JP2003206312A - CATALYST FOR alpha-OLEFIN POLYMERIZATION AND METHOD FOR MANUFACTURING alpha-OLEFIN POLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization catalyst for obtaining an α-olefin polymer of high quality and a method for manufacturing an α-olefin polymer. <P>SOLUTION: The catalyst for α-olefin polymerization is obtained by contacting the following (A), (B), (C) and (D) together: (A) a solid catalyst component comprising as essential ingredients Ti, Mg and a halogen; (B) an organoaluminum compound; (C) a compound bearing a -C-O-C-O-C- bonding group; and (D) an alkoxysilane compound. The method for manufacturing an α-olefin polymer comprises subjecting an α-olefin to homopolymerization or copolymerization using the catalyst for α-olefin polymerization. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art As a method for producing a polymer of .alpha.-olefin such as propylene and butene-1, the periodic table No. 4 is used.
~ It is well known to use so-called Ziegler-Natta catalysts consisting of a solid catalyst component prepared with a Group 6 transition metal compound and a Group 1, 2, 13 organometallic compound.

When producing an α-olefin polymer, an amorphous polymer is usually produced as a by-product in addition to a stereoregular α-olefin polymer which is industrially useful. This amorphous polymer has a low industrial utility value and exerts a great adverse effect on the mechanical properties when the α-olefin polymer is processed into an injection-molded product, a film, a fiber, or other processed products for use. In addition, the production of the amorphous polymer causes a loss of the raw material monomer, and at the same time requires a manufacturing facility for removing the amorphous polymer, which causes a great disadvantage from an industrial viewpoint. Therefore, the catalyst for producing the α-olefin polymer has no formation of such an amorphous polymer, or
Even if there is, it is desirable that it is extremely small.

By using a combination of a supported solid catalyst component obtained by supporting a tetravalent titanium halide on magnesium halide, an organoaluminum compound as a cocatalyst, and an organosilicon compound as a third polymerization component, α
It is known that highly stereoregular polymerization of olefins can be realized (Japanese Patent Laid-Open Nos. 57-63310 and 5).
8-83006, and JP-A-61-78803).

Further, a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound is treated with an ester compound, and then treated with a mixture of ether compound and titanium tetrachloride or an ether compound. In the combination of a trivalent titanium compound-containing solid catalyst component obtained by treating with a mixture of titanium tetrachloride and an ester compound, an organoaluminum compound as a cocatalyst, and an electron donating compound as a polymerization third component, α- It is known that highly stereoregular polymerization of olefins can be realized (JP-A-7-216017).

Furthermore, a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound is added in the order of a mixture of an ether compound and titanium tetrachloride and an organic acid halide compound. After the treatment, a trivalent titanium compound-containing solid catalyst component obtained by treating with a mixture of an ether compound and titanium tetrachloride, or a mixture of an ether compound, titanium tetrachloride and an ester compound, and an organoaluminum compound as a cocatalyst. It is known that highly stereoregular polymerization of α-olefin can be realized even in combination with an electron-donating compound as the third component of the polymerization (JP-A-10-212).
319).

In either case, it is at a level where it is feasible to produce a polymer having high stereoregularity by a non-extraction and deashing process, but further improvement is desired. Specifically, in order to improve the quality of the α-olefin polymer, it is desired to realize a higher stereoregular polymerization ability.

[0008]

Under the present circumstances,
The problem to be solved by the present invention, that is, the object of the present invention, is to provide a polymerization catalyst and α for obtaining a high-quality α-olefin polymer.
-To provide a method for producing an olefin polymer.

[0009]

The present invention provides an α-olefin polymerization catalyst obtained by contacting the following (A), (B), (C) and (D) and the α-olefin polymerization catalyst. The present invention relates to a method for producing an α-olefin polymer in which an α-olefin is homopolymerized or copolymerized. (A) Solid catalyst component containing Ti, Mg and halogen as essential components (B) Organoaluminum compound (C) -C-O-C-O-C-Compound having a bonding group (D) Alkoxysilicon compound

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. [Polymerization Catalyst] (C) -C-O-C-O-C- Bonding Group-Containing Compound As the above-mentioned -C-O-C-O-C-bonding group-containing compound (C), Examples thereof include compounds represented by the general formula. (R ^{1 to} R ⁸ are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon oxy group having 1 to 20 carbon atoms, and any combination thereof may be bonded to each other, The carbon atoms to which any two of them do not exist and which do not exist in the above general formula may be directly bonded to each other.)

Specific examples of R ^{1 to} R ⁸ include hydrogen atom, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tert-butyl group, normal pentyl group, isopentyl group, neopentyl group. Group, cyclopentyl group, normal hexyl group, isohexyl group, cyclohexyl group, normal heptyl group,
Normal octyl group, 2-ethylhexyl group, normal decyl group, isodecyl group, phenyl group, methoxy group, ethoxy group, normal propoxy group, isopropoxy group,
Examples thereof include a normal butoxy group, an isobutoxy group, a tert-butoxy group, a normal pentoxy group, an isopentoxy group, a neopentoxy group, a normal hexoxy group and an isohexoxy group.

Examples of compounds in which R ^{1 to} R ⁸ are independent substituents include dimethyl acetal, diethyl acetal, propylene aldehyde dimethyl acetal, normal octyl aldehyde dimethyl acetal, benzaldehyde dimethyl acetal, 2,2-dimethoxy propane, 3, 3-dimethoxyhexane, 2,6-dimethyl-4,4-dimethoxyheptane and the like can be mentioned.

A compound in which any combination of R ^{1 to} R ⁸ is bound to each other, or carbon atoms to which any two of R ^{1 to} R ⁸ are absent and which are not present in the above general formula are bound Examples of the compound in which is directly bonded are 1,1-dimethoxycyclopentane, 1,1-dimethoxycyclohexane, 1,1-diethoxycyclopentane, 1,1-diethoxycyclohexane, 2-methoxytrimethylene oxide, and 2-ethoxy. Trimethylene oxide, 2,4-dimethoxytrimethylene oxide, 2,4-diethoxytrimethylene oxide, 2-methoxytetrahydrofuran, 2-ethoxytetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, 2- Methoxytetrahydropyran, 2-ethoxytetrahydr Ropyran, 2,6-dimethoxytetrahydropyran, 2,6-diethoxytetrahydropyran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,2
-Dimethyl-1,3-dioxolane, 2,4-dimethyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 4-methoxy-1,3-dioxolane, 2,
2-dimethoxy-1,3-dioxolane, 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 2, 4-dimethyl-1,3-dioxane, 2
-Methoxy-1,3-dioxane, 4-methoxy-1,
3-dioxane, 2,2-dimethoxy-1,3-dioxane, 2,4-dimethoxy-1,3-dioxane, 1,
3-dioxepane, 2-methyl-1,3-dioxepane, 4-methyl-1,3-dioxepane, 5-methyl-
1,3-dioxepane, 2,4-dimethyl-1,3-dioxepane, 2,5-dimethyl-1,3-dioxepane, 2-methoxy-1,3-dioxepane, 4-methoxy-1,3-dioxepane, 5-methoxy-1,3-dioxepane, s-trioxane and the like can be mentioned.

Of these, the compound (C) is R
^A compound in which ¹ and R ⁸ are bonded to each other, or R ¹ and R ⁸ are not present and the carbon atoms to which they are bonded in the above general formula are directly bonded, that is, -C-
Compounds having an O—C—O—C— linking group in the closed ring structure are preferred. Particularly preferred is 1,3-dioxolane,
1,3-dioxane, 1,3-dioxepane, and s
-Trioxane.

(D) Alkoxy Silicon Compound The alkoxy silicon compound has the general formula R ³ _r Si
(OR ⁴ ) _4-r (In the formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hetero atom-containing substituent, and R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms. Represents, r
Represents a number satisfying 0 ≦ r <4. All R ³ and all R ⁴ may be the same or different. The alkoxy silicon compound represented by the formula (1) is preferably used. When R ³ is a hydrocarbon group, R ³ is a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, sec-butyl group, tert-butyl group, tert-group. Examples thereof include branched-chain alkyl groups such as amyl groups, cyclopentyl groups, cycloalkyl groups such as cyclohexyl groups, cycloalkenyl groups such as cyclopentenyl groups, aryl groups such as phenyl groups and tolyl groups. The same thing can be mentioned as R ⁴ . When R ³ is a hetero atom-containing substituent, examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, perhydro. Examples include isoindolyl group, perhydroquinolyl group, perhydroisoquinolyl group, perhydrocarbazolyl group, perhydroacridinyl group, furyl group, pyranyl group, perhydrofuryl group and thienyl group. However, a substituent in which the hetero atom can directly chemically bond with the silicon atom of the alkoxy silicon compound is preferable. As the alkoxy silicon compound (D), a silicon compound having at least one R ^{3 in} which the carbon atom directly bonded to the silicon atom is a secondary or tertiary carbon in the above general formula is preferable.

Specific preferred examples of the alkoxysilicon compound (D) include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane and te.
rt-butyl-n-propyldimethoxysilane, ter
t-butyl-n-butyldimethoxysilane, tert-
Amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane,
tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl- ter
t-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,
Cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-
Butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane , Diisobutyldiethoxysilane, di-ter
t-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldi Ethoxysilane, ter
t-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-
n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane,
Phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (per Hydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino)
Ethyldimethoxysilane, (perhydroisoquinolino)
Ethyldimethoxysilane, (perhydroquinolino) (n
-Propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimethoxysilane, and (perhydroisoquinolino) (tert-butyl) dimethoxysilane Is mentioned.

In the present invention, the compound (C) and the compound (D) are used together as a so-called external donor.
A known solid catalyst component may be appropriately selected as the solid catalyst component used in combination with these combined external donors, and a typical solid catalyst component is a solid catalyst component (A) containing Ti, Mg and halogen as essential components.

(A) Solid Catalyst Component The solid catalyst component (A) may be any known solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom. As the solid catalyst component, JP-B-46-34092, JP-B-47-41676, JP-B-55-23561 and JP-B-57-2.
4361, Japanese Patent Publication No. 52-39431, Japanese Patent Publication No. 52-36786, Japanese Patent Publication No. 1-28049, Japanese Patent Publication No. 3-43283, and Japanese Patent Laid-Open No. 4-8004.
4, JP-A-55-52309, JP-A-58.
-21405, JP 61-181807, JP 63-142008, JP 5-33
No. 9319, No. 54-148093, No. 4-227604, No. 6-2933, No. 64-6006, No. 6-1797.
No. 20, Japanese Patent Publication No. 7-116252, and Japanese Unexamined Patent Publication No. Hei 8
-134124, JP-A-9-31119,
JP-A-11-228628 and JP-A-11-802.
The solid catalyst components described in JP-A-34-34 and JP-A-11-322833 can be exemplified.

The solid catalyst component is preferably a solid catalyst component which further contains an electron donor in addition to the titanium atom, magnesium atom and halogen atom. As the electron donor, esters or ethers of organic acids described later are preferable. As the method for producing the solid catalyst component, the following methods (1) to (5) can be exemplified. (1) A method of bringing a magnesium halide compound and a titanium compound into contact with each other. (2) A method of bringing a magnesium halide compound, an electron donor and a titanium compound into contact with each other. (3) A method of dissolving a magnesium halide compound and a titanium compound in an electron donating solvent to obtain a solution, and then impregnating the solution into a carrier substance. (4) A method of bringing a dialkoxy magnesium compound, a titanium halide compound, and an electron donor into contact with each other. (5) A method of bringing a solid component containing a magnesium atom, a titanium atom and a hydrocarbon oxy group into contact with a halogenated compound, an electron donor and / or an organic acid halide. Among them, a method of contacting a solid component (a) containing a magnesium atom, a titanium atom and a hydrocarbon oxy group, a halogenated compound (b), an electron donor (c) and / or an organic acid halide (d). (5) is preferred.

(A) Solid Component The solid component (a) is a solid substance containing at least a magnesium atom, a titanium atom and a hydrocarbon oxy group. It is preferably a solid substance containing at least 20 wt% or more hydrocarbon oxy groups, and more preferably a solid substance containing 25 wt% or more hydrocarbon oxy groups. Specifically, a solid compound obtained by reducing a titanium compound () represented by the following general formula [I] with an organomagnesium compound () in the presence of an organosilicon compound () having a Si-O bond. The thing is preferable. At this time, coexistence of the ester compound () as an optional component is preferable because the polymerization activity and the stereoregular polymerization ability are further improved. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. )

Organosilicon compound having Si-O bond
Examples of () include those represented by the following general formula.
To be Si (OR^Ten)_tR¹¹ _4-t R¹²(R¹³ ₂SiO)_uSiR¹⁴ ₃, Or (R¹⁵ ₂SiO)_v R here^TenRepresents a hydrocarbon group having 1 to 20 carbon atoms,
R¹¹, R¹², R¹³, R ¹⁴And R¹⁵Each independently,
Represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom
You t represents an integer satisfying 0 <t ≦ 4, and u is 1 to 1
Represents an integer of 000, and v represents an integer of 2 to 1000.

Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane. , Tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane,
Dibutoxydibutylsilane, Dicyclopentoxydiethylsilane, Diethoxydiphenylsilane, Cyclohexyloxytrimethylsilane, Phenoxytrimethylsilane, Tetraphenoxysilane, Triethoxyphenylsilane, Hexamethyldisilohexane, Hexaethyldisilohexane, Hexapropyldiphenylsilane Examples thereof include siloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane and the like.

[0023] a preferred general formula Si (OR ¹⁰⁾ alkoxysilane compound represented by _t R ¹¹ _{4 -t} Among these organosilicon compounds, in which case t is preferably 1
It is a number that satisfies ≦ t ≦ 4, and tetraalkoxysilane having t = 4 is particularly preferable, and tetraethoxysilane is most preferable.

The titanium compound () is a titanium compound represented by the following general formula [I]. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. )

Specific examples of R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group. Examples thereof include an alkyl group, a phenyl group, a cresyl group, a xylyl group, an aryl group such as a naphthyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Of these groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Especially 2 carbon atoms
-18 straight chain alkyl groups are preferred.

Examples of the halogen atom for X ² include chlorine atom, bromine atom and iodine atom. A chlorine atom is particularly preferable. The hydrocarbon oxy group having 1 to 20 carbon atoms in X ² is a hydrocarbon oxy group having a hydrocarbon group having 1 to 20 carbon atoms similar to R ² . Particularly preferably, X ² is an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

In the titanium compound represented by the above general formula [I], a represents a number of 1 to 20, preferably 1≤a≤.
It is a number that satisfies 5.

Specific examples of the titanium compound will be given below.
Tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, tetra-iso
-Butoxy titanium, n-butoxy titanium trichloride, di-n-butoxy titanium dichloride, tri-n-
Butoxy titanium chloride, di-n-tetraisopropyl polytitanate (a = 2-10 mixture), tetra-n-butyl polytitanate (a = 2-10 mixture), tetra-n-hexyl polytitanate (A
= A mixture in the range of 2 to 10) and tetra-n-octyl polytitanate (a mixture in the range of a = 2 to 10). Moreover, the condensate of tetraalkoxy titanium obtained by reacting tetraalkoxy titanium with a small amount of water can be mentioned.

The titanium compound () is preferably a titanium compound in which a in the titanium compound represented by the above general formula [I] is 1, 2 or 4. Particularly preferred is tetra-n-butoxytitanium, tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer. The titanium compound () can be used in a mixed state of plural kinds.

The organomagnesium compound () is
Any type of organic magnesia having a sium-carbon bond
It is a compound. Especially the general formula R¹⁶MgX^Five(In the formula, Mg
Is a magnesium atom, R¹⁶Is charcoal having 1 to 20 carbon atoms
A hydrogenated group, X^FiveRepresents a halogen atom. )
Grignard compound or general formula R¹⁷R¹⁸Mg (formula
Inside, Mg is magnesium atom, R¹⁷And R¹⁸Is it
Each represents a hydrocarbon group having 1 to 20 carbon atoms. )
Dihydrocarbyl magnesium used is suitable
To be done. Where R¹⁷And R¹⁸Can be the same or different
Yes. R¹⁶~ R ¹⁸Examples of
Group, ethyl group, propyl group, isopropyl group, butyl
Group, sec-butyl group, tert-butyl group, isoamido
Group, hexyl group, octyl group, 2-ethylhexyl group
Groups having 1 to 20 carbon atoms such as groups, phenyl groups, benzyl groups, etc.
Alkyl group, aryl group, aralkyl group, alkenyl group
Is mentioned. Especially R¹⁶MgX^FiveRepresented by Grignard
Of the catalytic performance is the use of a ruthenium compound in an ether solution
Is preferred.

It is also possible to use a hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and an organometal which solubilizes the organomagnesium compound in hydrocarbon. Examples of the organometallic compound include Li, Be, B, Al or Z
The compound of n is mentioned.

As the ester compound (), mono- or polyvalent carboxylic acid esters are used, examples of which include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic compounds. Mention may be made of carboxylic acid esters. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl. Ethyl acid, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-phthalate n-octyl,
Examples thereof include di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate.

Of these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as phthalic acid esters are preferred, and dialkyl esters of phthalic acid are particularly preferred. .

The solid component (a) is a titanium compound () in the presence of the organosilicon compound () or in the presence of the organosilicon compound () and the ester compound ().
Is obtained by reduction with an organomagnesium compound ().

The titanium compound (), the organosilicon compound () and the ester compound () are preferably dissolved or diluted in a suitable solvent before use. Examples of such a solvent 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, and diether. Examples of the ether compound include isoamyl ether and tetrahydrofuran.

The reduction reaction temperature is usually -50 to 70 ° C, preferably -30 to 50 ° C, and particularly preferably -25 to 35 ° C.
The temperature range is ° C. The reaction time is not particularly limited, but is usually about 30 minutes to 6 hours. After that, 20 to 1 more
The post reaction may be carried out at a temperature of 20 ° C.

It is also possible to allow a porous carrier such as an inorganic oxide or an organic polymer to coexist during the reduction reaction and impregnate the porous carrier with the solid product. A known porous carrier may be used. SiO ₂ , Al
₂ O ₃ , MgO, TiO ₂ , ZrO _{2 and} other porous inorganic oxides, or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-
Methyl dimethacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethylmethacrylate, methylmethacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene Examples thereof include copolymers, polyvinyl chloride, polyethylene, and organic porous polymers such as polypropylene. Of these, preferably an organic porous polymer is used,
Among them, a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

The porous carrier has a pore radius of 200 to 2000.
The pore volume in Å is preferably 0.3 cc / g or more,
It is more preferably 0.4 cc / g or more, and the pore volume in this range is preferably 35% or more, more preferably 40% of the pore volume at a pore radius of 35 to 75000Å.
That is all. If the pore volume of the porous carrier is small, the catalyst component may not be effectively immobilized, which is not preferable. In addition, the pore volume of the porous carrier is 0.3 cc / g
Even if the above is the case, the catalyst component may not be effectively immobilized unless it is sufficiently present in the pore radius of 200 to 2000Å, which is not preferable.

The amount of the organosilicon compound () used is an atomic ratio of silicon atoms to titanium atoms in the titanium compound (), and usually Si / Ti = 1 to 500, preferably 1
To 300, particularly preferably 3 to 100. Further, the amount of the organomagnesium compound () used is usually (Ti + Si) /Mg=0.1 to 10, preferably 0.2 to 5.0, in terms of the sum of titanium atoms and silicon atoms and the atomic ratio of magnesium atoms. It is preferably in the range of 0.5 to 2.0. Further, the titanium compound (), the organosilicon compound (), the organomagnesium so that the value of the Mg / Ti molar ratio in the solid catalyst component is in the range of 1 to 51, preferably 2 to 31, and particularly preferably 4 to 26. Compound()
May be determined. The amount of the optional ester compound () used is a molar ratio of the ester compound to the titanium atom of the titanium compound (), and is usually ester compound / Ti = 0.05 to 100, preferably 0.1 to 100.
The range is 60, particularly preferably 0.2 to 30.

The solid product obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane, heptane or toluene. The solid component (a) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally exhibits amorphous or extremely weak crystallinity. From the viewpoint of catalytic performance, an amorphous structure is particularly preferable.

(B) Halogenated compound The halogenated compound is preferably a compound capable of substituting a halogen atom for a hydrocarbon oxy group in the solid component (a). Among them, a halogen compound of a Group 4 element, a halogen compound of a Group 13 element, or a halogen compound of a Group 14 element is preferable.

As the halogen compound of the Group 4 element, a general formula M (OR ⁹ ) _b X ⁴ _4-b (wherein M represents a Group 4 element and R ⁹ is a carbon atom having 1 to 20 carbon atoms) Represents a hydrogen group, X ⁴
Represents a halogen atom, and b represents a number satisfying 0 ≦ b <4. ) A halogen compound represented by Specific examples of M include titanium, zirconium and hafnium, with titanium being preferred. Specific examples of R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group. , Alkyl groups such as decyl group and dodecyl group, phenyl group, cresyl group, xylel group,
Examples thereof include an aryl group such as a naphthyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use halogen compounds of Group 4 elements having two or more different OR ⁹ groups.

Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom and an iodine atom. Among them, chlorine atom gives particularly preferable results.

_Fourth represented by the general formula M (OR ⁹ ) _b X ⁴ _4-b
B of the halogen compound of the group element is a number satisfying 0 ≦ b <4, preferably 0 ≦ b ≦ 2,
Particularly preferably, b = 0.

Specific examples of the titanium compound represented by the general formula M (OR ⁹ ) _b X _4-b include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium, methoxy. Titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, trihalogenated alkoxy titanium such as ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, Examples thereof include dihalogenated dialkoxytitanium such as diethoxytitanium dibromide, zirconium compounds and hafnium compounds corresponding thereto. Most preferably titanium tetrachloride

As the halogen compound of the group 13 element or the group 14 element, a compound represented by the general formula MR _ma X _a (in the formula, M is the first group)
Group 3 or Group 14 atom, R has 1 to 20 carbon atoms
X represents a halogen atom, and m represents a valence of M. The compound represented by a is preferably a number satisfying 0 <a ≦ m). Examples of the group 13 atom include B, Al, Ga, In and Tl, and B or A
1 is preferable, and Al is more preferable. Examples of the atom of Group 14 include C, Si, Ge, Sn, and Pb,
Si, Ge or Sn is preferable, and Si or Sn is more preferable.

M is the valence of M, for example, m = 4 when M is Si. a represents a number satisfying 0 <a ≦ m, and when M is Si, a is preferably 3 or 4.
Examples of the halogen atom represented by X include F, Cl, Br and I, with Cl being preferred.

Specific examples of R include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group. And other alkyl groups, phenyl groups, tolyl groups, cresyl groups, xylyl groups, naphthyl groups and other aryl groups, cyclohexyl groups, cyclopentyl groups and other cycloalkyl groups, propenyl groups and other alkenyl groups, benzyl groups and other aralkyl groups, etc. Can be mentioned. Preferred R is an alkyl group or an aryl group, and particularly preferred R is a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

Specific examples of the halogen compound of the Group 13 element include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum and methyldichloroaluminum. , Ethyldichloroaluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichloro Gallium, cyclohexyldichlorogallium, dimethyl Chlorogallium, methyl ethyl chlorogallium, indium chloride, indium trichloride, methyl indium dichloride, phenyl indium dichloride, dimethyl indium chloride, thallium chloride, thallium trichloride, methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride, and the like, The compound which changed chloro of these compound names into fluoro, bromo, or iodo is also mentioned.

Specific examples of the halogen compound of the group 14 element include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1, 1,2,2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, Dichlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, Methylchlorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monochlorogermane, trimethylchlorogermane, triethylchloro Germane, tri-n-butylchlorogermane, tetrachlorotin, methyltrichlorotin, n-butyltrichlorotin, dimethyldichlorotin, di-n-butyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin,
Examples thereof include divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, dichlorolead, methylchlorolead, phenylchlorolead, and compounds in which chloro in these compound names is changed to fluoro, bromo, or iodo.

As the halogenated compound (b), tetrachlorotitanium, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane or tetrachlorotin is used as a polymerization active. From the viewpoint of, it is particularly preferable.
As the halogenated compound (b), only one kind of the above compounds may be used, or plural kinds thereof may be used.

(C) Electron Donor In the present invention, the contact treatment using the electron donor (c) can be appropriately performed in the preparation of the solid catalyst component. In some cases, high stereoregular polymerization ability can be imparted by contact treatment with an electron donor. As the electron donor, ethers, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, acid amides of organic acids or inorganic acids, oxygen-containing electron-donating compounds such as acid anhydrides, Examples thereof include nitrogen-containing electron donating compounds such as ammonia, amines, nitriles, and isocyanates. Of these electron-donating compounds, organic acid esters and / or ethers are preferable, and carboxylic acid esters (c1) and / or ethers (c2) are more preferable.

Examples of the carboxylic acid esters (c1) include mono- and polyvalent carboxylic acid esters,
Examples thereof include saturated aliphatic carboxylic acid ester, unsaturated aliphatic carboxylic acid ester, alicyclic carboxylic acid ester, and aromatic carboxylic acid ester.
Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl. Ethyl acid, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-phthalate
n-hexyl, diheptyl phthalate, di-n-phthalate
Examples thereof include octyl, di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate.

Among these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid ester and maleic acid ester or aromatic carboxylic acid esters such as benzoic acid ester and phthalic acid ester are preferably used. Aromatic polycarboxylic acid esters are particularly preferred, and phthalic acid dialkyl esters are most preferred.

Examples of ethers (c2) include dial
Kill ether and general formula (However, R^Five ~ R⁸ Each independently has 1 to 2 carbon atoms
0 straight-chain, branched or alicyclic alkyl group, ant
Group or aralkyl group, and R⁶ And R ⁷ Haso
Each may independently be a hydrogen atom. ) Represented by
There may be mentioned ether compounds, one of these
One kind or two or more kinds are preferably used.

Specific examples include dimethyl ether, diethyl ether, di-n-butyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl- 2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2
-Isopropyl-2-3,7-dimethyloctyl-1,
3-dimethoxypropane, 2,2-diisopropyl-
1,3-dimethoxypropane, 2-isopropyl-2-
Cyclohexylmethyl-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3 -Dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-
2-cyclopentyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane and the like can be mentioned, and one or more of these are preferably used. . Ethers (c2)
Is particularly preferably dialkyl ether, and most preferably di-n-butyl ether. In addition,
The n-butyl ether may be simply referred to as dibutyl ether or butyl ether.

(D) Organic Acid Halide The organic acid halide (d) used in the preparation of the solid catalyst component of the present invention is preferably a mono- or polyvalent carboxylic acid halide, examples of which are aliphatic carboxylic acids. Examples thereof include acid halides, alicyclic carboxylic acid halides, and aromatic carboxylic acid halides. Specific examples include acetyl chloride, propionyl chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoic acid chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride. , Itaconic acid chloride, phthalic acid chloride and the like.

Among these organic acid halides, aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride, and phthalic acid chloride are preferable, more preferably aromatic dicarboxylic acid dichloride, and particularly phthalic acid chloride is preferably used. To be

(A) Preparation of Solid Catalyst Component The above-mentioned preferred solid catalyst component (A) is a solid component (a) containing a magnesium atom, a titanium atom and a hydrocarbyloxy group, a halogenated compound (b), , An electron donor (c) and / or an organic acid halide (d). All of these contact treatments are usually performed in an atmosphere of an inert gas such as nitrogen or argon.

As a concrete method of the contact treatment for obtaining the solid catalyst component, (a) is charged with (b) and (c) (arbitrary order),
Contact treatment method :-( a) is charged with (b) and (d) (arrangement order is arbitrary),
Method of contact treatment: -Adding a mixture of (b), (c) and (d) to (a),
Contact treatment method :-( a) mixture of (b) and (c), (d) (arbitrary order of addition), and contact treatment- (a) of (c), contact After the treatment, a method of charging (b) and performing contact treatment, after charging (c) to (a) and performing contact treatment, (b),
(C) Method of charging (contact order is arbitrary) and performing contact treatment ;-( a) is charged to (c) and contact-treated, and then a mixture of (b) and (c) is charged and contact-treated. Method, (a), (c) (arrangement order is arbitrary) is added to (b),
Method of contact treatment :-( b) is charged with (a), (d) (arbitrary order of charging),
Contact treatment method :-( b) is charged with (a), (c), (d) (arbitrary order of addition), and the like, and the like. Examples thereof include a method of performing contact treatment at least once in b) and a method of performing contact treatment at least once with a mixture of (b) and (c).

Of these, (a) is charged with (b) and (d) (arbitrary order of charging), contact treatment is carried out, (a) is a mixture of (b) and (c), and (d) is charged. (A), a mixture of (b) and (c) in (a), (d)
A method of charging (any order of charging), performing contact treatment, then charging the mixture of (b) and (c), and performing contact treatment one or more times,
A method in which (c) is added to (a), contact treatment is carried out, and then contact treatment is carried out once or more with a mixture of (b) and (c) is preferable, and a mixture of (b) and (c) is added to (a), (D) method of charging each in the order and contact treatment, (a) to (b)
And the mixture of (c) and (d) are added in this order,
After the contact treatment, the mixture of (b) and (c) was added and 1
It is more preferable to carry out the contact treatment more than once, or to add (c) to (a), carry out the contact treatment, and then carry out the contact treatment once or more with the mixture of (b) and (c). Particularly preferably, the mixture of (b) and (c2) is added to (a) in the order of (d), and after contact treatment, (b) and (c) are added.
A method in which the mixture of 1) and (c2) is charged, the contact treatment is performed, and the mixture is further contacted with the mixture of (b) and (c2) one or more times, or (c1) is charged in (a) and the contact treatment is performed. After that, the mixture of (b), (c1) and (c2) was added,
Contact treatment is performed, and then 1 with the mixture of (b) and (c2).
This is a method of performing contact treatment more than once.

The contact treatment can be carried out by any known method capable of bringing the respective components into contact with each other, such as a slurry method or mechanical crushing means such as a ball mill. However, mechanical crushing causes a large amount of fine powder in the solid catalyst component. It may occur and the particle size distribution may become broad, which is not preferable from an industrial viewpoint. Therefore, it is preferable to contact them in the presence of a diluent. Further, after the contact treatment, the following operation can be carried out as it is, but it is preferable to carry out a washing treatment with a diluent in order to remove an excess.

The diluent is preferably inert to the components to be treated, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane, Alicyclic hydrocarbons such as cyclopentane and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used. The amount of the diluent used in the contact treatment is usually 0.1 ml to 1000 ml per 1 g of the solid component (a) per one-step contact treatment. Preferably 1
It is 1 ml to 100 ml per g. Further, the amount of the diluent used in one washing operation is about the same. The number of times of the washing operation in the washing treatment is usually 1 to 5 times per one-step contact treatment.

The temperature of the contact treatment and / or the washing treatment is usually -50 to 150 ° C, preferably 0 to
It is 140 ° C, and more preferably 60 to 135 ° C. The contact treatment time is not particularly limited, but is preferably 0.
It is 5 to 8 hours, more preferably 1 to 6 hours. The washing operation time is not particularly limited, but preferably 1
To 120 minutes, more preferably 2 to 60 minutes.

The amount of the halogenated compound (b) used is usually 0.5 to 1000 mmol, preferably 1 to 200 mmol, and more preferably 2 to 100 mmol based on 1 g of the solid component (a). When the halogenated compound (b) is used, it is preferable to use the electron donor (c) together. In that case, the amount of (c) used is usually 1 to 100 mol, preferably 1.5 to 75 mol, and more preferably 2 to 50 mol, relative to 1 mol of (b).

The amount of the electron donor (c) used is usually 0.01 to 100 mmol, preferably 0.05 to 50 mmol, and more preferably 0.1 to 20 mmol based on 1 g of the solid component (a). is there.

The amount of the organic acid halide (d) to be used is usually 0.1 to 100 mmol, preferably 0.3 to 50 mmol, and more preferably 0.1 to 1 g of the solid component (a).
It is 5 to 20 mmol. The amount of the organic acid halide (d) used is usually 0.01 to 1.0 mol, preferably 0.1%, per 1 mol of the magnesium atom in the solid component (a).
It is from 03 to 0.5 mol. When the amount of (c) or (d) used is excessively large, the particles may disintegrate.

When the contact treatment is performed by using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once.

The obtained solid catalyst component may be used in the polymerization in a slurry state in combination with an inert diluent, or may be used in the polymerization as a free-flowing powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure and a method of removing volatile components under the flow of an inert gas such as nitrogen or argon. Drying temperature is 0-200
C. is preferable, and 50 to 100.degree. C. is more preferable. The drying time is preferably 0.01 to 20 hours, more preferably 0.5 to 10 hours.

(B) Organoaluminum Compound The organoaluminum compound (B) used for forming the α-olefin polymerization catalyst has at least one Al-carbon bond in the molecule. A typical one is shown below by a general formula. During ^{_{R 19 w AlY 3-w R}} 20 R 21 Al-O-AlR 22 R 23 ( wherein, R ¹⁹ to R ²³ is a hydrocarbon group having a carbon number of 1 to 20, Y is a halogen atom, a hydrogen atom or an alkoxy Represents a group, and w is a number satisfying 2 ≦ w ≦ 3.) Specific examples of the organoaluminum compound include trialkylaluminums such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, diethylaluminum hydride, diisobutyl. Dialkyl aluminum hydrides such as aluminum hydride, dialkyl aluminum halides such as diethyl aluminum chloride, mixtures of trialkyl aluminum and dialkyl aluminum halides such as mixtures of triethyl aluminum and diethyl aluminum chloride, tetra Chill di alumoxane, an alkyl alumoxane such as tetrabutyl di alumoxane can be exemplified.

Of these organoaluminum compounds,
Preference is given to trialkylaluminum, mixtures of trialkylaluminium and dialkylaluminium halides or alkylalumoxanes, especially triethylaluminum, triisobutylaluminum, mixtures of triethylaluminum and diethylaluminium chloride or tetraethyldialumoxane.

[Polymerization of Olefin] In the production of α-olefin using the catalyst for α-olefin polymerization obtained by the present invention, the α-olefin is an α-olefin having 3 or more carbon atoms. Specific examples of propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1,
Linear monoolefins such as 3-methylbutene-1,
Branched chain monoolefins such as 3-methylpentene-1 and 4-methylpentene-1, vinylcyclohexane and the like can be mentioned. One type of these α-olefins may be used, or two or more types may be used in combination. Among these α-olefins, homopolymerization using propylene or butene-1
Alternatively, it is preferable to copolymerize using a mixed olefin containing propylene or butene-1 as a main component, and homopolymerize using propylene, or perform a copolymerization using a mixed olefin containing propylene as a main component. Is particularly preferred. Further, in the copolymerization in the present invention, two or more kinds of olefins selected from ethylene and the above α-olefins can be mixed and used. Further, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. And, heteroblock copolymerization in which the polymerization is carried out in two or more stages can be easily carried out.

The α-olefin polymerization catalyst of the present invention comprises the above solid catalyst component (A), organoaluminum (B), and -C.
Α obtained by bringing the compound (C) having a —O—C—O—C— bond group into contact with the alkoxy silicon compound (D)
-Olefin polymerization catalyst. Contact here means
Any means may be used as long as the catalyst components (A) to (D) come into contact with each other to form a catalyst, and the components (A) to (D) may be mixed with the solvent in advance or diluted. A method of contacting, a method of separately supplying to the polymerization tank and contacting in the polymerization tank, and the like can be adopted. As a method of supplying the respective catalyst components to the polymerization tank, it is preferable to supply them in an inert gas such as nitrogen or argon without water. Each catalyst component may be supplied by contacting any two or three in advance.

It is possible to carry out the polymerization of α-olefin in the presence of the above-mentioned catalyst, but such polymerization (main polymerization)
The following pre-polymerization may be carried out before carrying out.

The prepolymerization is usually carried out in the presence of the solid catalyst component (A) and the organoaluminum compound (B) by supplying a small amount of olefin, and is preferably carried out in a slurry state. Examples of the solvent used for forming a slurry include propane, butane, isobutane, pentane, isopentane,
Inert hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene can be mentioned. Further, when making a slurry, a liquid olefin can be used in place of part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound used in the prepolymerization can be selected within a wide range, usually 0.5 to 700 mol, per mol of titanium atom in the solid catalyst component, but 0.8 to 500 mol is preferable. It is preferably 1 to 200 mol and particularly preferably 1 to 200 mol.

The amount of olefin prepolymerized is
It is usually 0.01 to 1000 g, preferably 0.05 to 500 g, and particularly preferably 0.1 to 1 g of the solid catalyst component.
It is 200 g.

The slurry concentration during the prepolymerization is from 1 to
500 g-solid catalyst component / liter-solvent is preferred,
Particularly, 3 to 300 g-solid catalyst component / liter-solvent is preferable. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase during the prepolymerization is 0.01 to 20 kg / c.
m ² is preferable, and 0.1 to 10 kg / cm ² is particularly preferable, but this is not the case for olefins that are liquid at the pressure and temperature of prepolymerization. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is suitable.

When carrying out the prepolymerization, the solid catalyst component (A), the organoaluminum compound (B) and the olefin can be supplied by contacting the solid catalyst component (A) with the organoaluminum compound (B). After that, any method such as a method of supplying an olefin and a method of contacting the solid catalyst component (A) with the olefin and then supplying an organoaluminum compound (B) may be used. Further, as the olefin supply method, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure or a method of initially supplying all of a predetermined amount of olefin may be used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the obtained polymer.

Further, when preliminarily polymerizing the solid catalyst component (A) with a small amount of olefin in the presence of the organoaluminum compound (B), if necessary, --C--O--C--O--C--
The compound (C) having a bonding group and / or the alkoxysilicon compound (D) may coexist. The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 1 mol of titanium atom contained in the solid catalyst component (A).
The amount is 100 mol, and usually 0.003 to 5 mol, preferably 0.005 to the organoaluminum compound (B).
3 mol, particularly preferably 0.01 to 2 mol.

There is no particular limitation on the method of supplying the compound (C) having a —C—O—C—O—C— bond group and the alkoxysilicon compound (D) during the prepolymerization, and the solid catalyst component (A) or It may be supplied separately from the organoaluminum compound (B) or may be supplied in contact with it in advance. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

After the prepolymerization as described above or without prepolymerization, the above-mentioned solid catalyst component (A), organoaluminum compound (B), -COC is used.
The main polymerization of the α-olefin can be carried out in the presence of the catalyst for α-olefin polymerization obtained by bringing the compound (C) having a —O—C— bond group and the alkoxysilicon compound (D) into contact with each other.

The amount of the organoaluminum compound used in the main polymerization can be selected within a wide range, such as 1 to 1000 mol, per 1 mol of titanium atom in the solid catalyst component (A). Ranges are preferred.

Further, --COC used in the main polymerization is used.
The compound (C) having a —O—C— bond group is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, especially 1 to 1 mol of titanium atom contained in the solid catalyst component (A). Preferably, it is 0.5 to 800 mol, and usually 0.001 to 5 mol with respect to the organoaluminum compound,
Preferably 0.005 to 3 mol, particularly preferably 0.0
It is 1 to 1 mol.

The alkoxysilicon compound (D) used in the main polymerization is usually 0.1 to 2000 mol, based on 1 mol of the titanium atom contained in the solid catalyst component (A).
Preferably 0.3 to 1000 mol, particularly preferably,
0.5-800 mol, usually 0.001-5 mol, preferably 0.005 mol, relative to the organoaluminum compound.
˜3 mol, particularly preferably 0.01 to 1 mol.

The main polymerization can be carried out usually at -30 to 300 ° C, preferably 20 to 180 ° C. The polymerization pressure is not particularly limited, but is generally atmospheric pressure to 100 kg in terms of being industrial and economical.
/ Cm ² , preferably a pressure of about ² to 50 kg / cm ² . The polymerization system may be either batch system or continuous system. Further, slurry polymerization or solution polymerization with an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature is also possible.

At the time of the main polymerization, a chain transfer agent such as hydrogen may be added to control the molecular weight of the polymer.

[0088]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the examples, evaluation methods for various physical properties of the polymer are as follows.

(1) 20 ° C. xylene soluble part (hereinafter referred to as CXS
1 g of the polymer is dissolved in 200 ml of boiling xylene, then gradually cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and left standing at 20 ° C. for 3 hours, followed by precipitation. The polymer obtained was filtered off. The weight percentage of the polymer remaining in the filtrate was defined as CXS (unit =%).
It can be said that the smaller the value of CXS, the higher the stereoregularity of polypropylene.

(2) Intrinsic viscosity (hereinafter abbreviated as [η]): Measured at 135 ° C. in a tetralin solvent.

(3) Bulk density: JIS K-6721-1
It was measured according to 966.

(4) The composition analysis of solid samples such as solid catalyst components was carried out as follows. That is,
Titanium atom content, after decomposing a solid sample with dilute sulfuric acid,
To this, an excess of hydrogen peroxide solution was added, and the characteristic absorption at 410 nm of the obtained liquid sample was measured using a Hitachi double-beam spectrophotometer U-2001 type, and determined by a calibration curve prepared separately. . The alkoxy group content was obtained by decomposing a solid sample with water, and determining the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample using a gas chromatography internal standard method, and converting the content into an alkoxy group content. The carboxylic acid ester content was obtained by decomposing a solid sample with water, extracting soluble components with a saturated hydrocarbon solvent, and determining the amount of carboxylic acid ester in the extract by a gas chromatography internal standard method.

Example 1 (1) Synthesis of solid component (a) A reactor equipped with a stirrer substituted with nitrogen was charged with 14.5 kg of diisobutyl phthalate, 670 liters of hexane, 349 kg of tetraethoxysilane and 38 kg of tetrabutoxytitanium. Charged and stirred. Next, 890 liters of a solution of butylmagnesium chloride in dibutyl ether (concentration 2.1 mol / liter) was added dropwise to the above stirring mixture over 5 hours while maintaining the temperature of the reactor at 8 ° C. After completion of dropping, the mixture was stirred at 20 ° C. for 1 hour and then filtered, and the obtained solid product was washed with 1100 liters of toluene three times at room temperature, and toluene was added so that the total volume became 843 liters to obtain a slurry. Turned into

(2) Synthesis of solid catalyst component (A) Toluene slurry of the solid product obtained in (1) above was added with 441 liters of toluene and stirred at 105 ° C. for 1 hour to prepare 200 liters of toluene and diisobutyl phthalate. 222 kg was added and the mixture was stirred at 95 ° C. for 0.5 hours.
Then, filtration and washing with 1100 liters of toluene were repeated twice, and toluene was added to make a total volume of 843 liters to form a slurry. Next, 19.0 kg of dibutyl ether, 15.0 kg of diisobutyl phthalate and 737 kg of titanium tetrachloride were added, and the mixture was stirred at 105 ° C for 3 hours. Then, filtration and washing with 1,100 liters of toluene were repeated three times at 95 ° C., and toluene was added to make a total volume of 843 liters to form a slurry. Next, 19.0 kg of dibutyl ether and 368 kg of titanium tetrachloride were added, and the mixture was stirred at 105 ° C for 1 hour. Then, filter and wash with 1100 liters of toluene 95
Washing with hexane at 1000 ° C. four times at room temperature was repeated three times at room temperature, followed by drying to obtain a solid catalyst component.
The solid catalyst component contained 2.0% by weight of titanium atom, 10.5% by weight of phthalate, 0.6% by weight of ethoxy group and 0.2% by weight of butoxy group.

(3) Polymerization of Propylene A stainless steel autoclave having an internal volume of 3 liters was replaced with argon, and 2.6 mmol of triethylaluminum as the component (B) and 0.26 mmol of 1,3-dioxolane as the component (C). , 0.26 mmol of cyclohexylethyldimethoxysilane as the component (D), and 6.13 mg of the solid catalyst component synthesized in the above (2) as the component (A) were charged, and hydrogen corresponding to a partial pressure of 0.033 MPa was added. . Next, 780 g of liquefied propylene was charged and the temperature of the autoclave was raised to 80 ° C.
Polymerization was carried out at 0 ° C for 1 hour. After the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure to obtain 186 g of polypropylene powder. The yield of polypropylene per 1 g of the solid catalyst component (hereinafter abbreviated as PP / cat) is PP / cat = 30300 (g / g),
The ratio of the components soluble in xylene at 20 ° C. in the total polymer yield is CXS = 0.69 (wt%), the intrinsic viscosity of the polymer is [η] = 2.14 (dl / g), and the bulk density is Is 0.3
It was 92 (g / ml).

Example 2 (1) Polymerization of Propylene The procedure of Example 1 (3) was repeated except that the input amount of 1,3-dioxolane was 0.13 mmol and the input amount of the solid catalyst component was changed to 6.6 mg. Polymerization was carried out according to PP / ca
t = 30200 (g / g), and the ratio of the components soluble in 20 ° C. xylene to the total polymer yield was CXS = 0.200.
79 (wt%), intrinsic viscosity of polymer is [η] = 2.0
7 (dl / g) and the bulk density was 0.397 (g / ml).

Example 3 (1) Polymerization of Propylene The same molar amount of 1,3-dioxane was used instead of 1,3-dioxolane, and the solid catalyst component was charged in an amount of 8.37 mg.
Polymerization was performed according to (3) of Example 1 except that the above was changed to. PP / cat = 30900 (g / g), the proportion of the components soluble in 20 ° C. xylene in the total polymer yield is CXS = 0.80 (wt%), and the intrinsic viscosity of the polymer is [η ] = 2.30 (dl / g), the bulk density is 0.3
It was 88 (g / ml).

Example 4 (1) Polymerization of Propylene Instead of 1,3-dioxolane, 2-methyl-1,3-
Polymerization was performed according to (3) in Example 1 except that the same molar amount of diosolane was used and the amount of the solid catalyst component input was changed to 8.88 mg. PP / cat = 29200 (g / g)
The ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS = 0.76 (wt%), and the intrinsic viscosity of the polymer is [η] = 2.19 (dl / g). The bulk density was 0.390 (g / ml).

Example 5 (1) Polymerization of Propylene The same molar amount of 3,3-dimethoxyhexane was used instead of 1,3-dioxolane, and the solid catalyst component was added in an amount of 6.
Polymerization was performed according to (3) of Example 1 except that the amount was changed to 82 mg. PP / cat = 26500 (g / g), the ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS = 0.95 (wt%), and the intrinsic viscosity of the polymer is [η ] = 2.21 (dl / g), the bulk density is
It was 0.394 (g / ml).

Comparative Example 1 (1) Polymerization of Propylene Polymerization was carried out according to (3) of Example 1 except that 1,3-dioxolane was not charged and the amount of the solid catalyst component was changed to 5.26 mg. It was PP / cat = 37100 (g /
g), and the ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS = 1.1 (wt%),
It was higher than that in the case where a compound having a —O—C—O—C— bond group was added. The intrinsic viscosity of the polymer is [η] =
2.12 (dl / g), bulk density is 0.399 (g / m
l).

Example 6 (1) Polymerization of Propylene Instead of cyclohexylethyldimethoxysilane, t-
Polymerization was carried out according to (3) of Example 1 except that the same molar amount of butyl-n-propyldimethoxysilane was used and the amount of the solid catalyst component input was changed to 6.10 mg. PP / c
at = 33900 (g / g), and the ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS =
0.60 (wt%), the intrinsic viscosity of the polymer is [η] =
2.97 (dl / g), the bulk density is 0.394 (g / m
l).

Comparative Example 2 (1) Polymerization of Propylene Polymerization was carried out according to (1) of Example 6 except that 1,3-dioxolane was not charged and the amount of the solid catalyst component was changed to 7.96 mg. It was PP / cat = 40700 (g /
g), and the proportion of the components soluble in 20 ° C. xylene in the total polymer yield is CXS = 0.82 (wt%),
It was higher than the case where the compound having the C—O—C—O—C— bond group was added. The intrinsic viscosity of the polymer is [η]
= 3.23 (dl / g), the bulk density is 0.396 (g /
ml).

Example 7 (1) Polymerization of Propylene The same molar amount of bisperhydroisoquinolinodimethoxysilane was used instead of cyclohexylethyldimethoxysilane, and the input amount of the solid catalyst component was changed to 6.48 mg.
Polymerization was performed according to (3) of Example 1 except that the partial pressure of hydrogen to be added was changed to 0.20 MPa. PP / cat
= 19,300 (g / g), and the ratio of the components soluble in 20 ° C xylene to the total polymer yield is CXS = 0.8.
9 (wt%), the intrinsic viscosity of the polymer is [η] = 1.73
(Dl / g) and the bulk density was 0.394 (g / ml).

Comparative Example 3 (1) Polymerization of Propylene Polymerization was carried out according to (1) of Example 7 except that 1,3-dioxolane was not charged and the amount of the solid catalyst component was changed to 5.80 mg. It was PP / cat = 32800 (g /
g), and the proportion of the components soluble in 20 ° C. xylene in the total polymer yield is CXS = 1.3 (wt%),
It was higher than that in the case where a compound having a —O—C—O—C— bond group was added. The intrinsic viscosity of the polymer is [η] =
1.57 (dl / g), the bulk density is 0.395 (g / m
l).

Example 8 (1) Synthesis of solid catalyst component (A) A 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen, and then the same procedure as in Example 1 (1) was carried out. 8 g of the obtained solid product slurry was made into a dry solid product, and toluene was extracted so that the volume of the slurry was 26.5 ml. The slurry was kept at about 40 ° C., a mixture of 16.0 ml of titanium tetrachloride and 0.8 ml of dibutyl ether was added thereto, and 2.4 ml of phthalic acid chloride (hereinafter sometimes abbreviated as OPC) and toluene 2. 4 ml of the mixture was added dropwise at 7.5 min. After the dropping was completed, the reaction mixture was stirred at 115 ° C. for 3 hours. Then, solid-liquid separation was performed at the same temperature, and 40 ml of toluene was washed 3 times at 115 ° C. After washing, add toluene so that the volume of the slurry becomes 26.5 ml, and add 105 ° C.
And A mixture of 0.8 ml of dibutyl ether and 16 ml of titanium tetrachloride was added thereto, and the mixture was stirred at 105 ° C for 1 hour. After that, solid-liquid separation was performed at the same temperature, and 40 ml of toluene was washed twice at 105 ° C. Next, add toluene so that the volume of the slurry becomes 26.5 ml, and add 105 ° C.
And A mixture of 0.8 ml of dibutyl ether and 16 ml of titanium tetrachloride was added thereto, and the mixture was stirred at 105 ° C for 1 hour. After that, solid-liquid separation was performed at the same temperature, and 40 ml of toluene was washed twice at 105 ° C. Further, add toluene so that the volume of the slurry becomes 26.5 ml, and add 105
℃ was made. A mixture of 0.8 ml of dibutyl ether and 16 ml of titanium tetrachloride was added thereto, and the mixture was stirred at 105 ° C for 1 hour. After that, solid-liquid separation was performed at the same temperature, and 40 ml of toluene was washed 3 times at 105 ° C. and 40 ml of hexane was washed 3 times at room temperature. This is dried under reduced pressure to obtain a solid catalyst component of 7.80.
g was obtained. The solid catalyst component contains 2.34 titanium atoms.
% By weight, 14.06% by weight of phthalates, 0.04% by weight of ethoxy groups and 0.08% by weight of butoxy groups.

(2) Polymerization of Propylene Implemented except that dicyclopentyldimethoxysilane was used in the same molar amount in place of cyclohexylethyldimethoxysilane and the solid catalyst component was changed to 6.43 mg of the solid catalyst component synthesized in (1) above. Polymerization was carried out according to (3) of Example 1. PP / cat = 39300 (g / g)
The ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS = 0.19 (wt%), and the intrinsic viscosity of the polymer is [η] = 3.04 (dl / g). The bulk density was 0.411 (g / ml).

Example 9 (1) Synthesis of solid catalyst component (A) In a flask equipped with a stirrer substituted with nitrogen, 3.99 g of anhydrous magnesium chloride, 17.8 ml of decane and 19.8 ml of 2-ethylhexanol were charged. Then, the mixture was stirred at 135 ° C. for 2 hours to obtain a uniform solution. Further, 1.30 g of 2,2-diisobutyl-1,3-dimethoxypropane was added, and 1
After stirring at 35 ° C for 1 hour, the mixture was cooled to room temperature. In a flask equipped with a stirrer that was replaced with nitrogen, 100 ml of titanium tetrachloride
Was added, the solution was cooled to -20 ° C, the solution synthesized above was added dropwise over 1 hour so that the internal temperature did not exceed -15 ° C, and then the temperature was raised to 110 ° C over 5 hours. Next 2,2-
Diisobutyl-1,3-dimethoxypropane 1.92 g
Was added and the mixture was stirred at 110 ° C. for 2 hours. The resulting slurry is filtered and washed with 30 ml of decane at 110 ° C for 10
This was repeated, washed with 30 ml of hexane three times at room temperature, and dried to obtain a solid catalyst component. 2.14% by weight of titanium atom was contained in the solid catalyst component.

(2) Polymerization of propylene The solid catalyst component synthesized in (1) above was used as the solid catalyst component 9.
Polymerization was carried out according to (3) of Example 1 except that the amount was changed to 73 mg. PP / cat = 19300 (g / g), the ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS = 1.6 (wt%), and the intrinsic viscosity of the polymer is [η ] = 1.65 (dl / g), the bulk density is 0.
It was 385 (g / ml).

Comparative Example 4 (1) Polymerization of Propylene Polymerization was carried out according to (2) of Example 9 except that 1,3-dioxolane was not added and the amount of the solid catalyst component added was changed to 7.53 mg. It was PP / cat = 26800 (g /
g), and the proportion of the components soluble in 20 ° C. xylene in the total polymer yield is CXS = 1.9 (wt%),
It was higher than that in the case where a compound having a —O—C—O—C— bond group was added. The intrinsic viscosity of the polymer is [η] =
1.60 (dl / g), bulk density is 0.383 (g / m
l).

[0110]

As described above, according to the present invention,
A catalyst for polymerization of α-olefin having a high stereoregular polymerization ability is provided, and a method for producing a highly stereoregular α-olefin polymer is provided. The α-olefin polymerization catalyst of the present invention exhibits a high polymerization activity, and its industrial utility value is extremely large.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Continued front page    F-term (reference) 4J028 AA02A AB01A AB02A AC01A                       AC02A AC06A AC25A BA03A                       BA03B BB01B BC06A BC25B                       BC34B CB30C EB04 EB05                       EB07 EB08 EB09 EB10 GA04                       GA09 GA12

Claims (5)

[Claims] 1. A catalyst for α-olefin polymerization obtained by contacting the following (A), (B), (C) and (D). (A) Solid catalyst component containing Ti, Mg and halogen as essential components (B) Organoaluminum compound (C) -C-O-C-O-C-Compound having a bonding group (D) Alkoxysilicon compound 2. The compound (C) having a —C—O—C—O—C— linking group is a compound having a —C—O—C—O—C— linking group in a ring-closed structure. The catalyst for α-olefin polymerization according to 1. 3. The catalyst for α-olefin polymerization according to claim 1, wherein the solid catalyst component (A) containing Ti, Mg and halogen as essential components further contains organic acid esters or ethers. 4. A solid catalyst component (A) wherein the solid catalyst component (a) contains a magnesium atom, a titanium atom and a hydrocarbon oxy group, a halogenated compound (b), an electron donor (c) and / or It is obtained by contacting with an organic acid halide (d).
The catalyst for α-olefin polymerization according to any one of 1. 5. A method for producing an α-olefin polymer in which an α-olefin is homopolymerized or copolymerized by using the α-olefin polymerization catalyst according to any one of claims 1 to 4.