JPH06279517A - Solid titanium catalyst component for polymerization of olefin, catalyst for polymerization of olefin, and polymerization of olefin by using the same catalyst - Google Patents

Abstract

PURPOSE:To provide the catalyst containing a solid titanium catalyst component and being capable of producing an olefin (co)polymer of excellent stereoregularity in high polymerization activity. CONSTITUTION:The catalyst component is obtained by bringing a product of contact among a titanium compound represented by the formula: Ti(OR<a>)nX4-n (wherein 0<n<=4; X is a halogen atom; and R<a> is a 1-20C hydrocarbon group), an organosilteene compound having Si-O bonds and an organo-magnesium compound into contact with a compound having at least two ether bonds separated from each other by two or more atoms, a liquid titanium compound, and ether and/or ester compounds. An olefin is polymerized in the presence of an olefin polymerization catalyst formed from this component, an organometallic compound catalyst component containing a metal selected from among the elements of groups I-III of the Periodic Table and optionally an electron donor.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization solid titanium catalyst component for producing an olefin polymer, an olefin polymerization catalyst containing the solid titanium catalyst component, and an olefin polymerization method.

[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. A contact product obtained by contacting an organosilicon compound and an organomagnesium compound,
A catalyst for olefin polymerization comprising a solid titanium catalyst component formed from a compound having two or more ether bonds existing through a plurality of atoms, a liquid titanium compound, and an ether compound and / or an ester compound. ,
The present invention has been completed by finding that an olefin can be polymerized with excellent polymerization activity and an olefin polymer having 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.
An object of the present invention is to provide a solid titanium catalyst component for olefin polymerization capable of producing a polymer with high polymerization activity, a catalyst for olefin polymerization containing the solid titanium catalyst component, and a method for olefin polymerization.

[0007]

SUMMARY OF THE INVENTION The solid titanium catalyst component for olefin polymerization according to the present invention comprises [A] (a) Ti (OR ^a ) _n X _4-n (0 <n ≦ 4, where X is a halogen atom). And R ^a is a hydrocarbon group having 1 to 20 carbon atoms), and (b) S
a contact product obtained by contacting an organosilicon compound having an i-O bond with (c) an organomagnesium compound, and [B] a compound having two or more ether bonds existing through a plurality of atoms, [C] It is obtained by bringing the titanium compound in a liquid state into contact with [D] an ether and / or ester compound, and has two or more ether bonds existing through titanium, magnesium, halogen and the above plurality of atoms. And a compound.

[B] 2 existing through a plurality of atoms
The compound having at least one ether bond is preferably 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 catalyst according to the present invention comprises the above-mentioned [I] olefin polymerization solid titanium catalyst component and [II] a metal selected from Group I to Group III of the periodic table. It is characterized in that it is formed from an organometallic compound catalyst component and, if necessary, a [III] electron donor.

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.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The solid titanium catalyst component for olefin polymerization, 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" refers to not only homopolymer but also copolymer. It may be used in a meaning including a polymer.

The solid titanium catalyst component [I] for olefin polymerization according to the present invention is [A] (a) of the formula Ti (OR ^a ) _n X _4-n (0 <n ≦ 4, where X is a halogen atom). And R ^a is a hydrocarbon group having 1 to 20 carbon atoms), and (b) S
a contact product obtained by contacting an organosilicon compound having an i-O bond with (c) an organomagnesium compound, and [B] a compound having two or more ether bonds existing through a plurality of atoms, [C] It is obtained by bringing the titanium compound in a liquid state into contact with [D] an ether and / or ester compound, and has two or more ether bonds existing through titanium, magnesium, halogen and the above plurality of atoms. And the compound.

First, the contact object [A] will be described. (a) Titanium compound In the present invention, the titanium compound (a) used when preparing the contact product [A] is represented by the formula: Ti (OR ¹ ) _n X _4-n .

In the formula, 0 <n ≦ 4 and X is a halogen atom. —OR ¹ is an alkoxy group having 1 to 20 carbon atoms. Specific examples of the (a) titanium compound represented by such a formula include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti
(OC ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (O-iso-C
₄ H _{9) 4,} Ti (tetraalkoxy titanium such as _{O-2-ethylhexyl) 4, Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 C
1, mono (halogenated trialkoxy titanium) such as Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₂ Cl
₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , T
i (OC ₂ H ₅ ) ₂ Br ₂ and other dihalogenated dialkoxy titanium, 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
Examples include trihalogenated alkoxy titanium such as H ₉ ) Br ₃ .

Of these, tetraalkoxytitanium having an alkoxy group having 3 or 4 carbon atoms is preferably used, specifically tetra-n-butoxytitanium and tetra-n-.
Propoxy titanium is preferably used.

(B) Organosilicon Compound The (b) organosilicon compound used in the present invention is Si—O.
It has a bond and is specifically represented by the following formula.

Si (OR ³ ) _4-m R ⁴ _m , R ⁵ (R ⁶ ₂ Si
O) pSiR ⁷ ₂ or (R ⁸ ₂ SiO) q where R ³ is a hydrocarbon group having 1 to 20 carbon atoms, and R ^3
4 , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. 0 <
m ≦ 4, p is an integer of 1 to 1000, and q is 2
Is an integer from 1000.

Specific examples of such (b) organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, triethoxyethylsilane and triethoxyethylsilane. Ethoxyphenylsilane, dimethyldimethoxysilane, diethoxydiethylsilane, diisopropoxydiisopropylsilane,
Dipropoxydipropylsilane, dibutoxydibutylsilane, dicycloventoxydiethylsilane, diethoxydiphenylsilane, ethoxytriethylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, octaethyltrisiloxane, hexamethyldisiloxane, hexaethyldisiloxane , Hexapropyldisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, and the like.

Of these, alkoxysilane compounds represented by the formula Si (OR ³ ) _m R ⁴ _4-m are preferred, and further 1
Compounds with ≦ m ≦ 4 are preferable, and tetraalkoxysilane compounds with m = 4 are particularly preferable.

(C) Organomagnesium compound In the present invention, as the (c) organomagnesium compound, an organomagnesium compound containing a magnesium-carbon bond is used without particular limitation, but preferably, specifically, The Grignard compound represented by (a-1) and the magnesium compound having two hydrocarbon groups represented by (a-2) are used.

R ⁹ MgX (a-1) In the formula, X is a halogen atom and R ⁹ has 1 to 20 carbon atoms.
Is a hydrogen-carbon group. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, isoamyl, hexyl, octyl, 2-ethylhexyl, phenyl and benzyl. And an alkyl group, an aryl group, an aralkyl group, and an alkenyl group.

R ¹⁰ R ¹¹ Mg (a-2) In the formula, R ¹⁰ and R ¹¹ are each a hydrocarbon group having 1 to 20 carbon atoms as described above, and they may be the same or different. May be.

Specific examples of the Grignard compound represented by the above formula (a-1) include methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, propylmagnesium chloride and propylmagnesium bromide. , Butylmagnesium chloride, butylmagnesium bromide, sec-butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, amylmagnesium chloride, isoamylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, etc. Can be mentioned.

Further, as the compound represented by the formula (a-2),
Specifically, diethyl magnesium, dipropyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-sec-butyl magnesium, di-tert-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, diphenyl magnesium, butyl ethyl magnesium, etc. Can be mentioned.

Of these, the Grignard compound represented by the formula (a-1) is preferably used, and particularly diethyl magnesium, dipropyl magnesium, dibutyl magnesium and butyl ethyl magnesium are preferably used.

These may be used alone or in combination of two or more. Further, in the present invention, as the (c) organomagnesium compound, a hydrocarbon-soluble complex of the above organomagnesium compound and an organometallic compound can be used. Examples of the organometallic compound forming such a complex include organic compounds of Li, Be, B, Al or Zn.

In the present invention, the above-mentioned (c) organomagnesium compound is preferably used as a solution of an ether compound solvent or a hydrocarbon solvent. Specific examples of such ether compounds include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether dioctyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole. , Tetrahydrofuran, tetrahydropyran and the like.

Specific examples of the hydrocarbon solvent include hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene and xylene.

These may be used alone or in combination of two or more kinds, for example, as a mixed solvent of an ether solvent and a hydrocarbon solvent. In the present invention, the organomagnesium compound (c) is preferably used as an ether solution, particularly as a solution of an ether compound having 6 or more carbon atoms or an ether compound having a cyclic structure.

Preparation of Contact Product [A] In the present invention, when preparing the solid titanium catalyst component [I], first, the above-mentioned (a) titanium compound, (b) organosilicon compound and (c) organomagnesium are prepared. A compound contact product [A] is prepared.

The contact of these (a) titanium compound, (b) organosilicon compound and (c) organomagnesium compound is carried out by the following method. A method in which (c) an organomagnesium compound is added to a mixture of (i) (a) a titanium compound and (b) an organosilicon compound.

(Ii) A method of adding (a) a titanium compound and (b) an organosilicon compound to a solution of the organomagnesium compound. Of these, the method (i) is preferable from the viewpoint of catalytic activity.

Upon contact, (a) a titanium compound and
The (b) organosilicon compound is preferably used after being dissolved or diluted in a suitable solvent. Such solvents include hexane, heptane, octane, aliphatic hydrocarbons such as decane, toluene, aromatic hydrocarbons such as xylene, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, diethyl ether, dibutyl ether. , Ether compounds such as diisoamyl ether and tetrahydrofuran.

When contacting as described above, the component (a)
In (b) and (c), a porous material such as an inorganic oxide or an organic polymer may coexist, and the contact substance may be supported on the porous material.

As such a porous material, the pore volume at a pore radius of 200 to 2000 angstrom is
0.3 ml / g or more, with an average particle size of 5 to 800 μm
Are preferred.

Specific examples of the porous inorganic oxide include A
l ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , SiO ₂ ·
Al ₂ O ₃ , MgO, MgO.Al ₂ O ₃ , MgO.Si
O ₂ · Al ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, Zn ₂ O,
Examples thereof include SnO ₂ , BaO, ThO and the like.

Specific examples of the porous organic polymer include polystyrene, styrene-divinylbenzene copolymer, styrene-N, N'-alkylenedimethacrylamide copolymer, styrene-ethyleneglycoldimethylmethacrylate copolymer. Combined, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethylmethacrylate, methylmethacrylate-divinylbenzene copolymer, polyethylene glycol di Methyl methacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methacrylic acid Alcohol copolymer, polystyrene, such as polypropylene, polyacrylate, polymethacrylic acid ester, polyacrylonitrile,
Examples thereof include polyvinyl chloride-based and polyolefin-based polymers.

Among these porous materials, SiO ₂ , A
I ₂ O ₂ and polystyrene polymers are preferably used. The contact temperature is -50 ° C to 70 ° C, preferably -30.
C. to 50.degree. C., particularly preferably -25.degree. C. to 35.degree.

The contact time is not particularly limited, but for example, the dropping time is usually 80 minutes to 6 hours. After completion of the reduction reaction, a post-reaction may be further carried out at a temperature of 20 to 120 ° C.

Upon contact, (b) the organosilicon compound,
(a) The atomic ratio (Si / Ti) of silicon atoms to titanium atoms in the titanium compound is usually 1 to 50, preferably 8
It is used in an amount of -30, particularly preferably 5-25.

The organomagnesium compound (c) has a sum of titanium atoms and silicon atoms and an atomic ratio of magnesium atoms (Ti + Si / Mg) of usually 0.1 to 10, preferably 0.2 to 5.0, It is preferably used in an amount of 0.5 to 2.0.

The contact product (solid product) obtained by the above contact is preferably subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane or heptane.

The contact product [A] thus obtained is
It contains titanium, magnesium and polyether compounds and generally exhibits amorphous or extremely weak crystallinity. The solid titanium catalyst component [I] according to the present invention comprises a contact product [A] formed as described above, and [B] a compound having two or more ether bonds existing through a plurality of atoms. , [C] a liquid titanium compound and [D] an ether compound and / or an ester compound are brought into contact with each other.

[B] Two or more existing through a plurality of atoms
The compound having an ether bond above [B] In the compound (polyether compound) having two or more ether bonds existing through a plurality of atoms used in the present invention, the atoms existing between the ether bonds are carbon atoms. , At least one selected from the group consisting of silicon, oxygen, sulfur, phosphorus, and boron, and the number of atoms is 2 or more. Of these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having a carbon number of 2 or more, preferably 3 or more and having a linear, branched or cyclic structure, Preferably, a substituent having a branched or cyclic structure is bonded. Further, in the atom existing between two or more ether bonds, a plurality of atoms, preferably 3 to
20, more preferably 3 to 10, particularly preferably 3 to 7.
Compounds containing carbon atoms of are preferred.

Such a [B] polyether compound is
For example, it is represented by the following formula.

[0049]

[Chemical 3]

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 [B] 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-dimethoxypropane, 2-cyclohexyl-2 -Cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-di Ethoxybutane, 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 (methoxy Methyl) 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-ethoxy Methyl-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 (methoxymethyl) ) Silane, cyclohexyl-t-butylbis (methoxymethyl) silane, i
-Propyl-t-butylbis (methoxymethyl) silane and the like.

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.

[C] Titanium Compound in Liquid State [C] The titanium compound in a liquid state used in the present invention specifically includes, for example, 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 compounds include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and 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
Trihalogenated alkoxy titanium such as (O-iso-C ₄ H ₉ ) Br ₃ ; 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, T
i (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC
₂ H _{5) 3} monohalogenated trialkoxy titanium such as _{Br, Ti (OCH 3) 4} , Ti (OC 2 H 5) 4, Ti (On-C 4 H
Examples thereof include tetraalkoxytitanium such as ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

The titanium compound in the liquid state [C] used in the present invention may be the same as the titanium compound (a) used in the preparation of the contact product [A]. Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination.

[D] Ether Compound and Ester Compound
As the ether compound used in the present invention, specifically, in addition to the above-mentioned polyether of [B], dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, Examples thereof include dialkyl (mono) ethers such as dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, ethyl isobutyl ether, diphenyl ether, tetrahydrofuran and anisole. Of these, preferred are the same polyether compounds as those mentioned above, dibutyl ether and diisoamyl ether.

In the present invention, examples of the ester compound include mono- or polycarboxylic acid esters. Specific examples of the ester compound include the following aliphatic carboxylic acid ester, olefin carboxylic acid ester, alicyclic carboxylic acid ester, and aromatic carboxylic acid ester.

Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate. , Methyl chloroacetate, ethyl dichloroacetate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Examples include monocarboxylic acid esters such as amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, and ethyl ethoxybenzoate.

Examples of the polycarboxylic acid ester include compounds having a skeleton represented by the following general formula.

[0060]

[Chemical 4]

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted hydrocarbon group. 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 malonate, dibutyl malonate and diethyl methyl malonate. , Diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dimethyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methyl glutarate, ethyl succinate Acid diaryl, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate,
Aliphatic polycarboxylic acid esters such as dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, 1,2-
Cyclohexanecarboxylic acid diisobutyl, tetrahydrophthalic acid diethyl, alicyclic 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, diisopropyl phthalate,
Di-n-butyl phthalate, Di-isobutyl phthalate, Di-n-heptyl phthalate, Di-2-ethylhexyl phthalate, Di-n-octyl phthalate, Dineopentyl phthalate, Didecyl phthalate, Benzyl butyl phthalate, Diphenyl phthalate, Examples thereof include aromatic polycarboxylic acid esters such as diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Other examples of polycarboxylic acid esters 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.

Of these ester compounds, olefinic carboxylic acid esters such as methacrylic acid ester and maleic acid ester and phthalic acid esters are preferable, and phthalic acid diesters are particularly preferable.

In the present invention, when preparing the solid titanium catalyst component [I], other electron donors may be used, if necessary, together with the above-mentioned [D] ether compound and / or ester compound. Good.

Such other electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of inorganic acids or esters of other organic acids, acid amides, acid anhydrides, Ammonia, amine, nitrile, isocyanate and the like can be mentioned. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl. C1-C18 alcohols such as alcohols, C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol , C6-20 phenols which may have a lower alkyl group such as naphthol, acetone, methyl ethyl ketone Emissions, methyl isobutyl ketone,
C2-C15 ketones such as acetophenone, benzophenone and benzoquinone, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other carbon atoms 2
~ 15 aldehydes, acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride and other acid halides having 2 to 15 carbon atoms, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N , Acid amides such as N-dimethylamide, amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, γ
-Butyrolactone, δ-valerolactone, coumarin, phthalide, organic acid esters such as ethyl carbonate, acetonitrile, benzonitrile, nitriles such as trinitrile,
Examples thereof include acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

Two or more of these compounds can be used in combination. The above-mentioned polyether compound, electron donor and the like may be derived from other compounds during the preparation of the catalyst component.

In the present invention, the solid titanium catalyst component [I] is used.
In preparing the above, each component (a) titanium compound, (b) organosilicon compound, (c) organomagnesium compound, [B] polyether compound, [C] liquid titanium compound and [D] Any of ether and / or ester compounds containing halogen, or (a), (b), (c), [B], [C]
Alternatively, when none of [D] contains halogen, a solid titanium catalyst component [I] containing halogen is finally obtained together with titanium, magnesium and a polyether compound by using a halogen-containing compound. It is preferable to obtain. Specific examples of the halogen-containing compound include silicon tetrachloride and halogen-containing silane compounds such as trimethylchlorosilane, oxyhalides such as thionyl chloride and phosgene, non-metal halides such as phosphorus trichloride and phosphorus pentachloride, and butyl magnesium chloride. Grignard compounds and the like.

Preparation of solid titanium catalyst component [I] The above-mentioned contact product [A], liquid titanium compound [C], polyether compound [B], ether compound and / or ester compound [D]. The contact is not particularly limited, but the following method can be specifically exemplified. (1) First, the contact substance [A] is brought into contact with the polyether compound [B], and then the liquid titanium compound [C] is brought into contact with the ether compound and / or the ester compound [D]. (2) [A] contact material, [B] polyether compound, [C]
After contacting the titanium compound in the liquid state, [D]
A method of contacting an ether and / or ester compound. (3) A method of contacting the [A] contact substance, the [D] ether and / or ester compound, and then contacting the [B] polyether compound and [C] liquid titanium compound. (4) [A] contact material, [B] polyether compound, [C]
A method of contacting a titanium compound in a liquid state with a [D] ether and / or ester compound. (5) A method of further contacting [B] a polyether compound with (1) to (4). (6) A method of further contacting [C] a liquid titanium compound with (1) to (4). (7) A method in which [B] a polyether compound and [C] a titanium compound in a liquid state are brought into contact with (1) to (6).

The method of preparing the solid titanium catalyst component [I] will be described more specifically by taking the case of the above (1) as an example. When the contact substance [A] is contacted with the polyether compound [B], the polyether compound [B] is 0.1 to 50 mol, based on 1 mol of the titanium atom in the contact substance [A].
The amount is more preferably 0.8 to 20 mol, particularly preferably 0.5 to 10 mol, and 0.01 to 1.0 mol, preferably 0.1 to 1.0 mol, per 1 mol of magnesium atom in the contact product [A]. Used in an amount of 08-0.5 mol. If the amount of the polyether compound [B] used is too large, the catalyst component particles may collapse.

Polyether compound [B] and contact product [A]
The contact with the solid catalyst component is carried out without particular limitation by a conventionally known contact method such as a mechanical pulverizing means such as a slurry method or a ball mill. The distribution tends to be wide.

In the present invention, this contacting is preferably carried out in the presence of a diluent. As the diluent, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Alicyclic hydrocarbons such as cyclohexane and cyclopentane, and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used. Of these, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferable.

Such a diluent is usually 0.1 ml to 1000 ml, preferably 1 ml to 10 ml per 1 g of the contact product [A].
Used in a volume of 0 ml. The contact temperature is usually -50 to 15
The temperature is 0 ° C., preferably 0 to 120 ° C., and the contact time is usually 10 minutes or longer, preferably 30 minutes to 8 hours.

The contact product [A] thus treated with the polyether compound [B] is preferably allowed to stand and undergo solid-liquid separation, and then washed several times with an inert hydrocarbon solvent. Next, the contact product [A] treated with the polyether compound [B] is contacted with the titanium compound [C] in the liquid state and the ether compound and / or the ester compound [D] as described above.

This contact is preferably carried out in a slurry state. Examples of the solvent for slurrying the contact substance [A] include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic rings such as cyclohexane, methylcyclohexane and decalin. Examples include halogenated hydrocarbons such as formula hydrocarbons, dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and trichlorobenzene. Of these, halogenated hydrocarbons and aromatic hydrocarbons are preferable.

The slurry concentration is usually 0.05 to 0.7 g.
Solid (contact [A]) / ml solvent, preferably 0.1-
0.5 g solid / ml solvent. The contact temperature is usually 80-
The temperature is 150 ° C, preferably 45 to 120 ° C, particularly preferably 60 to 100 ° C. The contact time is not particularly limited, but is preferably 80 minutes to 6 hours.

Examples of the method for bringing the contact product [A] treated with the polyether compound [B] into contact with the liquid titanium compound [B] and the ether compound and / or ester compound [D] include (i) ) In the contact product [A] treated with the polyether compound, the ether compound and / or
Alternatively, a method of adding an ester compound [D] and a titanium compound [C] in a liquid state, (ii) an ether compound and / or a solution of the titanium compound [C] in a liquid state and a polyether A method of adding the contact substance [A] treated with a compound can be mentioned.

In the former method (i), the ether compound and / or the ester compound [D] is added to the contact product [A] treated with the polyether compound, and then the titanium compound [C] in the liquid state is added. Alternatively, the ether compound and / or the ester compound [D] and the liquid titanium compound [C] may be added at the same time.

The contact of the contact product [A] treated with the polyether compound with the ether compound and / or the ester compound [D] and the liquid titanium compound [C] may be repeated twice or more.

In the present invention, the method (i) is preferable among them, and in particular, the ether compound and / or ester compound [D] and the titanium compound in the liquid state [ A method of simultaneously adding C] as a previously prepared mixture is preferable. Further, it is preferable to repeat this contact at least twice in terms of catalytic activity and stereoregularity.

In the contact as described above, the ether compound and / or the ester compound [D] is used in an amount of 0.0 to 1 mol of the titanium atom contained in the contact product [A].
It is used in an amount of 2 to 80 mol, preferably 0.05 to 15 mol, and particularly preferably 0.1 to 5 mol, and the titanium compound [C] in a liquid state is contained in the contact product [A]. It is used in an amount of 1-1000 mol, preferably 8-500 mol, particularly preferably 10-300 mol, per 1 mol of titanium atom.

The liquid titanium compound [C] is 30 to 1000 mol, preferably 50 to 7 mol, relative to 1 mol of the ether compound and / or ester compound [D].
It is used in an amount of 00 mol, particularly preferably 100 to 500 mol.

The solid titanium catalyst component [I] obtained as described above is preferably subjected to solid-liquid separation and then washed several times with an inert hydrocarbon solvent such as hexane or heptane. The solid titanium catalyst component [I] obtained by solid-liquid separation is 5
After washing with a large amount of halogenated hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent such as toluene at a temperature of 0 to 120 ° C. once or more, washing is repeated several times with an aliphatic hydrocarbon solvent such as hexane. After that, it is preferable to use for polymerization in terms of catalytic activity and stereoregularity.

Solid titanium catalyst component [I] as described above
In the preparation of, all the operations such as contact are preferably carried out under an atmosphere of an inert gas such as nitrogen or argon. The solid titanium catalyst component [I] thus obtained contains trivalent titanium, magnesium, halogen and a compound (polyether compound) having two or more ether bonds present through a plurality of atoms. ing.

In this solid titanium catalyst component [I], the magnesium / titanium (atomic ratio) is from 1 to 100,
It is preferably 2 to 50, particularly preferably 4 to 50,
The halogen / titanium (atomic ratio) is 2 to 200, preferably 4 to 90, particularly preferably 5 to 50, and the polyether compound / titanium (molar ratio) is 0.01 to 200,
Preferably 0.05 to 100, particularly preferably 0.1 to
50.

The method for producing the solid titanium catalyst component [I] according to the present invention is not limited to these embodiments. The catalyst for olefin polymerization according to the present invention comprises a solid titanium catalyst component [I] as described above and an organometallic compound catalyst component containing a metal selected from [II] Group I to Group III of the periodic table. And optionally [III] electron donor.

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 the hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group, and specific examples include 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, z
Is a positive number and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum represented by
Trialkenyl aluminum such as triisopropenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide such as dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, Alkyl aluminum sesquichlorides such as butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, diethyl aluminum hydride Dialkylaluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride, alkyl aluminum dihydride such as propyl aluminum dihydride and the like.

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, (3) R ¹ _n Al, such as Et ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Et ₃ ).
A compound represented by (OAlR ¹² ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) ₂ , (4) R ¹ _n A
a compound represented by 1 (NR ¹³ ₂ ) _3-n , for example, Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHEt Et ₂ AlN (Si Me ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ (5) R ¹ _n Al
A compound represented by (Si R ¹⁴ ₃ ) _3-n , for example, (iso-
Bu) ₂ AlSi Me _3, etc., (6) R ¹ _n Al [N (R ¹³ ).
AlR ¹⁶ ₂ ] _3-n , for example Et ₂ Al
N (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) A
l (iso-Bu) ₂ etc.

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 etc.

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. ) Specifically, diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride and the like can be mentioned.

These may be used alone or in combination. In the present invention, the [III] electron donor, which is optionally used when preparing the olefin polymerization catalyst, is specifically, when preparing the above-mentioned [I] solid titanium catalyst component. The indicated [B] polyether compound and electron donor are used, and it is also preferable to use the organosilicon compound represented by the following general formula.

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.

Further, in the present invention, as the [III] electron donor, a nitrogen-containing compound, another oxygen-containing compound, a phosphorus-containing compound or the like can be used. Specific examples of such nitrogen-containing compounds include the compounds shown below.

[0101]

[Chemical 5]

[0102]

[Chemical 6]

2,6-substituted piperidines such as

[0104]

[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.

Further, as the oxygen-containing compound, specifically,
The following compounds may be mentioned.

[0108]

[Chemical 8]

2,6-substituted tetrahydropyrans such as

[0110]

[Chemical 9]

2,5-substituted tetrahydropyrans such as The above compounds may be used in combination of two or more kinds.
These compounds can also be used when preparing a solid titanium catalyst component.

In the olefin polymerization method according to the present invention, an olefin is polymerized or copolymerized in the presence of the above-mentioned olefin polymerization catalyst. Examples of the olefin used in the present invention include α-olefins having 2 to 20 carbon atoms, 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-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. 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 to 200 mmol, preferably about 0.01 to 10
It is 0 mmol, particularly preferably 0.1 to 50 mmol.

The organometallic compound catalyst component [II] is used in an amount such that 0.1 to 1000 g, preferably 0.3 to 500 g of a polymer 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].

When the electron donor [III] is used, it is 0.01 to 100 mol, preferably 0.05 to 100 mol, per 1 mol of titanium atom in the solid titanium catalyst component [I].
It is used in an amount of 80 mol, more preferably 0.1 to 50 mol.

The prepolymerization of olefin can be carried out by either liquid phase polymerization method such as solution polymerization, 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 coexistence of an inert hydrocarbon medium, and the olefin and the above 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 in 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, 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 atom per 1 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 [III] electron donor is 100 mol or less, preferably 0.005 to 50 mol, and more preferably 0.01 to 30 mol, based on 1 mol of the [II] organometallic compound.
It is optionally used in a molar amount, particularly preferably 0.05 to 20 mol.

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 adjusting 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 any of a homopolymer, a random copolymer and a block copolymer. 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.

[0131]

EFFECTS OF THE INVENTION The solid titanium catalyst component for olefin polymerization according to the present invention has a high catalytic activity during polymerization and is capable of producing an olefin polymer excellent in stereospecificity in a high yield. Form a catalyst for use.

In the olefin polymerization method according to the present invention, an olefin is polymerized by using such an olefin polymerization catalyst according to the present invention, and the catalyst activity is high and the polymerization reaction can be carried out 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.

[0134]

Example 1 “Preparation of Solid Titanium Catalyst Component” (a) Synthesis of Organomagnesium Compound A 1-liter round-bottomed flask sufficiently replaced with nitrogen gas was charged with 82 g of magnesium metal powder. Next, 120 g of n-butyl chloride and 500 ml of dibutyl ether were placed in a dropping funnel, and 80 ml of this solution was added dropwise with stirring. After the dropping, the remaining solution was dropped at 50 ° C. over 4 hours. After the dropping was completed, the reaction was carried out at 60 ° C. for another hour. After that, the solution was cooled to room temperature and the solid matter was filtered off to obtain an organomagnesium compound. (b) Synthesis of reaction product In a 500 ml round bottom flask sufficiently replaced with nitrogen gas, 240 ml of hexane and 5.4 ml of tetrabutoxytitanium.
And 61.4 g of tetraethoxysilane were charged to obtain a uniform solution. Next, 150 ml of the organomagnesium compound synthesized in (a) was added dropwise from the dropping funnel over 4 hours while maintaining the temperature in the flask at 5 ° C. After the dropping is completed,
After reacting at room temperature for 1 hour, solid-liquid separation is performed, and hexane 240
After washing with ml eight times, it was dried under reduced pressure to obtain a solid product. (c) Treatment with ether compound In a 100 ml round-bottomed flask sufficiently replaced with nitrogen gas.
8.6 g of the solid product synthesized in (b), 48 ml of toluene and 4.8 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IPAMP) were added and the reaction was carried out at 95 ° C. for 1 hour. After carrying out the reaction, decantation was carried out at 95 ° C., and washing with 100 ml of toluene was carried out three times. (d) Synthesis of solid catalyst After washing in (c) above, 20 ml of toluene, 0.39 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 12.8 ml of TiCl ₄ were added to the flask and the mixture was stirred at 95 ° C. for 8 hours. The reaction was carried out over time. After completion of the reaction, decantation was carried out at 95 ° C., and washing with 50 ml of toluene was carried out twice at the same temperature. 2-isopropyl-2-isopentyl-1,3-as described above
The treatment with the mixture of dimethoxypropane and TiCl ₄ was repeated once more under the same conditions, and the solid catalyst was obtained by washing 3 times with 50 ml of hexane. The solid catalyst contained 2.8% by weight of titanium atoms. “Polymerization” 750 ml of purified n-hexane was inserted into an autoclave with an internal volume of 2 liters, and 0.75 mmol of triethylaluminum and 0.075 of cyclohexylmethyldimethoxysilane (CMMS) in a propylene atmosphere at 60 ° C.
And 0.0075 mmol Ti in terms of titanium atom based on the solid titanium catalyst component obtained as described above.
Charged.

150 ml of hydrogen was introduced, the temperature was raised to 70 ° C., and this was held for 2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 7 kg / cm ² G. The polymerization results are shown in Table 1.

[0136]

Example 2 “Preparation of solid titanium catalyst component” In Example 1,
(c) A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 7.2 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added in the step of treating with an ether compound. "Polymerization" In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component was changed to the above-mentioned one. The results are shown in Table 1.

[0137]

Example 3 "Polymerization" In Example 1, IPA was used instead of CMMS.
Polymerization of propylene was carried out in the same manner as in Example 1 except that 0.075 mmol of MP was used. The results are shown in Table 1.

[0138]

Example 4 “Preparation of solid titanium catalyst component” In Example 1,
(c) A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 7.2 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added in the step of treating with an ether compound. "Polymerization" In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component was changed to the above-mentioned one. The results are shown in Table 1.

[0139]

[Example 5] "Polymerization" Polymerization of propylene was carried out in the same manner as in Example 1 except that IPAMP was not added during the polymerization. The results are shown in Table 1.

[0140]

Example 6 “Preparation of solid titanium catalyst component” In Example 1,
(c) A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 7.2 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added in the step of treating with an ether compound. "Polymerization" In Example 5, propylene was polymerized in the same manner as in Example 5 except that the solid titanium catalyst component was replaced with the above. The results are shown in Table 1.

[0141]

Comparative Example 1 “Preparation of Solid Titanium Catalyst Component” In Example 1,
A solid titanium catalyst was prepared in the same manner as in Example 1 except that 5.0 g of (c) and 0.48 g of diisobutyl phthalate were used in (d) instead of isopropyl-2-isopentyl-1,3-dimethoxypropane. The ingredients were prepared. "Polymerization" Polymerization was carried out in the same manner as in Example 1 except that the above solid titanium catalyst component was used. The results are shown in Table 1.

[0142]

[Table 1]

[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 (4)

[Claims] 1. An [A] (a) formula Ti (OR ^a ) _n X _4-n (0
<N ≦ 4, X is a halogen atom, and R ^a is a hydrocarbon group having 1 to 20 carbon atoms), and (b) an organosilicon compound having a Si—O bond. ,
(c) a contact product obtained by contacting with an organomagnesium compound, [B] a compound having two or more ether bonds existing through a plurality of atoms, [C] a titanium compound in a liquid state, D] Olefin polymerization obtained by contacting with an ether and / or ester compound, and containing titanium, magnesium, halogen, and a compound having two or more ether bonds present through the above plurality of atoms. Solid titanium catalyst component for use. 2. The solid titanium catalyst component for olefin polymerization according to claim 1, wherein the compound having two or more ether bonds present through the plurality of atoms is represented by the following formula: [Chemical 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. [I] The solid titanium catalyst component for olefin polymerization according to claim 1, and [II] Group I to II of the periodic table.
An olefin polymerization catalyst, which is formed from an organometallic compound catalyst component containing a metal selected from Group I and, if necessary, a [III] electron donor. 4. 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 3.