of ethylene, 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 magnesium, halogen,
A catalyst using a solid titanium catalyst component consisting of titanium and a compound having two or more ether bonds existing through multiple atoms, a solid titanium catalyst component consisting of magnesium, titanium, halogen and an electron donor, and an organic We have discovered that a catalyst consisting of a metal compound and a compound having two or more ether bonds can achieve this objective,
The present invention has now been completed.

[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 it is possible to obtain an olefin (co)polymer with high catalytic activity and high stereospecificity, and to use a special electron donor. An object of the present invention is to provide a prepolymerization catalyst, an olefin polymerization catalyst, and an olefin polymerization method that are produced by the method.

[0009]

Summary of the Invention The first prepolymerized catalyst according to the present invention is a solid titanium catalyst containing titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms. An olefin is prepolymerized to an olefin polymerization catalyst formed from component (A1) and an organometallic compound catalyst component (B) containing a metal selected from Groups I to III of the Periodic Table. It is characterized by

According to the prepolymerized catalyst of the present invention, a solid titanium catalyst component (A1) using a compound having two or more ether bonds as described above as an electron donor.
When used, the activity is high even without the use of an electron donor (in this specification, an electron donor does not include a compound having two or more ether bonds as described above unless otherwise specified) during polymerization. , and it is possible to obtain an olefin polymerization catalyst that can produce a polymer with high stereospecificity.

The first olefin polymerization catalyst according to the present invention comprises the prepolymerized catalyst [Ia] and an organometallic compound catalyst component [II] containing a metal selected from Groups I to III of the Periodic Table. ] and, if necessary, the above-mentioned compound having two or more ether bonds and/or an electron donor (
b) Contains [III].

Further, in the olefin polymerization method according to the present invention, ethylene and/or α-olefin are polymerized 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, an organometallic compound catalyst component is used together with the prepolymerized catalyst [Ia] containing the compound having two or more ether bonds as an electron donor. When [II] is used, a polymer having high catalytic activity and efficient polymerization reaction can be obtained, and also a polymer having high stereospecificity can be obtained.

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, a compound having two or more ether bonds and/or a specific electron donor ( By using a catalyst containing b), a polymer with even higher stereoregularity can be obtained.

The second prepolymerized catalyst according to the present invention comprises titanium, magnesium, halogen, and an electron donor (a).
(A2), an olefin polymerization formed from an organometallic compound catalyst component (B) containing a metal selected from Groups I to III of the periodic table, and the above-mentioned compound (C) having two or more ether bonds. The catalyst is prepolymerized with olefin.

According to the second prepolymerization catalyst of the present invention, when a prepolymerization catalyst using a compound having two or more ether bonds as described above is used as an electron donor, during polymerization, Furthermore, it is possible to obtain an olefin polymerization catalyst that can produce a polymer with high activity and high stereospecificity without using an electron donor.

The olefin polymerization catalyst according to the present invention comprises the prepolymerized catalyst [Ib], an organometallic compound catalyst component [II] containing a metal selected from Groups I to III of the Periodic Table, and If necessary, the above-mentioned compound having two or more ether bonds and/or electron donor (b) [
III].

[0017] Furthermore, the second olefin polymerization method according to the present invention includes ethylene and/or α-olefin,
Polymerization or copolymerization is carried out using the above 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], an organometallic compound catalyst component [II] and the two or more of the above solid titanium catalyst components [Ib] are combined. By using a compound having an ether bond and/or an electron donor (b) [III], the catalytic activity is high and the polymerization reaction can be carried out efficiently.
Polymers 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 first prepolymerized catalyst according to the present invention comprises a solid titanium catalyst component (containing titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms). It is prepared using an olefin polymerization catalyst containing A1) and an organometallic compound catalyst component (B).

Further, the second prepolymerization catalyst according to the present invention contains titanium, magnesium, halogen, and an electron donor (
It contains a solid titanium catalyst component (A2) containing a), an organometallic compound catalyst component (B), and the above-mentioned compound (C) having two or more ether bonds.

[0022] Such a solid titanium catalyst component (A1)
Or (A2) is prepared by contacting a magnesium compound and a titanium compound with the compound having two or more ether bonds or the electron donor (a).

[0023] Magnesium compounds can be used in the preparation of the solid titanium catalyst components (A1) and (A2) used in the present invention. Magnesium compounds that do not have this can be mentioned.

[0024] Here, as the magnesium compound having reducing ability, for example, a compound having the formula is a cycloalkyl group,
When n is 0, the two R's may be the same or different, and X is a halogen).

Specific examples of organomagnesium compounds having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, and propylmagnesium. Examples include magnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, butylmagnesium hydride, and the like. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, and isopropoxymagnesium chloride. , butoxymagnesium chloride, alkoxymagnesium halides such as octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Examples include alkoxymagnesiums such as 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

[0028] Magnesium compounds include not only the above-mentioned magnesium compounds having reducing properties and non-reducing properties, but also complex compounds of the above-mentioned magnesium compounds with other metals, complex compounds with other metal compounds, etc. It may be a mixture. Furthermore, it may be a mixture of two or more of the above compounds, and may be used in a liquid or solid state. When the compound is solid, it can be liquefied using alcohols, carboxylic acids, aldehydes, amines, metal acid esters, and the like.

Among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

Solid titanium catalyst component [Ia
] and [Ib], the liquid titanium compound used, for example, has the general formula, Ti(OR)gX4-g (R is a hydrocarbon group, X is a halogen atom, 0
Examples include tetravalent titanium compounds represented by the formula ≦g≦4. More specifically, titanium tetrahalides such as TiCl4, TiBr4, TiI4; Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(On-C4H9)Cl3, Ti(OC2H5)Br3, Ti(OisoC4H9)Br3, etc. Trihalogenated alkoxytitanium 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)4 Tetraalkoxytitanium such as; monohalogenated alkoxytitanium such as Ti(OCH3)4, Ti(OC2H5)4, Ti(On-C4H9)4, Ti(Oiso-C4H9)4, Ti(O-2-ethylhexyl)4 etc. can be mentioned.

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.

The solid titanium catalyst component (A1) contained in the first prepolymerized catalyst according to the present invention has, in addition to the above-mentioned compounds, two or more ether bonds existing through a plurality of atoms. A compound is used.

The solid titanium catalyst component (A2) contained in the second prepolymerized catalyst according to the present invention also contains an electron donor (a) other than the compound having two or more ether bonds.
) is used.

The compounds having two or more ether bonds used in the preparation of the solid titanium catalyst component (A1) used in the present invention include carbon, silicon, oxygen, sulfur, etc., in which the atoms present between these ether bonds are , phosphorus, boron, or two or more selected from these, among which a relatively bulky substituent is bonded to the atom between the ether bonds, Preferably, the compound contains a plurality of carbon atoms in the atoms present in .

Examples of such compounds having two or more ether bonds include the following formulas:

[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 R2n, may jointly form a ring other than a benzene ring, and the main chain may contain atoms other than carbon. ) 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 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 (A1) according to the present invention contains, in addition to the above-mentioned magnesium compound, liquid titanium compound, and above-mentioned compound having two or more ether bonds, a carrier compound and a reaction aid. It may also be prepared by using organic and inorganic compounds containing silicon, phosphorus, aluminum, etc., which are used as organic compounds, electron donors (a) described below, etc., and bringing these into contact with each other.

[0041] As such a carrier compound, Al2O
3, SiO2, B2O3, MgO, CaO, TiO2,
Resins such as ZnO, ZnO2, SnO2, BaO, ThO, and styrene-divinylbenzene copolymer are used. Among these, Al2O3, SiO2 and styrene-divinylbenzene copolymer are preferred.

Further, the electron donor (a) does not necessarily have to be used as a starting material, but can also be generated during the process of preparing the solid titanium catalyst component (A1). The solid titanium catalyst component (A2) contained in the second prepolymerized catalyst according to the present invention is prepared using an electron donor (a) other than the above-mentioned compound having two or more ether bonds. Examples of such electron donors (a) include organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, aldehydes, tertiary amines, phosphites, phosphoric esters, phosphoric acid amides, and carboxylic acid esters. Examples include amides, nitriles, etc., specifically acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
Ketones having 3 to 15 carbon atoms such as benzophenone, cyclohexanone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, and ethyl acetate. , vinyl acetate, propyl acetate, octyl acetate,
Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, 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 ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
γ-butyrolactone, δ-valerolactone, coumarin,
Organic acid esters having 2 to 18 carbon atoms such as phthalide and ethylene carbonate; acetyl chloride, benzoyl chloride,
2 carbon atoms such as toluyl chloride and anisyl chloride
-15 acid halides; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid N,
Acid amides such as N-dimethylamide, benzoic acid N,N-diethylamide, and toluic acid N,N-dimethylamide; tertiary amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, and tetramethylethylenediamine; acetonitrile; Examples include nitriles such as 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:

[0044]

[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
When ~R6 is substituted, the substituent includes a heteroatom such as N, O, S, etc., such as C-O-C, COOR,
Examples include compounds having a skeleton represented by (having groups such as COOH, 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.

Other examples of polyvalent carboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Examples include esters of long chain dicarboxylic acids such as. Among these compounds, it is preferable to use carboxylic esters, and it is particularly preferable to use polyhydric carboxylic esters, especially phthalic esters.

[0048] These electron donors (a) do not necessarily have to be used as starting materials, but can also be produced during the process of preparing the solid titanium catalyst component (A2). In addition to the above-mentioned magnesium compound, liquid titanium compound, and electron donor (a), the solid titanium catalyst component (A2) also contains silicon, phosphorus, aluminum, etc. used as a carrier compound and a reaction aid. It may be prepared by using organic and inorganic compounds containing, electron donor (a), etc., and bringing them into contact.

Solid titanium catalyst component (A1
) is a magnesium compound as described above, a liquid titanium compound, a compound having two or more ether bonds, and if necessary, a carrier compound and an electron donor (a).
It is prepared by contacting with

[0050] Although there are no particular restrictions on the method for producing the solid titanium catalyst component (A1) using these compounds, several examples of the method will be briefly described below. (1) A method in which a magnesium compound, the compound having two or more ether bonds, and a titanium compound are contacted and reacted in any order. In this reaction, each component may be pretreated with a compound having two or more ether bonds and/or a reaction aid such as an electron donor (a), an organoaluminum compound, or a halogen-containing silicon compound. (2) A method of precipitating a solid magnesium-titanium complex by reacting a non-reducing liquid magnesium compound and a liquid titanium compound in the presence of the compound having two or more ether bonds. . (3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound. (4) The reaction product obtained in (1) or (2),
A method of further reacting an electron donor (a) and a titanium compound. (5) A method of treating a solid material obtained by pulverizing a magnesium compound, a compound having two or more ether bonds, and a titanium compound with either a halogen, a halogen compound, or an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, or the magnesium compound and the above-mentioned compound having two or more ether bonds, or the magnesium compound and the titanium compound. May be ground to the bottom. Further, after the pulverization, it may be pretreated with a reaction aid and then treated with a halogen or the like. In addition,
Examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds. (6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of contacting a contact reaction product with a metal oxide, an organomagnesium compound, and a halogen-containing compound with the compound having two or more ether bonds and the titanium compound. (8) A method of bringing a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or allyloxymagnesium into contact with the above compound having two or more ether bonds, and a titanium compound and/or a halogen-containing hydrocarbon. (9) A method of reacting a hydrocarbon solution containing at least a magnesium compound and an alkoxytitanium with a titanium compound, a compound having two or more ether bonds, and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound. (10) A non-reducing liquid magnesium compound and an organoaluminum compound are reacted to precipitate a solid magnesium-aluminum complex, and then,
A method of reacting the compound having two or more ether bonds and a titanium compound.

When producing the solid titanium catalyst component [Ia] by such a method, the amount of the magnesium compound, liquid titanium compound and compound having two or more ether bonds to be used depends on the type, contact Although it varies depending on conditions, contact order, etc., the compound having two or more ether bonds per mole of magnesium is
0.01 mol to 5 mol, particularly preferably 0.1 mol to 1 mol
The titanium compound in liquid state is used in a molar amount of 0.1
It is used in amounts of from 1 mol to 1000 mol, particularly preferably from 1 mol to 200 mol.

The temperature at which these compounds are brought into contact is:
Usually -70°C to 200°C, preferably 10°C to 150°C
It is. The solid titanium catalyst component (A1) obtained in this way contains titanium, magnesium and halogen,
The above-mentioned ether compound having two or more ether bonds is contained.

In this solid titanium catalyst component (A1), 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. ) is 0.01 to 100
, preferably from 0.2 to 10, and the magnesium/titanium (atomic ratio) is preferably from 2 to 100, preferably from 4 to 50.

[0054] The solid titanium catalyst component (A2) used in the present invention is prepared by contacting a magnesium compound, a liquid titanium compound, an electron donor (a), and, if necessary, a carrier compound. It is prepared by letting

[0055] Such a solid titanium catalyst component (A2)
Although there are no particular limitations on the method for preparing , several examples of the method will be briefly explained below. (1) A method of contacting and reacting a magnesium compound, an electron donor (a), and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor (a) and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor (a) is used at least once. (2) a liquid magnesium compound that does not have reducing properties;
A method of precipitating a solid magnesium-titanium complex by reacting a liquid titanium compound in the presence of an electron donor (a). (3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound. (4) The reaction product obtained in (1) or (2),
A method of further reacting an electron donor (a) and a titanium compound. (5) A method of treating a solid material obtained by pulverizing a magnesium compound, an electron donor (a), and a titanium compound with either a halogen, a halogen compound, or an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, a complex compound consisting of a magnesium compound and an electron donor, or a magnesium compound and a titanium compound. Also,
After pulverization, it may be pretreated with a reaction aid and then treated with a halogen or the like. Examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds. (6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of contacting a contact reaction product with a metal oxide, an organomagnesium, and a halogen-containing compound with an electron donor (a) and a titanium compound. (8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor (a), a titanium compound, and/or a halogen-containing hydrocarbon. (9) A hydrocarbon solution containing at least a magnesium compound and an alkoxy titanium, a titanium compound, an electron donor (
a) and, if necessary, a method of reacting with a halogen-containing compound such as a halogen-containing silicon compound. (10) A non-reducing liquid magnesium compound and an organoaluminum compound are reacted to precipitate a solid magnesium-aluminum complex, and then,
A method of reacting an electron donor (a) and a titanium compound.

When producing the solid titanium catalyst component (A2) by such a method, the amounts of the magnesium compound, the liquid titanium compound, and the electron donor (a) to be used depend on their types and contact conditions. The amount of the electron donor (a) is 0.01 mol to 5 mol, particularly preferably 0.01 mol to 5 mol per 1 mol of magnesium, although it varies depending on the order of contact and the like.
The titanium compound in liquid state is used in an amount of 1 mol to 1 mol, and the titanium compound in liquid state is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol.

The temperature at which these compounds are brought into contact is:
Usually -70°C to 200°C, preferably 10°C to 150°C
It is. The solid titanium catalyst component (A2) obtained in this way contains titanium, magnesium and halogen,
Contains an electron donor (a).

In this solid titanium catalyst component (A2), the halogen/titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and the electron donor (a)/titanium (molar ratio) is 0. 01 to 100, preferably 0.2 to 10, and the magnesium/titanium (atomic ratio) is 2 to 1.
00, preferably 4 to 50.

The first prepolymerized catalyst according to the present invention comprises a solid titanium catalyst component (A1) as described above and an organic metal containing a metal selected from Groups I to II of the periodic table. An olefin polymerization catalyst containing a compound catalyst component (B) is used.

[0060] Such organometallic compound catalyst component (B)
As the material, 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.

As the organic aluminum compound, for example, RanAlX3-n (wherein Ra is 1 carbon number
~12 hydrocarbon groups, X is halogen or hydrogen, and n is 1 to 3) can be exemplified.

In the above formula, Ra has 1 to 12 carbon atoms.
Hydrocarbon groups such as alkyl, cycloalkyl or aryl groups, specifically methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, etc.

[0063] As such an organoaluminum compound, the following compounds are specifically used. Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum. Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum 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, and Rb, Rc, Rd and Rh are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group. basis,
phenyl group, etc., Re is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and Rf and Rg are methyl group, ethyl group, etc.) can also be used. .

[0068] Specifically, the following compounds are used as such organoaluminum compounds. (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-n Et2AlN(Me)AlE
t2 (iso-Bu)2AlN(Et)Al(iso-Bu
)2 etc.

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 RkRlM2 (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. In addition, in the first prepolymerized catalyst according to the present invention, the above-mentioned compound having two or more ether bonds and/or the electron donor (b) is optionally added together with the organic compound catalyst component [II]. You may also use
As such an electron donor (b), the above-mentioned electron donor (a) and an organosilicon compound represented by the following general formula can be used, and among these, a compound having two or more ether bonds and a compound having two or more ether bonds can be used. Preferably, organosilicon compounds are used.

RnSi(OR')4-n
(In the formula, R and R' are hydrocarbon groups, and 0<n<4
) Specifically, the organosilicon compounds represented by the above general formula include trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-
Butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis p-Tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane Silane, 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, cyclopentyldimethylmethoxy Silane, 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. Two or more of these organosilicon compounds can also be used in combination.

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

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

[0077]

[C5]

[0078]

[C6]

2,6-substituted piperidines such as:

00
80]

[C7]

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

[0082] 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.

[0084]

[Chemical formula 8]

2,6-substituted tetrahydropyrans such as:

[0086]

[Chemical formula 9]

2,5-substituted tetrahydropyrans such as [0087] The second prepolymerized catalyst according to the present invention has a solid titanium catalyst component (A2) and an organometallic compound catalyst component (B) as described above, and two or more ether bonds existing through a plurality of atoms. An olefin polymerization catalyst containing the compound (C) is used.

Such an organometallic compound catalyst component [II
For example, a catalyst component made of the same organometallic compound as used in the preparation of the first olefin polymerization catalyst according to the present invention is used.

The compound [III] having two or more ether bonds as described above is a compound having two or more ether bonds similar to that used in the preparation of the first solid titanium catalyst component according to the present invention. A compound having the following is used.

Further, the second olefin polymerization catalyst according to the present invention may contain an electron donor in addition to the above-mentioned compound having two or more ether bonds, and such electron donor may include: For example, the electron donor (b) used in the preparation of the first olefin polymerization catalyst according to the present invention can be used.

First prepolymerized catalyst according to the present invention [Ia]
is formed by polymerizing an olefin onto an olefin polymerization catalyst containing a solid titanium catalyst component (A1) and an organometallic compound (B).

Further, the second prepolymerization catalyst according to the present invention [
Ib] is formed by polymerizing an olefin into an olefin polymerization catalyst containing an upper air solid titanium catalyst component (A2), an organometallic compound (B) and a compound (C) having two or more ether bonds. .

First and second prepolymerized catalysts according to the present invention [
Ia] and [Ib], this prepolymerization is carried out in an amount of 0.1 to 1000 g per 1 g of catalyst for olefin polymerization, preferably 0.
．． α in an amount of 3 to 500 g, particularly preferably 1 to 200 g
- carried out by prepolymerizing the olefin.

[0094] In the prepolymerization, a catalyst can be used at a higher concentration than the catalyst concentration in the system in the main polymerization. First and second prepolymerization catalysts [Ia] and [Ia] according to the present invention
b], the solid titanium catalyst component (A
The concentration of 1) or (A2) is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, particularly preferably 0.1 to 20 mmol in terms of titanium atoms per liter of liquid medium. It is desirable to set the range.

The amount of the organometallic compound catalyst component (B) is 0 per 1 g of the solid titanium catalyst component (A1) or (A2).
．． The amount may be such that 1 to 1000 g, preferably 0.3 to 500 g of polymer is produced, per mole of titanium atom in the solid titanium catalyst component (A1) or (A2).
Usually about 0.1 to 300 mol, preferably about 0.5 to 10
An amount of 0 mol, particularly preferably 1 to 50 mol is desirable.

First prepolymerization catalyst according to the present invention [Ia]
Then, these compounds are solid titanium catalyst component (A1)
It is used in an amount of 0.1 to 50 moles, preferably 0.5 to 30 moles, and more preferably 1 to 10 moles, per mole of titanium atoms in the titanium atom.

[0097] Furthermore, the second prepolymerization catalyst according to the present invention [
Ib], these compounds are solid titanium catalyst components (
0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 30 mol, per mol of titanium atom in A2)
It is used in an amount of 10 mol.

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. in this way,
If an inert hydrocarbon medium is used, the prepolymerization is preferably carried out batchwise. 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.

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.

[0100] 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

[0101] As mentioned above, the prepolymerization is carried out in an amount of about 0.1 to 1 per 1 g of solid titanium catalyst component (A1) or (A2).
000 g, preferably about 0.3 to 500 g, particularly preferably 1 to 200 g, of polymer.

The first olefin polymerization catalyst according to the present invention comprises the above prepolymerized catalyst [Ia] and an organometallic compound [II] containing a metal selected from Groups I to III of the Periodic Table. and, if necessary, a compound having two or more ether bonds existing through a plurality of atoms and/or an electron donor (b) [III].

Further, the second olefin polymerization catalyst according to the present invention comprises the prepolymerized catalyst [Ib] and an organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table. [II] and, if necessary, a compound having two or more ether bonds and/or an electron donor (b) [III] present via a plurality of atoms.

The organometallic compound catalyst component [II] used in the preparation of these olefin polymerization catalysts is the organometallic compound catalyst component (B
) can be used. Further, as the compound having two or more ether bonds and the electron donor (b), the compounds used in the preparation of the prepolymerization catalyst can be similarly used.

FIGS. 1 and 2 are explanatory diagrams of the process for preparing the olefin polymerization catalyst according to the present invention. and,
In the first and second olefin polymerization methods according to the present invention, olefins are polymerized using the first olefin polymerization catalyst according to the present invention.

In the first and second olefin polymerization methods of the present invention, olefins that can be used in the main polymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene and 1-butene. , 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. can be mentioned.

In the first and second polymerization methods according to 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-1,2,3,4,4a,5,8,8a
- cyclic olefins such as 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-
Dienes such as nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene, butadiene, etc. Compounds having polyunsaturated bonds such as conjugated dienes and non-conjugated dienes can also be used as polymerization raw materials.

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 slurry 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.

[0109] In the polymerization method of the present invention, the solid titanium catalyst component [Ia] or [Ib] is usually 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 first and second polymerization methods according to the present invention, if necessary, the compound having two or more ether bonds and/or the electron donor (b) may be
[II] Usually about 0.00 per mole of metal atoms of component
It is used in an amount of 1 mol to 10 mol, preferably 0.01 mol to 2 mol.

[0111] If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted, and a polymer with a high melt flow rate can be 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 100k.
g/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.

[0113] Furthermore, the Mw/Mn value, an index of molecular weight distribution 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.

[0115]

Effects of the Invention The first prepolymerized catalyst according to the present invention is a solid titanium catalyst containing titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms. An olefin is prepolymerized into an olefin polymerization catalyst formed from a component (A1) and an organometallic compound catalyst component (B) containing a metal selected from Groups I to III of the periodic table.

[0116] The second prepolymerization catalyst according to the present invention is selected from titanium, magnesium, halogen, electron donor (a) (A2), and groups I to III of the periodic table. An olefin is prepolymerized into an olefin polymerization catalyst formed from an organometallic compound catalyst component (B) containing a metal and the compound (C) having a plurality of ether bonds.

According to the first and second prepolymerization catalysts of the present invention, when an olefin polymerization catalyst using a compound having two or more ether bonds as described above is used as an electron donor, the catalyst It is possible to obtain an olefin polymerization catalyst that can produce a polymer with high activity and high stereospecificity without using an electron donor.

The first and second olefin polymerization catalysts according to the present invention contain the prepolymerized catalyst [Ia] or [Ib] and a metal selected from Groups I to III of the Periodic Table. The organometallic compound catalyst component [II] may also contain the compound having two or more ether bonds and/or the electron donor (a) [III] as required, and the present invention In the first and second olefin polymerization methods, ethylene and/or α-olefin are polymerized using the first and second olefin polymerization catalysts as described above.

According to the first and second olefin polymerization catalysts and olefin polymerization methods of the present invention, the solid titanium catalyst component [Ia] or When the organometallic compound catalyst component [II] is used together with [Ib], a polymer having high catalytic activity and efficient polymerization reaction can be obtained, and also a polymer having high stereospecificity can be obtained.

Further, the first and second olefin polymerization catalysts and olefin polymerization methods according to the present invention contain, in addition to the above two components, a compound having two or more ether bonds and/or a specific electron donor ( By using a catalyst containing a), a polymer with even higher stereoregularity can be obtained.

[0121]

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

[0122]

[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 heating the reaction at ℃ for 2 hours to obtain a homogeneous solution, 21.3 g of phthalic anhydride was added to this solution, and 1
Stirring and mixing were performed at 30° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was
The entire amount was dropped over 1 hour into 200 ml of titanium tetrachloride kept at 0°C. After the charging was completed, the temperature of the mixed solution was raised to 110° C. over 4 hours, and when it reached 110° C., 5.22 g of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After 2 hours of reaction, the solid part was collected by hot filtration, and this solid part was
After resuspending in 5 ml of titanium tetrachloride,
The heating reaction was carried out at ℃ 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 operation was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. Solid titanium catalyst component [A] thus obtained
The composition is 2.4% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium, and 13.% of diisobutyl phthalate.
It was 0% by weight. [Prepolymerization of solid titanium catalyst component [A]] 400ml
In a four-necked glass reactor equipped with a stirrer, 100 ml of purified hexane, 10 mmol of triethylaluminum, and 2-isopropyl-2-isopentyl-1,3- were added under a nitrogen atmosphere.
After adding 2 mmol of dimethoxypropane (IPAMP) and 1.0 mmol of the above solid Ti catalyst component [A] in terms of Ti atoms, propylene was added to the reactor at a rate of 3.2 Nl/hour at a temperature of 20°C for 1 hour. supplied. When the supply of propylene is finished, the inside of the reactor is purged with nitrogen, and a washing operation consisting of removing the supernatant liquid and adding purified hexane is performed twice, and then resuspended in purified hexane and the entire amount is transferred to a catalyst bottle. A prepolymerized catalyst (B) was obtained. [Polymerization] 750 ml of purified hexane was charged into an autoclave with an internal volume of 2 liters, and 0.75 mmol of triethylaluminum and the prepolymerized catalyst (B) were added to 0.75 mmol of triethylaluminum and the prepolymerized catalyst (B) in terms of titanium atoms at 60°C in a propylene atmosphere.
．． 015 mmol was charged.

After introducing 200 ml of hydrogen and raising the temperature to 70°C, propylene polymerization was carried out 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 400.6 g, the extraction residue with boiling heptane was 98.94%, and the MFR was 3.
．． 4dg/min, its apparent bulk specific gravity is 0.45g/m
It was l. On the other hand, 1.5 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity is 26,800g-PP
/mmol-Ti, and II (t.I
．． I. ) was 98.6%.

[0124]

[Example 2] In the prepolymerization in Example 1, IPAMP
Prepolymerization was carried out in the same manner as in Example 1, except that 1 mmol of was used, to obtain a prepolymerized catalyst (C).

[0125] Propylene polymerization was also carried out in the same manner as in Example 1 except that the catalyst was used. The results are shown in Table 1. Mw/Mn measured by GPC was 4.79.

[0126]

[Example 3] In the prepolymerization in Example 1, IPAMP
A prepolymerized catalyst (D) was obtained by carrying out prepolymerization in the same manner as in Example 1, except that 0.5 mmol of .

[0127] Furthermore, using the catalyst, IPAMP0.0
Polymerization of propylene was carried out in the same manner as in Example 1 except that 75 mmol was used. The results are shown in Table 1.

[0128]

Examples 4 and 5 Propylene polymerization was carried out in the same manner as in Example 3, except that prepolymerization catalysts (B) and (C) were used.

[0129] The results are shown in Table 1.

[0130]

[Example 6] [Preparation of solid titanium catalyst component [E]] After replacing a high-speed stirring device (manufactured by Tokushu Kika Kogyo) with an internal volume of 2 liters with sufficient N2, 700 ml of refined kerosene, commercially available Mg
10 g of Cl2, 24.2 g of ethanol, and 3 g of Emazol 320 (trade name, manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 20° C. and 800 rpm for 30 minutes. Under high-speed stirring, using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-liter glass flask (equipped with a stirrer) filled with 1 liter of refined kerosene pre-cooled to -10°C. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, the system was heated to 40°C, and after adding 1.3 ml of diisobutyl phthalate (DIBP), the system was heated to 100°C. The temperature rose. After stirring and mixing at 100° C. for 2 hours, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and stirred and mixed again at 130° C. for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid titanium catalyst component [E]. The components were 2.3% by weight of titanium, 63% by weight of chlorine, 20% by weight of magnesium, and 5.5% by weight of DIBP. [Prepolymerization of solid titanium catalyst component [E]] 400ml
In a four-necked glass reactor equipped with a stirrer, 100 ml of purified hexane, 10 mmol of triethylaluminum, and 2-isopropyl-2-isopentyl-1,3- were added under a nitrogen atmosphere.
After adding 2 mmol of dimethoxypropane and 1.0 mmol of the above solid titanium catalyst component [E] in terms of Ti atoms, propylene was supplied to the reactor at a rate of 3.3 Nl/hour at a temperature of 20° C. for 1 hour. did. When the supply of propylene is finished, the inside of the reactor is replaced with nitrogen, and a cleaning operation consisting of removing the supernatant liquid and adding purified hexane is carried out.
After circulating, the mixture was resuspended in purified hexane and the entire amount was transferred to a catalyst bottle to obtain a prepolymerized catalyst (F). [Polymerization] Polymerization of propylene was carried out in the same manner as in Example 1, except that the prepolymerization catalyst (F) was used.

[0132] The results are shown in Table 1. Mw/Mn measured by GPC was 4.48.

[0133]

Example 7 Propylene was polymerized in the same manner as in Example 3, except that the prepolymerization catalyst (F) was used.

[0134] The results are shown in Table 1. Mw/Mn measured by GPC was 4.72.

[0135]

[Table 1]

[0136]

[Examples 8 and 9] [Preparation of solid titanium catalyst component (G)] 95.2 g of anhydrous magnesium chloride, 442 ml of decane
and 390.6 g of 2-ethylhexyl alcohol at 1
After performing a heating reaction at 30°C for 2 hours to obtain a homogeneous solution, 21.3 g of phthalic anhydride was added to this solution, and further,
Stirring and mixing were performed at 130° C. for 1 hour, and phthalic anhydride was dissolved in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was
The entire amount was dropped over 1 hour into 200 ml of titanium tetrachloride kept at 0°C. 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-dimethoxypropane (IPAMP) 4.79ml
was added, and the mixture was kept 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, 63% by weight of chlorine, 22% by weight of magnesium, and IPAMP 9.
．． It was 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/cm3G. 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%. [Prepolymerization of solid titanium catalyst component (G)] Using 3.0 mmol of triethylaluminum and 1.0 mmol of solid titanium catalyst component (G) in terms of titanium atoms, I
Prepolymerization was carried out in the same manner as in Example 1, except that PAMP was not used, to obtain a prepolymerized catalyst (H). [Polymerization] Instead of prepolymerization catalyst (B), prepolymerization catalyst (
Using 0.0075 mmol of H) and 150 ml of hydrogen, IPAMP (Example 8) and cyclohexylmethyldimethoxysilane (CMM) were used as electron donors, respectively.
Polymerization was carried out in the same manner as in Example 1 except that 0.075 mmol of S) (Example 9) was used.

[0138] The results are shown in Table 2.

[0139]

[Example 10] [Polymerization] 300 ml of hydrogen, dicyclopentyldimethoxysilane (D
Example 8 except that 0.075 mmol of CPMS) was used.
Polymerization was carried out in the same manner.

[0140] The results are shown in Table 2.

[0141]

Example 11 [Polymerization] Polymerization was carried out in the same manner as in Example 8, except that triisobutylaluminum was used instead of triethylaluminum.

[0142]

[Example 12] [Prepolymerization of solid titanium catalyst component (G)] In a 400 ml four-necked glass reactor equipped with a stirrer, 100 ml of purified hexane, 3 mmol of triethylaluminum, and the above solid titanium catalyst component (G) were placed in a nitrogen atmosphere.
After adding 1.0 mmol of G) in terms of titanium atoms, 20
Propylene was fed to the reactor for 1 hour at a rate of 3.2 liters/hour at a temperature of .degree.

[0143] When the supply of propylene was completed, the inside of the reactor was purged with nitrogen, and a washing operation consisting of removing the supernatant liquid and adding purified hexane was performed twice, and then resuspended in purified hexane and placed in a catalyst bottle. The entire amount was transferred and the prepolymerized catalyst (I
) was obtained. [Polymerization] Purified n- in an autoclave with an internal volume of 2 liters
Insert 750ml of hexane, and at 60°C in a propylene atmosphere, triisobutylaluminum and ethylaluminum sesquichloride are converted to 2/2 in terms of aluminum atoms.
The compound mixed at a ratio of 1 (mol/mol) is 0.75 mmol in terms of aluminum atoms, and IPAMP is 0.075 mmol.
Millimole of Ti and prepolymerized catalyst (I) were charged in an amount of 0.0075 mmole in terms of titanium atoms.

After introducing 150 ml of hydrogen, the temperature was raised to 70°C and maintained at this temperature for 2 hours to carry out polymerization. The pressure during polymerization was maintained at 7 kg/cm2G. The results are shown in Table 2.

[0145]

[Table 2]

[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 a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (10)

[Claims] [Claim 1] Titanium, magnesium, halogen,
A solid titanium catalyst component (A1) containing a compound having two or more ether bonds existing through a plurality of atoms,
and an olefin polymerization catalyst formed from an organometallic compound catalyst component (B) containing a metal selected from Groups I to III of the Periodic Table, and an olefin prepolymerized therein. Polymerization catalyst. 2. The compound according to claim 1, 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. Prepolymerization catalyst. 3. The compound having two or more ether bonds 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. 3. The prepolymerization catalyst according to claim 2, wherein the prepolymerization catalyst is represented by the following formula: the main chain may contain atoms other than carbon. [Claim 4] [Ia] A solid titanium catalyst component containing titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms (
A1), and a prepolymerized catalyst component obtained by polymerizing an olefin to an olefin polymerization catalyst formed from an organometallic compound catalyst component (B) containing a metal selected from Groups I to III of the Periodic Table. and [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table, and optionally [III] the above-mentioned compound having two or more ether bonds and/ or an electron donor (b) (provided that the electron donor (b) does not include the compound having two or more ether bonds). 5. A method for polymerizing olefins, which comprises polymerizing ethylene and/or α-olefin using the olefin polymerization catalyst according to claim 4. [Claim 6] Titanium, magnesium, and halogen;
A solid titanium catalyst component (A2) containing an electron donor (a) (however, the electron donor (a) does not include a compound having an ether bond existing through multiple atoms), Olefin polymerization formed from an organometallic compound catalyst component (B) containing a metal selected from Groups I to III, and a compound (C) having two or more ether bonds existing through a plurality of atoms. A prepolymerization catalyst characterized by being made by prepolymerizing an olefin as a catalyst for use. 7. The compound according to claim 6, 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. Prepolymerization catalyst. 8. 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. 8. The prepolymerization catalyst according to claim 7, wherein the prepolymerization catalyst is represented by the following formula: the main chain may contain atoms other than carbon. Claim 9: [Ib] titanium, magnesium, halogen, and electron donor (a) (provided that electron donor (a)
is a solid titanium catalyst component (A
2), an organometallic compound catalyst component (B) containing a metal selected from Groups I to III of the periodic table, and a compound having two or more ether bonds existing through a plurality of atoms (C ), a prepolymerized catalyst formed by polymerizing an olefin to an olefin polymerization catalyst formed from [I
I] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table;
II] An olefin polymerization catalyst comprising the above compound having two or more ether bonds and/or the electron donor (b). 10. A method for polymerizing olefins, which comprises polymerizing ethylene and/or α-olefin using the olefin polymerization catalyst according to claim 9.