JPH06279533A - Production of porpylene copolymer - Google Patents

Abstract

PURPOSE:To produce a propylene-ethylene copolymer excellent in the balance between transparency and stiffness by using a polymn. catalyst component formed by bringing a specific solid catalyst component into contact with an olefin in the presence of an organoaluminum compd. and a specific organaosilicone compd. CONSTITUTION:A propylene copolymer having an ethylene content of 0.01-10wt.% is obtd. by copolymerizing propylene with ethylene in the presence of a polymn. catalyst component which is formed by bringing a solid catalyst component contg. a metal oxide, magnesium, titanium, a halogen, and an electron-donating compd. as an essential components into contact with an olefin in the presence of an organoaluminum compd. and an organosilicon compd. of the formula (wherein R<1> is a 1-10C hydrocarbon group; R<2> is a 1-10C divalent hydrocarbon group or-R<5>0-; R<3> is a 1-10C hydrocarbon group, R<6>0-, etc.; R<4> is methyl or ethyl; x is 1 or 2, y is 0 or 1, and z is 2 or 3 provided x+y+z=4; R' is a 1-10C divalent hydrocarbon group; and R<6> is a 3-10C hydrocarbon 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 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]

As a result of intensive studies, the inventors of the present invention can achieve the object of the present invention by polymerizing propylene with a small amount of ethylene using a specific polymerization catalyst component. It was found that the present invention has been completed.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that (A) a solid catalyst component containing a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organoaluminum compound and (C). ) 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 component of the catalyst component used in the present invention (hereinafter referred to as the catalyst component of the present invention) is a metal oxide, magnesium, titanium, halogen and electron. A donor compound is an essential component, and such a component is usually a metal oxide, a magnesium compound, a titanium compound and an electron donor compound, and in the case where each of the compounds does not have a halogen, a halogen-containing compound,
It is prepared by contacting each.

(1) Metal Oxide The metal oxide used in the present invention is a group II element of the periodic table of elements.
~ Is an oxide of an element selected from the group of Group IV elements,
For example, B₂O₃, MgO, Al ₂O₃，
SiO₂, CaO, TiO₂, ZnO, ZrO₂, Sn
O₂, BaO, ThO₂Etc. Among these
Also B₂O₃, MgO, Al₂O₃, SiO₂, Ti
O₂, ZrO₂Is desirable, especially SiO₂Is desirable.
Furthermore, complex oxides containing these metal oxides, such as Si
O₂-MgO, SiO₂-Al₂O₃, SiO₂-Ti
O₂, SiO₂-V₂O_Five, SiO₂-Cr₂O₃, S
iO₂-TiO₂-MgO etc. can also be used. These metals
The oxide is usually in powder form. Powder
The shape and size of the resulting olefin polymer
Since it often affects the shape of the
And is desirable. Metal oxides are used to remove poisonous substances.
For the purpose of removal, etc., bake at the highest temperature possible, and
It is desirable to handle it so that it does not come into direct contact with the air.

(2) 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. 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, and 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-} Pr 2, MgB
u ₂ , MgHe ₂ , MgOct ₂ , MgEtBu, Mg
Ph ₂ , MgcyHe ₂ , Mg (OMe) ₂ , Mg (O
Et) ₂ , Mg (OBu) ₂ , Mg (OHe) ₂ , Mg
(OOct) ₂ , Mg (OPh) ₂ , Mg (OcyH
e) ₂ , EtMgCl, BuMgCl, HeMgCl,
i-BuMgCl, t-BuMgCl, PhMgCl,
PhCH ₂ MgCl, EtMgBr, BuMgBr, P
hMgBr, BuMgI, EtOMgCl, BuOMg
Cl, HeOMgCl, PhOMgCl, EtOMgB
r, BuOMgBr, EtOMgI, MgCl ₂ , Mg
Br _2, MgI _2.

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when the component A is prepared. As 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.

Compounds where M is boron Formula B (OR)₃Included in B (OEt)₃, B (OB
u)₃, B (OHe) ₃, B (OPh)₃.

Compound when M is Aluminum Al (OMe) ₃ , Al contained in the formula Al (OR) ₃
(OEt) ₃ , Al (OPr) ₃ , Al (Oi-Pr)
₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al
(OHe) ₃ , Al (OPh) ₃ .

Compounds where M is phosphorus P (OR)₃Included in P (OMe)₃, P (OE
t)₃, P (OBu) ₃, P (OHe)₃, P (OP
h)₃.

Further, as the magnesium compound, a complex with an organic compound of Group II or 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.

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

(4) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples thereof include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, 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, 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,
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 and R ¹⁵ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ¹⁴ and R ¹⁵ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
Examples include diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether.

The component A is prepared by contacting a metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) in that order. After contacting component 1 and component 2,
Component 4 and component 3 are contacted in that order. Component 1 and component 2 are contacted, component 3 and component 4 are simultaneously used for contact, component 2 and component 3 are contacted, then component 4 and component 1 are contacted in that order, component 2 and component 4, then contacting component 3 and component 1 in that order,
A method may be employed in which the components 2, 3, and 4 are contacted at the same time, and then the component 1 is contacted. It is also possible to contact with the halogen-containing compound before contacting with component 3.

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 include 2-chloroethanol and 1-chloro-
2-propanol, 3-chloro-1-propanol, 1
-Chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6
-Chlor-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-
Chlorbenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-
(M, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol,
Chlorhydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p)
-Chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6
-Chlorthymol, 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)-
Bromphenol, 4-bromoresorcin, (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-tribromo-4-hydroxytoluene,
2,2,2-Trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetra Chlorbisphenol A, tetrabromobisphenol A, 2,2
3,3-tetrafluoro-1-propanol, 2,3
5,6-tetrafluorophenol, tetrafluororesorcin, etc. may 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 the component 1, the component 2, the component 3 and the component 4, and the halogen-containing compound which can be optionally contacted is carried out by mixing and stirring in the presence of an inert medium or in the absence thereof. This is done by mechanical 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. .

Specific examples of the method for preparing the component A in the present invention include JP-A-58-162607 and JP-A-55-949.
09, 55-115405, 57-10810.
No. 7, No. 61-21109, No. 61-174204
No. 61-174205, No. 61-174206
No. 62-7706 and the like. More specifically,

A method of bringing a reaction product of a metal oxide and magnesium dialkoxide into contact with an electron-donating compound and a tetravalent titanium halide (Japanese Patent Laid-Open No. 58-162).
No. 607), a method of bringing a reaction product of an inorganic oxide and a magnesium hydrocarbyl halide compound into contact with a Lewis base compound and titanium tetrachloride (JP-A-55-94909), a porous carrier such as silica, and an alkyl. A method in which a reaction product with a magnesium compound is brought into contact with an electron donating compound and a silicon halide compound before being brought into contact with a titanium compound (JP-A-55-115405 and JP-A-57-1081).
No. 07), a method of contacting a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polyvalent carboxylic acid having a carboxyl group at the ortho position or a derivative thereof, and a titanium compound (JP-A-61-174204), a metal. A method of bringing an oxide, an alkoxy group-containing magnesium compound, a silicon compound having a hydrogen-silicon bond, an electron-donating compound and a titanium compound into contact with each other (JP-A-61-161).
174205), a method of contacting a metal oxide, an alkoxy group-containing magnesium compound, a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound (JP-A-61-174206), metal oxide, dihydrocarbyl. Method of contacting a reaction product obtained by contacting an alcohol containing magnesium and a halogen with an electron donating compound and a titanium compound (JP-A-61-21109), containing metal oxide, hydrocarbyl magnesium and hydrocarbyloxy group A method of bringing a solid obtained by bringing a compound (corresponding to the alkoxy group-containing compound) into contact with a halogen-containing alcohol, and further bringing it into contact with an electron-donating compound and a titanium compound (JP-A-6-61)
2-7706). Among these, the method (1) is preferable, and the method (2) is particularly preferable.

Component A is prepared as described above,
Component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Further, the component A may further contain an olefin polymer produced in the component A by contacting with an olefin in the presence of an organoaluminum compound. The 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 The 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 within 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 which is one component of the catalyst of the present invention (hereinafter referred to as component C) 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, [Iso
Propenyl-COO- (CH₂)₃-] Si (OMe)
₃, [Allyl-COO- (CH₂)₂−] Si (OE
t)₃, [Cyclohexyl-COO- (CH₂)₃-]
Si (OMe)₃, [Cyclopentenyl-COO- (C
H₂)₂-] Si (OMe)₃, [Cyclopentadiene
Le-COO- (CH₂)₃-] Si (OMe)₃, [P
h-COO- (CH₂)₂−] Si (OEt)₃,〔I
Sopropenyl-COO- (CH₂)₂−] Si (OM
e)₂Me, [isopropenyl-COO- (CH₂)_Four
-] Si (OMe)₂(Oi-Pr), [cyclopentyl
Le-COO- (CH₂)₂−] Si (OEt)₂(Si
Me₃), [Me-COO- (CH₂)_FourO-] Si
(OMe)₂(OSiMe ₃), [Allyl-COO-
(CH₂)₂−] Si (OEt)₂(Ot-Bu),
[Me-COO- (CH₂)₂-]₂Si (OE
t)₂, [2-butenyl-COO- (CH₂)₃-]₂
Si (OMe)₂, [Cyclohexyl-COO- (CH
₂)₃-]₂Si (OMe)₂, [Cyclopentenyl-
COO- (CH₂)_Four-]₂Si (OMe)₂, [Siku
Lopentadienyl-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 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.

As the organosilicon compound, a Si--O--C bond is used.
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 into the component A by 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 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 that 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, 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.

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

The polymerization reaction may be carried out in 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.

[0067]

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 A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, silicon oxide (D
AVISON, trade name G-952) was fired in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours, and then 5 g and 40 ml of n-heptane were added. Furthermore n
-Butylethylmagnesium (hereinafter referred to as BEM)
20% n-heptane solution (manufactured by Texas Alkyls,
20 ml of trade name MAGALA BEM) was added and stirred at 90 ° C. for 1 hour. After cooling the above suspension to 0 ° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes. After completion of the dropping, the temperature was raised to 50 ° C. over 2 hours, and then 50
Stirring was continued for 1 hour at ° C. After the reaction was completed, the supernatant was removed by decantation, and the resulting solid was mixed with 60 ml of n-
It was washed with heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed 4 times. To the above solid, 50 ml of n-heptane was added to make a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol in 10 ml of n-heptane was added to the suspension at a temperature of 25 ° C. from a dropping funnel at 15 ° C. It took a minute and was dropped. After completion of dropping, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, the mixture was washed twice with 60 ml of n-heptane and three times with 60 ml of toluene at room temperature. When the obtained solid (solid component I) was analyzed,
SiO ₂ 36.6%, magnesium 5.1%, chlorine 3
It contained 8.5%. In the solid component I obtained above,
Add 10 ml of n-heptane and 40 ml of titanium tetrachloride, add 9
The temperature was raised to 0 ° C., and 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added over 5 minutes. afterwards,
The temperature was raised to 115 ° C. and the reaction was performed for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Furthermore, n-heptane 1
5 ml and 40 ml of titanium tetrachloride were added and reacted at 115 ° C. for 2 hours. After the reaction was completed, the solid substance obtained was mixed with 60 ml of n
-Washing was carried out 8 times with hexane at room temperature. Then, it was dried at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a catalyst component (component A). This component A contained 3.1% of titanium, silicon oxide, chlorine and di-n-butyl phthalate.

In a 500 ml reactor equipped with a prepolymerization stirrer, under a nitrogen gas atmosphere, 3.0 g of the component A obtained above and 3 parts of n-heptane.
00 ml was added and cooled to -5 ° C with stirring. Next, n-heptane solution (2.0 mol / liter) of triethylaluminum (hereinafter abbreviated as TEAL) and 4-oxa-5-oxo-6-methyl-6-heptenyltrimethoxysilane were added in the reaction system. TEAL and 4-oxa-5-oxo-6-methyl-6-heptenyltrimethoxysilane were 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, propylene in the gas phase was purged with nitrogen gas, and 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 1.5 g per 1 g of component A.

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. 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.

[0073]

[Table 1]

Polymerization : A solution containing 53.8 mg of the catalyst component obtained above and 0.6 mol of triethylaluminium in 1 liter of n-heptane was placed in a fully dried autoclave of 5 liters, which had been purged with nitrogen. 4 ml 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. Then
After pressurizing 2.0 liters of hydrogen and 3 liters of liquid propylene, the internal temperature of the autoclave was raised to 70 ° C,
Ethylene was continuously supplied to carry out polymerization 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 polymer obtained had an MFR of 15.7 g / 10 minutes and an ethylene content of 2.6%. When the physical properties were measured,
Flexural modulus is 10.55 × 10 ³ kg / cm ² , haze is 1.
It was 8.7%.

Using the polymerization catalyst components obtained in Examples 2 to 4 and Comparative Examples 1 and 2, propylene was copolymerized in the same manner as above, and the results are shown in Table 2. 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.

[0076]

[Table 2]

[0077]

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) Masashi Nakajima Inventor Masashi Nakajima 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Inventor Takayuki Taki, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture 3-3-1 Tonen Co., Ltd. Research Institute (72) Inventor Takeshi Ishihara 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Research Institute

Claims (1)

[Claims] 1. A metal oxide, magnesium, titanium
Solids containing halogen, an electron-donating compound and
The body catalyst component is (B) an organoaluminum compound and
(C) 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.