JPH06128315A - Production of propylene/ethylene block copolymer - Google Patents

Abstract

PURPOSE:To obtain a propylene/ethylene block copolymer having an excellent balance between impact resistance and rigidity by conducting the production of highly crystalline polypropylene, the copolymerization of propylene with ethylene, and the production of ethylene homopolymer in the presence of a specific polymerization catalyst. CONSTITUTION:The polymerization of propylene for producing highly crystalline polypropylene, the copolymerization of propylene with ethylene for producing a propylene/ethylene copolymer having an ethylene content of 30-95wt.%, and the production of ethylene homopolymer are conducted in the presence of a polymerization catalyst comprising a solid catalyst component comprising Mg, Ti, a halogen, and an electron-donating compound, an organometallic compound, and an organosilicon compound represented by the formula, wherein R<1> is a 1-10C hydrocarbon group or R<7>3Si; R<2> is a 1-10C hydrocarbon group or R<8>O; R<3> is a 1-10C hydrocarbon group or R<9>O; R<4> and R<5> each is a 1-10C hydrocarbon group; R<6> is a 1-10C hydrocarbon group, OR<10>, or SiR<11>; and R<7> to R<11> each is a 1-10C hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a propylene-ethylene block copolymer. For more details,
The present invention relates to a method for producing a propylene-ethylene block copolymer having an excellent balance between whitening resistance and rigidity by using a specific polymerization catalyst.

[0002]

2. Description of the Related Art Crystalline polypropylene is widely used because of its excellent rigidity, heat resistance and surface gloss. Furthermore, the propylene-ethylene block copolymer obtained by carrying out propylene homopolymerization in the first stage of the polymerization and propylene-ethylene copolymerization in the second stage supplements the impact resistance, which is a defect of crystalline polypropylene, and is excellent. As a polymer having a balance of rigidity and impact resistance, it is widely used in injection molded products and the like. However, such a block copolymer is generally inferior in transparency and gloss, and when it is further bent or given an impact, it causes a phenomenon in which the site does not return to its original state even if it is whitened. In recent years, various added values have been demanded as the applications of polypropylene have expanded, and depending on the field of application, not only mechanical properties but also such a beautiful appearance tends to be emphasized.

As a method for improving the whitening resistance, methods such as increasing the content of ethylene in the copolymer and adding polyethylene to the block copolymer have been proposed so far. Either method is an excellent method for improving the whitening resistance, but since the rigidity is lowered, its use may be limited depending on the use of the copolymer.

[0004]

SUMMARY OF THE INVENTION The present invention effectively
It is an object of the present invention to provide a method for producing a propylene-ethylene block copolymer having an excellent balance of rigidity and whitening resistance.

[0005]

As a result of intensive studies, the present inventors achieved the object of the present invention by carrying out copolymerization using a polymerization catalyst containing a specific organosilicon compound as an essential component. The inventors have found that it is possible and have completed the present invention.

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

[Chemical 2][However, R¹Is a hydrocarbon group having 1 to 10 carbon atoms or
R⁷ ₃Si, R²Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁸O, R³Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁹O, R^FourAnd R^FiveHave the same or different carbon numbers 1 to 1
0 hydrocarbon groups, R⁶Is a hydrocarbon having 1 to 10 carbon atoms
Group, OR^TenOr SiR¹¹ ₃And R ⁷~ R¹¹Is the same
It is a hydrocarbon group having 1 to 10 different carbon atoms. 〕so
Existence of polymerization catalyst consisting of represented organosilicon compound
Below, (1) propylene is polymerized to obtain highly crystalline polypropylene.
(A), (2) Propylene and ethylene for producing ethylene
Copolymerized with propylene having an ethylene content of 30 to 95% by weight.
A step (b) for producing a copolymer of len and ethylene;
(3) From the step (c) of producing a homopolymer of ethylene
Propylene-ethylene block copolymer
is there.

Solid Catalyst Component A solid catalyst component (hereinafter referred to as component A) which is one component of the catalyst used in the present invention (hereinafter referred to as catalyst of the present invention) is
Magnesium, titanium, a halogen and an electron donating compound are essential components, and such a component is usually a magnesium compound, a titanium compound and an electron donating compound, and in the case where each of the above compounds is a compound having no halogen, halogen containing The compounds are prepared by contacting each.

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

Specific examples of these compounds are shown below. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show. MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, 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 preparing the component A. As an example thereof, a compound containing metal magnesium, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1 to 20]
Hydrocarbon groups, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧ 0. ] The method of making it contact is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl, (Pr), i-propyl (iP
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (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(OM
e)₂, CH₂(OEt)₂, CH₂ClCH (OE
t)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 contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compound in which M is boron B (OEt) ₃ , B (OB) included in the formula B (OR) ₃
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.

(2) 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.

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

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

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

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

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

The component A is prepared by contacting a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) 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, IVa of the periodic table.
Examples thereof include halides of Group III and Group Va 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 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
-Chlor-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 and the like can be 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 is 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 brought into contact with (d) a halogen-containing alcohol and then (e) an electron-donating compound and (f) a titanium compound (JP-A-63-63).
-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) a titanium halide compound is contacted, and then (d) an electron-donating compound (if necessary, further contacted with a titanium halide compound). (JP-A-62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) contacting 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 the 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 a compound used in preparing the component A and a 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 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.
Particularly preferred are alkylaluminum compounds, preferably C2 to C6 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 monohalide such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monoalkyl aluminum dihalide 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 readily 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 bonded 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.

As the alkyl group, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl 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,
R ¹ / R ² / R ³ // OR ⁴ / OR ⁵ / R ⁶
Is displayed. In the following, Me = methyl and Et =
Represents ethyl, Pr = propyl, Bu = butyl, Amy = amyl, Hex = hexyl.

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 is the same, OR^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 , OR ⁵ and OR ¹⁰
When OR is 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 R³Is the same
R at the time of one¹And R¹And R²R are the same when¹ ₂/ R
³And OR^FourAnd OR^FiveAre the same (OR^Four)₂/ R⁶
Are 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 R
³R are the same when⁷ ₃Si / R¹ ₂And OR^FourAnd OR^Five
Are the same (OR^Four)₂/ R⁶Are displayed respectively
It ] Me₃Si / Me₂// (OMe)₂/ Me, Me₃Si
/ Me₂// (OEt) ₂/ Me, Et₃Si / Me₂//
(OMe)₂/ I-Pr, Et₃Si / Me₂// (OM
e)₂/ N-Hex.

5) When R ¹ , R ² and R ³ are hydrocarbon groups and R ⁶ is SiR ¹¹ ₃ [when R ¹ , R ² and R ³ are the same, R ¹ , R ² and R ³ R ² ₂ / R when are the same
^{When 3} is the same as OR ⁴ and OR ^5, (OR ⁴ ) ₂ / S
iR ¹¹ ₃ is displayed respectively. ] 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 R
³R are the same when⁷ ₃Si / R² ₂And OR^FourAnd OR^Five
Are the same (OR^Four)₂/ SiR¹¹ ₃And display respectively
To do. ] 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, When OR ⁴ , OR ⁵ and OR ¹⁰ are the same, OR ⁴ and when OR ⁴ and OR ⁵ are the same (O
R ⁴ ) ₂ / OR ¹⁰ is displayed. ] 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 , O
When R ⁵ and OR ¹⁰ are identical to the OR ^4, OR ⁴ and OR
^{When 5} is the same, it is 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 R²Is the same
R at the time of one¹ ₂/ R⁹O and OR^FourAnd OR^FiveAre the same
Time is (OR^Four)₂/ R⁶Are displayed respectively. ] 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/ R⁶Is displayed
It ] 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 R²But
R when same¹ ₂/ R⁹O and OR^FourAnd OR^FiveAre the same
At the time of (OR^Four)₂/ SiR¹¹ ₃Are displayed respectively
It ] 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 case of [OR
^FourAnd OR^FiveAre the same (OR^Four)₂/ SiR¹¹ ₃When
indicate. ] 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
^{When 8} O and R ³ are 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) ₂ and OR ⁴ ,
And OR ⁴ when OR ⁵ and OR ¹⁰ are the same, OR ⁴ and O
When R ⁵ is the same, it is displayed as (OR ⁴ ) ₂ / OR ¹⁰ . ] 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
And R⁹R when O is the same⁷ ₃Si / (R⁸O)₂And O
R^Four, OR ^FiveAnd OR^TenWhen is the same, OR^FourAnd OR^Four
And OR^FiveAre the same (OR^Four) ₂/ OR^TenAnd that
Displayed. ] 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 [R⁸
O and R⁹R when O is the same¹/ (R⁸O)₂And OR
^FourAnd OR^FiveAre the same (OR^Four)₂/ SiR¹¹ ₃When
Display each. ] 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
⁸ O, R ³ is R ⁹ O, and R ⁶ is SiR ¹¹ ₃ [R ⁸
When O and R ⁹ O are the same, R ⁷ ₃ Si / (R ⁸ O)
_{When 2} is the same as OR ⁴ and OR ⁵ and OR ^10, (OR
⁴ ) Display as ₂ / SiR ¹¹ ₃ , respectively. ] 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 gram 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.

Of the propylene-ethylene block copolymer
Manufacturing method The manufacturing method of a propylene-ethylene block copolymer is a step of polymerizing propylene to manufacture a highly crystalline polypropylene (step a), and copolymerizing propylene and ethylene to prepare propylene having an ethylene content of 30 to 95% by weight. And a step of producing a copolymer of ethylene (step b) and a step of producing a homopolymer of ethylene (step c).

(1) Step a Step a consists of polymerizing propylene in the presence of the above-mentioned polymerization catalyst. The polymerization reaction may be either a gas phase or a liquid phase, and when the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane,
It can be carried out in an inert hydrocarbon such as heptane, octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to +
It is in the range of 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer can be controlled by the presence of hydrogen or other known molecular weight regulator. In step a,
It is desirable that the polypropylene obtained there accounts for 40 to 98% by weight, particularly 70 to 90% by weight of the block copolymer. Further, in this step, the polypropylene obtained has a melt flow rate (MFR) of 0.01 to
It is preferably 200 g / 10 minutes, particularly 0.1 to 100 g / 10 minutes.

(2) Step b Copolymerization of propylene and ethylene is carried out in the presence of the above-mentioned polymerization catalyst. In the copolymerization, the ethylene content in the resulting copolymer is 30 to 95% by weight, preferably 4
It is made by contacting and reacting propylene and ethylene so that the content of propylene is 0 to 80% by weight. The copolymerization reaction is
It can be appropriately selected from the range of the polymerization conditions carried out in step a, and the use of a molecular weight regulator such as hydrogen can also be selected in step a.
Is the same as in. The amount of the copolymer obtained in step b is 50 to 1% by weight of the block copolymer, especially 30 to
It is preferably 5% by weight. Further, in the step b, the MFR of the obtained copolymer is 0.001 to 150 g / 10.
Min, particularly 0.01 to 100 g / 10 min.

(3) Step c The ethylene homopolymer is produced by the presence of the above-mentioned polymerization catalyst.
Below, it is carried out by polymerizing ethylene. Echire
The polymerization reaction of the polymerization is carried out in step a or step b.
It is selected from the range of conditions. Also, control the molecular weight of hydrogen, etc.
The use of the agent is the same as in the case of step a and step b. Process
The ethylene homopolymer obtained in step c is the block copolymer.
50 to 1% by weight of the body, especially 30 to 5% by weight is desired
More preferably, the MFR of the homopolymer is 10 ^-8~ 150g
/ 10 minutes, especially 10^-6~ 100g / 10min is desired
Good The method of the present invention includes steps a, b and c.
It consists of a serial system that performs these three steps in any order.
In addition, the three steps are performed in parallel, and the po
The method of uniting the limmer can be adopted, but this
Among them, step a, step b, and step c are performed in that order.
This method is advantageous and desirable in terms of the apparatus. in this way
The block copolymer obtained by the above is 0.001 to 150.
It has an MFR of g / 10 minutes, but preferably 0.01-
It is 100 g / 10 minutes.

[0063]

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. Flexural modulus: JIS K
According to 7203-1982. The MFR of the polymer is A
It was measured according to STM D-1238. The whitening area of the polymer was measured by the following method. Square sheet (thickness 2 mm) molded from polymer to 80 mm x 80 mm
DuPont impact strength (JIS K 7211-197
Place the needle on the pan of the measuring instrument in 6) and set the needle. A 500 g weight is dropped on the sheet from a height of 50 cm to whiten the sheet. A copy of the whitened sheet is taken with black paper as a back, and the whitened area is measured using an image processing device (SPICCA-II manufactured by Nippon Avionics Co., Ltd.).

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 mixed with 2
Hold at 5 ° C. Then, HC (OC ₂ H
₅ ) 35.7 ml of _{3 was} added dropwise over 1 hour. After the dropping is completed,
The reaction was carried out 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 the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, washed with 100 ml of n-hexane at room temperature 4 times each, 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 was filtered off at 110 ° C. and 1 each at room temperature.
Washed 7 times with 00 ml of n-hexane to obtain 5.5 g of component A
Got

Copolymerization of propylene and ethylene Into a fully dried 5 liter autoclave which had been purged with nitrogen, 27.8 mg of the component A obtained above and 0.3 liter of triethylaluminum in 1 liter of n-heptane were added. 0.0 in 4 ml of solution and 1 liter of n-heptane
3 ml of a solution containing 8 mol of 1,1-dimethoxy-1,2,2,2-tetramethyldisilane was mixed and held for 5 minutes. Next, 10.1 liters of hydrogen and 3 liters of liquid propylene were pressure-injected, the internal temperature of the autoclave was raised to 70 ° C., and the first stage polymerization (step a) was performed. After 1 hour, unreacted propylene and hydrogen were purged to adjust the internal pressure to 0.2 kg / cm ² -G. After collecting a small amount of the first-stage polymer, hydrogen was introduced into the system. Subsequently, in the second stage polymerization (step b), a mixed gas having a molar ratio of propylene and ethylene of 1.5 was supplied to maintain the internal pressure of the container at 6 kg / cm ² -G, and the temperature was 75 ° C. for 1 hour and 30 minutes. , Propylene and ethylene were copolymerized. After the polymerization was completed, the unreacted gas contained 0.6 mol% of hydrogen. After removing the unreacted gas, a small amount of polymer was collected. Furthermore, introducing hydrogen and ethylene gas, 75 ℃
Third stage polymerization (step c) was carried out for 30 minutes. As a result of the analysis, the amount of the polymer obtained by the second-stage copolymerization was 15%, and the content of ethylene was 50%.
The MFR of the polymer sampled after the completion of the first-stage polymerization was 33.6 g / 10 minutes. After completion of the 2nd stage polymerization, the sampled polymer has an MFR of 14.5.
It was g / 10 minutes. MFR of the final polymer is 5.1g
/ 10 minutes. The flexural modulus of the final polymer is 8.9.
It was 7 × 10 ³ kg / cm ² . The whitening area is 1
It was 35 mm ² .

Examples 1 to 4, Comparative Examples 1 and 2, 1,1-dimethoxy-used as Component C of the polymerization catalyst
Instead of 1,2,2,2-tetramethyldisilane, the organosilicon compound shown in Table 1 was used, and the MF shown in Table 1 was used.
Copolymerization of propylene and ethylene was carried out in the same manner as in Example 1 except that the amount of hydrogen was adjusted to R. The physical properties of the final polymer obtained are also shown in Table 1.

The flexural modulus and whitening area values of the block copolymers obtained in each of the Examples and Comparative Examples are plotted in FIG. 1. The copolymers obtained in each Example show rigidity and whitening resistance. It is clear from the results of FIG. 1 that the balance of properties is superior to those of the copolymers obtained in Comparative Examples.

[0068]

[Table 1]

[0069]

According to the method of the present invention, a propylene-ethylene block copolymer having excellent balance between rigidity and whitening resistance can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing the relationship between the flexural modulus and the whitened area of the block copolymers obtained in Examples of the present invention and Comparative Examples.

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

Front page continuation (72) Inventor Rinko Aoki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Kunihiko Imanishi 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute (72) Inventor Satoshi Ueki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Center

Claims (1)

[Claims] 1. A) magnesium, titanium, halogen and
And a solid catalyst component containing an electron-donating compound as an essential component,
(B) an organometallic compound and (C) a general formula:[However, R¹Is a hydrocarbon group having 1 to 10 carbon atoms or
R⁷ ₃Si, R²Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁸O, R³Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁹O, R^FourAnd R^FiveHave the same or different carbon numbers 1 to 1
0 hydrocarbon groups, R⁶Is a hydrocarbon having 1 to 10 carbon atoms
Group, OR^TenOr SiR¹¹ ₃And R ⁷~ R¹¹Is the same
It is a hydrocarbon group having 1 to 10 different carbon atoms. 〕so
Existence of polymerization catalyst consisting of represented organosilicon compound
Below, (1) propylene is polymerized to obtain highly crystalline polypropylene.
(A), (2) Propylene and ethylene for producing ethylene
Copolymerized with propylene having an ethylene content of 30 to 95% by weight.
A step (b) for producing a copolymer of len and ethylene;
(3) From the step (c) of producing a homopolymer of ethylene
The method for producing a propylene-ethylene block copolymer comprising