JPH0762047A - Production of block copolymer of propylene - Google Patents

Abstract

PURPOSE:To obtain a block copolymer having well balanced impact resistance and rigidity and useful as a molding material by polymerizing propylene and ethylene in the presence of a polymerization catalyst containing a specific organic silicon compound. CONSTITUTION:This block copolymer can be produced by (1) polymerizing propylene in the presence of a polymerization catalyst obtained by contacting (A) a solid catalyst component containing Mg, Ti, halogen and electron donative compound with (B) an olefin in the presence of (C) an organic aluminum compound and (D) an organic silicon compound of the formula I [R<1> is silicon- containing heterocyclic substituent such as the group of the formula II (Me is methyl); R<2> is 1-10C hydrocarbon group, R<4>O (R<4> is 3-10C hydrocarbon group), R<5>3Si (R<5> is 1-10C hydrocarbon group) or R<5>3SiO; R<3> is methyl or ethyl; (x) is 1 or 2; (y) is 0 or 1; (z) is 1 or 3; x+y+z=4] to obtain a highly crystalline PP and (2) (preferably successively) copolymerizing ethylene and propylene.

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 block copolymer, and more particularly to a method for producing a propylene block copolymer having an excellent balance of impact resistance and rigidity.

[0002]

2. Description of the Related Art Demand for highly crystalline polypropylene produced by using various types of highly stereoregular catalysts has been rapidly increasing in recent years because of its excellent rigidity and heat resistance. However, these properties are still insufficient depending on the purpose of use, and various methods for improving the rigidity have been proposed, but most of them are the methods of performing post-treatment such as adding a nucleating agent to polypropylene. is there. Therefore, the process cost is high, 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.

Further, since polypropylene originally has a drawback of low impact strength, a method of improving impact resistance by copolymerization with other olefins such as ethylene is widely used. Although this method improves impact resistance, it also decreases rigidity. Therefore, various methods have been proposed in which stepwise polymerization is performed while changing the polymerization ratio of other olefins of propylene, that is, a method for improving the balance between rigidity and impact resistance of the copolymer by carrying out multistage polymerization. However, even with these methods, a sufficiently excellent physical property balance cannot be obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to more effectively provide a method for producing a block copolymer of propylene having an excellent balance of impact resistance and rigidity.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the object of the present invention by copolymerizing with a polymerization catalyst component containing a specific organic silicon compound as an essential component. The inventors have found that it can be done and have completed the present invention.

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

[Chemical 2] [Wherein R ¹ is a heterocyclic substituent containing a silicon atom, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O-, R ⁵ ₃ Si-
Alternatively, R ⁶ ₃ SiO—, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3, x + y + z = 4, and R ⁴ has ³ to 1 carbon atoms.
Zero hydrocarbon group, R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms. ] In the presence of an organosilicon compound represented by the formula (D), in the presence of a polymerization catalyst component which is brought into contact with an olefin, (1) propylene is polymerized to produce a highly crystalline polypropylene (a) and (2) A method for producing a block copolymer of propylene comprising the step (b) of copolymerizing propylene and ethylene.

Solid Catalyst Component A solid catalyst component (hereinafter component A) which is one component of the polymerization catalyst component (hereinafter referred to as the catalyst component of the invention) used in the present invention.
Means that magnesium, titanium, a halogen and an electron donating compound are essential components, and such a component is 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. Are prepared by contacting each with a halogen-containing compound.

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ⁷ R ⁸ . In the formula, R ⁷ and R ⁸ are the same or different hydrocarbon groups, OR ⁹ groups (R ⁹ is a hydrocarbon group), and halogen atoms. More specifically, the hydrocarbon group represented by R ⁷ and R ⁸ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR ⁹ group is represented by R ⁹ 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. 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, 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 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 ; MeBuSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compound when B is M Formula B (OR)₃Included in B (OEt)₃, B (OB
u)₃, B (OHe) ₃, B (OPh)₃.

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

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 ⁷
It is represented by R ⁸ · n ₀ (M′R ¹⁰ _m0 ). The metal is aluminum, zinc, calcium or the like, and R ¹⁰ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. In addition, m ₀ is a metal M ′
, And n ₀ is a number of 0.1 to 10. M'R ¹⁰
Specific examples of the compound represented by _m0 include AlMe ₃ ,
_{AlEt 3, Ali-Bu 3,} AlPh 3, ZnM
e ₂ , ZnEt ₂ , ZnBu ₂ , ZnPh ₂ , CaEt
₂ , CaPh _{2 and the} like.

(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 R ¹¹ OH. In the formula, R ¹¹ 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 ¹² OR ¹³ . In the formula R ¹² ,
R ¹³ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl, and R ¹² and R
¹³ can be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether,
Di-2-ethylhexyl ether, diallyl ether,
Examples include ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole and ethyl phenyl ether.

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

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

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of 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, or by mechanical stirring. It is made by co-milling. The contact can be performed under heating at 40 to 150 ° C.

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

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

Further, the component A may further contain an olefin polymer produced in the component A by contacting with an olefin in the presence of the organoaluminum compound. The organic aluminum compound is selected from the organic aluminum compounds described below.

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

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

Organoaluminum Compound An organoaluminum compound (hereinafter referred to as component B) has a general formula R ¹⁴ _n1 AlX _{3- n1} (wherein R ¹⁴ is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom). And n ₁ is an arbitrary number in the range of 1 ≦ n ₁ ≦ 3), and examples thereof include trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkyl. Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as aluminum monoalkoxide and dialkylaluminum monohydride, or a mixture or complex compound thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum io Dialkyl aluminum monohalides such as diid, diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, etc. monoalkyl aluminum dihalides, ethyl aluminum aluminum Alkyl aluminum sesquihalides such as sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum Examples thereof include dialkyl aluminum hydrides such as hydride, dipropyl aluminum hydride and diisobutyl aluminum hydride.
Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable.

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In the formula, R ¹ is a silicon atom-containing heterocyclic substituent. The substituent may be represented by the formula _{-C n H 2n-2m-1} (SiR 7 R 8) l. In the above formula, n is 2 to 20, preferably 3 to 7, m is 0 to 10, preferably 0 to 5, and 1 is 1 to 5, preferably 1 to 2. However,
2m <n, n + 1 is 3 to 25, preferably 4 to 7
Is the number of. R ⁷ and R ⁸ are hydrocarbon groups having 1 to 10 carbon atoms, and particularly preferably alkyl groups having 1 to 6 carbon atoms.

Specific examples of the substituent R ¹ are shown below. In the following, Me represents a methyl group.

[0039]

[Chemical 3]

The hydrocarbon group represented by R ^{2 in} the general formula of the component C and the hydrocarbon group represented by R ⁴ , R ⁵ and R ⁶ in R ⁴ O-, R ⁵ ₃ Si- and R ⁶ ₃ SiO-, and the above general formula Examples of the hydrocarbon group represented by R ⁷ and R ^{8 in} the formula of the substituent R ^{1 in} the formula include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group and an aralkyl group. Can be mentioned.

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 component C is exemplified below. In the following,
The symbols such as [RA] and [RD] correspond to the above symbols of R ¹ in the general formula of the component C, Me is methyl, Et is ethyl, Pr is propyl, and Bu is butyl.
[RA] Si (OMe) ₂ Me, [RA] Si (OE
t) ₃ , [RA] Si (Oi-Pr) (OMe) ₂ ,
[RD] Si (OEt) ₃ , [RF] Si (OM
e) ₃ , [RF] Si (Os-Bu) (OMe) ₂ ,
[RF] Si (OEt) ₃ .

The prepolymerization of prepolymerized solid component (component A) is made by contacting the presence of an organoaluminum compound (component B) and the specific organosilicon compound (component C), an olefin (component D).

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.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane and methyltrimethoxy. Silane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltri Phenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, Methyl dihexyl silane,
Dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, Examples thereof include 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, etc., as a compound containing a sulfur atom, thiol Phenol, thiophene,
Ethyl 2-thiophenecarboxylate, Ethyl 3-thiophenecarboxylate, 2-Methylthiophene, Methyl mercaptan, Ethyl mercaptan, Isopropyl mercaptan, Butyl mercaptan, Diethyl thioether, Diphenyl thioether, Methyl benzene sulfonate, Methyl sulfite, Ethyl sulfite, etc. Is, as a compound containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,
2-ethyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetramethyl Tetrahydropyran, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, methyl-2,
6-di-t-butylphenyl ketone, 2-ethyl ethyl furarate, isoamyl 2-furarate, methyl 2-furarate, 2
-Propyl furarate and the like, as a compound containing a phosphorus atom, triphenylphosphine, tributylphosphine,
Examples thereof include triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like.

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

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

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

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

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

The catalyst component prepared as above is
Although it can be diluted or washed with the above-mentioned inert medium, washing is particularly preferable from the viewpoint of preventing storage deterioration of the catalyst component. 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 it is -50 ° C to + 30 ° C, especially -2 ° C.
A temperature range of 0 ° C to + 5 ° C is recommended.

Polymerization of α-Olefin The catalyst component obtained as described above is used in combination with an organometallic compound and, if necessary, an electron donating compound to homopolymerize an α-olefin having 3 to 10 carbon atoms. It is also useful as a catalyst for copolymerization with other mono-olefins or di-olefins having 3 to 10 carbon atoms, but particularly 3 carbon atoms.
To 6 α-olefins such as propylene, 1-
It exhibits extremely excellent performance as a catalyst for homopolymerization of butene, 4-methyl-1-pentene, 1-hexene, etc. or for random and block copolymerization with the above α-olefins and / or 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 4] Etc. can be illustrated.

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

The electron-donating compound which can be combined with the above-mentioned catalyst component and the organometallic compound, if necessary, is appropriately selected from the electron-donating compounds which may be used in the prepolymerization of the component A. To be elected. 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 relative to the above catalyst component is usually 1 per 1 gram atom of titanium in the catalyst.
˜2,000 gram moles, especially 20-500 gram moles are desirable.

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 electron-donating compound.
Selected in the range of 25 gram atoms.

Method for Producing Propylene-Ethylene Block Copolymer The method for producing a propylene-ethylene block copolymer comprises a step of polymerizing propylene to obtain a highly crystalline polypropylene (step a), and a step of producing propylene and ethylene. And a copolymerization step (step b).

(1) Step a Step a consists of polymerizing propylene in the presence of the above-mentioned polymerization catalyst. The polymerization reaction may be either a gas phase or a liquid phase, and when the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane,
It can be carried out in an inert hydrocarbon such as heptane, octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to +
It is in the range of 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer can be controlled by the presence of hydrogen or other known molecular weight regulator. In step a,
It is desirable that the polypropylene obtained there accounts for 50 to 98% by weight, particularly 70 to 95% by weight of the block copolymer.

(2) Step b Copolymerization of propylene and ethylene is carried out in the presence of the above-mentioned polymerization catalyst. In the copolymerization, the ethylene content in the resulting copolymer is 30 to 95% by weight, preferably 4
It is made by contacting and reacting propylene and ethylene so that the content of propylene is 0 to 80% by weight. The copolymerization reaction is
It can be appropriately selected from the range of the polymerization conditions carried out in step a, and the use of a molecular weight modifier such as hydrogen is the same as in step a. The amount of the copolymer obtained in the step b is usually 50 to 2% by weight of the block copolymer, and preferably 30 to 5% by weight.

The method of the present invention comprises steps a and b. Steps a and b are performed in the order or in reverse, or in addition to the series method, steps a and b are performed in parallel. A method of combining the polymers obtained in (1) can be adopted, and among these, the method of performing step a and step b in that order is advantageous and desirable in terms of the apparatus.

[0064]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Dissterial 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, test pieces were prepared by injection molding. Flexural modulus: JIS K 7
203-1982: DuPont Impact Strength: JIS K
Compliant with 7211-1976, respectively. Also, the polymer M
FR was measured according to ASTM D-1238.

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

In a 500 ml reactor equipped with a prepolymerization stirrer, 3.8 g of the component A obtained above and n-heptane 3 were added under a nitrogen gas atmosphere.
00 ml was added, and the mixture was cooled to 5 ° C with stirring. Next, n of triethylaluminum (hereinafter abbreviated as TEAL)
-Heptane solution (2.0 mol / l) and 3,3-
Dimethyl-3-silacyclopentyldimethoxymethylsilane was added so that the concentrations of TEAL and 3,3-dimethyl-3-silacyclopentyldimethoxymethylsilane in the reaction system were 60 mmol / liter and 10 mmol / liter, respectively, and 5 Stir for minutes. Then, after depressurizing the system, propylene gas was continuously supplied to polymerize propylene for 3.5 hours. After completion of polymerization
The 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 1.7 g per 1 g of component A.

Examples 2 to 4 In the prepolymerization of Example 1, 3,3-dimethyl-3-
Instead of silacyclopentyldimethoxymethylsilane,
The silane compounds shown in Table 1 are TEAL or triisobutylaluminum (hereinafter abbreviated as TIBAL).
Was used in the concentrations shown in Table 1, the electron-donating compounds shown in Table 1 were used in the concentrations shown in Table 1, and the prepolymerization conditions were changed as shown in Table 1. Preliminary polymerization of component A was performed to prepare a catalyst component.

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

Comparative Example 2 In the prepolymerization of Example 1, 3,3-dimethyl-3-
Without using silacyclopentyldimethoxymethylsilane,
Further, the catalyst component was prepared by preliminarily polymerizing the component A in the same manner as in Example 1 except that the prepolymerization conditions were as shown in Table 1.

Comparative Example 3 In the prepolymerization of Example 1, 3,3-dimethyl-3-
Without using silacyclopentyldimethoxymethylsilane,
Prepolymerization of component A was carried out in the same manner as in Example 1 except that TEAL and diphenyldimethoxysilane were used at the concentrations shown in Table 1 and the prepolymerization conditions were as shown in Table 1.
A catalyst component was prepared.

[0071]

[Table 1]

[0072]Copolymerization of propylene 5 liters of oak fully dried with nitrogen substitution
42.9 mg of the polymerization catalyst component obtained above, n
0.3 mol of triethylal in 1 liter of heptane
4 ml of a solution containing minium and 1 liter of n-heptane
Contains 0.08 mol of diphenyldimethoxysilane
3 ml of the solution was mixed and held for 5 minutes. Next
With 4.7 liters of hydrogen and 3 liters of liquid propylene
After press-fitting, the internal temperature of the autoclave was raised to 70 ° C.
Then, the first stage polymerization was performed. After 1 hour, unreacted propylene
And purging with hydrogen to bring the internal pressure to 0.2 kg / cm
²・ G. After collecting a small amount of the first-stage polymer,
Hydrogen was introduced into the system. Followed by propylene and ethyl
Gas mixture with a molar ratio of 1.5
-Ethylene copolymerization was carried out. Pressure inside the chamber is 6 kg / cm²
・ K was maintained at G and copolymerization was carried out at 75 ° C. for 2 hours. End of polymerization
After that, unreacted gas was purged, and the polymer was taken out and dried.
It was Unreacted gas contains 0.5 mol% hydrogen
It was The MFR of the obtained polymer was 9.04 g / 10 min.
there were. Polymer obtained by copolymerization as a result of analysis
The production amount of ethylene is 19% by weight, and the ethylene content is 52%.
The amount was%. Also, sampled after the first stage
The MFR of the polymer was 27.4 g / 10 minutes. Last
When the physical properties of the polymer were measured, the flexural modulus was 9.0.
6 x 10 ³kg / cm², DuPont impact strength is 72.7
It was kg · cm.

Copolymerization of propylene in the same manner except that the polymerization catalyst components obtained in Examples 2 to 4 and Comparative Examples 1 to 3 were used and the amount of hydrogen was adjusted so that the MFR was as shown in Table 2. I went. The physical properties of the final polymer obtained are also shown in Table 2.
It was shown to. From this, it can be seen that the material of the present invention has an excellent balance between flexural modulus and DuPont impact strength.

[0074]

[Table 2]

[0075]

According to the method of the present invention, it is possible to produce a propylene block copolymer having an excellent balance of impact resistance and rigidity.

[Brief description of drawings]

FIG. 1 is a graph showing plots of measured values of flexural modulus and DuPont impact strength 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) Inventor Takeshi Ishihara 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Co., Ltd. Research Institute (72) Seisaburo Kanazawa Nishitsuruokaoka, Oi-cho, Saitama-ken 3-3-1 Tonen Co., Ltd. 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 organoaluminum compound and (C) a general formula: [Wherein R ¹ is a heterocyclic substituent containing a silicon atom, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O-, R ⁵ ₃ Si-
Alternatively, R ⁶ ₃ SiO—, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3, x + y + z = 4, and R ⁴ has ³ to 1 carbon atoms.
Zero hydrocarbon group, R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms. ] In the presence of an organosilicon compound represented by the formula (D), in the presence of a polymerization catalyst component which is brought into contact with an olefin, (1) propylene is polymerized to produce a highly crystalline polypropylene (a) and (2) A method for producing a propylene block copolymer, comprising the step (b) of copolymerizing propylene and ethylene.