JPH08269123A - Production of propylene copolymer - Google Patents

Abstract

PURPOSE: To efficiently produce a random copolymer of propylene and ethylene, having a wide distribution of molecular weight and containing a small amount of a low stereoregular component. CONSTITUTION: This method for producing a propylene copolymer having 0.1-6wt.% ethylene content is to copolymerize propylene with ethylene using a polymerization catalyst comprising a solid catalyst component prepared by prepolymerizing (A) a solid component consisting essentially of magnesium, titanium, a halogen and an electron donative compound, (B) an organoaluminum compound, (C) an alkyltrialkoxysilane represented by the formula, R<1> Si(OR<2> )(OCH3 )2 (R<1> denotes a 3-6C branched or cyclic alkyl group; R<2> denotes a 3-6C branched alkyl group), the component (B) and (D) an alkyltrialkoxysilane represented by the formula, R<3> Si(OR<4> )2 (OCH3 ) (R<3> denotes a 3-6C straight-chain alkyl group; R<4> denotes a 3-5C branched alkyl group).

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 random copolymer of propylene and ethylene, and more particularly to a method for efficiently producing a propylene / ethylene random copolymer used in applications requiring a wide molecular weight distribution. Regarding

[0002]

2. Description of the Related Art A catalyst system containing a solid catalyst component containing magnesium, titanium, halogen and an electron-donating compound as essential components is highly active and can be omitted from the decatalyzing step, and is therefore widely used in the production of polypropylene. . It is widely known that the addition of alkylalkoxysilane as one of the catalyst components is effective for improving the stereoregularity of polypropylene in this catalyst system. However, in the case of producing a random copolymer of propylene and ethylene, the amount of the low stereoregularity component is larger than that in the case of the homopolymerization of propylene. Therefore, even if an alkylalkoxysilane is added as one of the catalyst components. In some cases, the effect was not sufficient. This is particularly noticeable when producing a random copolymer of propylene and ethylene having a wide molecular weight distribution, and because of the large amount of low stereoregular components, stickiness is the cause of stickiness in the drying step of the manufacturing process. Was sometimes significantly reduced.

[0003]

SUMMARY OF THE INVENTION The present invention has a wide molecular weight distribution and a low stereoregularity by using a specific catalyst system containing a solid catalyst component containing magnesium, titanium, a halogen and an electron donating compound as essential components. Provided is a method for efficiently producing a random copolymer of propylene and ethylene having a small amount of a sex component.

[0004]

[Means for Solving the Problem] Magnesium, titanium,
As a method for producing polypropylene having a wide molecular weight distribution using a catalyst system containing a solid catalyst component containing halogen and an electron-donating compound as essential components, a method of adding an alkylalkoxysilane having both branched alkyl groups and branched alkoxy groups is used. It was developed (JP-A-3-119004
No. 5,331,233), in the production of a random copolymer of propylene and ethylene, simple use of this type of alkylalkoxysilane results in a low stereoregular component even if the molecular weight distribution is widened. The volume did not get small enough. Therefore, the present inventors have focused their attention on the structure of the alkylalkoxysilane, and have conducted intensive studies on the relationship between the structure of the alkyl group and the alkoxy group, the molecular weight distribution, the amount of low stereoregular components, etc., and as a result, the present invention was completed. I arrived.

SUMMARY OF THE INVENTION That is, the gist of the present invention is to provide a solid catalyst component, a component (B) and a component (D) obtained by prepolymerizing propylene in the presence of the following components (A) to (C). A method for producing a propylene copolymer having an ethylene content of 0.1 to 6% by weight, which comprises copolymerizing propylene and ethylene using a polymerization catalyst comprising

(A) A solid component containing magnesium, titanium, a halogen and an electron donating compound as essential components. (B) Organoaluminum compound. (C) An alkyltrialkoxysilane represented by R ¹ Si (OR ² ) (OCH ₃ ) ₂ . (In the formula, R ¹ has 3 carbon atoms.
To 6 are branched or cyclic alkyl groups, and R ² is a branched alkyl group having 3 to 6 carbon atoms. ) (D) An alkyltrialkoxysilane represented by R ³ Si (OR ⁴ ) ₂ (OCH ₃ ). (In the formula, R ³ has ³ carbon atoms.
To 6 are straight-chain alkyl groups, and R ⁴ is a branched alkyl group having 3 to 5 carbon atoms. ) The polymerization catalyst used in the present invention is as follows.

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

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ⁵ R ⁶ . In the formula, R ⁵ and R ⁶ are the same or different hydrocarbon groups,
An OR 'group (R' is a hydrocarbon group) and a halogen atom are shown.
More specifically, the hydrocarbon group of R ⁵ and R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR ′ group is R ′ having a carbon number. Examples of the halogen atom include 1 to 12 alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups, and examples of the halogen atom include chlorine, bromine, iodine and fluorine. Specific examples of these compounds are shown below, but in the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, H.
e: hexyl, Oct: octyl, Ph: phenyl, c
yHe: represents cyclohexyl, respectively.

MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtOMgCl,
BuOMgCl, HeOMgCl, PhOMgCl, E
tOMgBr, BuOMgBr, EtOMgI, MgC
l ₂ , MgBr ₂ , MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing the component A. As one example thereof, metallic magnesium, a halogenated hydrocarbon and an alkoxy group-containing compound represented by the general formula X _n M (OR) _mn [in the formula,
X is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, and m is an atom of M. Value, m> n ≧ 0. ] The method of making it contact is mentioned.

The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr) and 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. And phenyl (Ph), tolyl, xylyl and other aryl groups, and phenethyl and 3-phenylpropyl and other aralkyl groups. 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.

Compound in which M is carbon C (OMe) ₄ , C (OE) included in the 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 included in the 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 Si (OMe) ₄ , Si Included in Formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (OE contained in the formula XSi (OR) ₃
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) ₃ ; Formula X ₂ Si (OR) ₂
Included in Me ₂ Si (OMe) ₂ and Me ₂ Si (OE
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ Si
H (OEt) ₂ ; MeBuSi (OEt) ₂ : X ₃ Si
Me ₃ SiOMe, Me ₃ SiOEt contained in OR,
Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE
t, Ph ₃ SiOEt, and the like.

Compound where M is Boron B (OEt) ₃ , B (OB) included in 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 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 and the} like can be mentioned. Compound in which M is phosphorus P (OMe) ₃ , P (OE) included in the formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ etc. are mentioned.

Further, as the magnesium compound, a complex with an organic compound of Group II or IIIa metal (M) of the periodic table can be used. The complex has the general formula MgR ⁵
It is represented by R ⁶ · n (MR ⁷ _m ). As the metal,
It is aluminum, zinc, calcium or the like, and R ⁷ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. Further, m represents the valence of the metal M, and n represents the number of 0.1 to 10. Specific examples of the compound represented by MR ⁷ _m include AlMe ₃ , AlEt ₃ ,
_{Ali-Bu 3, AlPh 3,} ZnMe 2, ZnE
t ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh
₂ etc.

(2) Titanium compound The titanium compound is a compound of divalent, trivalent and tetravalent titanium. Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium and dichlorotitanium. Examples thereof include rudiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlortributoxy titanium, tetrabutoxy titanium and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

(3) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples thereof include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic 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 isobutyrate, propyl pivalate, pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate,
Monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p
-Ethyl tertiary butyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used,
As specific examples thereof, 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 ⁸ OH. In the general formula, R ⁸ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol,
Examples include isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol.

The ethers are represented by the general formula R ⁹ OR ¹⁰ . In the general formula, R ⁹ and R ¹⁰ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ⁹ and R ¹⁰ 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, ethyl phenyl ether and the like.

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, and after contacting the components 1 and 3 with each other. The method of contacting the component 2, the method of contacting the component 1, the component 2 and the component 3 at the same time can be adopted. It is also possible to contact the halogen-containing compound before contacting component 2.

As the halogen-containing compound, halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, Group IIIa of the periodic table, I
Examples thereof include Va group and halides of Va group elements (hereinafter referred to as “metal halide”).

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetrachloride. Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins and the like, alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane and the like, and aromatic compounds include chlorobenzene, bromobenzene, o-dichloro. Examples thereof include benzene, 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. It is 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.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S.
_{iCl, H (CH 3) SiCl} 2, H (C 2 H 5) Si
Cl ₂ , H (t-C ₄ H ₉ ) SiCl ₂ , H (C
₆ H ₅ ) SiCl ₂ , H (CH ₃ ) ₂ SiCl, H (i
_{-C 3 H 7) 2 SiCl,} H 2 (C 2 H 5) SiCl,
_{H 2 (n-C 4 H} 9) SiCl, H 2 (C 6 H 4 C
_{H 3) SiCl, H (C} 6 H 5) 2 SiCl 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-58-198.
No. 503, No. 62-146904, and the like. More specifically, (a) magnesium metal, (b) halogenated hydrocarbon, (c) general formula X _n M (OR) _The magnesium-containing solid obtained by contacting the _mn compound (the same as the above-mentioned alkoxy group-containing compound) is contacted with (d) halogen-containing alcohol, and then (e) electron donating compound and (f) titanium compound. Method (JP-A-63 / 1988)
-264607 publication),

After contacting (a) the magnesium dialkoxide with the (b) silicon halide compound having a hydrogen-silicon bond, (a) contacting the titanium halide compound, and then (d) contacting with an electron donating compound. (A further contact with a titanium halide compound if necessary) (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 gazette). Among these, the most preferable method is the most preferable method. 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.

Organoaluminum Compound The organoaluminum compound (hereinafter referred to as component B) is
General formula, R ¹¹ _n AlX _3-n (wherein R ¹¹ 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 within the range of 1 ≦ n ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide and a dialkylaluminum monohalide having 1 to 18 carbon atoms, preferably Particularly preferred are alkylaluminum compounds having 2 to 6 carbon atoms or mixtures or complex compounds 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 croside, diethyl aluminum bromide, diethyl aluminum. Dialkyl aluminum monohalides such as iodide and diisobutyl aluminum chloride; monoalkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride; ethyl aluminum Seth Alkyl aluminum sesquihalides such as chlorides; dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisopropyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide; dimethyl aluminum hydride, diethyl aluminum hydride And dialkyl aluminum hydride such as dipropyl aluminum hydride and diisobutyl aluminum hydride. Among these,
Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable.

Organosilicon Compound The organosilicon compound (C), which is one component of the catalyst component of the present invention (hereinafter referred to as component C), has the general formula R ¹ Si (OR
² ) Alkyltrialkoxysilane represented by (OCH ₃ ) ₂ (wherein R ¹ is a branched or cyclic alkyl group having 3 to 6 carbon atoms, R ² is a branched alkyl group having 3 to 6 carbon atoms, respectively) shown.), and, R ¹ is for example i-
Examples thereof include a propyl group, a t-butyl group, a s-butyl group, a t-amyl group, a cyclopentyl group, and a cyclohexyl group, and R ² is, for example, an i-propyl group, a t-butyl group, a s- group.
Examples thereof include a butyl group and a t-amyl group. In particular,
t-butoxycyclopentyldimethoxysilane, i-propoxycyclopentyldimethoxysilane, s-butoxycyclopentyldimethoxysilane, t-amyloxycyclopentyldimethoxysilane, t-butoxycyclohexyldimethoxysilane, i-propoxycyclohexyldimethoxysilane, s-butoxycyclohexyldimethoxysilane, Examples thereof include t-amyloxycyclohexyldimethoxysilane.

Further, it is one component of the catalyst of the present invention (D).
Is an alkyltrialkoxysilane represented by the general formula R ³ Si (OR ⁴ ) ₂ (OCH ₃ ) (in the formula, R ³ has 3 to 6 carbon atoms). A linear alkyl group, R ⁴ represents a branched alkyl group having 3 to 5 carbon atoms, respectively, and R ³ is, for example,
Examples thereof include n-propyl group, n-butyl group, and n-hexyl group, and R ⁴ includes, for example, i-propyl group, t-butyl group, s-butyl group, t-amyl group and the like. Specifically, di i-propoxy methoxy n-propyl silane, di s-butoxy methoxy n-propyl silane, di t
-Butoxymethoxy n-propyl silane, di t-amyloxy methoxy n-propyl silane, di i-propoxy methoxy n-butyl silane, di s-butoxy methoxy n
-Butylsilane, di-t-butoxymethoxy n-butylsilane, di-t-amyloxymethoxy n-butyllsilane, di-i-propoxymethoxy n-hexylsilane, di-s-butoxymethoxy n-hexylsilane, di-t-butoxymethoxy n-hexylsilane Examples thereof include silane and di-t-amyloxymethoxy n-hexylsilane.

Preliminary Polymerization Preliminary polymerization in the present invention is carried out by contacting with propylene in the presence of a solid component (component A), an organoaluminum compound (component B) and an organosilicon compound (component C). The prepolymerization is preferably carried out in the presence of the above-mentioned inert medium. Prepolymerization is usually performed at a temperature of 100 ° C. or lower,
Desirably −30 ° C. to + 50 ° C., more desirably −20
It is carried out at a temperature from ℃ to +15 ℃. 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 1 to 50,000 mol, preferably 2 to 1,000 mol, per gram atom of titanium in the component A. Used. Component C is used so that the concentration in the prepolymerization system is 5 to 1000 mmol / liter, preferably 10 to 200 mmol / liter. Polypropylene is incorporated into component A by prepolymerization, but the amount of polymer is
It is desirable that the amount is 0.1 to 200 g, especially 0.5 to 50 g per 1 g. The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but it is particularly preferable to wash it from the viewpoint of preventing storage deterioration of the catalyst component. After washing, it may be dried if necessary. Also, when storing the catalyst component, it is desirable to store it at a low temperature as much as possible.
A temperature range of 0 ° C, especially -20 ° C to + 5 ° C, is recommended.

Copolymerization of Propylene In addition to the catalyst component obtained as described above, in the presence of a polymerization catalyst comprising the organoaluminum compound (component B) and the alkyltrialkoxysilane (component D) of (D), Copolymerization (main polymerization) of propylene and ethylene can be performed to obtain a propylene / ethylene random copolymer.

Examples of the organoaluminum compound (component B) that can be used include the compounds as described in the above section "Organoaluminum compound". Trialkylaluminum is another organoaluminum compound, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. It can be used together with.

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

Embedded image Etc. can be illustrated.

The amount of component B used with respect to the catalyst component of the present invention is usually 1 to 1 gram atom of titanium in the catalyst component.
2,000 gram moles, especially 20 to 500 gram moles are desirable. The ratio of the component B to the component D is selected in the range of 0.1 to 40, preferably 1 to 25 gram atom of the component B as aluminum based on 1 mol of the component D.

The propylene copolymerization reaction may be carried out either in the gas phase or in the liquid phase, and when the polymerization is carried out in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene. Can be carried out in an inert hydrocarbon and liquid monomers. The polymerization temperature is usually -8.
It is in the range of 0 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator.

[0043]

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. MFR is measured by ASTM D-
Measured according to 1238. The ether-soluble component (hereinafter abbreviated as ES) showing the ratio of low stereoregular components in the polymer is the amount extracted with boiling diethyl ether for 6 hours in a modified Soxhlet extractor. Mw / Mn (weight average molecular weight / number average molecular weight), which is a measure of molecular weight distribution
Is a gel permeation chromatograph (GPC)
(Waters 150-C type) using a measurement temperature of 1
The measurement was carried out at 35 ° C. using the measurement solvent orthodichlorobenzene.

Example 1 (a) Preparation of Solid Component (A) Containing Magnesium, Titanium, Halogen and Electron Donor Compound as Essential Components In a 1 liter reaction vessel equipped with a reflux condenser, under nitrogen gas atmosphere. Then, chip-shaped metal magnesium (purity 99.
5%, average particle size 1.6 mm) 8.3 g, and n-hexane 250 ml were added, the mixture was stirred at 68 ° C. for 1 hour, metal magnesium was taken out, and dried under reduced pressure at 65 ° C. to preactivate the metal. Obtained 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 / liter) were added to this metallic magnesium, and the suspension was kept at 55 ° C. n
-N-butyl chloride 3 in 50 ml of butyl ether
A solution in which 8.5 ml was dissolved was added dropwise over 50 minutes. After the reaction was carried out at 70 ° C for 4 hours with stirring, the reaction solution was kept at 25 ° C. Then, HC (OC ₂ H ₅₎ To the reaction solution ₃ 5
5.7 ml was added dropwise over 1 hour. After completion of the dropping, the reaction was carried out at 60 ° C. for 15 minutes, and the reaction product solid was added with n-hexane (3 parts each).
The solid was washed 6 times with 00 ml and dried under reduced pressure at room temperature for 1 hour to recover 31.6 g of a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine.

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 50 ml of n-heptane were put into a suspension under a nitrogen gas atmosphere to make a suspension, which was stirred at room temperature for 2,2. A mixed solution of 20 ml (0.02 mmol) of 2-trichloroethanol 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 solid obtained was filtered off, washed with 100 ml of n-hexane at room temperature four times each, and further washed twice with 100 ml each of toluene 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 obtained solid substance was filtered off at 110 ° C., and washed with 100 ml of n-hexane at room temperature seven times to obtain 5.5 g of component A.

(B) Prepolymerization In a 500 ml reactor which had been sufficiently replaced with nitrogen and dried,
In a nitrogen gas atmosphere, 4.0 g of the component A obtained above and 200 ml of n-hexane were put and stirred at -5 ° C.
And cooled. Then, triethylaluminum and isopropoxycyclopentyldimethoxysilane were each added to 2
0 mmol and 2 mmol were added, and the mixture was stirred for 5 minutes. Then, after decompressing the system, propylene gas was continuously supplied to polymerize propylene at 0 ° C. for 1 hour. After the polymerization was completed, the solid component was washed with 200 ml of n-hexane three times at room temperature. Further, the solid component was dried under reduced pressure at room temperature for 1 hour to obtain 16.2 g of a catalyst component. The amount of prepolymerization is component A
It was 3.05 g per 1 g.

(C) Copolymerization of Propylene and Ethylene In a 5 liter stainless autoclave that had been purged with nitrogen and sufficiently dried, under a nitrogen gas atmosphere, 130 mg of the above catalyst component, 1.2 mmol of triethylaluminum,
Diisopropoxymethoxy n-propylsilane 0.24
What was mixed with 7 mmol of n-heptane and n-heptane and kept for 5 minutes was added. Then, 4.0 liters of hydrogen as a molecular weight control agent (normal temperature and normal pressure), 3 liters of liquid propylene, and 12 g of ethylene were injected under pressure, and then the internal temperature of the autoclave was raised to 70 ° C. to continuously feed ethylene. Copolymerization was carried out by supplying 0.5 g of the amount.

After 1 hour, unreacted propylene, ethylene and hydrogen were purged, and the copolymer was taken out from the autoclave and dried. The total amount of the obtained copolymer was 810.
g, MFR 10.5 g / 10 minutes, ES 0.9% by weight, ethylene content 3.1% by weight, Mw / Mn 5.9.
Met.

(Examples 2 and 3) In (c) of Example 1, di-s-butoxymethoxy n-propylsilane and di-t-butoxymethoxy n-propylsilane were used instead of diisopropoxymethoxy n-propylsilane. Copolymerization of propylene and ethylene was performed using each. The amount of hydrogen was adjusted so that the MFR of the obtained copolymer was about 10 g / 10 min, and the amount of ethylene was adjusted so that the ethylene content was about 3%. The results are shown in Table 1.

(Embodiment 4) In (b) of Embodiment 1,
Preliminary polymerization was carried out using t-butoxycyclopentyldimethoxysilane instead of isopropoxycyclopentyldimethoxysilane to obtain a catalyst component. Using this catalyst component, propylene and ethylene were copolymerized in the same manner as in (c) of Example 1. The amount of hydrogen was adjusted so that the MFR of the obtained copolymer was about 10 g / 10 min, and the amount of ethylene was adjusted so that the ethylene content was about 3%. The results are shown in Table 1.

(Examples 5 and 6) In (c) of Example 4, di-s-butoxymethoxy n-propylsilane and di-t-butoxymethoxy n-propylsilane were used instead of diisopropoxymethoxy n-propylsilane. Copolymerization of propylene and ethylene was performed using each. The amount of hydrogen was adjusted so that the MFR of the obtained copolymer was about 10 g / 10 min, and the amount of ethylene was adjusted so that the ethylene content was about 3%. The results are shown in Table 1.

Comparative Examples 1 to 3 In (c) of Example 1, triethoxy n-propylsilane, cyclohexylmethyldimethoxysilane and isopropoxycyclopentyldimethoxysilane were used instead of diisopropoxymethoxy n-propylsilane. Copolymerization of propylene and ethylene was performed. The amount of hydrogen was adjusted so that the MFR of the obtained copolymer was about 10 g / 10 min.
The amount of ethylene was adjusted so that the ethylene content was about 3%. The results are shown in Table 1.

(Comparative Example 4) In (b) of Example 1,
Pre-polymerization was carried out using diisopropoxymethoxy n-propylsilane instead of isopropoxycyclopentyldimethoxysilane to obtain a catalyst component. Using this catalyst component, propylene and ethylene were copolymerized in the same manner as in (c) of Example 1. The amount of hydrogen was adjusted so that the MFR of the obtained copolymer was about 10 g / 10 min, and the amount of ethylene was adjusted so that the ethylene content was about 3%. The results are shown in Table 1.

[0056]

[Table 1]

[0057]

As is clear from the examples and comparative examples, by using the method of the present invention, a random copolymer of propylene and ethylene having a wide molecular weight distribution and a small amount of low stereoregular components can be efficiently prepared. It can be manufactured.

[Brief description of drawings]

FIG. 1 is a flow chart diagram of a catalyst component and a polymerization method in the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Ueki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. A solid catalyst component obtained by prepolymerizing propylene in the presence of the following components (A) to (C):
A method for producing a propylene copolymer having an ethylene content of 0.1 to 6% by weight, which comprises copolymerizing propylene and ethylene using a polymerization catalyst comprising the components (B) and (D). (A) A solid component containing magnesium, titanium, a halogen and an electron donating compound as essential components. (B) Organoaluminum compound. (C) An alkyltrialkoxysilane represented by R ¹ Si (OR ² ) (OCH ₃ ) ₂ . (In the formula, R ¹ represents a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R ² represents a branched alkyl group having 3 to 6 carbon atoms.) (D) R ³ Si (OR ⁴ ) ₂ ( Alkyltrialkoxysilane represented by OCH ₃ ). (In the formula, R ³ has ³ carbon atoms.
To 6 are straight-chain alkyl groups, and R ⁴ is a branched alkyl group having 3 to 5 carbon atoms. )