JPH04218508A - Production of alpha-olefinic polymer - Google Patents

Abstract

PURPOSE:A method for producing an alpha-olefinic polymer or copolymer which can produce in a high polymerization activity the alpha-olefinic polymer or copolymer having more excellent stereo-regularity and containing >=70mol% of >=4C alpha-olefins. CONSTITUTION:In the first method for producing an alpha-olefinic polymer, one or more kinds of alpha-olefins selected from >=2C alpha-olefins are polymerized to produce a polymer or copolymer containing >=70mol% of >=4C alpha-olefins in the presence of an olefinic polymerization catalyst comprising (Ia) a solid titanium catalyst component containing magnesium, titanium, a halogen and a compound having two or more ether bonds through plural atoms, and (II) an organometallic compound catalyst component containing a metal selected from the groups I, II and III metals in the periodic table.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to α-olefin copolymers, and more specifically, α-olefin copolymers having 4 or more carbon atoms.
The present invention relates to a method for producing a polymer or copolymer containing at least 70 mol% of olefin.

0002

Technical Background of the Invention Conventionally, titanium compounds supported on activated magnesium halides have been used as catalysts for producing olefin polymers such as homopolymers or copolymers of ethylene and α-olefins. Catalysts containing the following 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.

[0004] This catalyst is highly effective in the polymerization of α-olefins having 3 or more carbon atoms such as propylene and butene-1, as well as in the copolymerization of two or more selected from the α-olefins, as well as the polymerization of ethylene. It has activity, and can improve the stereoregularity and crystallinity of the obtained copolymer and give it a high melting point.

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, stereoregularity, and crystallinity, and found that two or more ether bonds were used as electron donors. The present inventors have discovered that the object can be achieved by a solid titanium catalyst component containing a compound having two or more ether bonds as an electron donor, and a catalyst containing a compound having two or more ether bonds as an electron donor, and have completed the present invention.

[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 above-mentioned prior art, and it is possible to obtain an α-olefin polymer with excellent stereoregularity and crystallinity with high catalytic activity. The object of the present invention is to provide a method for producing an α-olefin polymer.

[0009]

Summary of the Invention The first method for producing an α-olefin copolymer according to the present invention comprises [Ia] titanium, magnesium, a halogen, and two or more ether bonds existing through a plurality of atoms. and [II] a solid titanium catalyst component containing a compound having
In the presence of an olefin polymerization catalyst containing an organometallic compound catalyst component containing a Group I metal, an α-olefin having 2 or more carbon atoms and an α-olefin having 4 or more carbon atoms as a main component - It is characterized by producing a polymer or copolymer containing at least 70 mol % or more of α-olefin having 4 or more carbon atoms by polymerizing or copolymerizing olefins.

According to the first method for producing an α-olefin polymer according to the present invention, the solid titanium catalyst component [Ia] containing the compound having two or more ether bonds;
When a catalyst containing the organometallic compound catalyst component [II] is used, an α-olefin polymer having excellent crystallinity and stereoregularity can be produced with high catalytic activity.

[0011] The second method for producing an α-olefin polymer according to the present invention comprises [Ib] titanium, magnesium,
Halogen and electron donor (a) (however, electron donor (
a) does not include compounds having two or more ether bonds existing through multiple atoms); [II] Groups I to III of the periodic table;
an organometallic compound catalyst component containing a group metal, and [III
] In the presence of an olefin polymerization catalyst containing a compound having two or more ether bonds existing through a plurality of atoms, an α-olefin having 2 or more carbon atoms and an α-olefin having 4 or more carbon atoms - At least 70 mol% of α-olefins having 4 or more carbon atoms by polymerizing or copolymerizing α-olefins mainly composed of olefins.
It is characterized by producing a polymer or copolymer containing the above.

According to the second method for producing an α-olefin polymer according to the present invention, the solid titanium catalyst component [I
a], the organometallic compound catalyst component [II], and a compound having two or more ether bonds [III], it is possible to produce an α-olefin polymer with excellent crystallinity and stereoregularity. It can be produced with high catalytic activity.

[0013]

DETAILED DESCRIPTION OF THE INVENTION A method for producing an α-olefin polymer (including copolymer) according to the present invention will be specifically described below.

The first method for producing an α-olefin polymer according to the present invention comprises titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms. Solid titanium catalyst component [I
a] and a specific organometallic compound catalyst component [II] (hereinafter sometimes referred to as the second catalyst).

Further, in the second method for producing an α-olefin according to the present invention, a solid titanium catalyst component [I
b], a specific organometallic compound catalyst component [II], and the above-mentioned compound [III] having two or more ether bonds (hereinafter sometimes referred to as the second catalyst) is used.

The solid titanium catalyst component [Ia] or [Ib] constituting the first and second catalysts is composed of a magnesium compound, a titanium compound, and the above-mentioned compound having two or more ether bonds or an electron donor. It is prepared by contacting these compounds with body (a).

Solid titanium catalyst components [Ia] and [I
A magnesium compound can be used for the preparation of b], and examples of the magnesium compound include a magnesium compound having reducing ability and a magnesium compound not having reducing ability.

[0018] Here, as a 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. alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium Alkoxymagnesiums such as; 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.

[0022] 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.

The liquid titanium compounds used in preparing the solid titanium catalyst components [Ia] and [Ib] contained in the catalysts used in the first and second methods of the present invention include: For example, the general formula, Ti(OR)gX4-g (R is a hydrocarbon group, X is a halogen atom, 0
≦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.

In the preparation of the solid titanium catalyst component [Ia] contained in the first catalyst used in the present invention, in addition to the above-mentioned compounds, two or more ether bonds existing through a plurality of atoms are added. A compound having the following properties is used.

[0027] The solid titanium catalyst component [Ib] contained in the catalyst used in the second method of the present invention may be prepared by using an electron donor (a) other than the above-mentioned compound having two or more ether bonds. It is prepared by

Such a solid titanium catalyst component [Ia]
Compounds having two or more ether bonds used in the preparation of are compounds in which the atoms present between these ether bonds are carbon, silicon, oxygen, sulfur, phosphorus, boron, or two or more types selected from these. Among these, compounds in which a relatively bulky substituent is bonded to the atom between the ether bonds, and a plurality of carbon atoms are included in the atoms present between two or more ether bonds are preferable. .

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

[0030]

[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-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-dimethoxy Butane, 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 [Ia] used in the preparation of the first catalyst contains, in addition to the above-mentioned magnesium compound, a compound having two or more ether bonds, and a liquid titanium compound, a carrier compound. It may also be prepared by contacting organic and inorganic compounds containing silicon, phosphorus, aluminum, etc. used as reaction aids, electron donors (a) described below, and the like.

[0035] 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 produced during the process of preparing the solid titanium catalyst component [Ia]. The solid titanium catalyst component [Ib] contained in the catalyst used in the second method according to the present invention is prepared using an electron donor (a) other than the above-mentioned compound having two or more ether bonds. There is. Such electron donors (a) include organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, tertiary amines, phosphorous esters, phosphoric esters, phosphoric acid amides, carboxylic acid amides, Examples include nitrile, and 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, benzaldehyde,
2-1 carbon atoms such as tolualdehyde and naphthaldehyde
Aldehydes of 5; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton ethyl acid, 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, ethoxy Organic acid esters with 2 to 18 carbon atoms such as ethyl benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; 2-carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, etc. ~15
Acid halides; ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid N,N-dimethylamide, benzoic acid N,N-diethylamide , acid amides such as toluic acid N,N-dimethylamide, trimethylamine, triethylamine, tributylamine,
Tertiary amines such as tribenzylamine, tetramethylethylenediamine; acetonitrile, benzonitrile,
Examples include nitriles such as 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, polyhydric carboxylic acid esters can be cited as particularly preferable examples, and such polyhydric carboxylic acid esters have the following general formula:

[0038]

[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,
Aliphatic polycarboxylic acid esters such as diethyl nazic acid, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethylisobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate , 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.

[0042] These electron donors (a) do not necessarily need to be used as starting materials, but can also be produced during the process of preparing the solid titanium catalyst component [Ib]. In addition, the solid titanium catalyst component [Ib] is the above-mentioned magnesium compound, a compound having two or more ether bonds,
In addition to the liquid titanium compound, organic and inorganic compounds containing silicon, phosphorus, aluminum, etc. used as carrier compounds and reaction aids may be used and prepared by bringing these into contact.

The solid titanium catalyst component [Ia] contained in the first catalyst used in the method according to the present invention is a combination of the above-mentioned magnesium compound, liquid titanium compound, and two or more ether bonds. The compound is prepared by contacting the compound with a carrier compound, an electron donor (a), etc. as necessary.

[0044] Although there are no particular restrictions on the method for producing the solid titanium catalyst component [Ia] 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 in which a contact reaction product of a carrier compound such as a metal oxide, an organomagnesium compound, and a halogen-containing compound is brought into contact 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 compound having two or more ether bonds, a titanium compound, and, if necessary, a halogen-containing compound. (9) A method of reacting a solution containing at least a magnesium compound and an alkoxytitanium with a titanium compound, the above-mentioned 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, the liquid titanium compound, and the compound having two or more ether bonds to be used depends on the type, contact, etc. 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 [Ia] 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 [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. ) 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.

[0048] The solid titanium catalyst component [Ib] contained in the catalyst used in the present invention also contains a magnesium compound, a liquid titanium compound, an electron donor (a), and optionally a carrier compound. prepared by contacting

Such solid titanium catalyst component [Ib]
Although there are no particular limitations on the preparation method, several examples of this 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 in which a contact reaction product of a carrier compound such as a metal oxide, an organomagnesium, and a halogen-containing compound is brought into contact 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, if necessary, a halogen-containing compound. (9) A method of reacting a solution containing at least a magnesium compound and alkoxytitanium, a titanium compound, an electron donor (a), and optionally 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 [Ib] by such a method, the amounts of the magnesium compound, liquid titanium compound, and 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 [Ib] obtained in this way contains titanium, magnesium and halogen,
It contains an electron donor (a).

In this solid titanium catalyst component [Ib], 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 catalyst used in the first method according to the present invention comprises the solid titanium catalyst component [Ia] as described above,
Contains organometallic compound catalyst component [II]. FIG. 1 shows an explanatory diagram of the preparation process of the catalyst used in the first method according to the present invention.

Such an organometallic compound catalyst component [II
] For example, an organoaluminum compound, a complex alkylated product of group I metal and aluminum, an organometallic compound of group II metal, etc. can be used.

Such organometallic compound catalyst components include, for example, RanAlX3-n (wherein Ra is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, and n is 1≦n ≦3) can be exemplified.

In the above formula, Ra is a carbon number of 1 to 12
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.

[0057] Specifically, the following compounds are used as such organoaluminum compounds. Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, Dialkyl aluminum halides such as diisobutyl aluminum chloride, dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropylaluminium sesqui chloride,
Alkylaluminum sesquihalides such as butylaluminum sesquichloride and ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide; and the like.

Other examples of organoaluminum compounds include RanAlY3-n (wherein 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. .

[0059] 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(NRg
AlRh2)3-n Et2AlN(Me)AlEt2
(iso-Bu)2AlN(Et)Al(iso-Bu
)2 etc.

Examples of the above organoaluminum compounds include Ra3Al, RanAl(ORb)3-n, R
An organoaluminum compound represented by anAl(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. Furthermore, in the solid titanium catalyst component [Ia] contained in the catalyst used in the first method of the present invention,
Together with such an organometallic compound catalyst component [II], the above-mentioned compound having two or more ether bonds and/or the electron donor (b) may be used as necessary. ), the above-mentioned electron donor (a) and an organosilicon compound represented by the following general formula can be used, and among these, it is particularly preferable to use a compound having two or more ether bonds and an organosilicon compound.

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, hexenyltrimethoxysilane, Dicyclopentyl ethylmethoxysilane, 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. 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.

[0067] As such a nitrogen-containing compound, specifically, the following compounds can be used.

[0068]

[C5]

[0069]

[C6]

2,6-substituted piperidines such as:

00
71]

[C7]

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

[0073] 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.

[0075]

[Chemical formula 8]

2,6-substituted tetrahydropyrans such as:

[0077]

[Chemical formula 9]

2,5-substituted tetrahydropyrans such as the following. The catalyst used in the second method of the present invention comprises the solid titanium catalyst component [Ib] and organometallic catalyst component [II] as described above, and two or more ether bonds that exist through a plurality of atoms. It contains a compound [III] having the following.

FIG. 2 shows an explanatory diagram of the preparation process of the catalyst used in the second method according to the present invention. As such organometallic compound catalyst component [II], for example, a catalyst component made of the same organometallic compound as used in preparing the catalyst used in the first method 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 catalyst used in the second method according to the present invention may contain an electron donor in addition to the above-mentioned compound having two or more ether bonds. For example, the electron donor (b) used in the preparation of the catalyst used in the first method according to the invention can be used.

The first method for producing an α-olefin polymer according to the present invention is to prepare an α-olefin having two or more carbon atoms and a carbon atom in the presence of the first catalyst as described above. By polymerizing or copolymerizing α-olefins mainly composed of α-olefins having 4 or more carbon atoms, at least 70 mol% of α-olefins having 4 or more carbon atoms can be obtained.
or more, preferably 80 mol% or more, more preferably 9
Polymers or copolymers containing 0 mol% or more are produced.

The second method for producing an α-olefin polymer according to the present invention is to prepare an α-olefin having 2 or more carbon atoms and an α-olefin having 2 or more carbon atoms in the presence of the second catalyst as described above. By polymerizing or copolymerizing α-olefins mainly composed of α-olefins having 4 or more carbon atoms, at least 70 mol% of α-olefins having 4 or more carbon atoms can be obtained.
or more, preferably 80 mol% or more, more preferably 9
Polymers or copolymers containing 0 mol% or more are produced.

Examples of such α-olefins having 2 or more carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Examples include pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.

Furthermore, in the first and second polymerization methods according to the present invention, styrene, aromatic vinyl compounds such as allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane, cyclopentene, cycloheptene, norbornene, 5- Cyclic olefins such as methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-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
-decadiene, 7-methyl-1,6-decadiene, 6-
Compounds having polyunsaturated bonds such as conjugated dienes and non-conjugated dienes such as dienes such as methyl-1,6-undecadiene, isoprene and butadiene can also be used as polymerization raw materials.

[0086] In the first and second methods according to the present invention, it is preferable that α-olefin is prepolymerized in the catalyst. This prepolymerization is carried out at 0% per gram of olefin polymerization catalyst.
．． This is carried out by prepolymerizing the α-olefin in amounts of 1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g.

[0087] In the prepolymerization, a catalyst can be used at a higher concentration than the catalyst concentration in the system in the main polymerization.
In the first and second polymerization methods according to the present invention, the concentration of the solid titanium catalyst component [Ia] or [Ib] in the prepolymerization is usually about 0.001 to 0.001 per liter of liquid medium in terms of titanium atoms. 200 mmol, preferably about 0.0
A desirable range is 1 to 50 mmol, particularly preferably 0.1 to 20 mmol.

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 first and second polymerization methods according to the present invention, the above-mentioned compound having two or more ether bonds or the electron donor (b) can be used in the prepolymerization, if necessary.

In the first method according to the present invention, these compounds are used in an amount of 0.1 to 50 mol, preferably 0.1 to 50 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [Ia].
It is used in an amount of 5 to 30 moles, more preferably 1 to 10 moles.

In the second method according to the present invention, these compounds are used in an amount of 0.1 to 50 mol, preferably 0.1 to 50 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [Ib].
It is used in an amount of 5 to 30 moles, more preferably 1 to 10 moles.

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.

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.

[0094] The reaction temperature during prepolymerization is usually about -20
It is desirable that the temperature is in the range of ~+100°C, preferably about -20~+80°C, more preferably 0~+40°C. In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 35°C is about 0.2 dl/g or more,
Preferably, it is used in an amount of about 0.5 to 10 dl/g. As mentioned above, the prepolymerization is carried out at a rate of about 0 per gram of solid titanium catalyst component [Ia] or [Ib].
．． It is desirable to carry out the reaction in such a way that 1 to 1000 g, preferably about 0.3 to 500 g, particularly preferably 1 to 200 g of polymer are produced.

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 a reaction form of liquid phase polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, or an olefin that is liquid under the reaction conditions can also be used.

In the first and second polymerization methods 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. 0.5 mmol, preferably about 0.0
It is used in an amount of 0.05 to 0.1 mmol. In addition, the organometallic compound [II] usually contains about 1 to 20 metal atoms per mole of titanium atoms in the prepolymerization catalyst component in the polymerization system.
00 moles, preferably about 5 to 500 moles.

Furthermore, in the second polymerization method according to the present invention, the compound having two or more ether bonds is
[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.

[0098] 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.

[0099] Using the first and second catalysts as described above,
By polymerizing or copolymerizing an α-olefin which is an α-olefin having 2 or more carbon atoms and whose main component is an α-olefin having 4 or more carbon atoms, the intrinsic viscosity [η] is 0.01 to 0.01. 100dl/g, preferably 0.1
~50 dl/g of polymer can be obtained.

[0100] The α-olefin polymer obtained as described above may be added with a heat stabilizer, a weather stabilizer,
Antistatic agents, antiblocking agents, lubricants, nucleating agents, pigments, dyes, inorganic or organic fillers, etc. can also be blended.

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

[0102]

Effects of the Invention The first method for producing an α-olefin polymer according to the present invention is a method that uses titanium, magnesium, a halogen, and a compound having two or more ether bonds existing through a plurality of atoms. A solid titanium catalyst component [I
a], and an olefin polymerization catalyst containing an organometallic compound catalyst component [II] containing a Group I to III metal of the Periodic Table, an α-olefin having 2 or more carbon atoms and A polymer or copolymer containing 70 mol% or more of an α-olefin having 4 or more carbon atoms by polymerizing or copolymerizing an α-olefin whose main component is an α-olefin having 4 or more carbon atoms. is manufactured. Therefore, according to the method for producing an α-olefin polymer according to the present invention, the solid titanium catalyst component [
Ia] and the organometallic compound catalyst component [II], an α-olefin polymer having excellent stereoregularity and crystallinity can be produced with high catalytic activity.

The second method for producing an α-olefin polymer according to the present invention uses a solid titanium catalyst component containing titanium, magnesium, halogen, and an electron donor (a) [
Ib], an organometallic compound catalyst component [II] containing a metal from Group I to Group III of the periodic table, and a compound having two or more ether bonds existing through a plurality of atoms [
In the presence of an olefin polymerization catalyst containing [III], an α-olefin having 2 or more carbon atoms and an α-olefin having 4 or more carbon atoms as a main component is polymerized or copolymerized. By doing so, a polymer or copolymer containing 70 mol % or more of an α-olefin having 4 or more carbon atoms is produced. Therefore, according to the second method for producing an α-olefin polymer according to the present invention, the solid titanium catalyst component [Ia], the organometallic compound catalyst component [II], and two or more ether bonds When a catalyst containing the compound [III] having the above is used, an α-olefin polymer having excellent stereoregularity and crystallinity and a high melting point can be produced.

[0104]

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

[0105]

[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.
1 mmol of dimethoxypropane (IPAMP) and the above solid titanium catalyst component [A] were mixed in an amount of 1 mmol in terms of Ti atoms.
After addition of 0 mmol, propylene was fed to the reactor for 1 hour at a rate of 3.2 Nl/h at a temperature of 20°C. 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] 500 ml of n-hexane was added to a 2 liter autoclave under a nitrogen stream. After cooling the system to -50°C, 500 ml of liquid butene-1, 2.0 mmol of triethylaluminum, 0.2 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IPAMP) and 100 ml were added. of hydrogen was added to raise the temperature of the system to 60° C., and 0.01 mmol of prepolymerization catalyst (B) was added in terms of titanium atoms to start polymerization. After polymerizing for 1 hour, methanol was added to the system to stop the polymerization and unreacted butene-1 was removed. After pouring the reaction solution into a large amount of methanol, the resulting white solid was pulverized with a mixer, washed with methanol, and then dried under reduced pressure to obtain a butene-1 polymer.

Polymerization activity, stereoregularity index (n-
Table 1 shows the results of decane insoluble component ratio (abbreviated as II), MFR, and intrinsic viscosity [η] at 135° C. in decalin.

[0107]

[Example 2] [Polymerization] A 2 liter autoclave was cooled to -50°C, and 500 ml of butene-1, 1.0
After adding mmol of triethylaluminum, 0.1 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 0.01 mmol in terms of titanium atoms of prepolymerized catalyst (B) and 400 ml of hydrogen. The temperature was raised to 30°C. After polymerization was carried out at 30° C. for 2 hours, methanol was added to stop the polymerization and unreacted butene-1 was removed. The obtained white solid was washed with methanol to obtain a butene-1 polymer.

Table 1 shows the polymerization activity, II, MFR, and [η].

[0109]

[Comparative Example 1] [Prepolymerization of solid titanium catalyst component [A]] In Example 1, 1 mmol of diphenyldimethoxysilane (DPMS) was used instead of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The solid titanium catalyst component [
A] was prepolymerized to obtain a prepolymerized catalyst (C). [Polymerization] In place of the prepolymerization catalyst (B), (C),
Butene-1 was polymerized in the same manner as in Example 1, except that triisobutylaluminum was used instead of triethylaluminum and DPMS was used instead of IPAMP.

Table 1 shows the results.

[0111]

[Table 1]

[0112]

[Example 3] [Preparation of solid titanium catalyst component [D]] 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 2
After adding 1.33 ml of -isopropyl-2-isopentyl-1,3-dimethoxypropane, the temperature was raised to 100°C. 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 120° 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 [D]. The component is titanium 3.1 in terms of atoms.
% by weight, 58% by weight of chlorine, 17% by weight of magnesium, 2
-isopropyl-2-isopentyl-1,3-dimethoxypropane was 19.7% by weight. [Prepolymerization of solid titanium catalyst component [D]] 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 1 mmol of dimethoxypropane and 1.0 mmol of the above solid titanium catalyst component [D] in terms of Ti atoms, propylene was supplied to the reactor at a rate of 2.5 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 (E). [Polymerization] 500 ml of 4-methyl-1-pentene was added to a 1-liter glass reactor under a nitrogen stream, and the temperature was raised to 50°C. Next, 0.5 mmol of triethylaluminum, 0.05 mmol of cyclohexylmethyldimethoxysilane (CMMS), and 0.01 mmol of prepolymerized catalyst (E) were added to initiate polymerization. The reaction time was 1 hour,
Polymerization was stopped by adding methanol. The reaction solution was poured into a large amount of methanol, the solid portion was filtered off, washed with methanol, and dried under reduced pressure to obtain 4-methylpentene-
2.9 g of 1 polymer was obtained. The polymerization activity was 290 g/mmol Ti.

[0114]

[Example 4] Polymerization was carried out in the same manner as in Example 3, except that (B) was used instead of the prepolymerization catalyst (D) and IPAMP was used instead of CMMS, and 9.86 g of polymer was obtained. I got it. Polymerization activity is 990g/mmol Ti
Met.

[0115]

[Example 5] Butene- 1 was polymerized.

[0116] The results are shown in Table 2.

[0117]

[Example 6] [Preparation of solid titanium catalyst component (F)] 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, 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 triisobutylaluminum and ethylaluminum sesquichloride were mixed at 2/1 (in terms of aluminum atoms) at 40°C in a propylene atmosphere.
The compound (hereinafter abbreviated as mixed Al) mixed at a ratio of mol/mol) was 0.75 mmol Al in terms of aluminum atoms, and the titanium catalyst component was 0.007 in terms of titanium atoms.
5 mmol Ti was charged.

After heating to 60°C, 150 ml of hydrogen was introduced, and after 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 398.
2g, and the extraction residue rate with boiling heptane is 97.47%.
, MFR is 1.2dg/min, and its apparent bulk specific gravity is 0.
It was 45g/ml. On the other hand, 2.9 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity is 53,500
g-pp/mmol-Ti, and II (
t. I. I. ) was 96.8%. [Prepolymerization of solid titanium catalyst component (F)] 3.0 mmol of triethylaluminum and 1.0 mmol of solid titanium catalyst component (F) in terms of titanium atoms were used, except that IPAMP was not used. Prepolymerization was carried out in the same manner as in Example 1 to obtain a prepolymerized catalyst (G). [Polymerization] Prepolymerization catalyst (B) is replaced by prepolymerization catalyst (B).
G), Example 5 except that 200 ml of hydrogen was used.
Polymerization was carried out in the same manner.

The results are shown in Table 2.

[0120]

[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 (8)

[Claims] [Claim 1] [Ia] A solid titanium catalyst component comprising titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms;
and [II] α having 2 or more carbon atoms in the presence of an olefin polymerization catalyst characterized by containing an organometallic compound catalyst component containing a metal from Group I to Group III of the periodic table.
-Contains at least 70 mol% or more of an α-olefin having 4 or more carbon atoms by polymerizing or copolymerizing an α-olefin that is an olefin and has 4 or more carbon atoms as a main component. A method for producing an α-olefin polymer, which comprises producing a polymer or a copolymer. 2. The solid titanium catalyst component [Ia] is prepolymerized with at least one kind selected from α-olefins having 2 to 20 carbon atoms. A method for producing an α-olefin polymer as described in . 3. 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 via a plurality of carbon atoms. A method for producing an α-olefin polymer. 4. The compound having two or more ether bonds has the following formula: [Formula 1] (where n is an integer of 2≦n≦10, and R1 to
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. The method for producing an α-olefin polymer according to claim 3, wherein the α-olefin polymer is . Claim 5: [Ib] titanium, magnesium, halogen, and electron donor (a) (provided that electron donor (a)
does not include compounds having two or more ether bonds existing through multiple atoms); In the presence of an olefin polymerization catalyst containing a metal compound catalyst component and [III] a compound having two or more ether bonds present through a plurality of atoms, an α-olefin having two or more carbon atoms and Polymers or copolymers containing at least 70 mol% or more of α-olefins having 4 or more carbon atoms by polymerizing or copolymerizing α-olefins mainly composed of α-olefins having 4 or more carbon atoms. 1. A method for producing an α-olefin polymer, which comprises producing a polymer. 6. The solid titanium catalyst component [Ia] is prepolymerized with at least one kind selected from α-olefins having 2 to 20 carbon atoms. A method for producing an α-olefin polymer as described in . 7. The compound according to claim 5, 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. A method for producing an α-olefin polymer. 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. The method for producing an α-olefin polymer according to claim 7, wherein the α-olefin polymer is represented by .