JP2003105020A - METHOD FOR PRODUCING alpha-OLEFIN POLYMERIZATION SOLID CATALYST COMPONENT - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an α-olefin polymerization solid catalyst component having highly active polymerizability. SOLUTION: In the method for producing an α-olefin polymerization solid catalyst component comprising subjecting (a) a solid product to be obtained by reducing (2) a titanium compound to be represented by formula [II] (wherein a is a number of 2-20; R<2> is a 1-20C hydrocarbon group; and X<2> is a halogen atom or a 1-20C hydrocarbon oxy group) with (3) an organomagnesium in the presence of (1) an organosilicon compound having an Si-O bond, (b) an organic acid halide, and (c) a halogenated compound to contact treatment, the addition of the organic acid halide (b) to the solid product (a) is performed under the condition to be represented by formula [I] : 0.01<=bb÷(aa×time)<=0.1 [bb is a volume (ml) of component (b); aa is a weight (g) of component (a); and time is a dropping time (min) of component (b)].

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to an α-olefin polymer.
The present invention relates to a method for producing a combined solid catalyst component. [0002] 2. Description of the Related Art Alpha-olefins such as propylene and butene-1
As a method for producing the fin polymer, the fourth to
Solid catalyst component prepared using Group 6 transition metal compound
And a group 1, 2, 13 organic metal compound
It is well known to use Ziegler-Natta catalysts
ing. [0003] When producing an α-olefin polymer,
Usually, stereoregular α-olefins with high industrial value
In addition to the polymer, an amorphous polymer is by-produced. This amorphous polymerization
The product has low industrial utility value, α-olefin polymerization
Add the body to injection molded products, films, fibers, and other processed products.
Has a significant adverse effect on the mechanical properties of
You. In addition, the formation of amorphous polymer results in loss of raw material monomers.
At the same time, production facilities for removing amorphous polymers are required.
In short, it is extremely disadvantageous from an industrial point of view. Obedience
Therefore, a catalyst for producing an α-olefin polymer is
There is no formation of an amorphous polymer such as
Even if there is, it is desirable that it is very slight. Further, in the obtained α-olefin polymer,
Is usually a catalyst residue consisting of a transition metal component and an organometallic component.
The residue remains. This catalyst residue is an α-olefin polymer
Causes problems in various aspects such as the stability and workability of
So demineralization equipment is often used to remove and stabilize catalyst residues.
Is required. The disadvantage is that the formation per catalyst weight
Increase the catalytic activity expressed by α-olefin polymer weight
To improve the catalytic activity.
By realizing it, equipment for removing the catalyst residue will be
In short, lower the production cost of α-olefin polymers
Is also possible. [0005] A tetravalent halogen is added to a magnesium halide.
Supported solid catalyst obtained by supporting titanium oxide
Component, co-catalyst organoaluminum compound, polymerization third component
Α in combination with the organosilicon compound of
-It is known that high stereoregular polymerization of olefins can be realized.
(JP-A-57-63310, JP-A-5-63310)
8-83006, JP-A-61-78803
Information). Further, an organosilicon compound and esterification
Compound in the presence of a compound, an organomagnesium compound
Treatment of solid product obtained by reduction with ester compound
After that, if a mixture of ether compound and titanium tetrachloride
Of ether compound, titanium tetrachloride and ester compound
Trivalent titanation obtained by treating with a mixture
Compound containing solid catalyst component and co-catalyst with organoaluminum
Combination of the compound and the electron-donating compound as the third component of the polymerization
High stereoregular polymerization of α-olefins
It is known that this is possible (Japanese Patent Laid-Open No. 7-216017).
Gazette). Further, organosilicon compounds and esters
In the presence of a compound, a titanium compound is converted to an organomagnesium compound.
The solid product obtained by reduction with
Add the titanium tetrachloride mixture and the organic acid halide compound in this order.
After processing, mix the ether compound and titanium tetrachloride
Substance or ether compound and titanium tetrachloride and ester
Trivalent, obtained by treating with a mixture of compounds
Titanium compound-containing solid catalyst component and co-catalyst organic aluminum
Compound with an electron-donating compound as the third component of the polymerization
High stereoregularity of α-olefin even in combination
It is known that the combination can be realized (Japanese Patent Laid-Open No. 10-21)
No. 2319). [0008] In any case, no extraction, no decalcification process
Is at a level that can be achieved, but further improvements
Is desired. Specifically, the production of α-olefin polymer
Realization of higher active polymerization to reduce manufacturing cost
It is desired to do. Furthermore, as in the injection molding field,
In applications where higher rigidity of the polymer is desired,
Stereoregular polymer directly produces high rigidity quality
Therefore, without sacrificing high stereoregular polymerization ability,
The emergence of a catalyst having active polymerization ability is urgently desired. [0009] Under such circumstances,
The problem to be solved by the present invention, that is, the object of the present invention is to
Production of solid catalyst component for polymerization of α-olefin having polymerization ability
It is to provide a manufacturing method. [0010] SUMMARY OF THE INVENTION The present invention provides a Si—O bond
In the presence of an organosilicon compound having
The titanium compound () represented by the formula [II] is converted into an organic magnet
Solid product obtained by reduction with a compound ()
(A), an organic acid halide (b), and a halogenated compound
(C) for olefin polymerization by contact treatment
In the method for producing a solid catalyst component, the solid component (a)
The addition of the organic acid halide (b) is represented by the following formula [I].
Of Solid Catalyst Component for Olefin Polymerization Performed under Controlled Conditions
It depends on the method. 0.01 ≦ bb ÷ (aa × time) ≦ 0.1 [I] (Where bb is the capacity of the organic acid halide (b) (unit is m
l) wherein aa is the weight of the solid product (a) (unit is
g), and time is the time when the organic acid halide (b) is dropped.
Indicates the interval (the unit is minutes). ) (Where a represents a number of 2 to 20, R^TwoIs 1 carbon atom
Represents up to 20 hydrocarbon groups. X^TwoIs a halogen atom or
Represents a hydrocarbon oxy group having 1 to 20 carbon atoms,
X^TwoMay be the same or different. ) [0011] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described.
I will tell. (A) Solid product Solid products used in the preparation of the solid catalyst component of the present invention
(A) is an organosilicon compound having a Si—O bond
In the presence of (), titanium represented by the following general formula [II]
Reduction of compound () with organomagnesium compound ()
Is a solid product obtained by At this time,
When the ester compound () coexists with
It is preferable because the conformational polymerization ability is further improved. (Where a represents a number of 2 to 20, R^TwoIs 1 carbon atom
Represents up to 20 hydrocarbon groups. X^TwoIs a halogen atom or
Represents a hydrocarbon oxy group having 1 to 20 carbon atoms,
X^TwoMay be the same or different. ) Organosilicon compound having Si--O bond
Examples of () include those represented by the following general formula.
Can be Si (OR^Ten)_tR¹¹ _4-t R¹²(R¹³ _TwoSiO)_uSiR¹⁴ _ThreeOr (R¹⁵ _TwoSiO)_v Where R^TenRepresents a hydrocarbon group having 1 to 20 carbon atoms,
R¹¹, R¹², R¹³, R ¹⁴And R¹⁵Are independent of each other,
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 represents 1 to 1.
Represents an integer of 000, and v represents an integer of 2-1000. As a specific example of such an organosilicon compound,
Is tetramethoxysilane, dimethyldimethoxysila
, Tetraethoxysilane, triethoxyethylsila
, Diethoxydiethylsilane, ethoxytriethylsilicone
Orchid, tetraisopropoxysilane, diisopropoxy
-Diisopropyl silane, tetrapropoxy silane, di
Propoxydipropylsilane, tetrabutoxysilane,
Dibutoxydibutylsilane, dicyclopentoxydiethyl
Silane, diethoxydiphenylsilane, cyclohexyl
Roxytrimethylsilane, phenoxytrimethylsila
, Tetraphenoxysilane, triethoxyphenylsilane
Orchid, hexamethyldisilohexane, hexaethyldisi
Hexane, hexapropyldisiloxane, octaethyl
Rutrisiloxane, dimethylpolysiloxane, diphenyl
Polysiloxane, methylhydropolysiloxane,
Nylhydropolysiloxane and the like can be exemplified. Preferred among these organosilicon compounds
The thing is the general formula Si (OR^Ten)_tR¹¹ _{Four -t}Al represented by
A coxysilane compound, where t is preferably 1
≦ t ≦ 4, and especially a tetraal with t = 4
Coxysilane is preferred, most preferably tetraethoxy
Sisilane. The titanium compound () is represented by the following general formula [II]
It is a titanium compound represented. (Where a represents a number of 1 to 20,^TwoIs 1 carbon atom
Represents up to 20 hydrocarbon groups. X^TwoIs a halogen atom or
Represents a hydrocarbon oxy group having 1 to 20 carbon atoms,
X^TwoMay be the same or different. ) R^TwoSpecific examples of the methyl group, ethyl
Group, propyl group, isopropyl group, butyl group, isobutyl
, Amyl, isoamyl, hexyl, heptyl
Group, octyl group, decyl group, dodecyl group, etc.
Group, phenyl group, cresyl group, xylyl group, naphthyl group
Aryl group, cyclohexyl group, cyclopentyl group
Cycloalkyl group, propenyl group, etc.
And aralkyl groups such as an benzyl group. These groups
An alkyl group having 2 to 18 carbon atoms or a carbon atom
Aryl groups of the formulas 6 to 18 are preferred. Especially 2 carbon atoms
~ 18 linear alkyl groups are preferred. X^Two In the above, the halogen atom is chlorine
Atoms, bromine atoms and iodine atoms. Especially chlorine source
Children are preferred. X^Two Having 1 to 20 carbon atoms in
The hydrogenoxy group is represented by R^Two Same as 1 to 20 carbon atoms
It is a hydrocarbon oxy group having a hydride group. X^Two As
Particularly preferred is a linear alkyl having 2 to 18 carbon atoms.
Alkoxy groups having a group are preferred. A titanium compound represented by the above general formula [II]
A represents a number of 1 to 20, preferably 1 ≦ a ≦
This is a number that satisfies 5. Specific examples of such a titanium compound include:
Tetramethoxytitanium, tetraethoxytitanium, tetra
-N-propoxy titanium, tetra-iso-propoxy
Titanium, tetra-n-butoxytitanium, tetra-iso
-Butoxytitanium, n-butoxytitanium trichloride
, Di-n-butoxytitanium dichloride, tri-n-
Butoxytitanium chloride, di-n-tetraisopropyl
Rupolititanate (a mixture in the range of a = 2 to 10), te
Tora-n-butyl polytitanate (a = 2 to 10)
), Tetra-n-hexylpolytitanate (a
= Mixture in the range of 2-10), tetra-n-octylpo
Lititanate (a mixture in the range of a = 2 to 10) is mentioned.
It is. In addition, a small amount of water reacts with tetraalkoxy titanium.
Of condensates of tetraalkoxytitanium obtained by
You can also. Preferably, the titanium compound () is
A in the titanium compound represented by the general formula [II] is
1, 2, or 4. Especially preferred
Or tetra-n-butoxytitanium, tetra-n-buty
Lutitanium dimer or tetra-n-butyl titani
Um tetramer. In addition, the titanium compound ()
It is also possible to use a mixture of several types. [0021] The organomagnesium compound () is
Any type of organic magnesium having a carbon-carbon bond
Compound. In particular, the general formula R¹⁶MgX^Five(Wherein, Mg
Represents a magnesium atom, R¹⁶Is a char having 1 to 20 carbon atoms
A hydride group represented by X^FiveRepresents a halogen atom. )
Grignard compound represented by the general formula R¹⁷R¹⁸Mg (Formula
In the formula, Mg represents a magnesium atom, R¹⁷And R¹⁸Is it
Each represents a hydrocarbon group having 1 to 20 carbon atoms. )
Preferred use of dihydrocarbyl magnesium
Is done. Where R¹⁷And R¹⁸May be the same or different
No. R¹⁶~ R ¹⁸Specific examples 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, phenyl group, benzyl group, etc.
Alkyl group, aryl group, aralkyl group, alkenyl group
Is mentioned. Especially R¹⁶MgX^FiveGrignard represented by
Use of ether compounds in ether solution is a catalyst performance point
Is preferred. The above-mentioned organomagnesium compound and hydrocarbon
An organic metal that solubilizes the organomagnesium compound in water
Can also be used. Organic gold
Examples of genus compounds include Li, Be, B, Al or Z
n. As the ester compound (), mono- or
Is a polyvalent carboxylic acid ester.
Aliphatic carboxylic acid ester, unsaturated aliphatic carboxylic acid
Bonic acid ester, alicyclic carboxylic acid ester, aromatic
Rubonic acid esters can be mentioned. As a specific example
Is methyl acetate, ethyl acetate, phenyl acetate, propio
Methyl ester, ethyl propionate, ethyl butyrate, valeric acid
Ethyl, ethyl acrylate, methyl methacrylate, benzoate
Ethyl benzoate, butyl benzoate, methyl toluate, tolu
Ethyl ylate, ethyl anisate, diethyl succinate,
Dibutyl succinate, diethyl malonate, dibutyrate malonate
Dimethyl maleate, dibutyl maleate, itako
Diethyl phosphate, dibutyl itaconate, monoethyl phthalate
, Dimethyl phthalate, methyl ethyl phthalate, phthalate
Diethyl phthalate, di-n-propyl phthalate, diyl phthalate
Sopropyl, di-n-butyl phthalate, diisophthalate
Butyl, dipentyl phthalate, di-n-hexyl phthalate
, Diheptyl phthalate, di-n-octyl phthalate,
Di (2-ethylhexyl) phthalate, diisode phthalate
Sil, dicyclohexyl phthalate, diphenyl phthalate
And the like. Of these ester compounds, methacrylic
Unsaturated fatty acids such as
Aromatic esters such as rubonic esters or phthalic esters
Preference is given to rubonic esters, especially phthalic acid
Ester is preferably used. The solid product (a) is an organosilicon compound
() Or in the presence of organosilicon compounds () and
Compound ()
Is reduced with an organomagnesium compound (). Titanium compound (), organosilicon compound
() And ester compound () are dissolved in a suitable solvent
Alternatively, it is preferable to use it after diluting it. With such a solvent
Hexane, heptane, octane, decane, etc.
Aromatic hydrocarbons, aromatic hydrocarbons such as toluene and xylene
Element, cyclohexane, methylcyclohexane, decalin
Such as alicyclic hydrocarbons, diethyl ether, dibutyl ether
Ter, diisoamyl ether, tetrahydrofuran, etc.
Ether compounds. The reduction reaction temperature is usually -50 to 70 ° C, preferably
It is preferably −30 to 50 ° C., particularly preferably −25 to 35 ° C.
The temperature range is ° C. The reaction time is not particularly limited.
It is usually about 30 minutes to 6 hours. After that, another 20 ~
The post-reaction may be carried out at a temperature of 120 ° C. In the reduction reaction, an inorganic oxide and an organic
The solid product is made porous by coexisting a porous carrier such as
It is also possible to impregnate the carrier. Porous used
As the carrier, a known carrier may be used. SiO_Two, Al
_TwoO_Three, MgO, TiO_Two, ZrO_TwoPorous represented by etc.
Inorganic oxide or polystyrene, styrene-divinyl
Benzene copolymer, styrene-ethylene glycol-
Methyl dimethacrylate copolymer, poly (methyl acrylate)
, Polyethyl acrylate, methyl acrylate-divinyl
Benzene copolymer, polymethyl methacrylate,
Methyl lylate-divinylbenzene copolymer, polyacryl
Ronitrile, acrylonitrile-divinylbenzene copolymer
Coalescence, polyvinyl chloride, polyethylene, polypropylene
And other organic porous polymers. this
Among them, preferably an organic porous polymer is used,
Among them, styrene-divinylbenzene copolymer or
A acrylonitrile-divinylbenzene copolymer is particularly preferred.
New The porous carrier has a pore radius of 200 to 2000.
細孔 preferably has a pore volume of 0.3 cc / g or more,
More preferably, it is 0.4 cc / g or more, and the range
Has a fine pore volume at a pore radius of 35 to 75000 °.
Preferably 35% or more of pore volume, more preferably 40%
That is all. If the pore volume of the porous support is small, the catalyst component
May not be able to be effectively immobilized,
I don't. Further, the pore volume of the porous carrier is 0.3 cc / g.
Even if it is above, it is the pore radius of 200 ~ 2000Å
Effectively immobilizes catalyst components if not sufficiently present
May not be possible, which is not preferred. The amount of the organosilicon compound () used is
Of silicon atom to titanium atom in compound ()
Si / Ti = 1 to 500, preferably 1
To 300, particularly preferably 3 to 100. Sa
In addition, the amount of organomagnesium compound () used is
The sum of silicon and silicon atoms and the atomic ratio of magnesium atoms
Normally (Ti + Si) /Mg=0.1 to 10, preferably
0.2 to 5.0, particularly preferably 0.5 to 2.0
It is. Further, in the solid catalyst component, the molar ratio of Mg / Ti
The value of the ratio is from 1 to 51, preferably from 2 to 31, particularly preferably
Is a titanium compound () such that it is in the range of 4 to 26,
Silicon compounds (), organomagnesium compounds ()
May be determined. Also optional ester
The amount of compound () used is the same as titanium compound ()
The molar ratio of ester compound to atom
Compound / Ti = 0.05-100, preferably 0.1-
60, particularly preferably in the range of 0.2 to 30. The solid product obtained from the reduction reaction is usually
Liquid separation and inert carbon such as hexane, heptane and toluene
Wash several times with a hydride solvent. Obtained in this way
Solid component (a) is a trivalent titanium atom, magnesium atom
Containing hydrocarbyloxy groups and generally amorphous
Shows low or very weak crystallinity. In terms of catalyst performance
Therefore, an amorphous structure is particularly preferable. (B) Organic acid halide Organic acid halide used for preparation of solid catalyst component of the present invention
(B) is preferably a mono- or polyvalent carboxylic acid.
Acid halides are used, examples of which are aliphatic carbohydrates.
Acid halide, alicyclic carboxylic acid halide, aromatic car
Bonic acid halides can be mentioned. As a specific example
Means acetyl chloride, propionyl chloride,
Acid chloride, valeric acid chloride, acrylic acid chloride
Methacrylic acid chloride, benzoic acid chloride,
Ruyl acid chloride, anisic acid chloride, succinic acid chloride
Chloride, malonic acid chloride, maleic acid chloride
Chloride, itaconic chloride, phthalic chloride, etc.
I can do it. Of these organic acid halides, benzoic acid
Chloride, toluic acid chloride, phthalic acid chloride
And aromatic carboxylic acid chlorides such as
Preferred is an aromatic dicarboxylic acid dichloride,
Phthalic acid chloride is preferably used. (C) Halogenated compound As the halogenated compound, carbonization in the solid product (a) may be used.
Compounds capable of replacing a hydrogenoxy group with a halogen atom are preferred.
New Among them, halogen compounds of Group 4 elements and Group 13 elements
Halogen compounds of elements or halogenation of group 14 elements
Compounds are preferred. As the halogen compound of the Group 4 element,
General formula M (OR⁹)_bX^Four _4-b(In the formula, M represents a group 4 atom.
Then R⁹Represents a hydrocarbon group having 1 to 20 carbon atoms;^Four
Represents a halogen atom, and b represents a number satisfying 0 ≦ b <4.
Represent. ) Is preferred. M tool
Examples include titanium, zirconium, and hafnium.
And titanium is particularly preferred. R⁹As a specific example of
Methyl, ethyl, propyl, isopropyl
Group, butyl group, isobutyl group, tert-butyl group,
Mill group, isoamyl group, tert-amyl group, hexyl
Group, heptyl group, octyl group, decyl group, dodecyl group, etc.
Alkyl group, phenyl group, cresyl group, xyler group,
Aryl group such as naphthyl group, allyl such as propenyl group
And an aralkyl group such as a benzyl group. this
An alkyl group having 2 to 18 carbon atoms or a carbon source
An aryl group having 6 to 18 children is preferred. Especially the number of carbon atoms
Preferred are 2 to 18 linear alkyl groups. Also, two or more
Different OR on⁹Compound of group 4 element having group
It is also possible to use a thing. X^FourAs the halogen atom represented by
Elemental atoms, bromine atoms and iodine atoms can be exemplified. In this
In particular, a chlorine atom gives a preferable result. The general formula M (OR⁹)_bX^Four _4-bThe fourth represented by
B of the group III halogen compound satisfies 0 ≦ b <4.
A number, preferably a number satisfying 0 ≦ b ≦ 2,
Particularly preferably, b = 0. Specifically, the general formula M (OR⁹)_bX_4-bso
Titanium tetrachloride, tetrabromide
Titanium, titanium tetraiodide, etc.
Toxicitanium trichloride, ethoxytitanium trichloride
Ride, butoxytitanium trichloride, phenoxyti
Tantric chloride, ethoxy titanium tribromide, etc.
Trihalogenated alkoxy titanium, dimethoxy titanium
Dichloride, diethoxytitanium dichloride, dibut
Xytitanium dichloride, diphenoxytitanium dichlora
Dihalides such as ide and diethoxytitanium dibromide
Dialkoxy titanium, corresponding zirconium
And hafnium compounds. most
Preferably titanium tetrachloride Halogen of Group 13 element or Group 14 element
Compounds of the general formula MR_maX_a(Where M is the first
R is a Group 3 or 14 atom, and R has 1 to 20 carbon atoms.
X is a halogen atom, m is the valence of M
Represents a represents a number satisfying 0 <a ≦ m)
Are preferred. As an atom of group 13 here
Represents B, Al, Ga, In, Tl, and B or A
1 is preferred, and Al is more preferred. In addition, of the 14th
Examples of atoms include C, Si, Ge, Sn, and Pb.
Si, Ge or Sn is preferable, and Si or Sn is more preferable.
Is more preferable. M is the valence of M. For example, M is the valence of Si.
When m = 4. a represents a number satisfying 0 <a ≦ m.
When M is Si, a is preferably 3 or 4.
As a halogen atom represented by X, F, Cl, Br, and I
And Cl is preferred. Specific examples of R include a methyl group, ethyl
Group, normal propyl group, isopropyl group, normal group
Chill, isobutyl, amyl, isoamyl, hexyl
Sil group, heptyl group, octyl group, decyl group, dodecyl
Groups such as alkyl, phenyl, tolyl, cresyl
Group, an xylyl group, an aryl group such as a naphthyl group,
Cycloalkyl groups such as xyl groups and cyclopentyl groups;
Alkenyl groups such as a lophenyl group, aralkyl groups such as a benzyl group, etc.
And the like. Preferred R is an alkyl group or
A reel group, and particularly preferred R is a methyl group, an ethyl group;
Group, normal propyl group, phenyl group or paratolyl
Group. Specific examples of the halogen compounds of Group 13 elements
Typically, trichloroboron, methyldichloroboron, d
Tildichloroboron, phenyldichloroboron, cyclo
Hexyldichloroboron, dimethylchloroboron, methyl
Ruethylchloroboron, trichloroaluminum, methyl
Rudichloroaluminum, ethyldichloroaluminium
Phenyldichloroaluminum, cyclohexyldi
Chloroaluminum, dimethylchloroaluminum, di
Ethylchloroaluminum, methylethylchloroaluminum
, Ethyl aluminum sesquichloride, gallium
Muchloride, gallium dichloride, trichlorogallium
, Methyldichlorogallium, ethyldichlorogallium
Phenyldichlorogallium, cyclohexyldichloro
Rogallium, dimethylchlorogallium, methylethylc
Lologallium, indium chloride, indium tri
Chloride, methyl indium dichloride, phenyl
Indium dichloride, dimethyl indium chloride
, Thallium chloride, thallium trichloride,
Tiltallium dichloride, phenylthallium dichlora
And dimethyl thallium chloride.
From the compound name chloro to fluoro, bromo, or iodo
Compounds changed to are also included. Specific examples of the halogen compounds of Group 14 elements
Include tetrachloromethane, trichloromethane, dichloromethane
Dichloromethane, monochloromethane, 1,1,1-trichloromethane
Ethane, 1,1-dichloroethane, 1,2-dichloroethane
Tan, 1,1,2,2-tetrachloroethane, tetrac
Lorosilane, trichlorosilane, methyltrichlorosila
, Ethyl trichlorosilane, normal propyl tric
Lorosilane, normal butyltrichlorosilane, phenyl
Rutrichlorosilane, benzyltrichlorosilane, para
Tolyltrichlorosilane, cyclohexyltrichlorosi
Orchid, dichlorosilane, methyldichlorosilane, ethyl
Dichlorosilane, dimethyldichlorosilane, diphenyl
Dichlorosilane, methylethyldichlorosilane, monoc
Lorosilane, trimethylchlorosilane, triphenylc
Lorosilane, tetrachlorogermane, trichlorogermane
, Methyltrichlorogerman, ethyltrichlorogel
Man, phenyltrichlorogermane, dichlorogermane
Dimethyldichlorogermane, diethyldichlorogel
Man, diphenyldichlorogermane, monochlorogerma
, Trimethylchlorogerman, triethylchlorogel
Man, tri-n-butylchlorogermane, tetrachloro
Rotin, methyltrichlorotin, normal butyltrichloro
Tin, dimethyldichlorotin, di-n-butyldichloro
Tin, diisobutyldichlorotin, diphenyldichlorotin,
Divinyldichlorotin, methyltrichlorotin, phenylt
Lichlorotin, dichlorolead, methylchlorolead, phenylc
Lorolead and the like, and chloro in these compound names
Compounds changed to b, bromo, or iodo
You. As the halogenated compound (c), tetrac
Lorotitanium, methyldichloroaluminum, ethyldic
Loroaluminum, tetrachlorosilane, phenyltri
Chlorosilane, methyltrichlorosilane, ethyltrik
Lorosilane, n-propyltrichlorosilane or te
Trachlorotin is particularly preferred from the viewpoint of polymerization activity.
As the halogenated compound (c), one of the above compounds
Class may be used, or a plurality of classes may be used. (D) Electron donor In the present invention, an electron donor is used in the preparation of a solid catalyst component.
The contact treatment using (d) can be appropriately performed. Electron donor
To give high stereoregular polymerization ability by contact treatment with
And can be. Ether as the electron donor
, Ketones, aldehydes, carboxylic acids, organic acids
Esters of inorganic acids, acids of organic or inorganic acids
Oxygen-containing electron-donating compounds such as
Nears, amines, nitriles, isocyanates, etc.
Examples of the compound include a nitrogen-containing electron donating compound. these
Of the electron donating compounds of the above, preferably esters of organic acids
And / or ethers, more preferably
Rubonates (d1) and / or ethers
(D2). Examples of the carboxylic esters (d1)
Include mono- and polyvalent carboxylic esters;
Examples of these are saturated aliphatic carboxylic acid esters, unsaturated
Japanese aliphatic carboxylic acid ester, alicyclic carboxylic acid ester
And aromatic carboxylic acid esters.
Specific examples include methyl acetate, ethyl acetate, and phenyl acetate.
, Methyl propionate, ethyl propionate, butyric acid
Chill, ethyl valerate, ethyl acrylate, methacrylic acid
Methyl, ethyl benzoate, butyl benzoate, toluic acid
Methyl, ethyl toluate, ethyl anisate, succinic acid
Diethyl, dibutyl succinate, diethyl malonate, malo
Dibutyl phosphate, dimethyl maleate, dibutyl maleate
, Diethyl itaconate, dibutyl itaconate, phthalate
Monoethyl acid, dimethyl phthalate, methyl phthalate
, Diethyl phthalate, di-n-propyl phthalate, phthalate
Diisopropyl phthalate, di-n-butyl phthalate, lid
Diisobutyl luate, dipentyl phthalate, di-phthalate
n-hexyl, diheptyl phthalate, di-n-phthalate
Octyl, di (2-ethylhexyl) phthalate, phthalate
Diisodecyl acid, dicyclohexyl phthalate, phthalic acid
Diphenyl and the like can be mentioned. Of these carboxylic acid esters,
Unsaturated fats such as acrylate and maleate
Aliphatic carboxylic acid ester or benzoic acid ester, lid
Aromatic carboxylic acid esters such as luic acid esters are preferred
Used. Particularly preferably, aromatic polycarboxylic acid
And most preferably dialkyl phthalate
Tell. Examples of ethers (d2) include dial
Kill ether and general formula (However, R^Five ~ R⁸ Is independently 1 to 2 carbon atoms
0 linear, branched or alicyclic alkyl group,
Or an aralkyl group;⁶ And R ⁷ Haso
Each may be independently a hydrogen atom. )
And ether compounds.
Species or two or more species are suitably used. Specific examples include dimethyl ether and die
Tyl ether, di-n-butyl ether, methyl ethyl
Ether, methyl-n-butyl ether, methylcyclo
Hexyl ether, 2,2-diisobutyl-1,3-di
Methoxypropane, 2-isopropyl-2-isopentene
1,3-dimethoxypropane, 2,2-bis (sic
Rohexylmethyl) -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-dimethoxypropa
2-isopropyl-2-isobutyl-1,3-dimethyl
Toxipropane, 2,2-diisopropyl-1,3-di
Methoxypropane, 2,2-dipropyl-1,3-dimethyl
Toxipropane, 2-isopropyl-2-cyclohexyl
1,3-dimethoxypropane, 2-isopropyl-
2-cyclopentyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropa
2-heptyl-2-pentyl-1,3-dimethoxy
Propane and the like, and one of these
Alternatively, two or more kinds are preferably used. Ethers (e2)
Is particularly preferably a dialkyl ether,
Preferred is di-n-butyl ether. In addition,
n-butyl ether is simply dibutyl ether or
Sometimes referred to as chill ether. (A) Preparation of solid catalyst component The solid catalyst component (A) of the present invention comprises the solid component (a) described above.
, An organic acid halide (b) and a halogenated compound (c)
And, if necessary, contact treatment with the electron donor (d).
And is obtained by All of these contact treatments are usually
This is performed under an atmosphere of an inert gas such as nitrogen or argon. Specific method of the contact treatment for obtaining a solid catalyst component
As a law, ・ In (a), (b) and (c) (in any order)
Method of charging and contacting, ・ Put a mixture of (b), (c) and (d) into (a)
And contact treatment method, (A), (b), and a mixture of (c) and (d)
(Input order is optional) -(A) and (b) are added to (c), and contact treatment is performed.
how to, ・ In (c), (a), (b) and (d) ((a)
(The order of loading is optional except for loading (b) later)
How to enter and contact, A mixture of (c) and (d) with (a) and then (b)
And a contact treatment method.
After these contact treatments, the contact treatment is further performed at least once in (c).
Contact treatment with a mixture of (c) and (d) at least once
Method. Of these, (a), (b), and
(C) a method of charging (arbitrary charging order) and performing contact treatment;
(A), (b), and a mixture of (c) and (d)
(Arbitrary order of injection), (a), (b),
And the mixture of (c) and (d)
And after contact treatment, a mixture of (c) and (d) is injected.
And a contact treatment at least once is preferable. (A)
A mixture of (c) and (d), in the order of (b)
And the method of contact treatment or (a)
A mixture of (c) and (d), each in the order of (b)
After charging and contacting, the mixture of (c) and (d)
It is more preferable to perform the contact treatment once or more times. Special
More preferably, (a) is mixed with (c) and (d2).
Each of the materials was put in the order of (b) and subjected to contact treatment.
Thereafter, a mixture of (c), (d1) and (d2) is charged,
After the contact treatment, the mixture of (c) and (d2)
It is a method of charging and performing contact treatment at least once. In the present invention, such olefin polymerization
In the method for producing a catalyst component for use, the solid product (a)
The addition of the organic acid halide (b) is represented by the following formula [I].
It is performed under the conditions to be performed. 0.01 ≦ bb ÷ (aa × time) ≦ 0.1 [I] (Where bb is the capacity of the organic acid halide (b) (unit is m
l) wherein aa is the weight of the solid product (a) (unit is
g), and time is the time when the organic acid halide (b) is dropped.
Indicates the interval (the unit is minutes). Bb に お け る (aa)
× time) indicates the rate of addition of the organic acid halide (b).
And the addition rate is too high or too low.
Olefin polymerization solid catalyst component has higher polymerization activity
I can't show. The rate of addition is preferably 0.02.
Or more and less than 0.1, more preferably 0.3 or more.
9 or less. In the contact treatment, the two are contacted in the presence of a diluent.
It is preferred that After the contact treatment,
Operation, but in order to remove surplus,
It is preferable to perform a washing treatment with a diluent. As a diluent, there is no
Preferably active, pentane, hexane, hept
Aliphatic hydrocarbons such as tan and octane, benzene and tol
Aromatic hydrocarbons such as ene and xylene, cyclohexa
Cycloaliphatic hydrocarbons such as cyclopentane, 1,2-di
Halogenated carbonization of chloroethane, monochlorobenzene, etc.
Hydrogen can be used. Diluent usage in contact processing
Per 1 g of the solid component (a) per one-step contact treatment
It is usually 0.1 ml to 1000 ml. Preferably 1
It is 1 ml to 100 ml per g. Also, one wash
The amount of diluent used in the operation is similar. Cleaning process
The number of washing operations in
It is always 1 to 5 times. The contact treatment and / or cleaning treatment temperature is
Each is usually from -50 to 150 ° C, preferably from 0 to 150 ° C.
140 ° C., more preferably 60 to 135 ° C.
You. The contact treatment time is not particularly limited, but is preferably set to 0.1.
5 to 8 hours, more preferably 1 to 6 hours
You. The washing operation time is not particularly limited, but is preferably 1
~ 120 minutes, more preferably 2 ~ 60 minutes
is there. The amount of the organic acid halide (b) used depends on the solid component.
0.1 to 100 mmol, preferably 1 g, per 1 g of the component (a)
Preferably 0.3 to 50 mmol, more preferably 0.
5-20 mmol. In addition, the matrix in the solid component (a)
Organic acid halide (b) per mole of gonium atom
The amount used is usually 0.01 to 1.0 mol, preferably 0.1 mol.
03 to 0.5 mol. The amount of the halogenated compound (c) used is a solid
Usually 0.5 to 1000 mM per 1 g of the product (a)
, Preferably 1 to 200 mmol, more preferably
2 to 100 mmol. Also, halogenated compounds
When using (c), the electron donor (d) is used together.
Is preferred. (D) in that case, relative to 1 mole
The amount of (c) used is usually 1 to 100 mol, preferably
1.5 to 75 mol, more preferably 2 to 50 mol
You. The amount of the electron donor (d) used depends on the solid component.
(A) Usually 0.01 to 100 mmol, preferably 1 g, per 1 g
Preferably 0.05 to 50 mmol, more preferably
0.1 to 20 mmol. (B) and (d) usage
If the amount is too large, the particles may be disintegrated. It is to be noted that each compound is subjected to plural times.
In the case of performing contact treatment by using beforehand,
Each compound should be used only once and for each compound.
Indicates the amount used for each item. [0061] The obtained solid catalyst component is an inert diluent.
May be used for polymerization in a slurry state in combination with
It may be used for polymerization as a free-flowing powder obtained by drying.
No. As a drying method, volatile components are removed under reduced pressure.
Method, volatile components under the flow of inert gas such as nitrogen and argon
There is a method of removing. Drying temperature is 0 to 200
C., preferably 50 to 100 C.
More preferred. Drying time is 0.01-20 hours
And more preferably 0.5 to 10 hours.
Good. The solid catalyst component (A) according to the present invention has
Aluminum compound (B) and, if necessary, electron
Α-O obtained by contacting the donor compound (C)
As a catalyst for refin polymerization, used for α-olefin polymerization
You can. (B) Organoaluminum compound Organic compounds used to form olefin polymerization catalysts
The luminium compound (B) has at least one compound in the molecule.
It has an Al-carbon bond. Representative one
The general formula is shown below. R¹⁹ _wAlY_3-w R²⁰R^{twenty one}Al-O-AlR^{twenty two}R^{twenty three} (Where R¹⁹~ R^{twenty three}Is a hydrocarbon group having 1 to 20 carbon atoms
And Y represents a halogen atom, a hydrogen atom or an alkoxy group.
And w is a number satisfying 2 ≦ w ≦ 3. ) Specific examples of such organoaluminum compounds include
Is triethylaluminum, triisobutylaluminum
Trialkyl such as minium and trihexyl aluminum
Aluminum, diethyl aluminum hydride, di
Dialkyl alcohols such as isobutyl aluminum hydride
Luminium hydride, diethylaluminum chlora
Dialkylaluminum halides such as ido, triethyl
Mixing of aluminum with diethylaluminum chloride
Trialkylaluminum and dialkyla
Mixture with luminium halide, tetraethyl dialmo
Alkyl alkanes such as xane and tetrabutyl dialumoxane
Moxane can be exemplified. Of these organoaluminum compounds,
Trialkyl aluminum, trialkyl aluminum
And dialkylaluminum halide,
Is preferably an alkylalumoxane, especially
Chill aluminum, triisobutyl aluminum, tri
Ethyl aluminum and diethyl aluminum chloride
Mixtures with or tetraethyl dialumoxane are preferred
No. (C) Electron-donating compound Used as needed to form olefin polymerization catalysts
As the electron donating compound (C), the oxygen-containing compound
Substances, nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds
Among which oxygen-containing compounds or nitrogen-containing compounds
Compounds are preferred. As the oxygen-containing compound, alkoxy
Silicones, ethers, esters, ketones, etc.
And alkoxysilicons or ethers
Is preferred. As the alkoxysilicons, the general formula R
^Three _rSi (OR^Four)_4-r  (Where R ^ThreeIs 1 to 2 carbon atoms
0 hydrocarbon group, hydrogen atom or hetero atom-containing substituent
And R^FourRepresents a hydrocarbon group having 1 to 20 carbon atoms.
And r represents a number satisfying 0 ≦ r <4. All R^ThreeYou
And all R^FourAre the same but different
Is also good. ) Is preferred.
Commonly used. R^ThreeIs a hydrocarbon group, a methyl group,
Straight chain such as tyl, propyl, butyl, pentyl, etc.
Alkyl group, isopropyl group, sec-butyl group, te
branched-chain amino groups such as rt-butyl group, tert-amyl group, etc.
Alkyl, cyclopentyl, cyclohexyl, etc.
Cycloalkyl such as cycloalkyl and cyclopentenyl
Aryl groups such as kenyl, phenyl, and tolyl groups;
I can do it. Among them, silicon source of alkoxysilicon compounds
The carbon atom directly bonded to the secondary is tertiary or tertiary carbon
Some R^ThreeIt is preferable to have at least one. R^ThreeBut
In the case of a substituent containing a terror atom, the hetero atom is oxygen
Atom, nitrogen atom, sulfur atom and phosphorus atom. Ingredient
Physically, dimethylamino, methylethylamino,
Ethylamino group, ethyl n-propylamino group, di-n-
Propylamino group, pyrrolyl group, pyridyl group, pyrrolidi
Nyl, piperidyl, perhydroindolyl, per
Hydroisoindolyl group, perhydroquinolyl group, per
Hydroisoquinolyl group, perhydrocarbazolyl group,
-Hydroacridinyl, furyl, pyranyl, par
Hydrofuryl group, thienyl group and the like.
Terrorist atom directly with silicon atom of alkoxysilicon compound
Substituents capable of chemical bonding are preferred. As specific examples of the alkoxysilicon compound,
Is diisopropyldimethoxysilane, diisobutyldi
Methoxysilane, di-tert-butyldimethoxysila
Tert-butylmethyldimethoxysilane, ter
t-butylethyldimethoxysilane, tert-butyl
-N-propyldimethoxysilane, tert-butyl-
n-butyldimethoxysilane, tert-amylmethyl
Dimethoxysilane, tert-amylethyldimethoxy
Silane, tert-amyl n-propyldimethoxysila
Tert-amyl-n-butyldimethoxysilane,
Isobutylisopropyldimethoxysilane, tert-
Butylisopropyldimethoxysilane, dicyclobutyl
Dimethoxysilane, cyclobutyl isopropyl dimethoxy
Sisilane, cyclobutylisobutyldimethoxysilane,
Cyclobutyl-tert-butyldimethoxysilane, di
Cyclopentyl dimethoxysilane, cyclopentyl iso
Propyldimethoxysilane, cyclopentyl isobutyl
Dimethoxysilane, cyclopentyl-tert-butyl
Dimethoxysilane, dicyclohexyldimethoxysila
, Cyclohexylmethyldimethoxysilane, cyclohexane
Xylethyldimethoxysilane, cyclohexyl isop
Ropyldimethoxysilane, cyclohexylisobutyldi
Methoxysilane, cyclohexyl-tert-butyldi
Methoxysilane, cyclohexylcyclopentyl dimethoate
Xysilane, cyclohexylphenyldimethoxysila
Diphenyldimethoxysilane, phenylmethyldimene
Toxysilane, phenylisopropyldimethoxysila
Phenyl, phenylisobutyldimethoxysilane, phenyl-
tert-butyldimethoxysilane, phenylcyclope
Dimethyldimethoxysilane, diisopropyldiethoxy
Orchid, diisobutyldiethoxysilane, di-tert-
Butyldiethoxysilane, tert-butylmethyldie
Toxysilane, tert-butylethyldiethoxysila
Tert-butyl-n-propyldiethoxysila
Tert-butyl-n-butyldiethoxysilane,
tert-amylmethyldiethoxysilane, tert-
Amylethyldiethoxysilane, tert-amyl-n
-Propyldiethoxysilane, tert-amyl-n-
Butyldiethoxysilane, dicyclopentyldiethoxy
Silane, dicyclohexyldiethoxysilane, cyclohexane
Xylmethyldiethoxysilane, cyclohexylethyl
Diethoxysilane, diphenyldiethoxysilane,
Nylmethyldiethoxysilane, 2-norbornanemethyl
Dimethoxysilane, bis (perhydroquinolino) dimeth
Xysilane, bis (perhydroisoquinolino) dimethoxy
Sisilane, (perhydroquinolino) (perhydroisox
Norino) dimethoxysilane, (perhydroquinolino) meth
Tyldimethoxysilane, (perhydroisoquinolino) meth
Tyldimethoxysilane, (perhydroquinolino) ethyl
Dimethoxysilane, (perhydroisoquinolino) ethyl
Dimethoxysilane, (perhydroquinolino) (n-pro
Pill) dimethoxysilane, (perhydroisoquinolino)
(N-propyl) dimethoxysilane, ((perhydroxy
Norino) (tert-butyl) dimethoxysilane,
-Hydroisoquinolino) (tert-butyl) dimethoxy
Sisilane. The ethers include an electron donor (e2)
And the cyclic ether compound exemplified in
No. As cyclic ether compounds, few
Heterocyclic compounds having at least one -CO-C- bond
Things. Specific examples of the cyclic ether compound include
Len oxide, propylene oxide, trimethylene oxide
Sid, tetrahydrofuran, 2,5-dimethoxytetra
Hydrofuran, tetrahydropyran, hexamethylene
Oxide, 1,3-dioxepane, 1,3-dioxane,
1,4-dioxane, 1,3-dioxolan, 2-methyl
1,3-dioxolan, 2,2-dimethyl-1,3
Dioxolane, 4-methyl-1,3-dioxolane,
2,4-dimethyl-1,3-dioxolan, furan,
2,5-dimethylfuran or s-trioxane
Can be In particular, at least one -C-O-C in the ring system
Cyclic ether compounds having an -OC- bond are preferred.
No. Examples of the nitrogen-containing compound include 2,6-dimethyl
Lupiperidine, 2,2,6,6-tetramethylpiperidi
2,6-substituted piperidines such as
Lysines, N, N, N ', N'-tetramethylmethylenedi
Amine, N, N, N ', N'-tetraethylmethylenedia
Substituted methylene diamines such as min, 1,3-dibenzyl
Substituted imidazolidines such as Louis imidazolidine
I can do it. Of these, 2,6-substituted piperidines are preferred.
No. [Polymerization of olefin]
In the polymerization of olefins using a solid catalyst component, α
An olefin is an α-olefin having 3 or more carbon atoms.
There is a specific example of such an α-olefin
1, butene-1, pentene-1, hexene-1, hepte
-1, octene-1, decene-1, etc.
Olefin, 3-methylbutene-1,3-methylpente
-1,4-methylpentene-1, etc.
Olefin, vinylcyclohexane and the like can be mentioned.
One of these α-olefins may be used,
Alternatively, two or more kinds may be used in combination. this
Among these α-olefins, propylene or butene
Homopolymerization using propylene-1 or propylene
Olefin or butene-1 mixed olefin
It is preferable to carry out the copolymerization using propylene
Perform homopolymerization or use propylene as the main component.
It is particularly preferable to carry out copolymerization using mixed olefins.
New In the copolymerization of the present invention,
And two kinds selected from the above-mentioned α-olefins or
Is to use a mixture of more olefins
Can be. Furthermore, such as conjugated dienes and non-conjugated dienes
Compounds with polyunsaturation can be used for copolymerization
Noh. Then, the heterobub performed in two or more stages of polymerization.
Lock copolymerization can also be easily performed. Using the solid catalyst component obtained according to the present invention
The catalyst is a solid catalyst component (A), an organic aluminum
(B) and, if necessary, an electron donating compound (C)
A catalyst for polymerization of α-olefin obtained by contacting
You. Here, the contact means that the catalyst components (A) to (C) are in contact with each other.
Touch and by any means if a catalyst is formed
Often diluted with or without solvent in advance
Minutes (A) to (C) can be mixed and contacted separately or separately
Adopting a method of supplying to the polymerization tank and bringing it into contact in the polymerization tank
it can. As a method of supplying each catalyst component to the polymerization tank,
Operate in an inert gas such as nitrogen or argon without moisture.
It is preferred to supply. Each catalyst component is either two
You may contact and supply beforehand. The olefin polymerization is carried out in the presence of the above-mentioned catalyst.
It is possible to carry out such polymerization (main polymerization).
Before the application, the following prepolymerization may be performed. The prepolymerization is usually carried out using the solid catalyst component (A) and
A small amount of oleoresin in the presence of
It is performed by supplying fins, and is preferably performed in a slurry state.
Good. As a solvent used for slurrying, a professional
Bread, butane, isobutane, pentane, isopentane,
Hexane, heptane, octane, cyclohexane, ben
Examples of inert hydrocarbons such as zen and toluene
it can. In addition, when slurrying, inert hydrocarbons
Use liquid olefin instead of part or all of the solvent
Can be Use of organoaluminum compound during prepolymerization
The dose is generally given per mole of titanium atom in the solid catalyst component.
You can always choose a wide range as 0.5-700 mol
However, 0.8 to 500 mol is preferable, and 1 to 200 mol
Is particularly preferred. The amount of the olefin to be prepolymerized is
Usually 0.01 to 1000 g per gram of solid catalyst component, preferably
Preferably 0.05 to 500 g, particularly preferably 0.1 to 500 g
200 g. The slurry concentration for performing the pre-polymerization is 1 to
500 g-solid catalyst component / liter-solvent is preferred,
Particularly, 3 to 300 g-solid catalyst component / liter-solvent is preferred.
Good. The pre-polymerization temperature is preferably -20 to 100 ° C.
And particularly preferably 0 to 80 ° C. Also, during pre-polymerization,
The partial pressure of the olefin in the phase is 0.01 to 20 kg / c.
m^TwoIs preferred, especially 0.1 to 10 kg / cm^TwoIs preferred
Olefins that are liquid at the pressure and temperature of the prepolymerization
This is not always the case for fins. Furthermore, pre-polymerization
The time is not particularly limited, but usually 2 minutes to 15 hours is preferable
It is. In carrying out the prepolymerization, the solid catalyst component
(A), an organoaluminum compound (B), an olefin
As a method of supplying, the solid catalyst component (A) and the organic alcohol
Olefin after contacting minium compound (B)
The solid catalyst component (A) and the olefin
Supply organic aluminum compound (B) after touching
Any method may be used. Also,
As a method for supplying the fins, the pressure inside the polymerization tank is maintained at a predetermined pressure.
Who supply olefins sequentially while maintaining
Process, or first supply all olefins
Any of the methods may be used. Also the weight obtained
Add a chain transfer agent such as hydrogen to adjust the molecular weight of the coalescence
It is also possible to add. Further, the organic aluminum compound (B)
Preserve solid catalyst component (A) with a small amount of olefin in the presence
When polymerizing, if necessary, an electron donating compound (C)
May coexist. The electron donating compound used is
Part or all of the above electron donating compound (C)
You. The amount used is the amount of catalyst contained in the solid catalyst component (A).
Usually 0.01 to 400 mol, preferably 1 mol, per mol of tan atom.
It is preferably 0.02 to 200 mol, particularly preferably 0.1 to 200 mol.
03 to 100 mol, an organoaluminum compound
(B), usually 0.003 to 5 mol, preferably
0.005 to 3 mol, particularly preferably 0.01 to 2 mol
It is. In the prepolymerization, the electron donating compound (C)
There is no particular limitation on the supply method, and organoaluminum compounds
(A) may be supplied separately, or may be supplied in advance by contact
You may. Also, olefins used in prepolymerization
Is different even if it is the same as the olefin used in the main polymerization.
It may be. After performing the prepolymerization as described above,
Is the solid catalyst component described above without pre-polymerization.
(A), organoaluminum compound (B) and electron donation
Of an α-olefin polymerization catalyst comprising the reactive compound (C)
The main polymerization of an α-olefin can be carried out in the presence. Use of organoaluminum compound during main polymerization
The amount is usually 1 mole equivalent of titanium atom in the solid catalyst component (A).
Or can be selected over a wide range, from 1 to 1000 moles.
However, a range of 5 to 600 mol is particularly preferable. The electron donating compound used in the main polymerization may be used.
Compound (C) is titanium contained in solid catalyst component (A).
Usually 0.1 to 2000 mol, preferably 1 mol, per mol of atom
0.3 to 1000 mol, particularly preferably 0.5 to 1000 mol.
800 moles, based on the organoaluminum compound.
0.001-5 mol, preferably 0.005-3 mol
And particularly preferably 0.01 to 1 mol. The main polymerization is usually carried out at a temperature of -30 to 300 ° C.
20 to 180 ° C is preferred.
New There is no particular restriction on the polymerization pressure.
In general, in order to be economical,
/ Cm^Two, Preferably 2 to 50 kg / cm^TwoAbout pressure
Adopted. Batch type or continuous type
All are possible. Also, propane, butane, isobuta
Pentane, hexane, heptane, octane
Slurry polymerization with active hydrocarbon solvent or solution weight
When the polymerization temperature is a
Luc polymerization or gas phase polymerization is also possible. During the main polymerization, the molecular weight of the polymer was adjusted.
For this purpose, it is also possible to add a chain transfer agent such as hydrogen. [0085] The present invention will be described below with reference to Examples and Comparative Examples.
As will be described in further detail, the present invention is described by the following examples.
It is not particularly limited. In the examples, polymerization
The methods for evaluating various physical properties of the body are as follows. (1) 20 ° C. xylene-soluble portion (hereinafter referred to as CXS)
Abbreviated): 1 g of polymer in 200 ml of boiled xylene
After dissolving in ice water, gradually cool to 50 ° C and then in ice water.
Cool down to 20 ° C while immersing and stirring, and release at 20 ° C for 3 hours
After placing, the precipitated polymer was separated by filtration. Remains in the filtrate
The weight percentage of the polymer obtained was defined as CXS (unit =%).
The smaller the value of CXS, the higher the stereoregularity of polypropylene
Is high. (2) Intrinsic viscosity (hereinafter abbreviated as [η]):
Measured at 135 ° C. in a Toralin solvent. (3) Bulk density: JIS K-6721-1
It was measured according to 966. (4) A set of solid samples such as solid catalyst components
The composition analysis was performed as follows. That is,
Titanium atom content, after decomposing solid sample with dilute sulfuric acid,
An excess of aqueous hydrogen peroxide is added to this, and the resulting liquid sump is added.
Characteristic absorption at 410 nm of the double-beam spectroscopy of Hitachi
Measure using U-2001 type meter and prepare separately
It was determined by a calibration curve. The alkoxy group content is
After decomposing the sample with water, the alcohol
The amount of alcohol corresponding to the xy group is determined by gas chromatography.
Calculated using the internal standard method and converted to the alkoxy group content.
Calculated. Carboxylic acid ester content should be
After decomposition with water, extract the soluble components with a saturated hydrocarbon solvent and extract
Gas chromatography of the amount of carboxylic acid ester in the effluent
-Determined by the internal standard method. [Example 1] (1) Synthesis of solid product (a) In a reactor equipped with a stirrer purged with nitrogen, hexane 12
43 liters, 350 kg of tetraethoxysilane and
And 38.8 kg of tetrabutoxytitanium
did. Next, butylmagnesium magnesium was added to the stirred mixture.
Chloride in dibutyl ether (concentration 2.1 mol / l
Torr) Keep the reactor temperature at 17 ° C
The solution was dropped over 5 hours. After dropping, 1 hour at 20 ° C
After stirring for a while, the mixture was filtered.
The washing with 00 liters was repeated three times, and toluene was added.
First, it was turned into a slurry. The composition of this solid product was analyzed.
As a result, 2.09 weight of titanium atoms was found in the solid product.
%, 38.4% by weight of ethoxy groups, 3.2% of butoxy groups
4% by weight. The slurry concentration was 0.2
81 g-solid component / ml-slurry. (2) Synthesis of solid catalyst component 100 ml flask equipped with stirrer, dropping funnel and thermometer
After substituting nitrogen for nitrogen, the solid obtained in (1) above
28.5 ml of the product slurry was added, and the supernatant liquid 2 ml
, And keep the slurry at about 40 ° C.
Titanium 16.0ml, dibutyl ether 0.8ml
Of phthalic acid chloride (hereinafter, referred to as
OPC may be abbreviated. 1.6 ml and toluene
1.6 ml of mixture at constant speed over 2.5 minutes
(0.08 ml-OPC / g-solid product / min)
It was dropped. After completion of the dropwise addition, the reaction mixture was heated at 115 ° C. for 3 hours.
Stirred. Thereafter, solid-liquid separation is performed at the same temperature, and
Washing was performed three times with 40 ml of Ruen. After cleaning, slurry
Toluene was added so that the volume of-became 26.5 ml,
105 ° C. There dibutyl ether 0.8m
1, 0.45 ml of diisobutyl phthalate and titanium tetrachloride
Charge 16 ml of the mixture and stir at 105 ° C for 1 hour.
Stirred. Thereafter, solid-liquid separation is performed at the same temperature.
Washing was performed twice with 40 ml of ene. Next, the slurry
Toluene was added to a volume of 26.5 ml and 10
5 ° C. 0.8 ml of dibutyl ether, four
Charge a mixture of titanium chloride (16 ml), and add
Stirred for hours. Thereafter, solid-liquid separation is performed at the same temperature, and 105 ° C.
Was performed twice with 40 ml of toluene. In addition,
Toluene was added so that the volume of the rally became 26.5 ml.
And 105 ° C. There dibutyl ether 0.8
and a mixture of 16 ml of titanium tetrachloride.
Stirred at 5 ° C. for 1 hour. After that, solid-liquid separation at the same temperature,
3 times with 40 ml of toluene at 105 ° C, and hexane at room temperature
  Washing was performed three times with 40 ml. This is dried under reduced pressure and
6.38 g of a body catalyst component was obtained. In the solid catalyst component,
1.96% by weight of titanium atom, 1 of phthalic acid ester
2.21% by weight, 0.05% by weight of ethoxy group, Butoki
0.15% by weight of a siloxane group was contained. (3) Polymerization of propylene Stainless steel autoclave with 3 liter internal volume
Is replaced with argon, and triethyl aluminum is used as the component (B).
2.6 mmol, cyclohexyl as component (C)
0.26 mmol of silethyldimethoxysilane and
(A) The solid catalyst component synthesized in (2) above as the component
4.82 mg charged, equivalent to a partial pressure of 0.033 MPa
Hydrogen was added. Then 780 g of liquefied propylene
Charge, raise the temperature of the autoclave to 80 ° C.
Polymerization was carried out at a temperature of 1 hour. After the polymerization is completed,
Purged. The resulting polymer was dried under reduced pressure, and 231 g of the polymer was dried.
A polypropylene powder was obtained. 1 g of solid catalyst component
(Hereinafter abbreviated as PP / cat)
Is PP / cat = 47900 (g / g).
Was. In addition, soluble in xylene at 20 ° C which accounts for the total polymer yield
The ratio of the components is CXS = 0.52 (wt%),
The intrinsic viscosity is [η] = 2.13 (dl / g), and the bulk density is
0.453 (g / ml). [Example 2] (1) Synthesis of solid catalyst component The addition of OPC was carried out at a constant rate (0.04 ml
-OPC / g-solid product / min)
It was synthesized according to Example 1 (2). In solid catalyst components
Means that the titanium atom is 2.12% by weight and the phthalate is
10.84% by weight, 0.05% by weight of ethoxy group, buto
It contained 0.17% by weight of xyl groups. (2) Polymerization of propylene 4.85 mg of the solid catalyst component obtained in (1) was charged.
Other than the above, polymerization was carried out according to Example 1 (3), and
A propylene powder was obtained. Per gram of solid catalyst component
Yield of polypropylene (hereinafter abbreviated as PP / cat)
Was PP / cat = 47000 (g / g). Ma
In addition, the component soluble in xylene at 20 ° C in the total polymer yield
Is CXS = 0.61 (wt%), the ultimate viscosity of the polymer
The degree is [η] = 2.12 (dl / g) and the bulk density is 0.45
6 (g / ml). [Comparative Example 1] (1) Synthesis of solid catalyst component OPC was added at a constant rate (0.8 ml-
OPC / g-solid product / min)
Synthesized according to Example 1 (2). In the solid catalyst component,
1.91% by weight of titanium atom and 1 of phthalic acid ester
0.45% by weight, 0.03% by weight of ethoxy group, butoki
It contained 0.12% by weight of silyl groups. (2) Polymerization of propylene 4.50 mg of the solid catalyst component obtained in (1) was charged.
Other than the above, polymerization was carried out according to Example 1 (3), and
A propylene powder was obtained. Per gram of solid catalyst component
Yield of polypropylene (hereinafter abbreviated as PP / cat)
Is PP / cat = 33300 (g / g), and OP
C was lower than when C was dripped more slowly.
In addition, a component soluble in xylene at 20 ° C. in the total polymer yield.
The ratio of CXS is 0.59 (wt%), the limit of polymer
The viscosity is [η] = 2.17 (dl / g) and the bulk density is 0.4
44 (g / ml). [Comparative Example 2] (1) Synthesis of solid catalyst component OPC addition was carried out at a constant rate (0.0067
ml-OPC / g-solid product / min)
Others were synthesized according to Example 1 (2). In solid catalyst components
Contains 2.29% by weight of titanium atoms and phthalate esters
13.24% by weight, 0.03% by weight of ethoxy groups,
It contained 0.12% by weight of toxic groups. (2) Polymerization of propylene 5.84 mg of the solid catalyst component obtained in (1) was charged.
Other than the above, polymerization was carried out according to Example 1 (3), and
A propylene powder was obtained. Per gram of solid catalyst component
Yield of polypropylene (hereinafter abbreviated as PP / cat)
Is PP / cat = 39600 (g / g), and OP
C was lower than in the case where C was dropped more quickly. Also,
Percentage of components soluble in xylene at 20 ° C in total polymer yield
CXS = 0.60 (wt%), the intrinsic viscosity of the polymer is
[Η] = 2.21 (dl / g), bulk density is 0.453
(G / ml). [0099] As described above, according to the present invention,
Solid catalyst composition for α-olefin polymerization with high activity polymerization ability
And catalyst for polymerization of α-olefins
The present invention provides a method for producing an α-olefin polymer. Departure
The bright α-olefin polymerization catalyst has a high stereoregular polymerization ability.
That high active polymerization ability can be achieved without sacrificing
Therefore, its industrial utility value is very large.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 4J028 AA01A AA02A AB01A AB02A                       AC02A AC03A AC05A AC06A                       AC07A AC22A AC25A BA01B                       BB01B BC04A BC06A BC14B                       BC15B BC16B BC17B BC18B                       BC20B BC24B CB27C CB42A                       CB42C CB43A CB44A CB58A                       CB62C CB74C CB75C CB86C                       CB91A CB92A CB92C EA01                       EA02 EB01 EB02 EB03 EB04                       EB05 EB07 EB08 EB09 EC01                       EC02 FA02 GB01

Claims (1)

Claims: 1. A titanium compound represented by the following general formula [II] is reduced with an organomagnesium compound in the presence of an organosilicon compound having a Si-O bond. A solid product (a), an organic acid halide (b), and a halogenated compound (c), which are obtained by contacting the solid product (a) with the halogenated compound (c). )), Wherein the organic acid halide (b) is added under the conditions represented by the following formula [I]. 0.01 ≦ bb ÷ (aa × time) ≦ 0.1 [I] (where bb is the capacity of the organic acid halide (b) (unit is m
l), aa represents the weight (unit: g) of the solid product (a), and time represents the dripping time (unit: minute) of the organic acid halide (b). ) (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. 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. )