JPH0517532A - Production of propylene copolymer - Google Patents

Abstract

PURPOSE:To produce the subject copolymer having a good balance between the transparency and rigidity thereof and having a specific ethylene content by copolymerizing propylene with ethylene in the presence of a specified polymerization catalyst CONSTITUTION:Ethylene and propylene are copolymerized in an inert hydrocarbon such as toluene in the presence of a catalyst comprising (A) a solid catalyst component containing magnesium, titanium, a halogen and an electron-donating compound as main components, (B) an organic metal compound such as trimethyl aluminum and (C) an organic silicon compound of the formula [R<1> is 1-10C hydrocarbon, R<7>3Si (R<7> is 1-10C hydrocarbon); R<2> is 1-10C hydrocarbon, R<8>O (R<8> is the same as R<7>); R<3> is 1-10C hydrocarbon, R<9>O (R<9> is the same as R<7>); R<4>, R<5> are 1-10C hydrocarbon; R<6> is 1-10C hydrocarbon, OR<10> (R<10> is the same as R<7>), etc.,][e.g. Me3Si-Si(OMe)2Me] preferably at 40-120 deg.C under a 1-60 atmospheric pressure to provide the objective copolymer having an ethylene content of 0.01-10wt.% (preferably 0.1-5wt.%).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a propylene copolymer, more specifically, it is excellent in transparency and rigidity by randomly copolymerizing propylene and a small amount of ethylene by using a specific catalyst component. And a method for producing a polypropylene copolymer.

[0002]

2. Description of the Related Art Highly crystalline polypropylene produced by using various types of highly stereoregular catalysts is excellent in rigidity and heat resistance, but is a milky white resin and has a higher transparency depending on its use. May be desired. As a means for improving transparency, a method of producing a random copolymer by adding a small amount of ethylene when polymerizing propylene is well known. However, as the proportion of ethylene added increases, the transparency is improved, but the crystallinity of polypropylene is disturbed, and the rigidity, which is the original characteristic of polypropylene, is impaired.

On the other hand, various methods for improving the rigidity have been proposed, but most of them are methods in which post-treatment such as adding a nucleating agent to polypropylene is carried out. Therefore, the cost is high in terms of the process, and the appearance of the molded product may be impaired depending on the additive. Although a method of improving the rigidity by a polymerization method without treatment with an additive has been proposed, the rigidity is insufficient in each case.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for obtaining a propylene copolymer having an excellent balance of transparency and rigidity.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that the present invention can be carried out by polymerizing propylene with a small amount of ethylene using a polymerization catalyst containing a specific organosilicon compound as an essential component. The present invention has been completed by finding that the object of can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is (A) a solid catalyst component containing a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organometallic compound and (C). General formula

[Chemical 2] [However, R ¹ is a hydrocarbon group or R ₃ ⁷ Si of 1 to 10 carbon atoms, R ² is from 1 to 10 carbon atoms hydrocarbon group or R ⁸ O, R ³ is 1 to 10 carbon atoms Hydrocarbon group or R ⁹ O, R ⁴ and R ⁵ are the same or different and have 1 to 1 carbon
0 hydrocarbon group, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms, OR ¹⁰ or SiR ₃ ¹¹ , and R ^{7 to} R ¹¹ are the same or different hydrocarbon groups having 1 to 10 carbon atoms. is there. ] It exists in the manufacturing method of the propylene copolymer whose ethylene content is 0.01 to 10 weight% which consists of copolymerizing propylene and ethylene in the presence of the catalyst for polymerization which consists of the organosilicon compound represented by these.

Solid Catalyst Component The solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, contains metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components. Such components are usually prepared by bringing a metal oxide, a magnesium compound, a titanium compound and an electron donating compound into contact with each other, and in the case where each of the above compounds does not have a halogen, a halogen-containing compound.

(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. These metals
The oxide is usually used in powder form. Powder
The shape, such as size and shape, of the resulting olefin polymer
Since it often affects the shape of the
And is desirable. Metal oxides are used to remove poisonous substances.
For the purpose of removal, etc., bake at the highest temperature possible and
It is desirable to handle it so that it does not come into direct contact with the air.

(2) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² represent 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 magnesium compound can be prepared from metallic magnesium or another magnesium compound when the component A is prepared. As one example thereof, metal magnesium, a halogenated hydrocarbon and an alkoxy group-containing compound 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 2
0 hydrocarbon group, M is boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m
Indicates the valence of M, m> n ≧ 0. ] The method of making it contact is mentioned. X in the general formula of the alkoxy group-containing compound
Examples of the hydrocarbon group for R and R 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 (cyHe), 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.

Compounds where M is carbon C (OR)_FourIncluded in C (OMe)_Four, C (OE
t)_Four, C (OPr) _Four, C (OBu)_Four, C (Oi-
Bu)_Four, C (OHe)_Four, C (OOct)_Four: Formula X
C (OR)₃HC (OMe) contained in₃, HC (OE
t)₃, HC (OPr)_3,HC (OBu)₃, HC
(OHe)₃, HC (OPh)₃MeC (OM
e)₃, MeC (OEt)₃, EtC (OMe)₃ , E
tC (OEt)₃, CyHeC (OEt)₃, PhC
(OMe)₃, PhC (OEt)₃, CH₂ClC (O
Et)₃, MeCHBrC (OEt)₃, MeCHCl
C (OEt) ₃; ClC (OMe)₃, ClC (OE
t)₃, ClC (Oi-Bu)₃, BrC (OE
t)₃Formula X₂C (OR)₂Included in MeCH (O
Me)₂, MeCH (OEt)₂, CH₂(OMe)₂,
 CH₂(OEt)₂, CH₂ClCH (OEt)₂，
CHCl₂CH (OEt)₂, CCl₃CH (OEt)
₂, CH ₂BrCH (OEt)₂, PhCH (OEt)
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 (O contained in the formula XSi (OR) ₃
Et) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ ,
HSi (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 contained in Me ₂ Si (OMe) ₂ and Me ₂ Si (O
Et) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ S
iH (OEt) ₂ ; MeBeSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE included in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compound where M is boron Formula B (OR)₃Included in B (OEt)₃, B (OB
u)₃, B (OHe) ₃, B (OPh)₃.

Compound when 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 .

Compounds where M is phosphorus P (OR)₃Included in P (OMe)₃, P (OE
t)₃, P (OBu) ₃, P (OHe)₃, P (OP
h)₃.

Further, as the magnesium compound, a complex with an organic compound of Group II or Group IIIa metal (M) of the periodic table can be used. The complex has the general formula MgR ¹ R
It is represented by ² · n (MR ³ _m ). The metal is aluminum, zinc, calcium or the like, and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. Further, m represents the valence of the metal M, and n represents the number of 0.1 to 10. Specific examples of the compound represented by MR ³ _m include AlMe ₃ , AlEt ₃ ,
_{Ali-Bu 3, AlPh 3,} ZnMe 2, ZnE
t ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh
₂ etc.

(3) Titanium Compound The titanium compound is a divalent, trivalent or tetravalent titanium compound, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium and dichlorotitanium. 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 and carbonic acid esters. 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, 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-mentioned 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. It is also possible to use monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride.

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-tertiarybutylphenol,
Examples include n-octylphenol.

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 3,
Component 4 and component 3 are contacted in that order. Component 1 and component 2 are contacted, then 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 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, 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, tetra Chlorbisphenol A, tetrabromobisphenol A, 2,2
3,3-tetrafluoro-1-propanol, 2,3
5,6-tetrafluorophenol, tetrafluororesorcin, etc. may be mentioned.

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 SiCl
_{2, H (CH 3) 2} SiCl, H (i-C 3 H 7) 2 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 , TlC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are suitable.

The contact with the component 1, the component 2, the component 3 and the component 4 and, optionally, the halogen-containing compound which can be contacted, 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, No. 61-174205, No. 61-174206
No. 62-7706 and the like. More specifically,

A method in which a reaction product of a metal oxide and magnesium dialkoxide is contacted with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162).
No. 607), a method of contacting a reaction product of an inorganic oxide and a magnesium hydrocarbyl halide compound with a Lewis base compound and titanium tetrachloride (JP-A-55).
-94909), a reaction product of a porous carrier such as silica and an alkyl magnesium compound is contacted with an electron donating compound and a silicon halide compound before contacting with a titanium compound (JP-A-55-11540).
5, JP-A-57-108107), 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-6-63).
1-174204), a method of contacting a metal oxide, an alkoxy group-containing magnesium compound, a silicon compound having a hydrogen-silicon bond, an electron donating compound and a titanium compound (JP-A-61-174205),
A method of contacting a metal oxide, an alkoxy group-containing magnesium compound, a halogen element or a halogen-containing compound, an electron donating compound and a titanium compound (JP-A-61-161).
No. 174206), a method of contacting a reaction product obtained by contacting a metal oxide, dihydrocarbyl magnesium and a halogen-containing alcohol with an electron donating compound and a titanium compound (JP-A-61-161).
21109), 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, and further with an electron-donating compound and titanium. This is a method of contacting with a compound (Japanese Patent Laid-Open No. 62-7706).
Among these, the method (1) is preferable, and the method (2) is particularly preferable.

Component A is prepared as described above,
Component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

The component A may further contain an olefin polymer produced in the component A by contacting with an olefin in the presence of an organoaluminum compound. The organoaluminum compound is selected from the organometallic compounds described below, which are one component of the catalyst of the present invention.

As the olefin, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene can be used in addition to ethylene. The contact with the olefin is preferably carried out in the presence of the above-mentioned inert medium. Contact is usually 100 ° C or lower, preferably -10 to +
It is carried out at a temperature of 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 10 per 1 g of the component A.
It is 0 g.

For the contact between the component A and the olefin, an electron donating compound may be present together with the organoaluminum compound. The electron-donating compound is the compound used in preparing the component A and the Si—O—C bond or Si—N.
It is selected from organic silicon compounds having a -C bond. The component A contacted with the olefin can be washed with the above-mentioned inert medium, if necessary, and can be further dried.

Organometallic Compounds Organometallic compounds (hereinafter referred to as component B) are represented by I in the periodic table.
Organic compounds of Group III to Group III metals. As the component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R _n Al
X _3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1
It is an arbitrary number within the range of ≦ n ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide, a dialkylaluminum monohydride and the like having 1 to 18 carbon atoms.
Especially preferred are alkylaluminum compounds, preferably 2 to 6 carbon atoms, or mixtures or complex compounds thereof. Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide,
Dialkyl aluminum monohalides such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monoalkyl aluminum dihalides such as isobutyl aluminum dichloride, ethyl aluminum sesquichloride, etc. Alkyl aluminum sesquihalide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide and other dialkyl aluminum monoalkoxides, dimethyl aluminum hydride, diethyl ether Aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.

It is also possible to use an organoaluminum compound in which two or more aluminum atoms are bound to each other through an oxygen atom or a nitrogen atom. Examples of such compounds include

[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 .

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In the formula, the hydrocarbon group represented by R ^{1 to} R ¹¹ is an alkyl group,
Examples thereof include an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, 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, The decyl group and the like are alkenyl groups such as vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl and the like, cycloalkyl groups such as cyclopentyl, cyclohexyl and methylcyclohexyl groups, and cycloalkenyl groups such as cyclopentenyl. , A cyclohexenyl group, a methylcyclohexenyl group, etc., a cycloalkadienyl group, a cyclopentadienyl group, a methylcyclopentadienyl group, an indenyl group, etc., and an aryl group, a phenyl group, a tolyl group, a xylyl group, etc. Examples of the alkyl group include benzyl, phenethyl and 3-phenylpropyl groups. For R ⁴ and R ⁵ , especially methyl,
The ethyl group is preferred.

Specific examples of the component C will be listed below. In addition,
The above general formula is converted into R ¹ / R ² / R ³ // OR ⁴ / OR ⁵ / R ⁶
Is displayed. In the following, Me = methyl and Et =
Ethyl, Pr = propyl, Bu = butyl, Amy = amyl, Hex = hexyl, respectively.

1) R¹, R²And R³Is a hydrocarbon group
And R⁶Is OR^TenIn case of [R¹And R ²And R³Is the same
R at the time of one¹, R¹And R²R are the same when¹ ₂/ R³
And OR ^Four, OR^FiveAnd OR^TenWhen the same^FourWhen,
OR^FourAnd OR^FiveAre the same (OR^Four)₂/ OR^TenToso
Display each. ) Me // OMe, Me // OEt, Et // OMe, Et // O
Et, Me₂/ N-Pr // OMe, Me₂/ N-Pr //
OEt, Me₂/ T-Bu // OMe, Me₂/ T-Bu /
/ OEt, Et₂/ Me // OMe, Et₂/ Me // OE
t, Me // (OMe)₂/ OEt, Me // (OMe)₂
/ Oi-Pr, Me // (OMe)₂/ Ot-Bu, Me
// (OMe)₂/ On-Hex, Et // (OMe)₂/
Oi-Pr, Me₂/ T-Bu // (OMe)₂/ Ot-
Bu, Et₂/ Me // (OMe) ₂/ On-Hex.

2) When R ¹ is R ⁷ ₃ Si, R ² and R ³ are hydrocarbon groups and R ⁶ is OR ¹⁰ , [when R ² and R ³ are the same, R ⁷ ₃ Si / R ² ₂ OR
^{When 4} , OR ⁵ and OR ¹⁰ are the same, it is displayed as OR ^4, and when OR ⁴ and OR ⁵ are the same, it is displayed as (OR ⁴ ) ₂ / OR ¹⁰ . ] Me ₃ Si / Me ₂ // OMe, Me ₃ Si / Me ₂ // O
Et, Et ₃ Si / Me ₂ // OMe, Et ₃ Si / Me
₂ // OEt, Me ₃ Si / Et ₂ // OMe, Me ₃ Si
/ Et ₂ // OEt, Et ₃ Si / Et ₂ // OMe, Et
₃ Si / Et ₂ // OEt, Me ₃ Si / Me / Et // O
Me, Et ₃ Si / Me / Et // OEt, Me ₃ Si /
Et / i-Pr // OEt, Et 3 Si / Me / t-Bu
// OMe, Me ₃ Si / Me ₂ // (OMe) ₂ / Ot-
Bu, Me ₃ Si / Me ₂ // (OEt) ₂ / On-He
x, Et ₃ Si / Me ₂ // (OMe) ₂ / Os-Am
y, Me ₃ Si / Me / Et // (OMe) ₂ / Ot-B
_{u, Et 3 Si / Me /} Et // (OEt) 2 / On-H
ex, Et ₃ Si / Me / i-Pr // (OEt) ₂ / t
_{-Bu, Et 3 Si / Me /} t-Bu // (OMe) 2 /
Os-Amy.

3) R¹, R²And R³Is a hydrocarbon group
And R⁶Is a hydrocarbon group [R¹, R²And R³R are the same when¹And R¹And R
²R are the same when¹ ₂/ R³And OR^FourAnd OR^FiveAre the same
At the time of (OR^Four)₂/ R⁶Are displayed respectively. ] Me // (OMe)₂/ Me, Me // (OEt)₂/ M
e, Me // (OMe)₂/ Et, Me // (OEt)₂/
Et, Me // (OMe)₂/ I-Pr, Me // (OE
t)₂/ I-Pr, Me // (OMe)₂/ T-Bu, M
e // (OEt)₂/ T-Bu, Me // (OMe)₂/ N
-Bu, Me // (OEt)₂/ N-Bu, Me // (OM
e)₂/ S-Bu, Me // (OEt)₂/ S-Bu, E
t // (OMe)₂/ Me, Et // (OEt)₂/ Me,
Et // (OMe)₂/ I-Pr, Et // (OEt)₂/
i-Pr, Me₂/ N-Pr // (OMe)₂/ Me, M
e₂/ N-Pr // (OEt)₂/ Me, Me₂/ T-B
u // (OMe)₂/ Et, Me ₂/ T-Bu // (OE
t)₂/ Et, Me₂/ N-Bu // (OEt)₂/ M
e, Me₂/ N-Bu // (OEt)₂/ Me, Me₂/
n-Hex // (OMe)₂/ Me, Me₂/ N-Hex
// (OEt)₂/ Me, Me₂/ S-Amy // (OM
e)₂/ Me, Me₂/ S-Amy // (OEt)₂/ M
e, Me // (OMe)₂/ Cyclopentyl, Me // (O
Me)₂/ Cyclopentadienyl.

4) R¹Is R⁷ ₃Si, R²And R³But
Hydrocarbon group, R⁶Is a hydrocarbon group [R²And R³R are the same when⁷ ₃Si / R¹ ₂And O
R^FourAnd OR^FiveAre the same (OR^Four)₂/ R⁶And that
Displayed. ] Me₃Si / Me₂// (OMe)₂/ Me, Me₃Si
/ Me₂// (OEt) ₂/ Me, Et₃Si / Me₂//
(OMe)₂/ I-Pr, Et₃Si / Me₂// (OM
e)₂/ N-Hex.

[0049] 5) R ^1, R ² and R ³ is a hydrocarbon group, when if R ⁶ is a SiR ¹¹ ₃ [R ^1, R ² and R ³ are identical and R ^1, R ² and R
^{When 3} is the same, R ² ₂ / R ³ is displayed, and when OR ⁴ and OR ⁵ are the same, (OR ⁴ ) ₂ / SiR ¹¹ ₃ is displayed. ] Me // (OMe) ₂ / SiMe ₃ , Me // (OEt) ₂
/ SiMe ₃ , Me // (OMe) ₂ / SiEt ₃ , Et
// (OMe) ₂ / SiMe ₃ , Et // (OEt) ₂ / S
iMe ₃ , Et // (OMe) ₂ / SiEt ₃ , Et //
(OEt) ₂ / SiEt ₃ , Me ₂ / n-Pr // (OM
e) ₂ / SiMe ₃ , Me ₂ / t-Bu // (OMe) _{2
/ SiMe 3, Et 2 / i} -Pr // (OEt) 2 / Si
Et ₃ .

6) R¹Is R⁷ ₃Si, R²And R³But
Hydrocarbon group, R⁶Is SiR¹¹ ₃In case of [R²And R³R are the same when⁷ ₃Si / R² ₂And O
R^FourAnd OR^FiveAre the same (OR^Four)₂/ SiR¹¹ ₃When
Display each. ] Me₃Si / Me₂// (OMe)₂/ SiMe₃, Me
₃Si / Et₂// (OMe)₂/ SiMe₃, Me₃S
i / Me₂// (OEt)₂/ SiMe₃, Me ₃Si /
Me₂// (OMe)₂/ SiEt₃, Me₃Si / Me
/ Et // (OEt)₂/ SiMe₃, Et₃Si / Et
₂// (OEt)₂/ SiMe₃, Et₃Si / Et₂//
(OEt)₂/ SiEt₃, Me₃Si / Me / n-B
u // (OEt)₂/ SiMe₃.

7) When R ¹ and R ² are hydrocarbon groups, R ³ is R ⁹ O, and R ⁶ is OR ¹⁰ [When R ¹ and R ² are the same, R ¹ ₂ / R ⁹ O, O
When R ⁴ , OR ⁵ and OR ¹⁰ are the same, OR ⁴ and OR ⁴
And OR ⁵ are the same, they are displayed as (OR ⁴ ) ₂ / OR ¹⁰ . ] Me ₂ / MeO // OMe, Me ₂ / MeO // OEt, M
e ₂ / EtO // OMe, Me ₂ / EtO // OEt, Me
_{2 / i-PrO // OMe,} Me 2 / i-PrO // OE
t, Me ₂ / t-BuO // OMe, Me ₂ / t-BuO
_{// OEt, Me 2 / n-} HexO // OMe, Me 2 / n
-HexO // OEt, Et ₂ / MeO // OMe, Et ₂
/ MeO // OEt, Me / t-Bu / MeO // OMe,
Me / t-Bu / MeO // OEt, (i-Pr) ₂ / M
eO // OMe, (i-Pr) ₂ / MeO // OEt, Me
/ S-Amy / MeO // OMe, Me / s-Amy / M
eO // OEt, Me ₂ / MeO // (OMe) ₂ / OE
t, Me ₂ / MeO // (OEt) ₂ / Ot-Bu, Me
_{2 / EtO // (OMe) 2} / On-Hex, Me 2 / E
tO // (OEt) ₂ / Oi-Pr, Et ₂ / MeO //
(OMe) ₂ / OEt, Et ₂ / MeO // (OEt) ₂
/ Ot-Bu, Et ₂ / EtO // (OMe) ₂ / On-
_{Hex, Et 2 / EtO // (} OEt) 2 / Oi-Pr,
Me / t-Bu / MeO // OMe / OEt / Oi-P
r, Et / i-Pr / EtO // OMe / OEt / On-
Amy.

8) When R ¹ is R ⁷ ₃ Si, R ² is a hydrocarbon group, R ³ is R ⁹ O, and R ⁶ is OR ¹⁰ , [OR ⁴ , when OR ⁵ and OR ¹⁰ are the same, OR ⁴ and O
When R ⁴ and OR ⁵ are the same, they are displayed as (OR ⁴ ) ₂ / OR ⁹ . ] Me ₃ Si / Me / MeO // OMe, Me ₃ Si / Me
/ MeO // OEt, Me ₃ Si / Me / EtO // OM
e, Et ₃ Si / Et / MeO // OMe, Et ₃ Si /
Me / EtO // OMe, Et ₃ Si / Me / MeO // O
Et, Et ₃ Si / Et / EtO // OEt, Me ₃ Si
/ T-Bu / MeO // OMe , Et 3 Si / i-Pr /
EtO // OEt, Me ₃ Si / Me / MeO // (OM
e) ₂ / Ot-Bu, Me ₃ Si / Et / MeO // (O
Et) ₂ / On-Pr, Me ₃ Si / Et / EtO //
(OEt) ₂ / Oi-Pr, Et ₃ Si / Me / MeO
// (OEt) ₂ / Oi-Pr, Et ₃ Si / Et / Et
O // (OEt) ₂ / Oi-Pr, Et ₃ Si / Me / E
tO // (OMe) ₂ / Os-Amy.

9) R¹And R²Is a hydrocarbon group, R³But
R⁹O, R⁶Is a hydrocarbon group [R¹And R²R are the same when¹ ₂/ R⁹O and OR^Four
And OR^FiveAre the same (OR^Four)₂/ R⁶And each
indicate. ] Me₂/ MeO // (OMe)₂/ Me, Me₂/ MeO /
/ (OEt)₂/ Me, Me₂/ EtO // (OMe)₂
/ Me, Me₂/ EtO // (OEt)₂/ Me, Me₂
/ I-PrO // (OMe)₂/ Me, Me₂/ I-Pr
O // (OEt) ₂/ Me, Me₂/ S-BuO // (OM
e)₂/ Me, Me₂/ S-BuO // (OEt)₂/ M
e, Me₂/ T-AmyO // (OMe)₂/ Me, Me
₂/ T-AmyO // (OEt)₂/ Me, Me₂/ N-
HexO // (OMe)₂/ Me, Me₂/ N-HexO
// (OEt)₂/ Me, Et₂/ MeO // (OMe)₂
/ Me, Et₂/ MeO // (OEt)₂/ Me, Me /
n-Pr / MeO // (OMe)₂/ Et, Me / n-P
r / MeO // (OEt)₂/ Et, Me / t-Bu / M
eO // (OMe)₂/ Me, Me / t-Bu / MeO //
(OEt)₂/ Me, Me₂/ MeO // (OMe)₂/
Et, Me₂/ MeO // (OEt)₂/ Et, Me₂/
MeO // (OMe)₂/ I-Pr, Me₂/ MeO //
(OEt)₂/ I-Pr, Me₂/ MeO // (OMe)
₂/ T-Bu, Me₂/ MeO // (OEt)₂/ T-B
u, Me₂/ MeO // (OMe)₂/ Cyclohexyl,
Me₂/ MeO // OMe / OEt / Et, Me₂/ Et
O // OMe / OEt / t-Bu, Et₂/ MeO // OM
e / OEt / i-Pr, Me / t-Bu / MeO // OM
e / OEt / Me, Et / i-Pr / EtO // OMe /
OEt / n-Hex.

10) R¹Is R⁷ ₃Si, R²Carbonized water
Base, R³Is R⁹O, R⁶Is a hydrocarbon group [OR^FourAnd OR^FiveAre the same (OR^Four)₂/ R⁶When
indicate. ] Me₃Si / Me / MeO // (OMe)₂/ Me, Me
₃Si / Et / MeO // (OMe)₂/ Me, Me₃S
i / Et / EtO // (OMe)₂/ Me, Me ₃Si /
Et / EtO // (OEt)₂/ Et, Et₃Si / Me
/ MeO // (OMe)₂/ Me, Et₃Si / Et / M
eO // (OMe)₂/ Me, Et₃Si / Et / EtO
// (OMe)₂/ Me, Et₃Si / Et / EtO //
(OEt) ₂/ Et, Me₃Si / Et / MeO // (O
Et)₂/ T-Bu, Et₃Si / Me / EtO // (O
Me)₂/ S-Bu, Me₃Si / Me / MeO // OM
e / OEt / Me, Et₃Si / Et / MeO // OMe
/ OEt / i-Pr.

11) R¹And R²Is a hydrocarbon group, R³
Is R⁹O, R⁶Is SiR¹¹ ₃In case of [R¹And R²R are the same when¹ ₂/ R⁹O and OR^Four
And OR^FiveAre the same (OR^Four)₂/ SiR¹¹ ₃Toso
Display each. ] Me₂/ MeO // (OMe)₂/ SiMe₃, Me₂/
EtO // (OMe)₂/ SiMe₃, Me₂/ MeO //
(OEt)₂/ SiMe₃, Me₂/ MeO // (OM
e)₂/ SiEt₃, Et₂/ MeO // (OMe)₂/
SiMe₃, Et ₂/ EtO // (OMe)₂/ SiMe
₃, Et₂/ MeO // (OMe)₂/ SiEt₃, Et
₂/ EtO // (OEt)₂/ SiEt₃, Me / Et /
MeO // (OEt)₂/ SiMe₃, Me / Et / Et
O // (OMe)₂/ SiEt₃, Me / t-Bu / Et
O // (OMe)₂/ SiMe₃, Et / s-Amy / M
eO // (OEt)₂/ SiMe₃, I-Pr / n-Bu
/ MeO // (OMe)₂/ SiEt₃, Me / Et / M
eO // OMe / OEt / SiMe₃, Et / t-Bu /
MeO // OMe / OEt / SiEt₃.

12) R¹Is R⁷ ₃Si, R²Carbonized water
Base, R³Is R⁹O, R⁶Is SiR ¹¹ ₃In the case of [OR^FourAnd OR^FiveAre the same (OR^Four)₂/ SiR
¹¹ ₃Is displayed. ] Me₃Si / Me / MeO // (OMe)₂/ SiM
e₃, Me₃Si / Et / MeO // (OMe)₂/ Si
Me₃, Me₃Si / Me / EtO // (OMe)₂/ S
iMe₃, Et₃Si / Me / MeO // (OMe)₂/
SiMe₃, Et₃Si / Et / MeO // (OMe)₂
/ SiMe₃, Et₃Si / Et / EtO // (OMe)
₂/ SiMe₃, Et₃Si / Me / MeO // (OM
e)₂/ SiEt₃, Et₃Si / Et / EtO // (O
Et)₂/ SiEt₃, Me₃Si / Me / MeO // O
Me / OEt / SiMe₃, Et₃Si / Et / EtO /
/ OMe / OEt / SiMe₃.

13) R ¹ is a hydrocarbon group and R ² is R
⁸ O, R ³ is R ⁹ O, and R ⁶ is OR ¹⁰ [When R ⁸ O and R ⁹ O are the same, R ¹ / (R ⁸ O)
_{When 2} and OR ⁴ , OR ⁵ and OR ¹⁰ are the same, OR
^{When 4} is the same as OR ⁴ and OR ^5, (OR ⁴ ) ₂ / O
Display as R ¹⁰ , respectively. ] Me / (MeO) ₂ // OMe, Me / (MeO) ₂ // O
Et, Et / (MeO) ₂ // OMe, Et / (MeO)
₂ // OEt, Me / (EtO) ₂ // OMe, Me / (E
tO) ₂ // OEt, Me / (n-PrO) ₂ // OMe,
Me / (n-PrO) ₂ // OEt, Me / (MeO) /
(T-BuO) // OMe, Me / (MeO) / (t-B
uO) // OEt, Me / (MeO) ₂ // (OMe) ₂ /
Ot-Bu, Me / (MeO) ₂ // (OEt) ₂ / Oi
-Pr, Me / MeO / t-BuO // (OMe) ₂ / O
n-Hex, Et / EtO / i-PrO // (OEt) ₂
/ Oi-Bu, Me / EtO / n-BuO // OMe / E
tO / On-Hex.

14) R¹Is R⁷ ₃Si, R²Is R
⁸O, R³Is R⁹O, R⁶Is OR^TenIn case of [R⁸O and R⁹R when O is the same⁷ ₃Si / (R
⁸O)₂And OR^Four, OR ^FiveAnd OR^TenWhen the same
R^FourAnd OR^FourAnd OR^FiveAre the same (OR^Four) ₂/
OR^TenAre displayed respectively. ] Me₃Si / (MeO)₂// OMe, Me₃Si / (E
tO)₂// OMe, Me₃Si / (MeO)₂// OE
t, Et₃Si / (EtO)₂// OMe, Et₃Si /
(MeO)₂// OEt, Et₃Si / (EtO)₂// O
Et, Me₃Si / (n-PrO)₂// OMe, Et₃
Si / EtO // i-PrO // OEt, Me ₃Si / Me
O / n-BuO // OMe, Me₃Si / (MeO)₂//
(OMe) ₂/ Ot-Bu, Me₃Si / (EtO)₂
// (OMe)₂/ On-Hex, Et₃Si / (Me
O)₂// (OEt)₂/ Oi-Pr, Me₃Si / Me
O / t-BuO // (OMe)₂/ Os-Amy, Et₃
Si / EtO / i-PrO // OMe / OEt / On-H
ex.

15) R¹Is a hydrocarbon group, R²Is R
⁸O, R³Is R⁹O, R⁶Is a hydrocarbon group [R⁸O and R⁹R when O is the same¹/ (R⁸O)
₂And OR^FourAnd OR^FiveAre the same (OR^Four)₂/ R
⁶Are displayed respectively. ] Me / (MeO)₂// (OMe)₂/ Me, Me / (M
eO)₂// (OEt) ₂/ Me, Et / (MeO)₂//
(OMe)₂/ Me, Et / (EtO)₂// (OEt)
₂/ Me, i-Pr / (MeO)₂// (OMe)₂/ M
e, i-Pr / (MeO)₂// (OEt)₂/ Me, n
-Bu / (MeO)₂// (OMe)₂/ Me, n-Bu
/ (MeO)₂// (OEt)₂/ Me, Me / (n-P
rO)₂// (OMe)₂/ Me, Me / (n-PrO)
₂// (OEt)₂/ Me, Me / (s-BuO)₂//
(OMe)₂/ Me, Me / (s-BuO)₂// (OE
t) ₂/ Me, Me / MeO / n-HexO // (OM
e)₂/ Me, Me / MeO / n-HexO // (OE
t)₂/ Me, Et / (MeO)₂// (OMe)₂/ E
t, Et / (MeO)₂// (OEt)₂/ Et, vinyl
/ (MeO)₂// (OMe)₂/ Vinyl, vinyl / (E
tO)₂// (OEt)₂/ Vinyl, Me / (MeO)₂
// OMe / OEt / Me, Me / (EtO)₂// OMe
/ OEt / Et, Et / (EtO)₂// OMe / OEt
/ Me, Et / (EtO)₂// OMe / OEt / Et,
Me / MeO / EtO // OMe / OEt / Et, Et /
MeO / EtO // OMe / OEt / Et.

16) R¹Is a hydrocarbon group, R²Is R
⁸O, R³Is R⁹O, R⁶Is SiR¹¹ ₃In case of [R⁸O and R⁹R when O is the same¹/ (R⁸O)
₂And OR^FourAnd OR^FiveAre the same (OR^Four)₂/ S
iR¹¹ ₃Are displayed respectively. ] Me / (MeO)₂// (OMe)₂/ SiMe₃, Me
/ (MeO)₂// (OEt)₂/ SiMe₃, Me /
(MeO)₂// (OMe)₂/ SiEt₃, Et / (M
eO)₂// (OMe)₂/ SiMe₃, Et / (Et
O)₂// (OMe) ₂/ SiMe₃, Et / (MeO)
₂// (OEt)₂/ SiMe₃, Et / (MeO)₂//
(OMe)₂/ SiEt₃, Et / (EtO)₂// (O
Et)₂/ SiEt₃, Me / MeO / EtO // OMe
/ OEt / SiMe₃, Et / MeO / EtO // OMe
/ OEt / SiEt₃, I-Pr / (MeO)₂// (O
Me) ₂/ SiMe₃, N-Bu / (MeO)₂// (O
Me)₂/ SiEt₃, Me / (s-BuO)₂// (O
Et)₂/ SiMe₃, Vinyl / (MeO)₂// OMe
/ OEt / SiMe₃.

17) R ¹ is R ⁷ ₃ Si, R ² is R
^{When 8} O and R ³ are R ⁹ O and R ⁶ is SiR ¹¹ ₃ [When R ⁸ O and R ⁹ O are the same, R ⁷ ₃ Si / (R
^{When 8} O) ₂ and OR ⁴ and OR ⁵ and OR ¹⁰ are the same, they are displayed as (OR ⁴ ) ₂ / SiR ¹¹ ₃ . ] Me ₃ Si / (MeO) ₂ // (OMe) ₂ / SiM
e ₃ , Me ₃ Si / (EtO) ₂ // (OMe) ₂ / Si
Me ₃ , Me ₃ Si / (MeO) ₂ // (OEt) ₂ / S
iMe ₃ , Me ₃ Si / (MeO) ₂ // (OMe) ₂ /
SiEt ₃ , Me ₃ Si / (EtO) ₂ // (OEt) ₂
/ SiEt ₃ , Et ₃ Si / (MeO) ₂ // (OMe)
₂ / SiEt ₃ , Et ₃ Si / (EtO) ₂ // (OE
t) ₂ / SiEt ₃ , Me ₃ Si / MeO / EtO //
(OMe) ₂ / SiMe ₃ , Me ₃ Si / (EtO) ₂
// OMe / OEt / SiMe ₃ , Et ₃ Si / MeO /
EtO // (OMe) ₂ / SiMe ₃ , Et ₃ Si / Me
O / EtO // OMe / OEt / SiEt ₃ .

The catalyst of the present invention comprises component A, component B and component C, the composition ratios of which are such that component B is 1 to 2,000 gram mol per gram atom of titanium in component A,
Desirably 20 to 500 grams mol, component C is component B1
0.001 to 10 mol, preferably 0.0
It is used so as to be 1 to 1.0 mol.

[Copolymerization of Propylene] Copolymerization of propylene is carried out by copolymerizing propylene and ethylene in the presence of the above-mentioned polymerization catalyst. The polymerization reaction may be in a gas phase or a liquid phase, and when the polymerization is performed in the liquid phase,
It can be carried out in an inert hydrocarbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually −80 ° C. to + 150 ° C., preferably 40 to 12
It is in the range of 0 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The use ratio of propylene and ethylene is appropriately set so that the ethylene content in the obtained copolymer is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.
In the copolymerization reaction, the melt flow rate (MFR) of the obtained copolymer is 0.01 to 200 g / 10 minutes, and particularly 0.
The amount is preferably 1 to 100 g / 10 minutes, and the adjustment is usually made by adjusting the amount of hydrogen or a known molecular weight regulator used.

[0064]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-ditertiarybutyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, calcium stearate After adding 0.06% by weight of each of them to form pellets by melt-kneading, a test piece was prepared by injection molding (a sheet having a thickness of 1.0 mm was used for measuring haze). Flexural modulus: JIS K 720
3-1982, Haze: According to ASTM D1003. The MFR of the polymer was measured according to ASTM D-1238. The ethylene content of the copolymer was determined by measuring the transmittance of absorption at 733 cm ^-1 by the infrared absorption spectrum method. The test piece was obtained by subjecting a film having a thickness of about 0.5 mm by press molding to an annealing treatment.

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 the above suspension was cooled to 0 ° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes. After completion of the dropping, the temperature was raised to 50 ° C. over 2 hours, and then 50
Stirring was continued for 1 hour at ° C. After the reaction was completed, the supernatant was removed by decantation, and the resulting solid was mixed with 60 ml of n-
It was washed with 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 in 10 ml of n-heptane was added to the suspension at a temperature of 25 ° C. from a dropping funnel at 15 ° C. It took a minute and was dropped. After completion of dropping, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, the mixture was washed twice with 60 ml of n-heptane and three times with 60 ml of toluene at room temperature. When the obtained solid (solid component I) was analyzed,
SiO ₂ 36.6%, Magnesium 5.1%, Chlorine 3
It contained 8.5%. In the solid component I obtained above,
Add 10 ml of n-heptane and 40 ml of titanium tetrachloride, and add 9
The temperature was raised to 0 ° C., and 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added over 5 minutes. afterwards,
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 1
5 ml and 40 ml of titanium tetrachloride were added and reacted at 115 ° C for 2 hours. After the reaction was completed, the solid substance obtained was mixed with 60 ml of n
-Washing was carried out 8 times with hexane at room temperature. Then, it was dried under reduced pressure at room temperature for 1 hour to obtain 8.3 g of a catalyst component (component A). This component A contained 3.1% of titanium, silicon oxide, chlorine and di-n-butyl phthalate.

Copolymerization of Propylene Into a 5 liter autoclave, which had been purged with nitrogen and sufficiently dried, was added 35.0 mg of component A obtained above and 0.6 mol of triethylaluminium in 1 liter of n-heptane. In 4 ml of the solution containing and 1 liter of n-heptane,
0.08 mol of 1,1-dimethoxy-1,2,2,2-
3 ml of a solution containing tetramethyldisilane was mixed, and the mixture held for 5 minutes was added. Then 3.4 liters of hydrogen,
After pressurizing 3 liters of liquid propylene, the internal temperature of the autoclave was raised to 70 ° C., ethylene was continuously supplied, and polymerization was carried out for 1 hour. After completion of the polymerization, unreacted propylene, ethylene and hydrogen were purged and the polymer in the autoclave was taken out. MF of the obtained polymer
R was 15.5 g / 10 minutes and ethylene content was 1.9%. When the physical properties were measured, the flexural modulus was 10.93.
× 10 ³ kg / cm ² , haze was 20.3%.

Examples 2 to 5, Comparative Examples 1 to 2 Instead of 1,1-dimethoxy-1,2,2,2-tetramethyldisilane, the organosilicon compounds shown in Table 1 were used and the resulting copolymers were obtained. Copolymerization of propylene was carried out in the same manner as in Example 1 except that the amount of hydrogen was adjusted so that the MFR of the combined product had the value shown in Table 1, and the results are shown in Table 1.
The flexural modulus and haze values of the copolymers obtained in the respective examples and comparative examples are plotted in FIG. 1. The copolymers obtained in the respective examples show that the physical properties of the flexural modulus and the haze are balanced. ,
It is clear from the results of FIG. 1 that the copolymers obtained in Comparative Examples are superior to those of the copolymers obtained.

[Table 1]

[0068]

By carrying out the method of the present invention,
It is possible to obtain a polypropylene copolymer having an excellent balance of transparency and rigidity.

[Brief description of drawings]

FIG. 1 is a plot of measured flexural modulus and haze of the copolymers obtained in Examples and Comparative Examples of the present invention.

FIG. 2 is a flow chart diagram illustrating the method of the present invention.

Front page continued (72) Inventor Takayuki Taki, 1-3-1, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Corporation Research Institute (72) Inventor Takeshi Ishihara 1-3-3, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute (72) Inventor Rinko Aoki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside Tonen Research Institute

Claims (1)

Claims: 1. A solid catalyst component comprising (A) a metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components, (B) an organometallic compound and (C) a general formula: Chemical 1] [However, R ¹ is a hydrocarbon group or R ₃ ⁷ Si of 1 to 10 carbon atoms, R ² is from 1 to 10 carbon atoms hydrocarbon group or R ⁸ O, R ³ is 1 to 10 carbon atoms Hydrocarbon group or R ⁹ O, R ⁴ and R ⁵ are the same or different and have 1 to 1 carbon atoms.
0 hydrocarbon group, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms, OR ¹⁰ or SiR ₃ ¹¹ , and R ^{7 to} R ¹¹ are the same or different hydrocarbon groups having 1 to 10 carbon atoms. is there. ] The manufacturing method of the propylene copolymer of ethylene content 0.01-10 weight% which consists of copolymerizing propylene and ethylene in the presence of the catalyst for polymerization which consists of the organosilicon compound represented by these.