JPH06279527A - Catalyst for polymerization of olefin and polymerization of olefin by using the same catalyst - Google Patents

Abstract

(57) [Summary] [Object] The present invention provides an olefin polymerization catalyst and an olefin polymerization method capable of producing an olefin (co) polymer having excellent stereoregularity with high polymerization activity. A catalyst for olefin polymerization according to the present invention comprises: [I] [A] (a) a magnesium compound, and (b) a co-ground product obtained by contacting and co-ground an electron donor, B] obtained by contacting with a titanium compound in a liquid state,
A solid titanium catalyst component containing titanium, magnesium, halogen and an electron donor; [II] an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table; It is characterized in that it is formed from a compound having two or more ether bonds existing through the atom of. The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst for producing an olefin polymer and a method for polymerizing an olefin.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for olefin polymerization used for producing an olefin polymer by polymerizing or copolymerizing an olefin, a solid titanium catalyst component and an organometallic compound catalyst component (co-catalyst component) are used. ) And a catalyst formed from

As the solid titanium catalyst component as described above, it is known that a titanium compound is supported on magnesium halide in an active state and contains magnesium, titanium, halogen and an electron donor. According to the olefin polymerization catalyst containing the solid titanium catalyst component, olefins such as ethylene propylene and 1-butene can be polymerized or copolymerized with high polymerization activity (catalytic activity), and propylene, 1 -It is known that an olefin polymer having high stereospecificity can be obtained by polymerizing butene and the like.

Among these olefin polymerization catalysts, a solid titanium catalyst component containing an aromatic dicarboxylic acid diester as an electron donor, an organoaluminum compound as a cocatalyst component, and an organosilane compound as an electron donor. It is known that the catalyst formed from and exhibits excellent performance.

The present inventors conducted research to obtain an olefin polymerization catalyst capable of producing an olefin polymer having excellent stereoregularity with higher polymerization activity, and found that it contained an electron donor. An olefin polymerization catalyst formed from a solid titanium catalyst component, an organometallic compound catalyst component, and a compound having two or more ether bonds existing via a plurality of atoms has excellent olefin polymerization activity. The present invention has been completed by finding that an olefin polymer that can be polymerized and has excellent stereoregularity can be produced.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is an olefin (co) having excellent stereoregularity.
It is an object of the present invention to provide an olefin polymerization catalyst capable of producing a polymer with high polymerization activity and an olefin polymerization method.

[0007]

SUMMARY OF THE INVENTION A catalyst for olefin polymerization according to the present invention is a co-ground product obtained by bringing [I] [A] (a) magnesium compound and (b) an electron donor into contact with each other and co-ground. , [B] obtained by contacting with a titanium compound in a liquid state,
A solid titanium catalyst component containing titanium, magnesium, halogen and an electron donor; [II] an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table; It is characterized in that it is formed from a compound having two or more ether bonds existing through the atom of.

The compound [III] having two or more ether bonds existing through a plurality of atoms is preferably a compound represented by the following formula.

[0009]

[Chemical 2]

(In the formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having an element of R ¹
R ²⁶ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ).

The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

[0012]

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

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also copolymer. It may be used in a meaning including a polymer.

The olefin polymerization catalyst according to the present invention comprises: [I] [A] (a) a magnesium compound and (b) a co-ground product obtained by contacting and co-ground an electron donor; B] obtained by contacting with a titanium compound in a liquid state,
A solid titanium catalyst component containing titanium, magnesium, halogen and an electron donor; [II] an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table; And a compound having two or more ether bonds existing through the atoms of

First, (A) co-pulverization obtained by bringing (a) a magnesium compound and (b) an electron donor used in the preparation of the solid titanium catalyst component [I] used in the present invention into contact and co-pulverization Describe the thing.

(A) Magnesium Compound Examples of the magnesium compound used for preparing the solid titanium catalyst component [I] include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Examples of the magnesium compound having a reducing ability include organomagnesium compounds represented by the following formula. During X _n MgR _2-n wherein, n = 0 ≦ n <2, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group, two when n is 0 R's may be the same or different, and X is halogen.

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

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, magnesium methoxy chloride, magnesium ethoxy chloride, isopropoxy chloride. Alkoxy magnesium halides such as magnesium, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halides such as methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexyl Alkylo magnesium such as alkoxy magnesium such as soxy magnesium, phenoxy magnesium, dimethyl phenoxy magnesium, etc. Examples thereof include carboxylic acid salts of magnesium such as xymagnesium, magnesium laurate, and magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability can be prepared by using a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound. It may be contacted with a compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability are the organic metal compounds described later, such as aluminum and zinc.
It may form a complex compound or a double compound with another metal such as boron, beryllium, sodium or potassium, or may be a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more kinds of the above compounds may be combined, and may be used in a liquid state or a solid state.

Further, an electron donor as described below may be used to prepare a solid adduct of a magnesium compound, or it may be liquefied before use. The above magnesium compound can be derived from other compounds when preparing the catalyst component.

Of these, halogen-containing magnesium is particularly preferably used. (b) electron donor (b) electron donor used in the present invention, alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic acids or inorganic acids,
Ether, acid amide, acid anhydride, ammonia, amine,
Examples thereof include nitrile and isocyanate. This
(b) The electron donor does not include a compound (polyether compound) [III] having two or more ether bonds existing via a plurality of atoms as described below.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol, and C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone , Acetaldehyde, propionaldehyde, octyl aldehyde,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde, naphthaldehyde, 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, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
2 to 2 carbon atoms such as ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate
18 organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and other acid halides having 2 to 15 carbon atoms, methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethyl Acid amides such as amides, amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, trinitrile, acids such as acetic anhydride, phthalic anhydride, benzoic anhydride Anhydrous etc. are mentioned.

In addition to these, water, anionic, cationic and nonionic surfactants can also be used.
Further, as the organic acid ester, a polyvalent carboxylic acid ester can be mentioned as a particularly preferable example, and as such a polyvalent carboxylic acid ester, compounds having a skeleton represented by the following general formula can be given.

[0026]

[Chemical 3]

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted group. Alternatively, it is an unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Also R ³
And R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C-
O-C, COOR, COOH, OH, SO 3 H, -C-
It has groups such as N—C— and NH ₂ .

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate and isopropyl malonate. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, aliphatic polycarboxylic acid esters such as dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclyl Hexacarboxylic acid diisobutyl, tetrahydrophthalic acid diethyl, adicyclic polycarboxylic acid ester such as diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, Di-isopropyl phthalate, Di-n-butyl phthalate, Diisobutyl phthalate, Di-n-heptyl phthalate, Di-2-ethylhexyl phthalate, Di-n-octyl phthalate, Dineopentyl phthalate, Phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, 3,4-furandicarboxylic acid, etc. Examples thereof include cyclic polycarboxylic acid esters.

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

Two or more of these compounds can be used in combination. In the present invention, a halogen-containing compound may be used when preparing the co-ground product [A].

As such a halogen-containing compound,
For example, the general formula SiX _m R _4-m (X is a halogen atom, R is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms)
Is a cycloalkyl group or an aryl group having 6 to 20 carbon atoms, and m is a real number of 1 to 4. ) And a halogen-containing silicon compound represented by the formula (1).

As the halogen-containing silicon compound, more specifically, when m = 4 in the above formula, tetrachlorosilane, tetrabromosilane, tetraiodosilane, tetrafluorosilane, trichlorobromide is used. Silane, trichloroiodosilane, trichlorofluorosilane, dichlorodibromosilane, dichlorodiiodosilane, dichlorodifluorosilane, chlorotribromosilane, chlorotriiodosilane, chlorotrifluorosilane, bromotriiodosilane, bromotrifluorosilane Examples of tetrapasilanes include silane, dibromodiiodosilane, dibromodifluorosilane, tribromoiodosilane, tribromofluorosilane, iodotrifluorosilane, diiododifluorosilane, and triiodofluorosilane.

In the formula, when m = 3, methyltrichlorosilane, ethyltrichlorosilane, n-or
i-Propyltrichlorosilane, n-, i-, sec- or tert
-Butyltrichlorosilane, n- or i-amyltrichlorosilane, n-hexyltrichlorosilane, n-heptyltrichlorosilane, n-octyltrichlorosilane, n-dodecyltrichlorosilane, n-tetradecyltrichlorosilane, n-hexadecyltrichlorosilane Unsaturated alkyltrichlorosilane having an unsaturated alkyl group having 1 to 4 carbon atoms, such as alkyltrichlorosilane having a saturated alkyl group having 1 to 6 carbon atoms, such as silane, vinyltrichlorosilane, isobutenyltrichlorosilane, chloro Methyltrichlorosilane, dichloromethyltrichlorosilane,
Trichloromethyltrichlorosilane, (2-chloroethyl) trichlorosilane, (1,2-dibromoethyl) trichlorosilane, trifluoromethyltrichlorosilane,
Saturated or unsaturated cycloalkyltrichlorosilanes such as haloalkyl or unsaturated haloalkyltrichlorosilanes such as (vinyl-1-chloro) trichlorosilane, cyclopropyltrichlorosilane, cyclopentyltrichlorosilane, cyclohexenyltrichlorosilane, 3-cyclohexenyltrichlorosilane. Aryl or aralkyltrichlorosilane such as phenyltrichlorosilane, 2-, 3- or 4-tolyltrichlorosilane, benzyltrichlorosilane, methyldifluorochlorosilane,
Methylfluorodichlorosilane, ethyldifluorochlorosilane, ethylfluorodichlorosilane, n- or i-
Propyldifluorochlorosilane, n-butyldifluorochlorosilane, n-butylfluorodichlorosilane, phenyldifluorochlorosilane, methyldichlorobromosilane, ethyldichlorobromosilane, methyldichloroiodosilane, (trifluoromethyl ) Examples include alkyl- or haloalkyl-mixed trihalosilanes such as difluorobromsilane.

In the formula, when m = 2, dimethyldichlorosilane, diethyldichlorosilane, di-n-or-
i-Propyldichlorosilane, di-n-, -i-, -sec- or -t
ert-Butyldichlorosilane, di-n- or -i-amyldichlorosilane, di-n-hexyldichlorosilane, di-n-heptyldichlorosilane, di-n-octyldichlorosilane, etc. Halosilane, dicyclopentyldichlorosilane, dicyclohexyldichlorosilane, dicyclohexyldibromosilane, dicyclohexyldiiodosilane, dicycloalkyldihalosilane such as dicyclohexyldifluorosilane, diphenyldichlorosilane,
Examples thereof include diaryl or diaralkyldihalosilanes such as di-2-,-3- or -4-tolyldichlorosilane and dibenzyldichlorosilane.

In the formula, when m = 1, trimethylchlorosilane, triethylchlorosilane, tri (n- and i-propyl) chlorosilane, tri (n- and i-butyl) chlorosilane, tri (n-hexyl) ) Chlorsilane,
Tri (n-heptyl) chlorosilane, tri (n-octyl)
Trialkylhalosilanes such as chlorosilane, dimethyl (ethyl) chlorosilane, methyl (diethyl) chlorosilane, triphenylchlorosilane, tri (2-, 3- or 4-tolyl) chlorosilane, triaryl or triaryl such as tribenzylchlorosilane. Examples include aralkylhalosilane.

Among these, tetrachlorosilane, trichlorobromosilane, dichlorodibromosilane, chlorotribromosilane and mono-, di- or trichlorosilane in which R is methyl, ethyl or phenyl are preferable.

As the halogen-containing compound, halogen-containing alcohols can be exemplified. Specific examples of the halogen-containing alcohols include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol and 4-chloro-1.
-Butanol, 5-chloro-1-pentanol, 6-chloro-1-
Hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethyl Phenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenyl Phenol, 6-chlorothymol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1
-Brom-2-propanol, 1-Brom-2-butanol, 2-
Brom-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p) -bromophenol, 4-bromoresorcin, (m, o, p) -fluorophenol, p -Iodophenol, 2,2-dichloroethanol, 2,3-dichloro-1-
Propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl-1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,
4-dibromophenol, 2,4-dibromo-1-naphthol,
2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β-trichloro-tert-butanol,
2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-
Trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol, 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromo Bisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,
Examples include 3,5,6-tetrafluorophenol and tetrafluororesorcin.

As other halogen-containing compounds, halogen in the elemental state such as chlorine, bromine and iodine, hydrogen halide such as hydrogen chloride, hydrogen bromide and hydrogen iodide,
Carbon tetrachloride, chloroform, ethane dichloride, ethane tetrachloride, methylene chloride, trichlene, methyl chloride, ethyl chloride, haloalkanes such as -n-butyl chloride, -n-octyl chloride, sulfuryl chloride, thionyl chloride, nitrosyl chloride,
Non-metal oxyhalides such as phosphorus oxychloride and phosgene, metal halides such as phosphorus trichloride and phosphorus pentachloride, metal or ammonium halides such as aluminum chloride and ammonium chloride, ethyl magnesium chloride, propyl magnesium chloride, There can also be mentioned alkyl magnesium halides such as butyl magnesium chloride, hexyl magnesium chloride and amyl magnesium chloride.

These halogen-containing compounds may be used alone or in combination of two or more. In the present invention,
The above-mentioned (b) electron donor and the like may be derived from another compound during the adjustment of the catalyst component.

[A] Co-Pulverized Product In preparing the solid titanium catalyst component [I] used in the present invention, first, the above-mentioned (a) magnesium compound and (b) electron donor are brought into contact with each other. Co-mill to prepare [A] co-mill.

As a method for preparing such [A] co-ground product, (1) (a) a magnesium compound and (b) an electron donor are co-ground using a ball mill, a vibro mill, etc. ]
A method for obtaining a co-ground product can be exemplified.

(2) Obtained by the method of (1) above [A]
A method of bringing the co-ground product into contact with the electron donor (b) may also be mentioned. In the present invention, when the [A] co-ground product is prepared,
The amount of the (a) magnesium compound and (b) the electron donor used varies depending on the type, contact conditions, contact sequence, etc., but is usually (a) magnesium compound 1 mol, (b)
The electron donor is 0.01 to 10 mol, preferably 0.0
It is used in an amount of 5 to 5 mol, particularly preferably 0.1 to 1 mol.

The contact of these compounds is usually from -70 ° C to 2 ° C.
It is carried out under a temperature condition of 00 ° C, preferably -50 ° C to 150 ° C. [B] Liquid Titanium Compound The solid titanium catalyst component [I] used in the present invention is obtained by contacting the [A] co-ground product prepared as described above with the [B] liquid titanium compound. It is manufactured by

Specific examples of such a liquid titanium compound [B] include a tetravalent titanium compound represented by the following formula. In the formula Ti (OR) _g X _4-g , R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.

Specific examples of such a compound include T
Tetrahalogenated titanium such as iCl ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On
-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄
H ₉ ) Br ₃ and other trihalogenated alkoxy titanium, Ti
_{(OCH 3) 2 Cl 2,} Ti (OC 2 H 5) 2 Cl 2, Ti (On-C 4
_{H 9) 2 Cl 2, Ti} (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{2 Br 2, Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3
Monohalogenated trialkoxy titanium such as Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ).
₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (On-C ₄
Examples thereof include tetraalkoxytitanium such as H ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ , and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

In the present invention, the solid titanium catalyst component [I] is used.
In preparing any of the components (a) a magnesium compound, (b) an electron donor and [B] a titanium compound in a liquid state, any one of them contains a halogen, or (a) When no halogen is contained in any of (b), (b) or [B], a halogen-containing compound is used to finally obtain a solid titanium catalyst component containing halogen together with titanium, magnesium and an electron donor. It is preferable to obtain [I].

Further, in the present invention, [A] co-ground product and [B]
When brought into contact with a titanium compound in a liquid state, the electron donor (b) shown in the preparation of the [A] co-ground product may be allowed to coexist, if necessary.

In the present invention, when the solid titanium catalyst component [I] is produced, the amount of the [A] co-ground product and the [B] liquid titanium compound used depends on the kind, contact conditions, contact sequence, etc. Although different, usually, the titanium compound in the liquid state [B] is 0.05 mol to 1000 mol, preferably 0.05 mol to 500 mol, and particularly preferably 0 mol, relative to 1 mol of magnesium in the co-ground product. It is used in an amount of 1 mol to 200 mol.

The contact between the co-ground product [A] and the titanium compound [B] in a liquid state is usually carried out at 0 to 130 ° C. for 30 minutes or more. In the present invention, this contact is
It may be carried out in the presence of an aliphatic hydrocarbon or an aliphatic alcohol.

The aliphatic hydrocarbon used in the present invention is a liquid aliphatic hydrocarbon at -30 ° C to 150 ° C. Examples of such an aliphatic hydrocarbon include an aliphatic hydrocarbon having 5 to 12 carbon atoms, and specifically,
Pentane, hexane, heptane, octane, nonane, decane, dodecane and the like can be mentioned.

The aliphatic alcohol used in the present invention is a liquid aliphatic alcohol at -30 ° C to 150 ° C. Examples of such an aliphatic alcohol include aliphatic alcohols having 2 to 10 carbon atoms, and specifically, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol. And so on.

These may be used alone or in combination. The solid titanium catalyst component [I] obtained by such contact is, if necessary,
It may be washed with an organic solvent such as n-heptane or toluene, and the liquid titanium compound [B] and the electron donor (b) may be repeatedly contacted.

In the production of the solid titanium catalyst component [I] as described above, the operations such as contact and pulverization are preferably carried out in the absence of oxygen and water. The method for producing the solid titanium catalyst component [I] used in the present invention is not limited to these embodiments.

The solid titanium catalyst component [I] thus obtained contains titanium, magnesium, an electron donor and halogen. In this solid titanium catalyst component [I], magnesium / titanium (atomic ratio) is
1 to 100, preferably 2 to 50, particularly preferably 4 to
50, and the electron donor / titanium (molar ratio) is 0.01.
To 100, preferably 0.05 to 50, and particularly preferably 0.05 to 50, halogen / titanium (atomic ratio)
Is 2 to 200, preferably 4 to 90, and particularly preferably 5 to 50.

The solid titanium catalyst component [I] according to the present invention as described above may be supported on a solid carrier. Such carriers include Al ₂ O ₃ , SiO ₂ ,
B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Zn
Resins such as ₂ O, SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Of these, Al ₂ O ₃ , SiO ₂ , and styrene-divinylbenzene copolymer are preferable.

The olefin polymerization catalyst according to the present invention is an organometallic compound containing a solid titanium catalyst component [I] as described above and a metal selected from [II] Group I to Group III of the periodic table. It is formed from a catalyst component and [III] a compound having two or more ether bonds existing through a plurality of atoms.

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

As such an organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified. In the formula of R ¹ _n AlX _3-n , R ¹ is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3.

Examples of such a hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethylaluminum, triethylaluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, trialkyl aluminum Nim and tri 2-ethylhexyl aluminum, the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z [Where x,
y and z are positive numbers, and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum, trialkenyl aluminum such as triisopropenyl aluminum, dimethyl aluminum chloride,
Diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride,
Dialkyl aluminum halides such as dimethyl aluminum bromide, methyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquibromide, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, diethyl Examples thereof include dialkyl aluminum hydrides such as aluminum hydride and dibutyl aluminum hydride, and alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride.

As the organoaluminum compound, compounds represented by the following formula can also be mentioned. R ¹ _n AlY _{3-n In the} formula, R ¹ is the same as the above formula, Y is a —OR ¹⁰ group,
OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group, -S
iR ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group.
R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is hydrogen, a methyl group, an ethyl group,
It is an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group or the like. n is 1-2.

Specific examples of the organoaluminum compound represented by the above formula include the following compounds. (1) Compounds represented by R ¹ _n Al (OR ¹⁰ ) _3-n , for example, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, ethyl aluminum sesquiethoxide, butyl aluminum Sesquibutoxide and partially alkoxylated alkylaluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 , ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide and the like. And halogenated alkylaluminums. (2) a compound represented by R ¹ _n Al (OSi R ¹¹ ₃ ) _3-n ,
For example, Et ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Et ₃ ), etc. (3) R ¹ _n Al (OAlR ¹² ₂ ) _3- a compound represented by _n ,
For example, a compound represented by (4) R ¹ _n Al (NR ¹³ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) ₂ , such as Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHET Et ₂ AlN (Si Me ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) _{2 and} other compounds represented by (5) R ¹ _n Al (Si R ¹⁴ ₃ ) _3-n , for example, , (Iso-Bu) ₂ AlSi Me _3, etc., (6) compounds represented by R ¹ _n Al [N (R ¹³ ) AlR ¹⁶ ₂ ] _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (i
so-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Organoaluminum used in the present invention
The compound is an organic compound component of a metal other than aluminum.
It may be contained in a small amount. Among these, R¹ ₃Al,
R¹ _nAl (OR^Ten)_3-n, R¹ _nAl (OAlR¹² ₂)
_3-nThe organoaluminum compound represented by is preferred.

Examples of complex alkylated products of Group I metal and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (wherein M ¹ is Li, Na, K, and R ^j is 1 carbon atom)
~ 15 hydrocarbon groups. ) Specifically, LiAl
_{(C 2 H 5) 4,} LiAl (C 7 H 15) 4 and the like.

Examples of the group II metal organometallic compound include compounds represented by the following general formula. R ^k R ^l M ² (provided that R ^k and R ^l are a hydrocarbon group having 1 to 15 carbon atoms or a halogen atom, and they may be the same or different from each other, but they are excluded when they are halogen atoms. M
² is Mg, Zn and Cd. ) Specific examples include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride and the like.

These may be used alone or in combination. [III] Two or more ethers existing through multiple atoms
Compound having a ru bond [III] In the present invention, in the compound having two or more ether bonds existing through a plurality of atoms (hereinafter sometimes referred to as a polyether compound), an atom existing between these ether bonds is used. Is carbon, silicon, oxygen, sulfur,
It is one or more selected from the group consisting of phosphorus and boron, and has 2 or more atoms. Of these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more, having a linear, branched or cyclic structure, and more preferably a branched substituent. Those in which a substituent having a ring-like or cyclic structure is bonded are desirable. In addition, the atom existing between two or more ether bonds has a plurality of atoms,
A compound containing preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms is preferable.

Examples of such a [III] polyether compound include compounds represented by the following formula.

[0069]

[Chemical 4]

However, in the formula, n is an integer of 2 ≦ n ≦ 10, R ^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen,
It is a substituent having at least one element selected from sulfur, phosphorus, boron and silicon, and has any R ^{1 to} R
²⁶ , preferably R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon.

Specific examples of the above-mentioned (a) polyether compound 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- (pt-butylphenyl) -1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-
Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl
-2-Cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-
Bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2 , 2-Diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-
1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-
Isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di
-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-
Dimethoxypropane, 2-isopropyl-2-isopentyl-
1,3-dimethoxypropane, 2-phenyl-2-isopropyl-
1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-
Dimethoxypropane, 2-benzyl-2-isopropyl-1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-s-butyl-1,3-
Dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 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, 1,3- Diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 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 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2- Ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-
2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-
Isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenyl Bis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-
Butylbis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
Examples thereof include t-butylbis (methoxymethyl) silane.

Of these, 1,3-diethers are preferably used, and 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, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3 -Dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane , 2-cyclohexyl-2-s-butyl-1,3-
Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-
Dimethoxypropane, 2-phenyl-2-isopropyl-1,3-
Dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-
1,3-dimethoxypropane is preferably used.

In the present invention, when preparing the olefin polymerization catalyst, an organosilicon compound represented by the following general formula may be used together with the above [III] polyether compound.

R _n Si (OR ') _4-n (wherein R and R'are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethylsilane Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchid, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane.

Of 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, cyclopentyldimethylmethoxysilane, etc. It is preferably used. These may be used alone or in combination.

In the present invention, a nitrogen-containing compound, another oxygen-containing compound,
A phosphorus-containing compound or the like can also be used. Specific examples of such nitrogen-containing compounds include the compounds shown below.

[0078]

[Chemical 5]

[0079]

[Chemical 6]

2,6-substituted piperidines such as

[0081]

[Chemical 7]

2,5-substituted piperidines such as N, N, N ', N'-
Substituted methylenediamines such as tetramethylmethylenediamine, N, N, N ', N'-tetraethylmethylenediamine, 1,
Substituted imidazolines such as 3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

Specific examples of the phosphorus-containing compound include phosphite esters shown below. Triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite,
Phosphorous acid esters such as triisobutyl phosphite, diethyl n-butyl phosphite, and diethyl phenyl phosphite.

Specific examples of the oxygen-containing compound include:
The following compounds may be mentioned.

[0085]

[Chemical 8]

2,6-substituted tetrahydropyrans such as

[0087]

[Chemical 9]

2,5-substituted tetrahydropyrans such as Two or more of the above compounds can be used in combination. Olefin Polymerization Method In the olefin polymerization method according to the present invention, an olefin is polymerized or copolymerized in the presence of the above-described olefin polymerization catalyst.

As the olefin used in the present invention,
Examples of the α-olefin having 2 to 20 carbon atoms include, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-
Hexene, 3-methyl-1-butene, 3-methyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1- Examples include hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. These may be used alone or in combination.

Further, aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalene, substituted vinylnaphthalene, allylnaphthalene and substituted allylnaphthalene, vinylcyclopentane, substituted vinylcyclopentanes. , Vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, alicyclic vinyl compounds such as allyl norbornane, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1 -Hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-
Silane unsaturated compounds such as decene, cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene Such as cyclic olefins, 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- Conjugate or non-conjugate of dienes such as ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene and butadiene. A conjugated diene or the like can also be used.

Of these, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, 3-methyl-1-butene, 7-
Methyl-1,6-octadiene, 1,7-octadiene, 1,9-decadiene, allyltrimethylsilane and the like are preferably used.

In the olefin polymerization method according to the present invention,
The olefin can be preliminarily polymerized with the olefin polymerization catalyst prior to the polymerization (main polymerization). This prepolymerization is 0.1 to 1000 per 1 g of the olefin polymerization catalyst.
g preferably 0.3 to 500 g, particularly preferably 1 to 2
It is carried out by prepolymerizing an olefin as described above in an amount of 00 g.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the solid titanium catalyst component [I] in the prepolymerization is usually about 0.
001-200 mmol, preferably about 0.01-50
Mmol, particularly preferably 0.1 to 20 mmol.

The organometallic compound catalyst component [II] is used in such an amount that a polymer of 0.1 to 1000 g, preferably 0.3 to 500 g, is produced per 1 g of the solid titanium catalyst component [I]. It is generally used in an amount of about 0.1 to 300 mol, preferably about 0.5 to 100 mol, and particularly preferably 1 to 50 mol, per mol of titanium atom in the titanium catalyst component [I].

The polyether compound [III] corresponds to 1 mol of titanium atom in the solid titanium catalyst component [I],
It is used in an amount of 0.01 to 50 mol, preferably 0.05 to 30 mol, and more preferably 0.08 to 10 mol.

The prepolymerization of olefin can be carried out by any of liquid phase polymerization method such as solution polymerization and suspension polymerization (slurry polymerization) or gas phase polymerization method. The prepolymerization can be carried out batchwise or continuously.

In the present invention, this prepolymerization can be carried out in the presence of an inert hydrocarbon medium, and the olefin and the above-mentioned catalyst components are added to the inert hydrocarbon medium and the prepolymerization is carried out under relatively mild conditions. It is preferable. As the inert hydrocarbon medium used in this case, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and combinations thereof. Of these inert hydrocarbon media, it is particularly preferred to use aliphatic hydrocarbons.

On the other hand, the olefin itself can be used as a solvent to carry out the prepolymerization, or the olefin itself can be prepolymerized in a substantially solvent-free state. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization, and specifically, propylene is preferable.

The reaction temperature during the prepolymerization is usually about -20.
It is desirable that the temperature is from about + 100 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C. In the prepolymerization, a molecular weight modifier such as hydrogen can be used.

The prepolymerization, as described above, is about 0.1 to 1000 g, preferably about 0.3 to 500 g, and particularly preferably 1 to 200 g per 1 g of the solid titanium catalyst component [I].
It is desirable to carry out so that a polymer of If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

In the olefin polymerization method according to the present invention, the main polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the main polymerization takes the reaction form of slurry polymerization, the above-mentioned inert hydrocarbon may be used as the reaction solvent, or a liquid olefin at the reaction temperature may be used.

In the polymerization method of the present invention, the solid titanium catalyst component [I] is usually about 0.001 to 1 mmol, preferably about 0.005 in terms of Ti atoms per liter of polymerization volume. Used in an amount of 0.5 mmol. The organometallic compound [II] is used in an amount such that the metal atom is usually about 1 to 2000 mol, preferably about 5 to 500 mol, based on 1 mol of the titanium atom in the polymerization system. The polyether compound [III] is 0.001 to 50 mol, preferably 0.01 to 3 mol, based on the organometallic compound [II].
It is used in an amount of 0 mol, particularly preferably 0.05 to 20 mol.

When the prepolymerization catalyst as described above is used during the main polymerization and the prepolymerization catalyst contains the organometallic compound [II] and the polyether compound [III], the organometallic compound [II] ], And the polyether compound [III] may not need to be newly used.

When hydrogen is used in the main polymerization, a polymer having a high melt flow rate can be obtained, and the molecular weight of the obtained polymer can be adjusted by the hydrogenation amount. In the present invention, the polymerization of olefins is usually carried out at a temperature of about 20.
To 200 ° C, preferably about 50 to 150 ° C, the pressure is usually atmospheric pressure to 100 kg / cm ² , preferably about ^{2 to} 50 kg / cm ² .
^It is performed under the conditions of ² .

In the polymerization method of the present invention, such polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, 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, especially propylene polymerization, is carried out using the above olefin polymerization catalyst, the isotactic index (II) represented by the boiling heptane extraction residue is 70% or more, preferably 85% or more, more preferably 90%. Above all, particularly preferably 95% or more of a propylene polymer is obtained.

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

[0108]

The olefin polymerization catalyst according to the present invention is
An olefin polymer having excellent stereospecificity can be produced with high polymerization activity.

In the olefin polymerization method according to the present invention, olefin is polymerized by using the olefin polymerization catalyst according to the present invention, and the catalyst activity is high and the polymerization reaction can be performed efficiently and the stereospecificity is high. A polymer can be obtained.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0111]

Example 1 “Preparation of solid titanium catalyst component (A)” In a nitrogen atmosphere,
20 g of magnesium chloride in a SUS ball mill container with an internal volume of 0.8 liter containing 2.8 kg of SUS balls.
(210 mmol), diisopropyl phthalate (DIB
P) Charge 8.6 ml (32 mmol), and use a vibration mill for 8
It was vibrated for a time and crushed.

10 g of the crushed product was placed in a 400 ml glass reactor and 150 ml of titanium tetrachloride was added. While stirring this, the temperature was raised to 80 ° C. and kept for 2 hours. After completion of the reaction, hot filtration is carried out, followed by washing with decane at 80 ° C. three times, and solid titanium catalyst component (A)
Got

The solid titanium catalyst component (A) thus obtained contained 3.8% by weight of titanium, 15% by weight of magnesium, 54% by weight of chlorine and 20.7% by weight of DIBPP. "Polymerization" Purified n- in an autoclave with an internal volume of 2 liters
Insert 750 ml of hexane, and in a propylene atmosphere at 40 ° C., 0.75 mmol of triethylaluminum (Et ₃ Al), 0.075 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IPAMP) and the above. The solid titanium catalyst component (A) thus obtained was charged in an amount of 0.015 mmol Ti in terms of titanium atom.

After the temperature was raised to 60 ° C., 200 ml of hydrogen was introduced, and this was kept at 70 ° C. for 2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 7 kg / cm ² G. After the completion of the polymerization, the slurry containing the produced solid was filtered to separate a white powder and a liquid phase part. The yield of the white powdery polymer after drying was 246.4 g, and the extraction residual rate with boiling heptane was 98.6.
%, MFR 5.4 g / min, apparent bulk specific gravity 0.33 g
/ Ml. On the other hand, 1.1 g of a solvent-soluble polymer was obtained by concentrating the liquid phase part. Therefore, the activity is 16,500 g
-PP / mM-Ti, and II (t-I.
I. ) Was 98.2%.

[0115]

[Example 2] "Polymerization" In Example 1, except that triisobutylaluminum was used instead of triethylaluminum,
Polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0116]

Example 3 “Polymerization” Polymerization of propylene in the same manner as in Example 1 except that 0.5 mmol of triisobutylaluminum and 0.25 mmol of ethylaluminum sesquichloride were used in place of triethylaluminum. I went. The results are shown in Table 1.

[0117]

Comparative Example 1 “Polymerization” Polymerization was carried out in the same manner as in Example 1 except that cyclohexylmethyldimethoxysilane (CMMS) was used instead of IPAMP. The results are shown in Table 1.

[0118]

[Table 1]

In the table, * 1) i-Bu ₃ Al / Et _1.5 Al
Cl _1.5 = 2/1 (molar ratio)

[0120]

[Examples 4 to 6] "Preparation of solid titanium catalyst component [B]" Solid titanium was prepared in the same manner as in Example 1 except that 10.8 ml (40 mmol) of DIBP was used. The catalyst component was prepared to obtain a solid titanium catalyst component [B]. The solid titanium catalyst component [B] thus obtained contained 4.2% by weight of titanium, 15% by weight of magnesium, 53% by weight of chlorine, and DI.
It contained 24.6% by weight of BP. Other than using the "polymerized" solid titanium catalyst component [B],
Polymerization of propylene was carried out in the same manner as in Examples 1 to 3. The results are shown in Table 2.

[0121]

[Table 2]

In the table, * 1) i-Bu ₃ Al / Et _1.5 Al
Cl _1.5 = 2/1 (molar ratio)

[0123]

[Examples 7 to 9] "Preparation of solid titanium catalyst component [C]" Example 1 was repeated except that 150 ml of titanium tetrachloride was used and the step of contacting at 80 ° C for 2 hours was repeated twice. A solid titanium catalyst component was prepared in the same manner as in 1. to obtain a solid titanium catalyst component [C]. The solid titanium catalyst component [C] thus obtained contained 4.6% by weight of titanium and 1% of magnesium.
5% by weight, chlorine 53% by weight, DIBP 18.1% by weight
Was included. Other than using the "polymerized" solid titanium catalyst component [C],
Polymerization of propylene was carried out in the same manner as in Examples 1 to 3. The results are shown in Table 3.

[0124]

[Table 3]

In the table, * 1) i-Bu ₃ Al / Et _1.5 Al
Cl _1.5 = 2/1 (molar ratio)

[Brief description of drawings]

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

Claims (3)

[Claims] 1. A magnesium compound [I] [A] (a)
(b) a co-ground product obtained by contacting with an electron donor and co-ground, and [B] a titanium compound in a liquid state.
A solid titanium catalyst component containing titanium, magnesium, halogen and an electron donor; [II] an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table; A catalyst for olefin polymerization, which is formed from a compound having two or more ether bonds existing via atoms. 2. The olefin polymerization according to claim 1, wherein the compound [III] having two or more ether bonds existing through a plurality of atoms is represented by the following formula: 1] (In the formula, n is an integer of 2 ≦ n ≦ 10, and R ¹ to
R ²⁶ is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ are jointly other than a benzene ring. May form a ring, and the main chain may contain atoms other than carbon. ). 3. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.