JPH0517531A - 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 the presence of catalyst comprising (A) a solid catalyst component containing magnesium, titanium, a halogen and an electron-donating compound (preferably formic acid or methanol) as main components, (B) an organic metal compound (preferably, trimethyl aluminum) and (C) an organic silicon compound of the formula [R'' is 1-IOC 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.,], the component B being preferably 20-500g mole per g atomic weight of titanium in the component A, and the component C being preferably 0.01-0.1mole per mole of the component B, to provide the objective copolymer having an ethylene content of 0.01-10wt.%.

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 to provide a solid catalyst component containing (A) magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organometallic compound and (C) a 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 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. ] 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 magnesium, titanium, halogen and an electron donating compound as essential components. A magnesium compound, a titanium compound, an electron-donating compound, and in the case where each of the above compounds is a compound having no halogen, a halogen-containing compound is prepared by bringing them into contact with each other.

(1) 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, EtMgCl, B
uOMgCl, HeOMgCl, PhOMgCl, Et
OMgBr, BuOMgBr, EtOMgI, MgCl
₂ , MgBr ₂ , MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds 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 .

The compound of formula P (OR) when M is phosphorus₃Included 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 compound of divalent, trivalent and tetravalent titanium. 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, 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. 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. Ethers are represented by the general formula ROR ¹ . In the formula, R and R ¹ are alkyl having 1 to 12 carbons, alkenyl, cycloalkyl,
It is aryl or aralkyl, 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, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether,
Examples include anisole and ethyl phenyl ether.

As the method for preparing the component A, a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) are contacted in that order. After contacting component 1 and component 3, component 2 is contacted. A method such as contacting the components 1, 2 and 3 at the same time can be adopted. It is also possible to contact with the halogen-containing compound before contacting with component 2.

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 the hydroxyl group in the 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 are 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 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) -bromophenol, 4-
Bromresorcin, (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-tribrom-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-tetrafluorophenol, tetrafluororesorcin, etc. are mentioned.

The silicon halide compound having a hydrogen-silicon bond includes HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S.
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 Component 1, Component 2 and Component 3, and optionally with a halogen-containing compound which can be optionally contacted is carried out by mixing and stirring in the presence or absence of an inert medium, but mechanically. It is made by 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. ..

A preferable method for preparing the component A in the present invention is described in JP-A-63-264607 and JP-A-58-19850.
No. 3, No. 62-146904 and the like. More specifically, it can be obtained by bringing (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound) into contact with each other. A method in which a magnesium-containing solid is contacted with (d) a halogen-containing alcohol, and then (e) an electron-donating compound and (f) a titanium compound (JP-A-6-61).
3-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting with a silicon halide compound having a silicon bond, (c) contact with a titanium halide compound, and then (d) contact with an electron donating compound (if necessary, further contact with a titanium halide compound) (JP-A-62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting with a silicon halide compound having a silicon bond, (c) contact with an electron donating compound, and then (d)
Method of contacting with titanium compound (JP-A-58-1985)
No. 03). Of these, the method (1) is most 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.

Further, 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.

In 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 listed in Periodic Table I.
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.
Further, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can also be used. 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.

Examples of the alkyl group include 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 are 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
^4, and OR ⁵ and OR ¹⁰ is OR ⁴ when the same, OR ⁴ and OR ⁵ is when the same displays respectively _{^{(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.

[0045] 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 ratio of which is 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.

[Propylene Copolymerization] Propylene copolymerization 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.
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.

[0060]

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 In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity 99.
5%, average particle size 1.6 mm) 8.3 g and n-hexane 2
After adding 50 ml and stirring at 68 ° C. for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65 ° C. to obtain pre-activated metallic magnesium. Next, 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butyl magnesium chloride (1.75 mol / l) were added to this metallic magnesium at 55 ° C.
A solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After reacting at 70 ° C. for 4 hours with stirring, the reaction solution was added to
Hold at 5 ° C. Then, HC (OC ₂ H
₅ ) 35.7 ml of _{3 was} added dropwise over 1 hour. After finishing the dropping
The reaction was performed at 60 ° C. for 15 minutes, the reaction product solid was washed 6 times with 300 ml of n-hexane each time, and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. 31.6 g was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, magnesium-containing solid 6.3 in a nitrogen gas atmosphere.
G and n-heptane (50 ml) were added to form a suspension, and 2,2,2-trichloroethanol (20 ml) was stirred at room temperature.
A mixed solution of (0.02 mmol) and 11 ml of n-heptane was added dropwise from a dropping funnel over 30 minutes and further stirred at 80 ° C for 1 hour. The obtained solid was filtered, washed with 100 ml of n-hexane at room temperature four times, and further washed with 100 ml of toluene twice each to obtain a solid component. 40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, and then the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 90 ° C. and washed twice with 100 ml of toluene each time at 90 ° C. Further, titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained is filtered off at 110 ° C. and 1 each at room temperature.
Component A5.5 was obtained by washing 7 times with 00 ml of n-hexane.
g was obtained.

Copolymerization of Propylene Into a sufficiently dried 5 liter autoclave which had been purged with nitrogen, 24.7 mg of the component A obtained above and 0.3 mol of triethylaluminium in 1 liter of n-heptane were added. 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 3.6 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 14.5 g / 10 minutes and ethylene content was 3.1%. When the physical properties were measured, the flexural modulus was 10.69.
× 10 ³ kg / cm ² , haze was 19.6%.

Examples 2 to 4 and Comparative Examples 1 to 2 In place 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]

[0064]

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 containing (A) magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organometallic compound and (C) a general formula: [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.