JPH06271615A - Production of propylene copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer excellent in balance between transparency and rigidity by copolymerizing a small amount of ethylene with propylene using a specific polymerization catalyst. CONSTITUTION:(A) A solid catalyst component consisting essentially of Mg, Ti, a halogen and an electron donative compound is brought into contact with an olefin in the presence of (B) an organoaluminum compound (preferably triethylaluminum, etc.) and (C) an organosilicon compound expressed by the formula {R<1> is l-10C hydrocarbon; R<2> is 1-10C bivalent hydrocarbon or R<5>O (R<5> is 1-10C bivalent hydrocarbon); R<3> is R<1> or R<6>O (R<6> is 3-10C hydrocarbon); R<4> is CH3 or C2H5; (x) is 1 or 2; (y) is 0 or 1; (z) is 2 or 3, with the proviso that [(x)+(y)+(z)] is 4}. The resultant polymerization catalyst is then used to copolymerize propylene with ethylene. Thereby, the objective copolymer with 0.01-10wt.% ethylene content is obtained.

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, and more specifically, it is excellent in transparency and rigidity by randomly copolymerizing propylene with a small amount of ethylene 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 may have 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 improves, 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 becomes high from the viewpoint of the process, and the appearance of the molded product may be impaired depending on the additive. A method of improving rigidity by a polymerization method without treatment with an additive has been proposed, but the rigidity is insufficient in both cases.

[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 inventors have found that the object of the present invention can be achieved by polymerizing propylene with a small amount of ethylene using a specific polymerization catalyst component. And 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 organoaluminum compound and (C) a general formula.

[Chemical 2][However, R¹Is a hydrocarbon group having 1 to 10 carbon atoms, R²Is
A divalent hydrocarbon group having 1 to 10 carbon atoms or -R^FiveO
-, R³Is a hydrocarbon group having 1 to 10 carbon atoms, R ⁶O-,
R⁷ ₃Si- or R⁸ ₃SiO-, R^FourIs a methyl group
Or an ethyl group, x is 1 or 2, y is 0 or
1, z represents 2 or 3, x + y + z = 4, and R^FiveIs
A divalent hydrocarbon group having 1 to 10 carbon atoms, R⁶Has 3 carbons
-10 hydrocarbon groups, R⁷And R⁸Has 1 to 10 carbon atoms
Shows the number of hydrocarbon groups. ] An organosilicon compound represented by
Of (D) olefin in the presence of
Copolymerizing propylene and ethylene in the presence of components
Of ethylene having an ethylene content of 0.01 to 10% by weight.
It is in the method for producing a ren copolymer.

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

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ⁹ R ¹⁰ . In the formula, R ⁹ and R ¹⁰ are the same or different hydrocarbon groups, OR ¹¹ groups (R ¹¹ is a hydrocarbon group), and halogen atoms. More specifically, the hydrocarbon group of R ⁹ and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR ¹¹ group is R ¹¹ having a carbon number. As the halogen atom, 1 to 12 alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups are chlorine, 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 magnesium metal, 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 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 (i-P).
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 ; MeBuSi (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 when B is M 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 ⁹ R
It is represented by ¹⁰ · n ₀ (MR ¹² _m ). As the metal,
R ¹² 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 ₀ represents a number of 0.1 to 10. Specific examples of the compound represented by MR ¹² _m include AlMe ₃ and AlE.
_{t 3, Ali-Bu 3,} AlPh 3, ZnMe 2, Zn
Et ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaP
h _{2 and the} like can be mentioned.

(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-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutylate, 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 R ¹³ OH. In the formula, R ¹³ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol,
Isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol and the like. The ethers are represented by the general formula R ¹⁴ OR ¹⁵ . In the formula R ¹⁴ ,
R ¹⁵ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl, and R ¹⁴ and R
¹⁵ can 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,
Examples include ethyl allyl ether, butyl allyl ether, diphenyl ether, 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 IIIa 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 these 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, or by mechanical stirring. 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 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 the organoaluminum compound. The organic aluminum compound is selected from the organic aluminum compounds described below.

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.

Organoaluminum Compound An organoaluminum compound (hereinafter referred to as component B) has the general formula R ¹⁶ _n1 AlX _{3- n1} (wherein R ¹⁶ is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom). And n ₁ is an arbitrary number in the range of 1 ≦ n ₁ ≦ 3), and examples thereof include trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkyl. Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as aluminum monoalkoxide and dialkylaluminum monohydride, or a mixture or complex compound thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide. Dialkyl aluminum monohalides such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monobutyl aluminum dihalides such as isobutyl aluminum dichloride, ethyl aluminum aluminum Alkyl aluminum sesquihalides such as sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum Examples thereof include dialkyl aluminum hydrides such as hydride, dipropyl aluminum hydride and diisobutyl aluminum hydride.
Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable.

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, hydrocarbon groups of R ¹ and R ³ and R ⁶ O—, R ⁷ ₃ S
The hydrocarbon group represented by R ⁶ , R ⁷ and R ⁸ in i-, R ⁸ ₃ SiO- is an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group or an aralkyl group. Etc.

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, isopropenyl, 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 cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl groups, and cycloalkenyl groups such as cyclopentenyl, cyclohexenyl and methylcyclohexenyl groups. Etc., the cycloalkadienyl groups include cyclopentadienyl, methylcyclopentadienyl, indenyl groups, etc., the aryl groups include phenyl, tolyl, xylyl groups, etc., and the aralkyl groups include benzyl, phenethyl group. , 3-phenylpropyl group and the like.

The divalent hydrocarbon group represented by R ² in the above general formula and the hydrocarbon group represented by R ⁵ in —R ⁵ O— are an alkylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group or a cycloalkenyl group. Examples thereof include a dienylene group and an arylene group.

The alkylene group has the _formula- (CH ₂ ) _n2
A straight chain alkylene group represented by-(n ₂ = 1 to 10), for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene group, etc., as well as a side chain of propylene, isopropylene group, etc. The alkylene group having, as the alkenylene group, vinylene, propenylene, 1-butenylene, 2-butenylene, 1-hexenylene, 1-octenylene group and the like, as the cycloalkylene group, cyclopentylene, cyclohexylene, methylcyclohexylene Groups, etc., as cycloalkenylene group, cyclopentenylene, cyclohexenylene group, etc., as cycloalkadienylene, etc.
Cyclopentadienylide Ren, methyl cyclopentadienylide Ren, indenylene group. Examples of the arylene group include phenylene, tolylene, xylylene, -Ph-CH ₂ - (P
h: phenylene) and the like.

Specific examples of the component C are shown below. The smell below
, Me is methyl group, Et is ethyl group, Pr is propyl
Group, Bu represents a butyl group, and Ph represents a phenyl group.
You [Me-COO-CH₂-] Si (OMe)₃，
[Pr-COO- (CH₂) ₂-] Si (OMe)₃，
[Isopropenyl-COO- (CH₂)₃−] Si (O
Me)₃, [Allyl-COO- (CH₂)₂-] Si
(OEt)₃, [Cyclohexyl-COO- (CH₂)
₃-] Si (OMe)₃, [Cyclopentenyl-COO
-(CH₂)₂-] Si (OMe)₃, [Cyclopenta
Dienyl-COO- (CH₂)₃−] Si (OM
e)₃, [Ph-COO- (CH₂)₂−] Si (OE
t)₃, [Isopropenyl-COO- (CH₂)₂-]
Si (OMe)₂Me, [isopropenyl-COO-
(CH₂)_Four-] Si (OMe)₂(Oi-Pr),
[Cyclopentyl-COO- (CH₂)₂−] Si (O
Et)₂(SiMe₃), [Me-COO- (CH₂)
_FourO-] Si (OMe)₂(OSiMe ₃), [Allyl
-COO- (CH₂)₂−] Si (OEt)₂(Ot-
Bu), [Me-COO- (CH₂)₂-]₂Si (O
Et)₂, [2-butenyl-COO- (CH₂)₃-]
₂Si (OMe)₂, [Cyclohexyl-COO- (C
H ₂)₃-]₂Si (OMe)₂, [Cyclopentenyl
-COO- (CH₂)_Four-]₂Si (OMe)₂, [Shi
Clopentadienyl-COO-CH₂-]₂Si (OE
t)₂, [Ph-COO- (CH₂)₂O-]₂Si
(OEt)₂, [Me-COO-cyclohexylene-]
Si (OEt)₃, [2-butenyl-COO-cyclope
Polyethylene-] Si (OMe)₃, [Isopropenyl-C
OO-cyclopentylene-] Si (OEt)₃, [Iso
Propenyl-COO-cyclopentenylene-]₂Si
(OEt)₂, [Cyclohexyl-COO-cyclohexyl
Siren-] ₂Si (OMe)₂.

Prepolymerization The prepolymerization of the solid component (component A) is carried out by contacting it with an olefin (component D) in the presence of an organoaluminum compound (component B) and an organosilicon compound represented by the above general formula (component C). Made by.

If necessary, an electron donating compound (hereinafter referred to as component E) may be added together with the components B and C during the prepolymerization of the component A. As the electron donating compound, an electron donating compound composed of an organic silicon compound or an electron donating compound containing a hetero atom such as nitrogen, sulfur, oxygen or phosphorus can be used.

The organic silicon compound is a Si--O--C bond.
And an organic silicon compound having a Si—N—C bond is mentioned.
However, preferably a compound having a Si-O-C bond
Is. Such compounds include those represented by the general formula R¹⁷ _n3S
i (OR¹⁸)_4-n3[However, R¹⁷Is a hydrocarbon group or halogen
Atom, R¹⁸Is a hydrocarbon group, 0 ≦ n₃≦ 3 is shown. 〕so
The compounds represented may be mentioned. R in the above general formula¹⁷
The hydrocarbon group of is an alkyl group, cycloalkyl
Group, aryl group, aralkyl group, alkenyl group, ar group
Cadienyl group, cycloalkenyl group, cycloalkadini
And the like. R¹⁷The halogen atom of is a salt
Examples thereof include elemental, bromine and iodine. Also, R¹⁸Hydrocarbon
As the group, an alkyl group, a cycloalkyl group, an aryl
Groups, alkenyl groups and the like. Furthermore, n ₃R¹⁷
Hydrocarbons and (4-n₃) OR¹⁸R¹⁸Hydrocarbon
The groups may be the same or different.

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

Specific examples of the electron-donating compound containing a hetero atom include compounds containing a nitrogen atom:
6,6-Tetramethylpiperidine, 2,6-Dimethylpiperidine, 2,6-Diethylpiperidine, 2,6-Diisopropylpiperidine, 2,6-Diisobutyl-4-methylpiperidine, 1,2,2,6,6- Pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine,
2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 1,2,
2,5,5-pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 1, Two
4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-methylpyrrole, 2,5
-Dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine and the like, as a compound containing a sulfur atom, thio Phenol, thiophene,
Ethyl 2-thiophenecarboxylate, Ethyl 3-thiophenecarboxylate, 2-Methylthiophene, Methyl mercaptan, Ethyl mercaptan, Isopropyl mercaptan, Butyl mercaptan, Diethyl thioether, Diphenyl thioether, Methyl benzene sulfonate, Methyl sulfite, Ethyl sulfite, etc. Is, as a compound containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,
2-ethyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetramethyl Tetrahydropyran, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, methyl-2,
6-di-t-butylphenyl ketone, 2-ethyl ethyl furarate, isoamyl 2-furarate, methyl 2-furarate, 2
-Propyl furarate and the like, as a compound containing a phosphorus atom, triphenylphosphine, tributylphosphine,
Examples thereof include triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like.

Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

As olefins, in addition to ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-
Alpha-olefins such as pentene may be used. The prepolymerization is preferably carried out in the presence of the above-mentioned inert medium. The prepolymerization is usually performed at a temperature of 100 ° C or lower, preferably -30.
C. to + 30.degree. C., more preferably -20.degree. C. to + 15.degree. The polymerization method may be a batch method or a continuous method, or may be a multi-step polymerization of two or more steps. When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed.

Component B has a concentration of 10 to 5 in the prepolymerization system.
It is used in an amount of 00 mmol / liter, preferably 30 to 200 mmol / liter, and is used in an amount of 1 to 50,000 mol, preferably 2 to 50 mol, per gram atom of titanium in the component A. .

Component C has a concentration of 5 to 10 in the prepolymerization system.
It is used in an amount of 00 mmol / l, preferably 10 to 200 mmol / l.

The olefin polymer is incorporated in the component A by the prepolymerization, and the amount of the polymer is preferably 0.1 to 200 g, particularly 0.5 to 50 g per 1 g of the component A.

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

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

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

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

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

[Chemical 3] Etc. can be illustrated.

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

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

The amount of the organometallic compound used with respect to the catalyst component of the present invention is usually 1 to 2,000 gram moles, preferably 20 to 500 gram moles per gram atom of titanium in the catalyst.

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

[Propylene Copolymerization] Propylene copolymerization is carried out by copolymerizing propylene and ethylene in the presence of the above-mentioned polymerization catalyst component.

The polymerization reaction may be carried out in either a gas phase or a liquid phase. When the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in inert hydrocarbons and in liquid monomers. The polymerization temperature is usually -80 ° C to +1.
It is in the range of 50 ° C, preferably 40 to 120 ° 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. Further, the copolymerization reaction is carried out at a melt flow rate (MFR) of the obtained copolymer of 0.01 to 200 g / 10 min.
It is particularly preferably 0.1 to 100 g / 10 minutes, and the adjustment is usually carried out by adjusting the amount of hydrogen or a known molecular weight regulator used.

[0064]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-ditertiarybutyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, calcium stearate After adding 0.06% by weight of each of them to form pellets by melt-kneading, a test piece was prepared by injection molding (a sheet having a thickness of 1.0 mm was used for measuring haze). Flexural modulus: JIS K 720
3-1982: Haze: according to ASTM D1003. The MFR of the polymer was measured according to ASTM D-1238. The ethylene content of the copolymer was determined by measuring the transmittance of absorption at 733 cm ^-1 by infrared absorption spectroscopy. 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 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 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 material obtained was filtered off at 110 ° C. and 100 at room temperature.
It was washed 7 times with ml of n-hexane to obtain 5.5 g of component A.

In a 500 ml reactor equipped with a prepolymerization stirrer, under a nitrogen gas atmosphere, 3.5 g of the component A obtained above and 3 parts of n-heptane.
00 ml was added and cooled to 0 ° C. with stirring. Next, n of triethylaluminum (hereinafter abbreviated as TEAL)
-Heptane solution (2.0 mol / liter) and 4-oxa-5-oxo-6-methyl-6-heptenyltrimethoxysilane were added to TEAL and 4-oxa-5-oxo-6-methyl- in the reaction system. The 6-heptenyltrimethoxysilane was added so that the concentrations thereof were 60 mmol / liter and 10 mmol / liter, respectively, and the mixture was stirred for 5 minutes. Then, after depressurizing the system, propylene gas was continuously supplied to polymerize propylene for 3.5 hours.
After completion of the polymerization, purge propylene in the gas phase with nitrogen gas,
The solid phase portion was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 1.3 g per 1 g of component A.
Met.

Examples 2 to 4 In the prepolymerization of Example 1, instead of 4-oxa-5-oxo-6-methyl-6-heptenyltrimethoxysilane, the silane compounds shown in Table 1 were used, TEAL or Triisobutylaluminum (hereinafter abbreviated as TIBAL) was used at the concentrations shown in Table 1, the electron-donating compounds shown in Table 1 were used at the concentrations shown in Table 1, and the prepolymerization conditions were changed as shown in Table 1. Example 1 except that
Preliminary polymerization of component A was carried out in the same manner as in 1. to prepare a catalyst component.

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

Comparative Example 2 In the prepolymerization of Example 1, 4-oxa-5-oxo-6-methyl-6-heptenyltrimethoxysilane was not used, and the prepolymerization conditions were as shown in Table 1. In the same manner as in Example 1, component A was preliminarily polymerized to prepare a catalyst component.

[0070]

[Table 1]

Polymerization of Propylene In a fully dried 5 liter autoclave which had been purged with nitrogen, 30.5 mg of the polymerization catalyst component obtained above, n
4 ml of a solution containing 0.3 mol of triethylaluminium in 1 liter of heptane and 3 ml of a solution containing 0.08 mol of diphenyldimethoxysilane in 1 liter of n-heptane were mixed and held for 5 minutes. I put it in. Next, 2.0 liters of hydrogen and 3 liters of liquid propylene were injected under pressure, 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. The MFR of the obtained polymer was 15.7 g / 10.
The ethylene content was 2.5%. When the physical properties were measured, the flexural modulus was 10.87 × 10 ³ kg / cm ² , and the haze was 21.1%. The results are shown in Table 2.

Other than using the polymerization catalyst components obtained in Examples 2 to 4 and Comparative Examples 1 and 2, and adjusting the amount of hydrogen so that the MFR of the copolymers obtained would be the values shown in Table 2, Copolymerization of propylene was carried out in the same manner, and the results are shown in Table 2.
It was shown to. 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 flexural modulus and 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 in Comparative Examples.

[0073]

[Table 2]

[0074]

By carrying out the method of the present invention,
A polypropylene copolymer having an excellent balance of transparency and rigidity can be obtained.

[Brief description of drawings]

FIG. 1 is a plot of measured values of flexural modulus and haze of the 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masatoshi Okura, Masatsuto Okura, Nishitsurugaoka 1-3-1, Oi-cho, Iruma-gun, Saitama Prefecture, Tonen Co., Ltd. 3-3-1 Tonen Co., Ltd. Research Institute (72) Inventor Satoshi Ueki 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Research Institute

Claims (1)

[Claims] 1. (A) Magnesium, titanium, halogen
And a solid catalyst component containing an electron-donating compound as an essential component
Are represented by (B) an organoaluminum compound and (C) a general formula:[However, R¹Is a hydrocarbon group having 1 to 10 carbon atoms, R²Is
A divalent hydrocarbon group having 1 to 10 carbon atoms or -R^FiveO
-, R³Is a hydrocarbon group having 1 to 10 carbon atoms, R ⁶O-,
R⁷ ₃Si- or R⁸ ₃SiO-, R^FourIs a methyl group
Or an ethyl group, x is 1 or 2, y is 0 or
1, z represents 2 or 3, x + y + z = 4, and R^FiveIs
A divalent hydrocarbon group having 1 to 10 carbon atoms, R⁶Has 3 carbons
-10 hydrocarbon groups, R⁷And R⁸Has 1 to 10 carbon atoms
Shows the number of hydrocarbon groups. ] An organosilicon compound represented by
Of (D) olefin in the presence of
Copolymerizing propylene and ethylene in the presence of components
A polypropylene containing 0.01 to 10% by weight of ethylene
A method for producing a copolymer.