JPH06128328A - Production of propyleme copolymer - Google Patents

Abstract

PURPOSE:To produce a propylene copolymer excellent in the balance between clarity and stiffness. CONSTITUTION:A propylene copolymer having an ethylene content of 0.01-10wt.% is produced by copolymerizing propylene with ethylene in the presence of a catalyst comprising a solid catalyst component contg. magnesium, titanium, a halogen, and an electron-donating compd., an organoaluminum compd., and an organosilicon compd. of the formula wherein R<1> and R<2> are each independently a 1-10C hydrocarbon group, OR<4>, OSiR<5>3, or SiR<6>3; R<3> is a 1-10C divalent hydrocarbon group; and R<4>, R<5>, and R<6> are each a 1-10C 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]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that the present invention can be carried out by polymerizing propylene with a small amount of ethylene using a polymerization catalyst containing a specific organosilicon compound as an essential component. The present invention has been completed by finding that the purpose of can be achieved.

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

[Chemical 2] [Wherein R ¹ and R ² are the same or different hydrocarbon groups having 1 to 10 carbon atoms, OR ⁴ , OSiR ⁵ ₃ or SiR ⁶ ₃ ,
R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ^3
4 , R ⁵ and R ⁶ are each a hydrocarbon group having 1 to 10 carbon atoms. ] It exists in the manufacturing method of the propylene copolymer whose ethylene content is 0.01-10 weight% which consists of copolymerizing propylene and ethylene in the presence of the polymerization catalyst which consists of the organosilicon compound represented by these.

Solid Catalyst Component A solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, contains magnesium, titanium, halogen and an electron donating compound as essential components. 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.

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

Specific examples of these compounds are shown below. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show. MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtMgCl, B
uOMgCl, HeOMgCl, PhOMgCl, Et
OMgBr, BuOMgBr, EtOMgI, MgCl
₂ , MgBr ₂ , MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing the component A. As an example thereof, a compound containing metal magnesium, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1 to 20]
Hydrocarbon groups, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧ 0. ] The method of making it contact is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl, (Pr), i-propyl (iP
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHe), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. Alkenyl group, phenyl (Ph), tolyl, aryl group of xylyl group, phenethyl, aralkyl such as 3-phenylpropyl, and the like. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Specific examples of the alkoxy group-containing compound will be given below.

Compounds where M is carbon C (OR)_FourIncluded in C (OMe)_Four, C (OE
t)_Four, C (OPr) _Four, C (OBu)_Four, C (Oi-
Bu)_Four, C (OHe)_Four, C (OOct)_Four: Formula X
C (OR)₃HC (OMe) contained in₃, HC (OE
t)₃, HC (OPr)_3,HC (OBu)₃, HC
(OHe)₃, HC (OPh)₃MeC (OM
e)₃, MeC (OEt)₃, EtC (OMe)₃ , E
tC (OEt)₃, CyHeC (OEt)₃, PhC
(OMe)₃, PhC (OEt)₃, CH₂ClC (O
Et)₃, MeCHBrC (OEt)₃, MeCHCl
C (OEt) ₃; ClC (OMe)₃, ClC (OE
t)₃, ClC (Oi-Bu)₃, BrC (OE
t)₃Formula X₂C (OR)₂Included in MeCH (O
Me)₂, MeCH (OEt)₂, CH₂(OM
e)₂, CH₂(OEt)₂, CH₂ClCH (OE
t)₂, CHCl₂CH (OEt)₂, CCl₃CH
(OEt)₂, CH ₂BrCH (OEt)₂, PhCH
(OEt)₂.

Compound when M is silicon Si (OMe) ₄ , Si contained in the formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (O contained in the formula XSi (OR) ₃
Et) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ ,
HSi (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR)
₂ contained in Me ₂ Si (OMe) ₂ and Me ₂ Si (O
Et) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ S
iH (OEt) ₂ ; MeBeSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

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

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

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

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

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

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

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

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

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

Alcohols are represented by the general formula ROH. In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol,
Propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tertiarybutylphenol,
Examples include n-octylphenol. Ethers are represented by the general formula ROR ¹ . In the formula, R and R ¹ are alkyl having 1 to 12 carbons, alkenyl, cycloalkyl,
It is aryl or aralkyl, and R and R ¹ may be the same or different. Specific examples thereof include diethyl ether,
Diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether,
Examples include anisole and ethyl phenyl ether.

The component A is prepared by contacting a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) in that order. After contacting component 1 and component 3, component 2 is contacted. A method such as contacting the components 1, 2 and 3 at the same time can be adopted. It is also possible to contact with the halogen-containing compound before contacting with component 2.

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, Group IIa, IVa of the periodic table.
Examples thereof include halides of Group III and Group Va elements (hereinafter referred to as metal halides).

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetrachloride. Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins are chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene and hexachlorocyclohexane for alicyclic compounds, and chlorobenzene, bromobenzene, o- for aromatic compounds.
Examples thereof include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride and p-chlorobenzotrichloride. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, any one or two or more hydrogen atoms other than hydroxyl groups in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule are substituted with halogen atoms. Means a compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is preferable.

Examples of these compounds are 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chlor-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol,
1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-
Naphthol, (m, o, p) -bromophenol, 4-
Bromresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3- Chlor-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-
1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-
1-naphthol: 2,2,2-trichloroethanol,
1,1,1-trichloro-2-propanol, β, β,
β-trichloro-tert-butanol, 2,3,4-
Trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6
-Tribromophenol, 2,3,5-tribromo-2
-Hydroxytoluene, 2,3,5-tribrom-4-
Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol,
2,4,6-Triiodophenol: 2,3,4,6-
Tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-
Propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like can be mentioned.

The silicon halide compound having a hydrogen-silicon bond includes HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S.
iCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ ,
_{H (t-C 4 H 9} ) SiCl 2, HC 6 H 5 SiCl
_{2, H (CH 3) 2} SiCl, H (i-C 3 H 7) 2 S
_{iCl, H 2 C 2 H 5} SiCl, H 2 (n-C 4 H 9)
SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiC
1 (C ₆ H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples thereof include chlorides, fluorides, bromides, and iodides of i, particularly BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are suitable.

The contact with Component 1, Component 2 and Component 3, and optionally with a halogen-containing compound which can be optionally contacted is carried out by mixing and stirring in the presence or absence of an inert medium, but mechanically. It is made by co-milling. The contact can be performed under heating at 40 to 150 ° C.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. .

A preferable method for preparing the component A in the present invention is described in JP-A-63-264607 and JP-A-58-19850.
No. 3, No. 62-146904 and the like. More specifically, it is obtained by bringing (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound) into contact with each other. A method in which a magnesium-containing solid is brought into contact with (d) a halogen-containing alcohol and then (e) an electron-donating compound and (f) a titanium compound (JP-A-63-63).
-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) a titanium halide compound is contacted, and then (d) an electron-donating compound (if necessary, further contacted with a titanium halide compound). (JP-A-62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) contacting with an electron donating compound, and then (d)
Method of contacting with titanium compound (JP-A-58-1985)
No. 03). Of these, the method (1) is most preferable. 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 the organoaluminum compound. The organoaluminum compound is selected from the organometallic compounds described below, which are one component of the catalyst of the present invention.

As the olefin, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene can be used in addition to ethylene. The contact with the olefin is preferably carried out in the presence of the above-mentioned inert medium. Contact is usually 100 ° C or lower, preferably -10 to +
It is carried out at a temperature of 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 10 per 1 g of the component A.
It is 0 g.

For the contact between the component A and the olefin, an electron donating compound may be present together with the organoaluminum compound. The electron-donating compound is a compound used in preparing the component A and a Si—O—C bond or Si—N.
It is selected from organic silicon compounds having a -C bond. The component A contacted with the olefin can be washed with the above-mentioned inert medium, if necessary, and can be further dried.

Organometallic compounds Organometallic compounds (hereinafter referred to as component B) are listed in Periodic Table I.
Organic compounds of Group III to Group III metals. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R _n Al
X _3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1
It is an arbitrary number within the range of ≦ n ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide, a dialkylaluminum monohydride and the like having 1 to 18 carbon atoms.
Particularly preferred are alkylaluminum compounds, preferably C2 to C6 or mixtures or complex compounds thereof. Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide,
Dialkyl aluminum monohalide such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monoalkyl aluminum dihalide such as isobutyl aluminum dichloride, ethyl aluminum sesquichloride, etc. Alkyl aluminum sesquihalide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide and other dialkyl aluminum monoalkoxides, dimethyl aluminum hydride, diethyl ether Aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially readily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.
Further, an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include

[Chemical 3] Etc. can be illustrated.

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

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In the formula, hydrocarbon groups of R ¹ and R ² and OR ⁴ and OSiR ⁵
Examples of the hydrocarbon group represented by R ⁴ , R ⁵ and R ⁶ in ₃ , SiR ⁶ ₃ include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group and an aralkyl group. To be

As the alkyl group, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl and the like, cycloalkyl groups such as cyclopentyl, cyclohexyl and methylcyclohexyl groups, and cycloalkenyl groups such as cyclopentenyl. , A cyclohexenyl group, a methylcyclohexenyl group, etc., a cycloalkadienyl group, a cyclopentadienyl group, a methylcyclopentadienyl group, an indenyl group, etc., and an aryl group, a phenyl group, a tolyl group, a xylyl group, etc. Examples of the alkyl group include benzyl, phenethyl and 3-phenylpropyl groups.

R ³ in the above general formula is a divalent hydrocarbon group, and specific examples thereof include groups represented by the following general formula.

[Chemical 4] In the above, m is 1-10 and n, p, and q are 2-8, respectively.

Specific examples of the groups (1) to (4) are as follows.

[Chemical 5]

[Chemical 6]

[0042]

[Chemical 7]

[0043]

[Chemical 8]

[0044]

[Chemical 9]

Component C is usually of the general formula R ¹ R ² SiX ₂
(X is a halogen atom) and a compound represented by the general formula HO
The compound represented by R ³ OH is reacted in the presence of a dehydrohalogenating agent such as pyridine or quinoline, or is represented by the general formula R ¹ R ² Si (OR ⁷ ) ₂ (R ⁷ is a hydrocarbon group). It can be synthesized by reacting a compound with a compound represented by the general formula HOR ³ OH in the presence of an acid or base catalyst.

The catalyst of the present invention comprises component A, component B and component C, the composition ratio of which is such that component B is 1 to 2,000 gram mol per gram atom of titanium in component A,
Desirably 20 to 500 gram mol, component C is component B1
0.001 to 10 mol, preferably 0.0
It is used so as to be 1 to 1.0 mol.

[Propylene Copolymerization] Propylene copolymerization is carried out by copolymerizing propylene and ethylene in the presence of the above-mentioned polymerization catalyst. The polymerization reaction may be in a gas phase or a liquid phase, and when the polymerization is performed in the liquid phase,
It can be carried out in an inert hydrocarbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually −80 ° C. to + 150 ° C., preferably 40 to 12
It is in the range of 0 ° 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.
In the copolymerization reaction, the melt flow rate (MFR) of the obtained copolymer is 0.01 to 200 g / 10 minutes, and especially the value of 0.
The amount is preferably 1 to 100 g / 10 minutes, and is usually adjusted by adjusting the amount of hydrogen or a known molecular weight regulator used.

[0048]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-ditertiarybutyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, calcium stearate After adding 0.06% by weight of each of them to form pellets by melt-kneading, a test piece was prepared by injection molding (a sheet having a thickness of 1.0 mm was used for measuring haze). Flexural modulus: JIS K 720
3-1982: Haze: according to ASTM D1003. The MFR of the polymer was measured according to ASTM D-1238. The ethylene content of the copolymer was determined by measuring the transmittance of absorption at 733 cm ^-1 by infrared absorption spectroscopy. The test piece was obtained by subjecting a film having a thickness of about 0.5 mm by press molding to an annealing treatment.

Example 1 Preparation of Component A In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity 99.
5%, average particle size 1.6 mm) 8.3 g and n-hexane 2
After adding 50 ml and stirring at 68 ° C. for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65 ° C. to obtain pre-activated metallic magnesium. Next, 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butyl magnesium chloride (1.75 mol / l) were added to this metallic magnesium at 55 ° C.
A solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After reacting at 70 ° C. for 4 hours with stirring, the reaction solution was mixed with 2
Hold at 5 ° C. Then, HC (OC ₂ H
₅ ) 35.7 ml of _{3 was} added dropwise over 1 hour. After the dropping is completed,
The reaction was carried out at 60 ° C. for 15 minutes, the reaction product solid was washed 6 times with 300 ml of n-hexane each time, and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. 31.6 g was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, magnesium-containing solid 6.3 in a nitrogen gas atmosphere.
g and n-heptane (50 ml) were added to form a suspension, and 2,2,2-trichloroethanol (20 ml) was stirred at room temperature.
A mixed solution of (0.02 mmol) and 11 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, washed with 100 ml of n-hexane at room temperature 4 times each, and further washed with 100 ml of toluene twice each to obtain a solid component. 40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, and then the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 90 ° C. and washed twice with 100 ml of toluene each time at 90 ° C. Further, titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 110 ° C. and 1 each at room temperature.
Washed 7 times with 00 ml of n-hexane to obtain 5.5 g of component A
Got

Polymerization of Propylene In a fully dried 5 liter autoclave which had been purged with nitrogen, 25.2 mg of component A obtained above and 0.3 mol of triethylaluminium in 1 liter of n-heptane were added. 4 ml of the solution and 0.08 mol of 2-cyclohexyl-2-methyl-2-per 1 liter of n-heptane.
Mix 3 ml of a solution containing sila-1,3-dioxane and mix 5
What was held for minutes was added. Then, 1.2 liters of hydrogen and 3 liters of liquid propylene were injected under pressure, the internal temperature of the autoclave was raised to 70 ° C., ethylene was continuously supplied, and polymerization was carried out for 1 hour. After completion of the polymerization, unreacted propylene, ethylene and hydrogen were purged, and the polymer in the autoclave was taken out. The polymer obtained had an MFR of 15.9 g / 10 min and an ethylene content of 2.5.
%Met. When the physical properties were measured, the flexural modulus was 1
It was 0.70 × 10 ³ kg / cm ² and the haze was 19.6%.

Examples 2-5, Comparative Examples 1,2,2 -Cyclohexyl-2-methyl-2-sila-1,3-
In the same manner as in Example 1 except that the organosilicon compound shown in Table 1 was used in place of dioxane, and the amount of hydrogen was adjusted so that the MFR of the obtained copolymer had the value shown in Table 1. Copolymerization was performed and the results are shown in Table 1. Similarly, comparative examples are shown in Table 2. The values of flexural modulus and haze of the copolymers obtained in each Example and Comparative Example are shown in FIG.
The results of FIG. 1 show that the copolymers obtained in the respective Examples are superior in the balance of flexural modulus and the physical properties of haze to those of the copolymers obtained in Comparative Examples. It's obvious.

[Table 1]

[Table 2]

[0052]

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.

Front Page Continuation (72) Inventor Takayuki Taki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Inventor Takeshi Ishihara 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute (72) Inventor Rinko Aoki 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside Tonen Research Institute

Claims (1)

[Claims] 1. A solid catalyst component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) an organometallic compound and (C) a general formula: [Wherein R ¹ and R ² are the same or different hydrocarbon groups having 1 to 10 carbon atoms, OR ⁴ , OSiR ⁵ ₃ or SiR ⁶ ₃ ,
R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ^3
4 , R ⁵ and R ⁶ are each a hydrocarbon group having 1 to 10 carbon atoms. ] The manufacturing method of the propylene copolymer of ethylene content 0.01-10 weight% which consists of copolymerizing propylene and ethylene in the presence of the polymerization catalyst which consists of the organosilicon compound represented by these.