JP2001122921A - Method for producing propylene-ethylene random copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a propylene-ethylene random copolymer having excellent fluidity. SOLUTION: This method for producing the propylene-ethylene random copolymer comprises using a polymerization catalyst composed of (A) a solid catalytic component constituted of magnesium, titanium, a halogen and an electron donor as essential components, (B) an organoaluminum compound, (C) an alkoxysilane compound component of the formula R1mSi(OR2)4-m and (D) a halogen compound component of the formula MXn (M is Mg, B, Al, In, Ga, C, Si, Ge, Sn, Sb or a transition metal atom) in a ratio R of the amount of the component (D) to the (C) in the range of 0.1<R<10 (mol/mol).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a propylene-ethylene random copolymer having excellent fluidity.

[0002]

2. Description of the Related Art A propylene-ethylene copolymer is used as a polypropylene resin having improved impact resistance.
It has excellent heat resistance, chemical resistance, and electrical properties, and has good rigidity, tensile strength, optical properties, and workability, and is used in injection molding, film molding, sheet molding, press molding, etc., and polypropylene Has a low specific gravity, and is widely used in the fields of containers, packaging materials, general goods and the like. As a catalyst for producing propylene, a catalyst system containing a solid catalyst component containing magnesium, titanium, halogen and an electron donor compound as essential components is widely used because it has high activity and can omit a decontact step. It is widely known that in this catalyst system, it is effective to add alkylalkoxysilane as one of the catalysts to improve the stereoregularity of polypropylene. However, the polypropylene obtained with this catalyst system generally has poor flowability. The better the fluidity, the lower the melt viscosity,
For products that are molded at a high shear rate, such as injection molding, highly stretched films, and heat fusible fibers, low melt viscosity is advantageous because productivity is improved and energy costs are reduced.

[0003] Generally, in order to control the flowability of polypropylene, hydrogen is used as a molecular weight control agent during polymerization. Therefore, as a means for improving the fluidity, there is a method of increasing the amount of hydrogen added to the reaction system. However, in this catalyst system, even if hydrogen is introduced to the pressure limit of the reaction vessel, the molecular weight is not sufficiently reduced, and a predetermined fluidity may not be obtained. In particular, a propylene-ethylene random copolymer has a higher polymerization pressure than homopolymerization of propylene because ethylene is added to the polymerization system. Further propylene-
It is generally known that in an ethylene random copolymer, at the same hydrogen concentration, the flowability of the obtained polymer deteriorates as the ethylene content increases.

As another method for improving fluidity, there is a method for selecting an alkylalkoxysilane which can produce a propylene-ethylene random copolymer having good fluidity with a small amount of hydrogen added. However,
Generally, such alkylalkoxysilanes have problems such as low catalytic activity, low stereoregularity, and a large amount of low molecular weight components. Also, as in the case described above, the fluidity deteriorates as the ethylene content increases at the same hydrogen concentration, and the fluidity decreases at a high ethylene content. For these reasons, it is difficult to obtain a propylene-ethylene random copolymer having a high ethylene content and excellent fluidity.

[0005]

An object of the present invention is to provide a method for obtaining a propylene-ethylene random copolymer having excellent fluidity.

[0006]

Means for Solving the Problems The present inventors have repeatedly studied a method for producing a propylene-ethylene random copolymer, and as a result, added a specific amount of a specific halogen compound to carry out random copolymerization of propylene and ethylene. The present inventors have found that a propylene-ethylene random copolymer having high fluidity and not deteriorating in fluidity even when the ethylene content increases at the same hydrogen concentration can be obtained, and completed the present invention.

That is, the present invention provides (A) a solid catalyst component comprising magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organoaluminum compound,
(C) R ¹ _m Si (OR ² ) _4-m (wherein R ¹ is a linear aliphatic, branched aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and m ≧ 2 May be two or more different substituents; R ² is a linear aliphatic, branched aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms, and m ≦
In the case of 2, two or more different substituents may be used;
Is an arbitrary integer in the range of 0 ≦ m ≦ 3), and (D) MX _n (M: M
g, B, Al, In, Ga, C, Si, Ge, Sn, S
b or a transition metal atom, X: halogen, n: element M
Propylene and ethylene using a polymerization catalyst comprising a compound component represented by the formula (V), wherein the addition ratio R of (D) to (C) is 0.1 <R <10 (mol / mol). A method for producing a propylene-ethylene random copolymer, characterized by copolymerizing.

[0008]

Embodiments of the present invention will be described below. 1. Solid Catalyst Component (A) The solid catalyst component (hereinafter referred to as component A) used in the present invention contains magnesium, titanium, halogen and an electron donating compound as essential components, and such a component is usually a magnesium compound. By contacting a halogen-containing compound with a titanium compound and an electron-donating compound, as an essential component when each of the compounds does not have a halogen, and as an optional component when any of the compounds has a halogen, Prepared. Hereinafter, each component will be described.

(1) Magnesium compound The magnesium compound is represented by the general formula MgR ³ R ⁴ . In the formula, R ³ and R ⁴ represent the same or different hydrocarbon groups, OR ′ groups (R ′ is a hydrocarbon group), and halogen atoms. More specifically, the hydrocarbon group of R ³ and R ⁴ includes an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group having 1 to 20 carbon atoms. Examples of the halogen atom include 1 to 12 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, such as chlorine, bromine, iodine, and fluorine.

Specific examples of these compounds are shown below. In the following chemical formula, Me: methyl, Et: ethyl, Pr:
Propyl, i-Pr: isopropyl, Bu: butyl, i
-Bu: isobutyl, t-Bu: tertiary butyl,
He: hexyl, Oct: octyl, Ph: phenyl,
cyHe: represents cyclohexyl.

[0011] MgMe ₂ , MgEt ₂ , Mg (i-P
r) ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , Mg
EtBu, MgPh ₂ , MgcyHe ₂ , Mg (OM
e) ₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg
(OHe) ₂ , Mg (OOct) ₂ , Mg (OP
h) ₂ , Mg (OcyHe) ₂ , EtMgCl, BuM
gCl, HeMgCl, i-BuMgCl, t-BuM
gCl, PhMgCl, PhCH ₂ MgCl, EtMg
Br, BuMgBr, PhMgBr, BuMgI, Et
OMgCl, BuOMgCl, HeOMgCl, PhO
MgCl, EtOMgBr, BuOMgBr, EtOM
gI, MgCl ₂ , MgBr ₂ , MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or another magnesium compound when preparing component A. As an example, metallic magnesium, halogenated hydrocarbons and the general formula _{X n M (OR) m-} n alkoxy group-containing compound (wherein, X represents a hydrogen atom, a halogen atom or a C1-20
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 the valence of M, and mn ≧ 0. ) Is contacted.

The hydrocarbon group of X and R in the general formula of the alkoxy group-containing compound includes methyl (Me), ethyl (Et), propyl (Pr), isopropyl, (i-P
r), alkyl groups such as butyl (Bu), isobutyl (i-Bu), hexyl (He) and octyl (Oct); cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl; alkenyl such as allyl, propenyl and butenyl. Groups, aryl groups such as phenyl (Ph), tolyl, and xylyl, and aralkyl groups such as phenethyl and 3-phenylpropyl. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

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

Compound when M is silicon Formula Si (OR)₄(OMe) contained in₄, Si
(OEt)₄, Si (OBu)₄, Si (Oi-Bu)
₄, Si (OHe)₄, Si (OOct)₄, Si (O
Ph)₄Formula XSi (OR)₃HSi (OE
t)₃, HSi (OBu)₃, HSi (OHe)₃, H
Si (OPh)₃, MeSi (OMe)₃, MeSi
(OEt)₃, MeSi (OBu)₃, EtSi (OE
t)₃, PhSi (OEt) ₃, EtSi (OP
h)₃, ClSi (OMe)₃, ClSi (OE
t)₃, ClSi (OBu)₃, ClSi (OP
h)₃, BrSi (OEt)₃Formula X₂Si (OR)₂
Me included in₂Si (OMe)₂, Me₂Si (OE
t)₂, Et₂Si (OEt)₂, MeClSi (OE
t)₂, CHCl₂SiH (OEt)₂, CCl₂Si
H (OEt)₂, MeBuSi (OEt)₂X₃Si
Me included in OR₃SiOMe, Me₃SiOEt,
Me₃SiOBu, Me₃SiOPh, Et₃SiOE
t, Ph₃SiOEt and the like.

Compound when M is Boron B (OEt) ₃ , B (OB) contained in the formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) _{3 and the} like.

Compound when M is Aluminum Al (OMe) ₃ , Al contained in 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 and the} like.

Compounds wherein M is phosphorus P (OMe) ₃ , P (OE) contained in formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) _{3 and the} like.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group II or Group IIIa of the periodic table can be used. The complex has the general formula MgR ³
It is represented by R ⁴ · n (MR ⁵ _m ). As the metal,
Aluminum, zinc, and calcium, and the like, R ⁵ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group. M represents the valence of the metal M, and n represents a number of 0.1 to 10. Specific examples of the compound represented by MR ⁵ _m include AlMe ₃ , AlEt ₃ , A
_{l (i-Bu) 3,} AlPh 3, ZnMe 2, ZnEt
₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh ₂
And the like.

(2) Titanium compound Titanium compounds are trivalent and tetravalent titanium compounds,
To illustrate them, titanium tetrachloride, titanium tetrabromide, trichloroethoxy titanium, trichlorobutoxy titanium,
Examples thereof include dichlorodiethoxytitanium, dichlorodibutoxytitanium, dichlorodiphenoxytitanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

(3) Electron-donating compounds The electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines,
Amides, nitriles, aldehydes, alcoholates, phosphorus bonded to an organic group via carbon or oxygen,
Examples include arsenic and antimony compounds, phosphoamides, thioethers, thioesters, and carbon esters. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, and ethers are preferably used.

(A) Carboxylic acids Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid and crotonic acid. Carboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, and aliphatic oxycarboxylic acids such as tartaric acid;
Cycloaliphatic carboxylic acids such as cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid,
Anisic acid, p-tert-butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimeltic acid, trimesic acid, pyromellitic acid, And aromatic polycarboxylic acids such as melitic acid.

(B) Carboxylic anhydride As the carboxylic anhydride, anhydrides of the above-mentioned carboxylic acids can be used.

(C) Carboxylic acid ester As the carboxylic acid ester, mono- or polyhydric esters of the above carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, and the like. Propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, glutaric acid Dibutyl, 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, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butyl benzoate, ethyl p-anisate, ethyl o-naphthoate, isobutyl o-naphthoate, ethyl cinnamate, monomethyl phthalate Monoethyl phthalate, monobutyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphthalic phthalate Nyl, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate and the like. .

(D) Carboxylic acid halide As the carboxylic acid halide, acid halides of the above carboxylic acids can be used, and 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, Malon Acid bromide, succinic chloride,
Succinic bromide, glutaric chloride, glutaric bromide, adipic chloride, adipic bromide, sebacic chloride, sebacic bromide, maleic chloride, maleic bromide, fumaric chloride, fumaric bromide, tartaric chloride, tartaric 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, o-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. or,
Monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, butyl phthalate chloride may also be used.

(E) Alcohols Alcohols are represented by the general formula R ⁶ OH. In the formula, R ⁶ is an alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-
Ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, pt-butylphenol, n-octylphenol and the like.

(F) Ethers Ethers are represented by the general formula R ⁷ OR ⁸ . In the formula, R ⁷ and R ⁸ are alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbons,
R ⁷ and R ⁸ 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, anisole, and ethylphenyl ether. .

(4) Halogen-containing compounds Examples of halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, groups IIIa and IVa of the periodic table,
Halides of Va group elements (hereinafter referred to as metal halides) and the like can be mentioned.

(A) Halogenated Hydrocarbon The halogenated hydrocarbon is a mono- or polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon having 1 to 12 carbon atoms. Specific examples of those compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride,
Carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methyl chloroform, methyl bromoform, methyl iodoform, 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 and the like, and alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, and the like.Aromatic compounds include chlorobenzene, bromobenzene, and o. -Dichlorobenzene, p-dichlorobenzene,
Hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like can be mentioned. These compounds may be used alone or in combination of two or more.

(B) Halogen-Containing Alcohol As the halogen-containing alcohol, one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are included. Compounds substituted with halogen atoms can be used. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, and a chlorine atom is preferable.

Examples of these compounds include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chloro-o-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlororesorcin, 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-
Bromoresorcin, (m, o, p) -fluorophenol, p-iodophenol, 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro- 1- (α-chloromethyl) -1-propanol, 2,3-dibromo-
1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-
1-naphthol, 2,2,2-trichloroethanol,
1,1,1-trichloro-2-propanol, β, β,
β, -trichloro-tert-butanol, 2,3,4
-Trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4
6-tribromophenol, 2,3,5-tribromo-
2-hydroxytoluene, 2,3,5-tribromo-4
-Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol,
2,4,6-triiodophenol, 2,3,4,6-
Tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,8 tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin, and the like. Can be

(C) Halogen having a hydrogen-silicon bond
Silicon halide compound A silicon halide compound having a hydrogen-silicon bond
HSiCl₃, H₂SiCl₂, H₃SiCl,
HSiMeCl₂, HSiEtCl₂, HSi (t-B
u) Cl₂, HSiPhCl₂, HSiMe₂Cl, H
Si (i-Pr)₂Cl, H₂SiEtCl, H₂Si
(N-Bu) Cl, H₂(C₆H₄CH ₃) SiCl,
HSiPh₂Cl and the like.

(D) Metal halides As metal halides, B, Al, Ga, In, Tl,
Chloride of Si, Ge, Sn, Pb, As, Sb, Bi,
Fluoride, bromide, iodide, especially BC
l₃, BBr₃, BI₃, AlCl₃, AlBr₃, G
aCl₃, GaBr ₃, InCl₃, TlCl₃, Si
Cl₄, SnCl₄, SbCl₅, SbF₅Etc. are preferred
is there.

(5) Preparation of Component A As a method for preparing Component A, a magnesium compound (Component 1), a titanium compound (Component 2), and an electron donating compound (Component 3) are contacted in this order. After contacting the component 3, the component 2 may be contacted, the component 1, the component 2 and the component 3 may be contacted at the same time. Also, the halogen-containing compound can be contacted before contacting the component 2.

The contact with the component 1, the component 2 and the component 3, and the halogen-containing compound which can be brought into contact as required, may be carried out by mixing and stirring in the presence or absence of an inert medium, or mechanically. This is done 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, and aromatic hydrocarbons such as benzene, toluene and xylene can be used.

A desirable method for preparing the component A used in the present invention is described in JP-A-57-63310 and JP-A-58-198303.
Nos. 62-146904 and 63-264607
And JP-A-4-8709, JP-A-7-216017, JP-A-7-258323 and JP-A-2578408. More specifically, by contacting (i) metallic magnesium, (b) halogenated hydrocarbons, (iii) the general formula X _{n M} (OR) compound of _m-n (the same as the alkoxy group-containing compound) A method in which the obtained magnesium-containing solid is contacted with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (Japanese Patent Laid-Open No.
JP-A-3-264607), (a) after contacting a magnesium dialkoxide with a silicon halide compound having a hydrogen-silicon bond, (c) contacting a titanium halide compound, and then (d) electron donation Contacting with a reactive compound (and, if necessary, a titanium halide compound)
146904), (a) contacting a magnesium dialkoxide with (b) a silicon halide compound having a hydrogen-silicon bond, (c) contacting with an electron donating compound, and then (d)
A method of contacting a titanium compound (JP-A-58-1985)
No. 03 publication), and among these, the method is most desirable. The component A is prepared as described above, and the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

2. Organoaluminum Compound (B) As the organoaluminum compound (hereinafter, referred to as component B), R ⁹ _n AlX ′ _3-n (where R ⁹ is an alkyl group or an aryl group, X ′ is a halogen atom, an alkoxy group) Or a hydrogen atom, and n is an arbitrary number in the range of 1 ≦ n ≦ 3), for example, trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide , Dialkylaluminum monoalkoxides and dialkylaluminum monohydrides having 1 to 18 carbon atoms, preferably 2 carbon atoms
Particularly preferred are -6 alkylaluminum compounds or mixtures or complex compounds thereof.

Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, Monoalkylaluminum monohalides such as diethylaluminum monohalide such as diethylaluminum iodide and diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride Dihalides, alkyl aluminum sesquihalides such as ethyl aluminum 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 Examples include dialkyl aluminum hydrides such as aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, and the like. Among these, trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or mixtures or complex compounds thereof, which are easily available industrially. Can be used together.

An organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄
H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , ((C ₂ H ₅ ) ₂
Al) ₃ N and the like.

3. Alkylalkoxysilane (C) R in the alkylalkoxysilane compound component represented by R ¹ _m Si (OR ² ) _4-m (hereinafter referred to as component C).
¹ is a linear aliphatic, branched aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and 2 when m ≧ 2.
More than one kind of different substituents may be used. R ² is a linear aliphatic, branched aliphatic or alicyclic hydrocarbon group having 1 to 10, preferably 1 to 6 carbon atoms, and when m ≦ 2, two or more different substituents Group. Also, m is 0
It is any integer in the range of ≦ m ≦ 3.

As R ¹ , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a se
c-butyl group, tert-butyl group, n-pentyl group,
Isoamyl group, tert-amyl group, cyclopentyl group, cyclohexyl group, norbornyl group, indenyl group, indanyl group, 4,5,6,7-tetrahydroindenyl group, 4,5,6,7-tetrahydroindanyl group, α -Naphthyl group, β-naphthyl group, [4,4,0]
Examples include a bicyclodecane-2-yl group and a [4,4,0] bicyclodecane-3-yl group. R ¹ is preferably selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group.

As R ² , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a se
c-butyl group, tert-butyl group, n-pentyl group,
Examples include an isoamyl group, a tert-amyl group, a cyclopentyl group, a cyclohexyl group, and a menthyl group. R
² is preferably a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a tert-butyl group,
-Selected from amyl groups.

Specific examples of the compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetra-n-butoxysilane;

Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, sec-butyltrimethoxysilane, tert-butyltrimethoxysilane, n-pentyltrimethoxysilane , Isoamyltrimethoxysilane, tert-amyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornyltrimethoxysilane, indenyltrimethoxysilane, indanyltrimethoxysilane, 4,5,6,7-
Tetrahydroindenyltrimethoxysilane, 4,5
6,7-tetrahydroindanyltritrimethoxysilane, α-naphthyltrimethoxysilane, β-naphthyltrimethoxysilane, [4,4,0] bicyclodecane-2
-Yltrimethoxysilane, [4,4,0] bicyclodecane-3-yltrimethoxysilane;

Methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, sec-butyltriethoxysilane, tert-butyltriethoxysilane, n-pentyltriethoxysilane , Isoamyltriethoxysilane, tert-amyltriethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, norbornyltriethoxysilane, indenyltriethoxysilane, indanyltriethoxysilane, 4,5,6,7-
Tetrahydroindenyltriethoxysilane, 4,5,
6,7-tetrahydroinindanyltriethoxysilane, α-naphthyltriethoxysilane, β-naphthyltriethoxysilane, [4,4,0] bicyclodecane-2
-Yltriethoxysilane, [4,4,0] bicyclodecane-3-yltriethoxysilane;

Tert-butylethoxydimethoxysilane, tert-butylpropoxydimethoxysilane, t
tert-butyl isopropoxydimethoxysilane, te
rt-butyl-n-butoxydimethoxysilane, ter
t-butyl-sec-butoxydimethoxysilane, te
rt-butyl-tert-butoxydimethoxysilane,
tert-butylcyclopentyloxydimethoxysilane, tert-butylcyclohexyloxydimethoxysilane, tert-butylmenthoxydimethoxysilane;

Cyclopentylethoxydimethoxysilane, cyclopentylpropoxydimethoxysilane, cyclopentylisopropoxydimethoxysilane, cyclopentyl-n-butoxydimethoxysilane, cyclopentyl-sec-butoxydimethoxysilane, cyclopentyl-tert-butoxydimethoxysilane, cyclopentylcyclopentyloxydimethoxysilane, cyclopentyl Cyclohexyloxydimethoxysilane, cyclopentylmentoxydimethoxysilane;

Cyclohexylethoxydimethoxysilane, cyclohexylpropoxydimethoxysilane, cyclohexylisopropoxydimethoxysilane, cyclohexyl-n-butoxydimethoxysilane, cyclohexyl-sec-butoxydimethoxysilane, cyclohexyl-tert-butoxydimethoxysilane, cyclohexylcyclopentyloxydimethoxysilane, cyclohexyl Trialkoxysilanes such as cyclohexyloxydimethoxysilane and cyclohexylmentoxydimethoxysilane;

Dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, di-sec-butyldimethoxysilane, di-te
rt-butyldimethoxysilane, di-n-pentyldimethoxysilane, diisoamyldimethoxysilane, di-t
ert-amyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane,
Bis ([4,4,0] bicyclodecane-2-yl) dimethoxysilane, bis ([4,4,0] bicyclodecane-
3-yl) dimethoxysilane;

Dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, di-sec-butyldiethoxysilane, di-te
rt-butyldiethoxysilane, di-n-pentyldiethoxysilane, diisoamyldiethoxysilane, di-t
ert-amyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane,
Bis ([4,4,0] bicyclodecane-2-yl) diethoxysilane, bis ([4,4,0] bicyclodecane-
3-yl) diethoxysilane;

Methylethyldimethoxysilane, methylpropyldimethoxysilane, methylisopropyldimethoxysilane, methyl n-butyldimethoxysilane, methyl-sec-butyldimethoxysilane, methyl-tert
-Butyldimethoxysilane, methyl-n-pentyldimethoxysilane, methylisoamyldimethoxysilane, methyl-tert-amyldimethoxysilane, methylcyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane, methylnorbornyldimethoxysilane, methylindenyldimethoxysilane, methyl Indanyldimethoxysilane, methyl-4,5,6,7-tetrahydroindenyldimethoxysilane, methyl-4,
5,6,7-tetrahydroinindanyldimethoxysilane, methyl-α-naphthyldimethoxysilane, methyl-β-naphthyldimethoxysilane, methyl ([4,4
0] bicyclodecane-2-yl) dimethoxysilane, methyl ([4,4,0] bicyclodecane-3-yl) dimethoxysilane;

Ethylpropyldimethoxysilane, ethylisopropyldimethoxysilane, ethyl-n-butyldimethoxysilane, ethyl-sec-butyldimethoxysilane, ethyl-tert-butyldimethoxysilane, ethyl-n-pentyldimethoxysilane, ethylisoamyldimethoxysilane, Ethyl-tert-amyldimethoxysilane, ethylcyclopentyldimethoxysilane,
Ethylcyclohexyldimethoxysilane, ethylnorbornyldimethoxysilane, ethylindenyldimethoxysilane, ethylindanyldimethoxysilane, ethyl-
4,5,6,7-tetrahydroindenyldimethoxysilane, ethyl-4,5,6,7-tetrahydroindanyldimethoxysilane, ethyl-α-naphthyldimethoxysilane, ethyl-β-naphthyldimethoxysilane,
Dialkoxysilanes such as ethyl ([4,4,0] bicyclodecane-2-yl) dimethoxysilane and ethyl ([4,4,0] bicyclodecane-3-yl) dimethoxysilane;

Monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, tert-butyldimethylmethoxysilane and the like can be mentioned.

4. M of the compound in component (D) represented by MX _n compound represented by the component (D) MX _n is, Mg,
B, Al, In, Ga, C, Si, Ge, Sn, Sb or a transition metal atom; Ti, Mg, B, Al, Co,
Rh, Ni, Pd, Zn, C, and Si are desirable, and B, Al, and C are particularly desirable. X represents a halogen atom;
r and I are desirable, and Br is particularly desirable. Specific compounds include boron tribromide, boron triiodide, boron trichloride, aluminum tribromide, palladium dibromide, nickel dibromide, zinc dibromide, magnesium dibromide, carbon tetrabromide Etc., especially boron tribromide, boron triiodide,
Aluminum tribromide and carbon tetrabromide are preferred.

5. Component A, Component B, Component C and Component D Use Ratio The catalyst used in the present invention comprises the above-mentioned components. The amount of Component B used with respect to Catalyst Component A is based on 1 mole of titanium in Catalyst Component A. , Usually 1 to 2000 mol, especially 20
Component C is usually 0.2 to 400 mol, preferably 5 to 2 mol, per 1 mol of titanium in component A.
00 mole is desirable. As a feature of the present invention, it is essential that the addition ratio R of the component D to the component C is in the range of 0.1 <R <10 (mol / mol), and particularly 0.1 <R.
<2.0 is preferred. When R ≦ 0.1, the effect of improving the fluidity is not sufficient, and when R ≧ 10, problems such as a decrease in catalytic activity and an increase in low molecular weight components arise. Further, the catalyst component A
May be preliminarily polymerized and used if necessary.

6. Ethylene-propylene random copolymerization The random copolymerization of propylene and ethylene is carried out using a catalyst comprising the above components. The random copolymerization reaction of ethylene and propylene may be performed in a gas phase or a liquid phase. When the reaction is performed in a liquid phase, the reaction can be performed in an inert hydrocarbon such as propane, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene and in a liquid monomer. The polymerization temperature is usually -8
The reaction is performed at a temperature of 0 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atm.
The molecular weight of the resulting polymer is controlled by the presence of hydrogen or other known molecular weight regulators and the use of Component D. The polymerization reaction is carried out by a continuous or batch reaction, and the condition may be a commonly used condition. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages. Furthermore, in the ethylene-propylene random copolymer of the present invention, other olefins such as 1-
Similar effects can be obtained even if a small amount of butene, 1-hexene, 4-methyl-1-pentene or the like is copolymerized.

[0057]

The present invention will be specifically described below with reference to examples and comparative examples. The MFR (melt flow rate) of the polymer was measured according to ASTM D-1238. The ethylene content in the ethylene-propylene random copolymer was measured by IR. The melting point of the polymer was determined by using Perkin Elmer DSC-7 from room temperature to 20 ° C.
Raise the temperature to 0 ° C, hold at 200 ° C for 10 minutes,
0 ℃ / min, 1 min to 200 ℃ after holding at 40 ℃ for 10min
The measurement was performed under the condition of a temperature rise of 0 ° C./min. The percentages (%) are by weight unless otherwise specified.

Example 1 (Example 1-1) (1) Preparation of solid catalyst component A containing magnesium, titanium, halogen and an electron donating compound as essential components In a 1 liter reaction vessel equipped with a reflux condenser, Under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity 99.
8.39 g of 5% and an average particle diameter of 1.6 mm) and 250 ml of n-hexane were added, and the mixture was stirred at 68 ° C. for 1 hour.
Metal magnesium was removed and dried under reduced pressure at 65 ° C. to obtain preactivated metal magnesium. next,
140 ml of n-butyl ether and n-butylmagnesium chloride
A suspension obtained by adding 0.5 ml of a -butyl ether solution (1.75 mol / l) was maintained at 55 ° C., and a solution obtained by dissolving 38.5 ml of n-butyl chloride in 50 ml of n-butyl ether was added for 50 minutes. It was dropped. After conducting the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was kept at 25 ° C. Then, 55.7 ml of ethyl orthoformate was added dropwise to the reaction solution over 1 hour.
After the completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, and the reaction product solid was washed six times with 300 ml each of n-hexane,
Dry under reduced pressure at room temperature for 1 hour, magnesium 19.0%,
31.6 g of a magnesium-containing solid containing 28.9% of chlorine
Was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 6.3 g of magnesium-containing solid and n-heptane 50 were placed under a nitrogen gas atmosphere.
Milliliter was added as a suspension, and a mixed solution of 20 ml (0.02 mmol) of 2,2,2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel for 30 minutes while stirring at room temperature. Stirred at 80 ° C. for 1 hour. The obtained solid was filtered, washed four times with 100 ml each of n-hexane at room temperature, and twice with 100 ml each of toluene to obtain a solid component.

40 ml of toluene was added to the above solid component, and the volume ratio of titanium tetrachloride / toluene was 3/3.
Titanium tetrachloride was added so that the temperature became 2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance was separated by filtration at 90 ° C.,
Washed at 90 ° C. twice. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene became 3/2, and the mixture was stirred at 120 ° C. for 2 hours. The obtained solid substance is
The mixture was filtered at 10 ° C. and washed 7 times with 100 ml of n-hexane at room temperature seven times to obtain 5.5 g of a component A.

(2) Polymerization In a 1.5-liter stainless steel autoclave provided with a stirrer and purged with nitrogen and sufficiently dried, 0.4 mmol of triethylaluminum, 0.08 mmol of cyclohexylmethyldimethoxysilane, and boron tribromide were added. 0.01
6 mmol was added. The catalyst component A obtained above and 100 ml of propylene were placed in a catalyst holder attached to an autoclave. Then, 1600 ml of hydrogen (normal temperature and normal pressure, the same applies hereinafter) and 900 ml of liquid propylene were injected into the autoclave.
Thereafter, the temperature in the autoclave was raised to 68 ° C., and then the catalyst holder was pressurized with nitrogen, and the catalyst and propylene contained therein were introduced into the autoclave to perform propylene homopolymerization. After one hour, unreacted propylene and hydrogen were purged, the polymer was removed from the autoclave and dried. The total amount of the obtained polymer was 158 g (catalytic activity: 34800 g-p
poly / g-cat), MFR is 14.9 g / 10 min,
Melting point was 161.5 ° C. The pressure in the autoclave during the polymerization was 3.30 MPa.

(Example 1-2) (Example 1-1 (2))
In the above, after injecting liquid propylene,
Propylene-ethylene random copolymerization was carried out in the same manner as in (Example 1-1) except that 400 ml was injected and ethylene was introduced into the autoclave at a rate of 60 ml / min during the polymerization. Table 1 shows the results.

(Example 1-3) The amount of ethylene introduced before the polymerization was 4000 ml, and the amount of ethylene introduced during the polymerization was 1
Except that the rate was 00 ml / min (Example 1-
Propylene-ethylene random copolymerization was performed in the same manner as in 2). Table 1 shows the results.

Example 2 (Examples 2-1 to 2-3) The addition amount of boron tribromide was 0.0
Homopolymerization and propylene-ethylene random copolymerization with different ethylene contents were performed in the same manner as in Example 1 except that the amount was changed to 4 mmol. Table 1 shows the results.

Example 3 (Examples 3-1 to 3-3) The addition amount of boron tribromide was 0.0
Propylene homopolymerization and propylene-ethylene random copolymerization with different ethylene contents were carried out in the same manner as in Example 1 except that the amount was changed to 8 mmol. Table 1 shows the results.

Comparative Example 1 (Comparative Examples 1-1 to 1-3) Propylene homopolymerization and propylene-ethylene random copolymers having different ethylene contents were carried out in the same manner as in Example 1 except that boron tribromide was not added. Polymerization was performed. Table 1 shows the results.

Comparative Example 2 (Comparative Examples 2-1 to 2-3) The addition amount of boron tribromide was 0.0
Propylene homopolymerization and propylene with a different ethylene content were carried out in the same manner as in Example 1 except that the amount was changed to 08 mmol.
Ethylene random copolymerization was performed. Table 1 shows the results.

Comparative Example 3 Propylene-ethylene random copolymerization was carried out in the same manner as in Example 1-2, except that the amount of boron tribromide added was changed to 0.8 mmol. Table 1 shows the results.

Comparative Example 4 (Comparative Examples 4-1 to 4-3) Propylene homopolymerization and ethylene content were carried out in the same manner as in Example 1 except that boron tribromide was not added and the amount of hydrogenation was changed to 5000 ml. Was changed, and propylene-ethylene random copolymerization was performed.
Table 1 shows the results.

Comparative Example 5 (Comparative Examples 5-1 to 5-3) Propylene homopolymerization and ethylene content were measured in the same manner as in Comparative Example 1 except that n-propyltriethoxysilane was used instead of cyclohexylmethyldimethoxysilane. A modified propylene-ethylene random copolymerization was performed. Table 1 shows the results.

[0070]

[Table 1]

As is clear from Table 1, when the random copolymerization of propylene and ethylene is carried out with a constant hydrogenation amount as in Comparative Examples 1 and 4, the fluidity decreases as the ethylene content increases. When boron tribromide is added during the random copolymerization of propylene and ethylene as in Examples 1 to 3, the MFR does not depend on the ethylene content at a constant hydrogenation amount, but depends only on the addition amount of boron tribromide. Become.
However, when the addition ratio of boron tribromide to cyclohexylmethyldimethoxysilane is 0.1 mol / mol or less as in Comparative Example 2, the fluidity decreases as the ethylene content increases. Here, the addition of boron tribromide does not change the catalytic activity, melting point and the like of the propylene-ethylene random copolymer as compared with the system without the addition.

When the addition ratio of boron tribromide to cyclohexylmethyldimethoxysilane is 10 mol / mol or more as in Comparative Example 3, the MFR increases but the catalytic activity decreases significantly. Further, by increasing the hydrogenation amount without adding boron tribromide as in Comparative Example 4, a propylene-ethylene random copolymer having a similarly high MFR can be obtained. However, in this case, the polymerization pressure is increased, so that a required amount of hydrogen may not be added in a polymerization reactor having a low pressure resistance. Especially high ethylene content and high M
FR propylene-ethylene random copolymer can be obtained only by a method of adding component D due to the problem of polymerization pressure. Further, as a method for obtaining a propylene-ethylene random copolymer having a high MFR, there is a method of changing to a polymerization third component having good MFR responsiveness to the hydrogenation amount as in Comparative Example 5. However, even in this case, since the fluidity decreases as the ethylene content increases, the amount of hydrogenation is limited, and the propylene-ethylene random copolymer having high fluidity and high ethylene content as in the Examples is You can't get it.

[0073]

As is clear from the examples and comparative examples of the present invention, the same hydrogenation amount can be obtained by adding a specific polymerization fourth component in a specific range during propylene-ethylene random copolymerization. Even if the ethylene content increases, the MFR of the obtained sample does not decrease. Therefore, a propylene-ethylene random copolymer having good fluidity can be produced. Propylene by addition of the fourth component-
There is no change in physical properties such as the melting point of the ethylene random copolymer.
By this method, propylene having high flowability at a low polymerization pressure is used.
It becomes possible to produce an ethylene random copolymer.

Continued on the front page (72) Inventor Masafumi Imai 3-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term (reference) 4J028 AA01A AA02A AB01A AB02A AC04A AC05A AC06A AC07A AC15A BA00A BA01A BA02A BA02B BA03A BB00A BB01A BB02A BB02B BC05A BC06A BC07A BC15A BC15B BC16B BC17B BC19B BC24B BC33A BC34A BC34B BC35A CA02C CA14A CA14C CA15A CA15C CA16A CA17A CA17C CA18A CA18C CA19A CA20A CB12A CB14A CB23A CB25A CB26A CB27A CB37A CB38A CB43A CB44A CB54A CB57A CB58A CB88A CB92A CB92B CB93A CB95A CB96A EA01 EB02 EB04 EB05 EB09 EB10 EC03 EC04 FA01 FA02 FA04 FA07 FA09 GA07 GA19 GB01 4J100 AA02Q AA03P CA04 DA36 FA09

Claims (1)

[Claims] 1. A solid catalyst component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) an organoaluminum compound, (C) R ¹ _m Si (O
R ² ) _4-m (wherein, R ¹ is a linear aliphatic, branched aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and when m ≧ 2, two or more types are used) R ² is a straight-chain aliphatic, branched aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms, and when m ≦ 2, two or more different substituents M is an arbitrary integer in the range of 0 ≦ m ≦ 3); and (D) MX _n (M: Mg, B, Al,
In, Ga, C, Si, Ge, Sn, Sb or a transition metal atom, consisting of a compound component represented by X: halogen, n: valence of element M), and addition of (D) to (C) A method for producing a propylene-ethylene random copolymer, characterized in that propylene and ethylene are copolymerized using a polymerization catalyst having a quantitative ratio R in a range of 0.1 <R <10 (mol / mol).