JPH06100619A - Catalyst component for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the title component with which a polymer having excellent rigidity is obtained in high yield, by contacting a given solid ingredient with a specific organic Si compound in the presence of an organic Al compound. CONSTITUTION:A solid ingredient comprising as the essential components a metal oxide, Mg, Ti, a halogen, and an electron-donating compound (e.g., one comprising SiO2, n-butylethylmagnesium, TiCl4, and di-n-butyl phthalate) is contacted with an organosilicon compound represented by the formula [wherein R<1> is a 1-10C alkylene or arylene; R<2> is a 1-10C aliphatic, alicyclic, or aromatic hydrocarbon group or a group represented by the formula R<4>O (where R<4> is a 3-10C aliphatic, alicyclic, or aromatic hydrocarbon group); R<3> is the same as R<4>; x is 1 or 2; y is 0 or 1; and z=4-x-y] in the presence of an organic A1 compound (e.g., triethylaluminum).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for .alpha.-olefin polymerization. More specifically, it relates to a catalyst component for α-olefin polymerization capable of producing a polymer having excellent rigidity with a high yield.

[0002]

2. Description of the Related Art Demand for highly crystalline polypropylene produced by using various types of highly stereoregular catalysts has been rapidly increasing in recent years because of its excellent rigidity and heat resistance. However, these properties are still insufficient depending on the purpose of use, and various methods for improving the rigidity have been proposed, but most of them are the methods of performing post-treatment such as adding a nucleating agent to polypropylene. is there. Therefore, the process cost is high, and the appearance of the molded product may be impaired depending on the additive. A method of improving rigidity by a polymerization method without treatment with an additive has been proposed, but the rigidity is insufficient in both cases.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an α-olefin polymerization catalyst component capable of producing an α-olefin polymer such as polypropylene having excellent rigidity in a high yield.

[0004]

As a result of intensive studies by the present inventors, the catalyst component obtained by contacting a metal oxide- and magnesium-containing solid catalyst component with a specific organosilicon compound is The present invention has been completed by finding that the object can be achieved. That is, the present invention is
(A) a solid component containing a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) In the presence of an organoaluminum compound, (C) the general formula

[Chemical 2] [However, R ¹ is an alkylene group or arylene group having 1 to 10 carbon atoms, R ² is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms or R ⁴ O and R ³ are carbon atoms. An aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms, R ⁴ is an aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms which is the same as or different from R ³ . x is 1 or 2, y is 0 or 1, and z is 4-xy. ] Α formed by contacting with an organosilicon compound represented by
-Summary is a catalyst component for olefin polymerization.

Solid Component Solid component used in the present invention (hereinafter referred to as component A)
Contains a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components. Such components are usually a metal oxide, a magnesium compound, a titanium compound and an electron donating compound, and further, each of the above compounds is a halogen compound. In the case of a compound having no, it is prepared by bringing halogen-containing compounds into contact with each other.

(1) Metal Oxide The metal oxide used in the present invention is a group II element of the periodic table.
~ Is an oxide of an element selected from the group of Group IV elements,
For example, B₂O₃, MgO, Al ₂O₃,
SiO₂, CaO, TiO₂, ZnO, ZrO₂, Sn
O₂, BaO, ThO₂Etc. Among these
Also B₂O₃, MgO, Al₂O₃, SiO₂, Ti
O₂, ZrO₂Is desirable, especially SiO₂Is desirable.
Furthermore, complex oxides containing these metal oxides, such as Si
O₂-MgO, SiO₂-Al₂O₃, SiO₂-Ti
O₂, SiO₂-V₂O_Five, SiO₂-Cr₂O₃, S
iO₂-TiO₂-MgO etc. can also be used.

The shape of these metal oxides is usually powder. Since the shape, such as the size and shape of the powder, often affects the shape of the obtained olefin polymer, it is desirable to adjust it appropriately. The metal oxide is
For the purpose of removing poisonous substances during use, it is desirable to handle them at a temperature as high as possible and to avoid direct contact with the atmosphere.

(2) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² are the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms.
More specifically, the hydrocarbon group of R ¹ and R ² is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR group is R having 1 to 10 carbon atoms Twelve alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups have chlorine as a halogen atom,
Examples include bromine, iodine and fluorine.

Specific examples of these compounds are shown below. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show. MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtOMgCl,
BuOMgCl, HeOMgCl, PhOMgCl, E
tOMgBr, BuOMgBr, EtOMgI, MgC
l _2, MgBr _2, MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing the component A. As an example thereof, a compound containing metal magnesium, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1 to 20]
Hydrocarbon groups, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧ 0. ] The method of making it contact is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr), i-propyl (iP
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHr), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. Alkenyl group, phenyl (Ph), tolyl, aryl group of xylyl group, phenethyl, aralkyl such as 3-phenylpropyl, and the like. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Specific examples of the alkoxy group-containing compound will be given below.

Compound wherein M is carbon C (OMe) ₄ , C (OE contained in the formula C (OR) ₄
t) ₄ , C (OPr) ₄ , C (OBu) ₄ , C (Oi-
Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC
HC (OMe) ₃ , HC (OE contained in (OR) ₃
t) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC
(OHe) ₃ , HC (OPh) ₃ ; MeC (OM
e) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC
(OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (O
Et) ₃ , MeCHBrC (OEt) ₃ , MeCHCl
C (OEt) ₃ ; ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ ; MeCH (OM included in the formula X ₂ C (OR) ₂
e) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ ,
CH ₂ (OEt) ₂ , CH ₂ ClCH (OEt) ₂ , C
HCl ₂ CH (OEt) ₂ , CCl ₃ CH (OE
t) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) ₂ .

Compound when M is Silicon Si (OMe) ₄ , Si contained in the formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (OE contained in the formula XSi (OR) ₃
t) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ , H
Si (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR) ₂
Included in Me ₂ Si (OMe) ₂ and Me ₂ Si (OE
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ Si
H (OEt) ₂ ; MeBrSi (OEt) ₂ : X ₃ Si
Me ₃ SiOMe, Me ₃ SiOEt contained in OR,
Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE
t, Ph ₃ SiOEt.

Compound in which M is Boron B (OEt) ₃ and B (OB contained in Formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

Compound in which M is aluminum Al (OMe) ₃ , Al contained in the formula Al (OR) ₃
(OEt) ₃ , Al (OPr) ₃ , Al (Oi-Pr)
₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al
(OHe) ₃ , Al (OPh) ₃ .

Compound in which M is Phosphorus P (OMe) ₃ , P (OE) included in Formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ .

Further, the magnesium compound is a periodic table.
Complexes of Group II or Group IIIa metal (M) with organic compounds
Can also be used. The complex has the general formula MgR¹R²
・ N (MR³ _m). As the metal,
Minium, zinc, calcium, etc., R³Has 1 carbon
~ 12 alkyl groups, cycloalkyl groups, aryl
And an aralkyl group. In addition, m is the valence of the metal M
And n represents a number of 0.1 to 10. MR³ _mRepresented by
Specific examples of the compound include AlMe₃, AlEt ₃,
Ali-Bu₃, AlPh₃, ZnMe₂,, ZnEt
₂, ZnBu₂, ZnPh₂, CaEt₂, CaPh₂
Etc.

(3) Titanium Compound The titanium compound is a compound of divalent, trivalent and tetravalent titanium. Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxy titanium, trichlorobutoxy titanium and dichloro. Examples thereof include rudiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlortributoxy titanium, tetrabutoxy titanium and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

(4) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples thereof include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols and ethers are preferably used.

Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, and malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
Examples thereof include aromatic polycarboxylic acids such as mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate,
Monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p
-Ethyl tertiary butyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used,
Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
Butyric acid bromide, butyric acid iodide, pivalic acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, Succinic acid chloride, succinic acid bromide,
Glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride,
Sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-
Cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride,
Benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride,
Examples thereof include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol,
2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-
Octylphenol and the like.

The ethers are represented by the general formula ROR ¹ . In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R and R ¹ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether,
Examples include diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole and ethyl phenyl ether.

The component A is prepared by contacting a metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) in that order. After contacting component 1 and component 2,
Component 4 and component 3 are contacted in that order. Component 1 and component 2 are contacted, component 3 and component 4 are simultaneously used for contact, component 2 and component 3 are contacted, then component 4 and component 1 are contacted in that order, component 2 and component 4, then contacting component 3 and component 1 in that order,
A method may be employed in which the components 2, 3, and 4 are contacted at the same time, and then the component 1 is contacted. It is also possible to contact with the halogen-containing compound before contacting with component 3.

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, Group IIa and IVa of the periodic table.
Examples thereof include halides of group elements and Va group elements (hereinafter referred to as metal halides).

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetrachloride. Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins are chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene and hexachlorocyclohexane for alicyclic compounds, and chlorobenzene, bromobenzene, o- for aromatic compounds.
Examples thereof include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride and p-chlorobenzotrichloride. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, any one or two or more hydrogen atoms other than hydroxyl groups in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule are substituted with halogen atoms. Means a compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is preferable. Examples of these compounds include 2-chloroethanol and 1-chloro-
2-propanol, 3-chloro-1-propanol, 1
-Chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6
-Chlor-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-
Chlorbenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-
(M, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol,
Chlorhydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p)
-Chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6
-Chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2-butanol,
2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p)-
Bromphenol, 4-bromoresorcin, (m, o,
p) -fluorophenol, p-iodophenol: 2,
2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-
Chlor-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1- Naphthol: 2,2,2-
Trichloroethanol, 1,1,1-trichloro-2-
Propanol, β, β, β-trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,4,5
-Trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3
5-tribromo-2-hydroxytoluene, 2,3,5
-Tribromo-4-hydroxytoluene, 2,2,2-
Trifluoroethanol, α, α, α-trifluoro-
m-cresol, 2,4,6-triiodophenol:
2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetra Examples thereof include fluorophenol and tetrafluororesorcin.

As the silicon halide compound having a hydrogen-silicon bond, HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S may be used.
iCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ ,
_{H (t-C 4 H 9} ) SiCl 2, HC 6 H 5 SiC
l ₂ , H (CH ₃ ) ₂ SiCl, H (i-C ₃ H ₇ ) S
_{iCl, H 2 C 2 H 5} SiCl, H 2 (n-C 4 H 9)
SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiC
1 (C ₆ H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples thereof include chlorides, fluorides, bromides and iodides of i, particularly BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlCl ₃ ,
SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferable.

The contact with the component 1, the component 2, the component 3 and the component 4, and the halogen-containing compound which can be contacted as necessary is carried out by mixing and stirring in the presence or absence of an inert medium. This is done by mechanical co-milling. The contact can be performed under heating at 40 to 150 ° C.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. .

Specific examples of the method for preparing the component A in the present invention include JP-A-58-162607 and JP-A-55-949.
09, 55-115405, 57-10810.
No. 7, No. 61-21109, No. 61-174204
No. 61-174205, No. 61-174206
No. 62-7706 and the like. More specifically,

A method of bringing a reaction product of a metal oxide and magnesium dialkoxide into contact with an electron-donating compound and a tetravalent titanium halide (Japanese Patent Laid-Open No. 58-162).
No. 607),

A method of bringing a reaction product of an inorganic oxide and a magnesium hydrocarbyl halide compound into contact with a Lewis base compound and titanium tetrachloride (JP-A-55-9).
4909 publication),

A method of bringing a reaction product of a porous carrier such as silica and an alkylmagnesium compound into contact with an electron-donating compound and a silicon halide compound before bringing them into contact with a titanium compound (JP-A-55-115405; 5
7-108107),

A method of contacting a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polyvalent carboxylic acid having a carboxyl group at the ortho position or a derivative thereof, and a titanium compound (JP-A-61-174204).

A method of bringing a metal oxide, an alkoxy-containing magnesium compound, a silicon compound having a hydrogen-silicon bond, an electron donating compound and a titanium compound into contact with each other (JP-A-61-174205),

A method of contacting a metal oxide, an alkoxy-containing magnesium compound, a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound (JP-A-61-174206),

A method of bringing a reaction product obtained by bringing a metal oxide, dihydrocarbyl magnesium and a halogen-containing alcohol into contact with an electron-donating compound and a titanium compound (JP-A-61-21109).
Issue),

A solid obtained by contacting a metal oxide, hydrocarbyl magnesium and a hydrocarbyloxy group-containing compound (corresponding to the alkoxy group-containing compound) with a halogen-containing alcohol;
Further, it is a method of bringing the compound into contact with an electron donating compound and a titanium compound (JP-A-62-7706). Among these, the method (1) is preferable, and the method (2) is particularly preferable. Although the component A is prepared as described above, the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Organoaluminum Compound An organoaluminum compound (hereinafter referred to as component B) has the general formula R _n AlX _3-n (wherein R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, n is any number within the range of 1 ≦ n ≦ 3), and examples thereof include trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide, and Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkylaluminum monohydride, or mixtures or complex compounds thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum io Dialkyl aluminum monohalides such as diid, diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, etc. monoalkyl aluminum dihalides, ethyl aluminum aluminum Alkyl aluminum sesquihalides such as sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum Hydride, dipropyl aluminum hydride,
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride can be mentioned. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable.

Organosilicon Compound An organosilicon compound (hereinafter referred to as component C) which is brought into contact with a solid component (component A) in the presence of an organoaluminum compound (component B).
Say. ) Is represented by the above general formula.

In the formula, the alkylene group for R ¹ is --C _n
H _2n − (n = 1 to 10), preferably −
It is represented by (poly) methylene group, and an iso-propylene group - (CH _{2) n.} The arylene group represents a divalent aromatic hydrocarbon, preferably a phenylene group, a biphenylene group or a naphthylene group, more preferably a phenylene group.

[0044] Examples of the aliphatic hydrocarbon group R ⁴ in R ^2, R ³ and OR ^4, alkyl group, such as an alkenyl group, as the肪環hydrocarbon group, cycloalkyl group, cycloalkenyl group, Shikuroaruka Examples of the aromatic hydrocarbon group such as a dienyl group and the like include an aryl group and an aralkyl group.

As the alkyl group, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl, 1-methylethenyl, 1-ethylethenyl, 1-n-propylethenyl, 1-n-butylethenyl and the like are cycloalkyl. Examples of the group include cyclopentyl, cyclohexyl, and methylcyclohexyl groups, examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, and methylcyclohexenyl groups, and examples of the cycloalkadienyl group include cyclopentadienyl and methylcyclopentadienyl. Examples of aryl groups include phenyl and indenyl groups, and phenyl, tolyl,
A xylyl group and the like are benzyl as an aralkyl group,
Examples include phenethyl and 3-phenylpropyl groups.

Specific examples of the component C are listed below. In addition,
In the following, V is CH₂= CH, and Me is CH
₃(Methyl group), Et is C₂H_Five(Ethyl group), Pr is
(C ₃H₇(Propyl group), Bu is C_FourH₉(Butyl
Group), Pe is C_FiveH₁₁(Pentyl group), Hex is C₆H
₁₃(Hexyl group), Ph is C₆H_Five(Phenyl group), c
y represents cyclo, respectively. In the chemical formula below
[OC (= CH₂) Me] C (= CH₂) Me is 1-
Methylethenyl was replaced with [OC (= CH₂) Et] C (=
CH₂) Et represents 1-ethylethenyl, respectively.

(1) When x = 1, y = 0, z = 3 VC₂H_Four-Si (Oi-Pr)₃, V-C₂H_Four−
Si (On-Bu)₃, V-C₂H_Four-Si (Os-B
u)₃, V-C₂H_Four-Si (Ot-Bu)₃, V-C
₂H_Four-Si (On-Pe)₃, V-C₂H_Four-Si
(On-Hex) ₃, V-C₂H_Four-Si [OC (= C
H₂) Me]₃, V-C₂H_Four-Si [OC (= C
H₂) Et]₃, V-C₃H₆-Si (Oi-P
r)₃, V-C₃H₆-Si (On-Bu)₃, V-C
₃H₆-Si (Os-Bu)₃, V-C₃H₆-Si
(Ot-Bu)₃, V-C₃H₆-Si (On-Pe)
₃, V-C₃H₆-Si (On-Hex) ₃, V-C₃
H₆-Si [OC (= CH₂) Me]₃, V-C₃H₆
-Si [OC (= CH₂) Et]₃, V-C_FourH₈-S
i (Oi-Pr)₃, V-C_FourH₈-Si (On-B
u)₃, V-C_FourH₈-Si (Os-Bu)₃, V-C
_FourH₈-Si (Ot-Bu)₃, V-C_FourH₈-Si
(On-Pe)₃, V-C_FourH₈-Si (On-He
x) ₃, V-C_FourH₈-Si [OC (= CH₂) Me]
₃, V-C_FourH₈-Si [OC (= CH₂) Et]₃，
V-C_FiveH_Ten-Si (Oi-Pr)₃, V-C_FiveH_Ten−
Si (On-Bu)₃, V-C_FiveH_Ten-Si (Os-B
u)₃, V-C_FiveH_Ten-Si (Ot-Bu)₃, V-C
_FiveH_Ten-Si (On-Pe)₃, V-C_FiveH_Ten-Si
(On-Hex) ₃, V-C_FiveH_Ten-Si [OC (= C
H₂) Me]₃, V-C_FiveH_Ten-Si [OC (= C
H₂) Et]₃, V-C₆H₁₂-Si (Oi-P
r)₃, V-C₆H₁₂-Si (On-Bu)₃, V-C
₆H₁₂-Si (Os-Bu)₃, V-C₆H₁₂-Si
(Ot-Bu)₃, V-C₆H₁₂-Si (On-Pe)
₃, V-C₆H₁₂-Si (On-Hex) ₃, V-C₆
H₁₂-Si [OC (= CH₂) Me]₃, V-C₆H₁₂
-Si [OC (= CH₂) Et]₃, V-C₂H_Four-S
i (OPh)₃, V-C₂H_Four-Si (OcyHex)
₃, V-C_FourH₈-Si (OPh)₃, V-C_FourH₈−
Si (OcyHex)₃, V-C₆H₁₂-Si (OP
h)₃, V-C₆H₁₂-Si (OcyHex)₃, V-
C₆H_Four-Si (Oi-Pr)₃, V-C₆H_Four-Si
(Ot-Bu)₃.

(2) When x = 1, y = 1, z = 2 VC₂H_Four-Si (Me) (Oi-Pr)₂, V-C
₂H_Four-Si (Me) (Ot-Bu)₂, V-C₂H_Four
-Si (Et) (Oi-Pr)₂, V-C₂H _Four-Si
(N-Pr) (Ot-Bu)₂, V-C₂H_Four-Si
(Ot-Bu) (Oi-Pr)₂, V-C_FourH₈-Si
(Me) (Oi-Pr)₂, V-C_FourH₈-Si (E
t) (Ot-Bu)₂, V-C_FourH₈-Si (n-P
r) (Oi-Pr)₂, V-C_FourH₈-Si (i-P
r) (Ot-Bu)₂, V-C_FourH₈-Si (Ot-B
u) (Oi-Pr)₂, V-C₆H₁₂-Si (Me)
(Oi-Pr)₂, V-C₆H₁₂-Si (Me) (Ot
-Bu)₂, V-C₆H₁₂-Si (Ot-Bu) (Oi
-Pr)₂, V-C₆H₁₂-Si (Oi-Pr) (Ot
-Bu)₂, V-C₂H_Four-Si (Ph) (Oi-P
r)₂, V-C₂H_Four-Si (cyHex) (Oi-P
r)₂, V-C_FourH₈-Si (Ph) (Oi-P
r)₂, V-C_FourH₈-Si (cyHex) (Oi-P
r)₂, V-C₆H₁₂-Si (Ph) (Oi-P
r)₂, V-C₆H₁₂-Si (cyHex) (Oi-P
r)₂, V-C₆H_Four-Si (Me) (Oi-P
r)₂, V-C₆H_Four-Si (Me) (Ot-B
u)₂.

(3) When x = 2, y = 0, z = 2 (VC₂H_Four)₂Si (Oi-Pr)₂, (VC₂
H_Four)₂Si (On-Bu)₂, (VC₂H_Four)₂S
i (Os-Bu)₂, (VC₂H_Four)₂Si (Ot-
Bu)₂, (VC₂H_Four)₂Si (On-Pe)₂，
(VC₂H_Four)₂Si (On-Hex)₂, (VC
₂H_Four)₂Si [OC (= CH₂) Me]₂, (VC
₂H_Four)₂Si [OC (= CH₂) Et]₂, (VC
₃H₆)₂Si (Oi-Pr)₂, (VC₃H₆)₂
Si (On-Bu)₂, (VC₃H₆)₂Si (Os
-Bu)₂, (VC₃H₆)₂Si (Ot-B
u)₂, (VC₃H₆)₂Si (On-Pe)₂，
(VC₃H₆)₂Si (On-Hex)₂, (VC
₃H₆)₂Si [OC (= CH₂) Me]₂, (VC
₃H₆)₂Si [OC (= CH₂) Et]₂, (VC
_FourH₈)₂Si (Oi-Pr)₂, (VC_FourH₈)₂
Si (On-Bu)₂, (VC_FourH₈)₂Si (Os
-Bu)₂, (VC_FourH₈)₂Si (Ot-B
u)₂, (VC_FourH₈)₂Si (On-Pe)₂，
(VC_FourH₈)₂Si (On-Hex)₂, (VC
_FourH₈)₂Si [OC (= CH₂) Me]₂, (VC
_FourH₈)₂Si [OC (= CH₂) Et]₂, (VC
_FiveH_Ten)₂Si (Oi-Pr)₂, (VC_FiveH_Ten)₂
Si (On-Bu)₂, (VC_FiveH_Ten)₂Si (Os
-Bu)₂, (VC_FiveH_Ten)₂Si (Ot-B
u)₂, (VC_FiveH_Ten)₂Si (On-Pe)₂，
(VC_FiveH_Ten)₂Si (On-Hex)₂, (VC
_FiveH_Ten)₂Si [OC (= CH₂) Me]₂, (VC
_FiveH_Ten)₂Si [OC (= CH₂) Et]₂, (VC
₆H₁₂)₂Si (Oi-Pr)₂, (VC₆H₁₂)₂
Si (On-Bu)₂, (VC₆H₁₂)₂Si (Os
-Bu)₂, (VC₆H₁₂)₂Si (Ot-B
u)₂, (VC₆H₁₂)₂Si (On-Pe)₂，
(VC₆H₁₂)₂Si (On-Hex)₂, (VC
₆H₁₂)₂Si [OC (= CH₂) Me]₂, (VC
₆H₁₂)₂Si [OC (= CH₂) Et]₂, (VC
₆H₁₂) ₂Si (OPh)₂, (VC₆H₁₂)₂Si
(OcyHex)₂.

(4) When x = 2, y = 1, z = 1 (VC₆H₁₂)₂Si (Me) (Ot-Bu), (V
-C₆H₁₂)₂Si (Me) (On-Pe), (VC)
₆H₁₂)₂Si (Et) (On-Hex), (VC)₆
H₁₂)₂Si (Ot-Bu) (Oi-Pr), (VC)
₆H₁₂)₂Si (On-Hex) (Ot-Bu), (V
-C₆H₁₂)₂Si (Ph) (OPh) ₂, (VC₆
H₁₂)₂Si (cyHex) (OcyHex).

The contact between the prepolymerized solid component (component A) and the organosilicon compound (component C) is carried out in the presence of the organoaluminum compound (component B). The polymer of the component C is incorporated into the component A by this catalyst (hereinafter referred to as prepolymerization).

The prepolymerization is preferably carried out in the presence of the above-mentioned inert medium. The prepolymerization is usually performed at a temperature of 100 ° C. or lower, preferably −30 ° C. to + 50 ° C., more preferably −30 ° C.
It is carried out at a temperature of 5 ° C to + 30 ° C. The polymerization method may be a batch method or a continuous method, or may be a multi-step polymerization of two or more steps. When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed. Component B is used so that the concentration in the prepolymerization system is 50 to 500 mmol / liter, preferably 80 to 200 mmol / liter, and 4 to 50
It is used in an amount of 000 mol, preferably 6 to 1,000 mol.

The prepolymerization may be carried out in the presence of an electron donating compound. The electron-donating compound is appropriately selected from the above-mentioned compounds used when preparing the component A, and also includes an electron-donating compound composed of an organosilicon compound and a hetero atom such as nitrogen, sulfur, oxygen or phosphorus. An electron donating compound containing can also be used.

The organic silicon compound may be an organic silicon compound having a Si--O--C bond or a Si--N--C bond, preferably a compound having a Si--O--C bond. Such compounds include those represented by the general formula R _n Si
(OR ¹ ) _4-n [wherein R represents a hydrocarbon group or a halogen atom, R ¹ represents a hydrocarbon group, and 0 ≦ n ≦ 3 is shown. ] The compound represented by these is mentioned. Examples of the hydrocarbon group represented by R in the above general formula include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkadienyl group, a cycloalkenyl group and a cycloalkazinyl group. Examples of the halogen atom of R include chlorine, bromine, iodine and the like. Examples of the hydrocarbon group for R ¹ include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. Furthermore, n hydrocarbons of R and (4-
n) The hydrocarbon groups of R ¹ of OR ¹ may be the same or different.

Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, Isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexadiene Syloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, Examples thereof include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

Specific examples of the electron-donating compound containing a hetero atom include compounds containing a nitrogen atom:
6,6-Tetramethylpiperidine, 2,6-Dimethylpiperidine, 2,6-Diethylpiperidine, 2,6-Diisopropylpiperidine, 2,6-Diisobutyl-4-methylpiperidine, 1,2,2,6,6- Pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine,
2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 1,2,
2,5,5-pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 1, Two
4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-methylpyrrole, 2,5
-Dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc., as a compound containing a sulfur atom, thiol Phenol, thiophene,
Ethyl 2-thiophenecarboxylate, Ethyl 3-thiophenecarboxylate, 2-Methylthiophene, Methylmercaptan, Ethylmercaptan, Isopropylmercaptan, Butylmercaptan, Diethylthioether, Diphenylthioether, Methylbenzenesulfonate, Methylsulfite, Ethylsulfite Etc., as a compound containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,
2-methyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetrahydropyran , Dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, methyl-2,6-di-t-butylphenyl ketone, 2- Ethyl fullerate, isoamyl 2-furate, methyl 2-furate, propyl 2-furate and the like are compounds containing a phosphorus atom, such as triphenylphosphine, tributylphosphine, triphenylphosphite and triben. Ruhosufaito, diethyl phosphate, and diphenyl phosphate and the like.

The electron-donating compound used if necessary is used so that the concentration in the prepolymerization system is 1 to 100 mmol / liter, preferably 5 to 50 mmol / liter.

The polymer of the component C incorporated in the component A by the prepolymerization is added in an amount of 0.05 to 500 g per 1 g of the component A,
In particular, it is desirable that the amount is 0.2 to 50 g.

The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but from the viewpoint of preventing storage deterioration of the catalyst component,
It is particularly desirable to wash. After washing, it may be dried if necessary. When the catalyst component is stored, it is desirable to store it at a low temperature as much as possible, and a temperature range of -50 ° C to + 30 ° C, particularly -20 ° C to + 5 ° C is recommended.

Polymerization of α-Olefin The catalyst component of the present invention obtained as described above is used in combination with an organometallic compound and, if necessary, an electron donating compound to form an α-olefin having 3 to 10 carbon atoms. Are useful as catalysts for the homopolymerization of 1 or of other mono-olefins or copolymers with other mono-olefins or di-olefins having 3 to 10 carbon atoms, in particular α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4 -Methyl-1-pentene, homopolymerization of 1-hexene or the like or the above α-olefins and / or
Alternatively, it exhibits extremely excellent performance as a catalyst for random and block copolymerization with ethylene.

Organometallic compounds that can be used are organic compounds of metals of groups I to III of the periodic table. As the compound, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. The organoaluminum compound that can be used is appropriately selected from the compounds used in the prepolymerization of the solid component (component A), but trialkylaluminum, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially readily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.

Also, two or more via oxygen and nitrogen atoms.
Organo-aluminum compound with aluminum
It can be used. Examples of such compounds include (C
₂H_Five)₂AlOAl (C₂H_Five)₂, (C_FourH₉)₂
AlOAl (C_FourH ₉)₂,

[Chemical 3] Etc. can be illustrated.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride and diethylzinc, and LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

The electron donating compound which can be optionally combined with the catalyst component and the organometallic compound of the present invention is selected from electron donating compounds which may be used in the prepolymerization of the component A. It is selected appropriately. Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

The amount of the organometallic compound used with respect to the catalyst component of the present invention is, based on 1 gram atom of titanium in the catalyst component,
Usually 1 to 2,000 gram moles, especially 20 to 500 gram moles are desirable.

The ratio of the organometallic compound to the electron donating compound is 0.1 to 40, preferably 1 to 40, preferably 1 to 10 mol of the electron donating compound.
Selected in the range of 25 gram atoms.

The polymerization reaction of the α-olefin may be either a gas phase or a liquid phase. When the polymerization is carried out in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane,
It can be carried out in an inert hydrocarbon such as benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres.
Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. The amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually 3 with respect to the α-olefin.
It is selected up to 0% by weight, especially in the range 0.3 to 15% by weight. The polymerization reaction is carried out by a continuous or batch reaction, and the conditions therefor may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

[0068]

EXAMPLES The present invention will be specifically described with reference to examples and application examples. The percentages (%) in the examples are by weight unless otherwise specified. The flexural modulus in the polymer was measured according to JIS K 7203-1982. Example 1 Preparation of component A A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, silicon oxide (D
AVISON, trade name G-952) was fired in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours, and then 5 g and 40 ml of n-heptane were added. Furthermore n
-Butylethylmagnesium (hereinafter referred to as BEM)
20% n-heptane solution (manufactured by Texas Alkyls,
20 ml of trade name MAGALA BEM) was added, and the mixture was stirred at 90 ° C. for 1 hour.

After cooling the suspension to 0 ° C., a solution prepared by dissolving 11.2 g of tetraethoxysilane in 20 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes. After the dropping is completed, the temperature is raised to 50 ° C over 2 hours, and the temperature is 50 ° C.
The stirring was continued for 1 hour. After completion of the reaction, the supernatant was removed by decantation, the produced solid was washed with 60 ml of n-heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed 4 times.

To the above solid, 50 ml of n-heptane was added to form a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added to the suspension through a dropping funnel. The solution was added dropwise at 15 ° C over 15 minutes. After completion of dropping, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, 2 at room temperature with 60 ml of n-heptane.
Each time, it was washed three times with 60 ml of toluene.
To the solid component I obtained above, 10 ml of n-heptane and 40 ml of titanium tetrachloride were added, the temperature was raised to 90 ° C., and 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added.
Add over minutes. Then, the temperature was raised to 115 ° C. and the reaction was performed for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Furthermore, n-heptane 15 ml and titanium tetrachloride 40
ml was added and reacted at 115 ° C. for 2 hours. After the reaction,
The solid substance obtained was stirred with 60 ml of n-hexane at room temperature for 8 hours.
Washed twice. Then, it was dried at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a catalyst component (component A). This component A contained 3.1% of titanium, silicon oxide, magnesium, chlorine and di-n-butyl phthalate.

In a 500 ml reactor equipped with a prepolymerization stirrer, under a nitrogen gas atmosphere, 2.1 g of component A obtained above and 1 part of n-heptane were added.
80 ml was added and cooled to 10 ° C with stirring. Next, an n-heptane solution (2.0 mol / liter) of triethylaluminum (hereinafter abbreviated as TEAL) was added so that the TEAL concentration in the final reaction system would be 100 mmol / liter, and the mixture was stirred for 5 minutes. . Then add 100 ml of 1-hexenyltriisopropoxysilane,
It was polymerized for 4 hours. After completion of the polymerization, the solid phase portion was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 1.3 g per 1 g of component A.

Examples 2 to 6 In the prepolymerization of Example 1, 1-hexenyltriisopropoxysilane was replaced with an organosilicon compound shown in Table 1 and TEAL or TEAL was replaced with triisobutylaluminum (TIBAL). Were used at the concentrations shown in Table 1 and the prepolymerization conditions were changed as shown in Table 1 to polymerize Component C in the same manner as in Example 1 to prepare a catalyst component. In Examples 3 to 5, the electron-donating compounds shown in Table-1 were used at the concentrations shown in Table-1.

Comparative Example 1 A catalyst component (component A) was prepared in the same manner as in Example 1 except that prepolymerization was not carried out.

Comparative Examples 2 to 4 In the same manner as in Example 1, except that propylene or an organosilicon compound shown in Table 1 was used in place of 1-hexenyltriisopropoxysilane in the prepolymerization of Example 1. A catalyst component was prepared. In Comparative Example 3, T
TIBAL was used instead of EAL.

[Table 1]

Application Example 1 In a 1.5 liter stainless steel autoclave equipped with a propylene polymerization stirrer, 4 ml of a TEAL n-heptane solution (0.1 mol / liter) and n-diphenyldimethoxysilane were placed in a nitrogen gas atmosphere. 2 ml of a heptane solution (0.02 mol / l) was mixed and held for 5 minutes. Then, 1 liter of hydrogen gas as a molecular weight control agent and 1 liter of liquid propylene were injected under pressure, and then the reaction system was heated to 70 ° C. After 40 mg of the catalyst component obtained in Example 1 was charged into the reaction system, propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain white polypropylene powder. Ingredient A (1 g) · Polypropylene production amount (CE) per hour was 13.7 kg. The flexural modulus of the obtained polymer is 14,100 kgf / cm.
^{Was 2} .

Application Examples 2 to 10 The catalyst components obtained in Examples 2 to 6 and Comparative Examples 1 to 4 were used in place of the catalyst components obtained in Example 1, and diphenyldimethoxysilane was used instead of the table. Polymerization of propylene was carried out in the same manner as in Application Example 1 except that the electron-donating compound shown in 2 was used. The results are shown in Table-2.

[Table 2] Table-2 Application example Catalyst component Electron donating compound CE Bending elastic modulus (kg / g · component A) (kgf / cm ² ) 1 Example 1 Ph ₂ Si (OMe) ₂ 13.7 14,100 2 〃 2 〃 12.5 14,300 3 〃 3 〃 13.7 15,000 4 〃 4 〃 14.2 14,800 5 〃 5 PhSi (OEt) ₃ 11.0 14,500 6 〃 6 6 〃 12.8 14,100 7 Comparative example 1 Ph ₂ Si (OMe) ₂ 14.1 11,900 8 Si 〃 2 Ph ₃ 9.6 12,300 9 〃 3 〃 5.8 12,200 10 〃 4 Ph ₂ Si (OMe) ₂ 7.0 12,300

[0077]

EFFECTS OF THE INVENTION According to the present invention, by adopting the above constitution, the obtained catalyst component can be used for the polymerization of α-olefin to produce a highly rigid polymer in a high yield, and the organosilicon Since the compound is pre-polymerized, the catalyst particles have high strength, and therefore, it is possible to prevent pulverization of the polymer.

[Brief description of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst component of the present invention.

Front Page Continuation (72) Inventor Rinko Aoki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. A solid component containing (A) a metal oxide, magnesium, titanium, a halogen, and an electron-donating compound as essential components, and (B) an organoaluminum compound in the presence of:
(C) General formula: [However, R ¹ is an alkylene group or arylene group having 1 to 10 carbon atoms, R ² is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms or R ⁴ O and R ³ are carbon atoms. An aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms, R ⁴ is an aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms which is the same as or different from R ³ . x is 1 or 2, y is 0 or 1, and z is 4-xy. ] Α formed by contacting with an organosilicon compound represented by
-Olefin polymerization catalyst component.