JP2984092B2 - Method for producing propylene-ethylene block copolymer - Google Patents

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-ethylene block copolymer, and more particularly, to a propylene-ethylene block copolymer having a good balance between impact resistance and rigidity and a high polymer falling speed. The present invention relates to a method for producing a coalescence.

[0002]

2. Description of the Related Art In recent years, the demand for highly crystalline polypropylene produced by using various kinds of highly stereoregular catalysts has been rapidly increasing because of its excellent rigidity and heat resistance. However, these properties are still inadequate depending on the purpose of use, and various methods for improving rigidity have been proposed, but most of them are methods in which post-treatment such as adding a nucleating agent to polypropylene is performed. is there. Therefore, the cost is high in the process, and some additives impair the appearance of the molded product. A method of improving rigidity by a polymerization method without treatment with an additive has also been proposed, but none of these methods has insufficient rigidity. In addition, polypropylene is inherently
Because of the drawback of low impact strength, methods for improving impact resistance by copolymerizing with other olefins such as ethylene are widely used. Although the impact resistance is improved by this method, the rigidity is reduced accordingly. Therefore, various methods have been proposed in which polymerization is performed stepwise while changing the polymerization ratio of propylene and other olefins, that is, a method of improving the balance between rigidity and impact resistance of the copolymer by performing multistage polymerization. However, even with these methods, a sufficiently good balance of physical properties cannot be obtained.

[0003] Further, the conventional powder of polymer produced by block copolymerization with propylene ethylene sometimes deteriorates in slipperiness, which may cause a blockage trouble in the step of transferring from the reactor. Was. For this reason, measures such as reducing the composition ratio or ethylene content of the copolymerization stage are inevitable, and adverse effects may occur such that the produced polymer does not satisfy the desired physical properties.

[0004]

DISCLOSURE OF THE INVENTION The present invention is to produce a propylene-ethylene block copolymer having more excellent balance between impact resistance and rigidity, a high polymer falling speed, and improved slipperiness. The purpose is to provide a way to:

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the object of the present invention by adopting a polymerization method in which a specific organic silicon compound is added during the copolymerization of propylene and ethylene. I have come up with something that I can do.

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) Si—O— In the presence of a polymerization catalyst comprising an organic silicon compound having a C bond, (a) from the step (a) of polymerizing propylene to produce a highly crystalline polypropylene and (2) the step (b) of copolymerizing propylene with ethylene In the method for producing a propylene-ethylene block copolymer, wherein the step (b) is further performed in the presence of an organosilicon compound represented by the following general formula. : (D) General formula

Embedded image [However, R ¹ is an aliphatic or alicyclic hydrocarbon group having 3 to 10 carbon atoms, R ² is an aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms or R ⁴ O, 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 is the same as R ¹ ].

Solid catalyst component A solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst used in the present invention (hereinafter referred to as the catalyst of the present invention), comprises:
Magnesium, titanium, halogen and an electron donating compound are essential components. Such components are usually magnesium compounds, titanium compounds and electron donating compounds, and when each of the above compounds has no halogen, it contains halogen. The compounds are prepared by contacting each.

(1) Magnesium compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² represent the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms.
More specifically, as the hydrocarbon group of R ¹ and R ² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group is used. 12 alkyl groups, cycloalkyl group, aryl group, aralkyl group is chlorine as a halogen atom,
Bromine, iodine, fluorine and the like.

Specific examples of these compounds are shown below. In the chemical formula, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, and cyHe: cyclohexyl 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, EtOMgl, MgCl
₂ , MgBr ₂ , MgI ₂ .

The above magnesium compound can be prepared from metallic magnesium or another magnesium compound when preparing component A. Examples thereof include metallic magnesium, halogenated hydrocarbons and alkoxy group-containing compounds of the general formula X _n M (OR) _mn wherein X is a hydrogen atom, a halogen atom or a C 1-20
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. ] Is contacted. Examples of the hydrocarbon group of X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl, (Pr), and i-propyl (i-P
r), alkyl groups such as butyl (Bu), i-butyl (i-Bu), hexyl (He) and octyl (Oct); cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl; allyl, propenyl, butenyl and the like. Phenyl (Ph), tolyl, aryl groups such as 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. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

Compounds wherein M is carbon Formula C (OR)_Four(OMe) contained in_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)_Three(OMe) contained in_Three, HC (OE
t)_Three, HC (OPr)_3,HC (OBu)_Three, HC
(OHe)_Three, HC (OPh)_ThreeMeC (OM
e)_Three, MeC (OEt)_Three, EtC (OMe)_Three , E
tC (OEt)_Three, CyHeC (OEt)_Three, PhC
(OMe)_Three, PhC (OEt)_Three, CH_TwoClC (O
Et)_Three, MeCHBrC (OEt)_Three, MeCHCl
C (OEt) _Three; ClC (OMe)_Three, ClC (OE
t)_Three, ClC (Oi-Bu)_Three, BrC (OE
t)_ThreeFormula X_TwoC (OR)_TwoMeCH (O
Me)_Two, MeCH (OEt)_Two, CH_Two(OM
e)_Two, CH_Two(OEt)_Two, CH_TwoClCH (OE
t)_Two, CHCl_TwoCH (OEt)_Two, CCl_ThreeCH
(OEt)_Two, CH _TwoBrCH (OEt)_Two, PhCH
(OEt)_Two.

Compound when M is silicon Si (OMe) ₄ , Si contained in formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (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 , 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 when M is boron B (OEt) ₃ , B (OB) contained in formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

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

Compound where M is phosphorus Formula P (OR)_Three(OMe) contained in_Three, P (OE
t)_Three, P (OBu) _Three, P (OHe)_Three, P (OP
h)_Three.

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

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

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

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid and crotonic acid, and malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tert-butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
And aromatic polycarboxylic acids such as melitic acid. As the carboxylic acid anhydride, the 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. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and 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
-Tert-butyl ethyl benzoate, ethyl p-anisate,
α-ethyl ethyl naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetraethyl pyromellitate And the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetate chloride, acetate bromide, acetate iodide, propionate chloride, butyrate 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 chloride, succinic 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 include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride can also be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples include methanol, ethanol,
Propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol,
and n-octylphenol. Ethers represented by the general formula ROR ^1. In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl having 1 to 12 carbons,
Aryl and 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,
Anisole, ethyl phenyl ether and the like.

As a method for preparing component A, a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) are contacted in that order. After contacting component 1 with component 3, component 2 is contacted. A method of simultaneously contacting the component 1, the component 2, and the component 3 can be adopted. It is also possible to contact with a 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, groups IIa and IVa of the periodic table.
And halides of Group Va elements (hereinafter referred to as metal halides).

Halogenated hydrocarbons include those having 1 to 1 carbon atoms.
Mono- and poly-halogen substituents of 12 saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons. Specific examples of such compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, Carbon 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
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins are chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentagen, and hexachlorocyclohexane for alicyclic compounds, and chlorobenzene, bromobenzene, o-
Examples thereof include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

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

Examples of these compounds include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chloro-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-tribromo-4-
Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol,
2,4,6-triiodophenol: 2,3,4,6-
Tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-
Propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

Examples of the silicon halide compound having a hydrogen-silicon bond include 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
l (C ₆ H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
and i) chlorides, fluorides, bromides, and iodides, especially BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TIC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are preferred.

The contact with the component 1, the component 2 and the component 3, and further with the halogen-containing compound which can be brought into contact, if necessary, is carried out by mixing and stirring in the presence or absence of an inert medium. This is done by co-milling. The contact can be performed under heating at 40 to 150 ° C.

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

The preferred method for preparing 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 can be obtained by contacting (a) metal 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). A method of contacting a magnesium-containing solid with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63
-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting with a silicon halide compound having a silicon bond, (c) contact with a titanium halide compound, and then (d) contact with an electron donating compound (and further contact with a titanium halide compound as necessary) (A) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) contact with an electron donating compound, and then (d)
Method of contacting with a titanium compound (Japanese Patent Application Laid-Open No. 58-1985)
03 publication). Of these, the particular method is most desirable. Component A is prepared as described above,
Component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

The component A may further contain an olefin polymer formed in the component A upon contact with an olefin in the presence of an organoaluminum compound. The organoaluminum compound is selected from the below-mentioned organometallic compounds 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 less, preferably -10 to +
It is performed at a temperature of 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 10 per component Alg.
0 g.

The contact between the component A and the olefin may be carried out in the presence of an electron donating compound together with the organoaluminum compound. The electron donating compound includes a compound used for preparing the component A and a Si—O—C bond or a Si—N
It is selected from organic silicon compounds having a -C bond. Component A, which has come into contact with the olefin, can be optionally washed with the above-mentioned inert medium and further dried.

Organometallic compounds Organometallic compounds (hereinafter referred to as component B) are listed in the Periodic Table I.
Organic compounds of Group III or Group III metals. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, an organoaluminum compound is particularly preferable. The organoaluminum compound may be used, the general formula R _n Al
X _3-n (where R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n represents 1
It is an arbitrary number in the range of ≦ n ≦ 3. And C1 to C18 such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride.
And preferably an alkylaluminum compound having 2 to 6 carbon atoms or a mixture or complex compound thereof. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide,
Monoalkylaluminum dihalides such as dialkylaluminum monohalide such as diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, and ethylaluminum sesquichloride Dialkyl aluminum monoalkoxides such as alkyl aluminum sesquihalide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl Aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable. Further, these trialkylaluminums are other organic aluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or mixtures or complex compounds thereof, which are easily available industrially. Etc. can be used in combination.
An organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example,

Embedded image Etc. can be exemplified.

Examples of organic compounds of metals other than aluminum metal include LiAl (C), such as diethyl magnesium, ethyl magnesium chloride, diethyl zinc and the like.
_{2 H 5) 4, LiAl (} C 7 H 15) compounds such as _4.

Organic silicon compound having Si--O--C bond
(Hereinafter referred to as component C) represented by the general formula R_nSi
(OR¹)_4-n[However, R is a hydrocarbon group or a halogen atom.
Child, R ¹Represents a hydrocarbon group and 0 ≦ n ≦ 3. ]
Compounds. R hydrocarbon in the above general formula
As an alkyl group, an alkyl group, a cycloalkyl group, an aryl
Group, aralkyl group, alkenyl group, alkadienyl
Group, cycloalkenyl group, cycloalkazinyl group, etc.
I can do it. As the halogen atom for R, chlorine, bromine,
And urine. Also, R¹As hydrocarbon groups of
Alkyl group, cycloalkyl group, aryl group, alkenyl
And the like. Further, n hydrocarbons of R and (4-
n) ORs¹R¹Hydrocarbon groups are the same but different
Is also good.

Specific examples of component C include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, citrabenzyloxysilane, methyltrimethoxysilane , Methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxy Silane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyl Hexyloxy silane, dimethyl diphenoxy silane, diethyl diethoxy silane,
Diethyl diisobutoxy silane, diethyl diphenoxy silane, dibutyl diisopropoxy silane, dibutyl dibutoxy silane, dibutyl diphenoxy silane, diisobutyl diethoxy silane, diisobutyl diisobutoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, diphenyl dibutoxy silane, Examples include dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane. Of course, the use of the organosilicon compound used in the step b described later of the present invention is not limited.

The polymerization catalyst used in the present invention comprises a combination of the above components A, B and C. Component B is used in an amount of usually 1 to 2,000 gmol, especially 20 to 50 gmol, per 1 g atom of titanium in component A.
0 gmol is desirable. The ratio of the component B to the component C is 0.1 to 40 gram atoms, preferably 1 to 25 gram atoms of the component B as aluminum atoms with respect to 1 mol of the component C.
Selected in the range of gram atoms.

Method for Producing Propylene-Ethylene Block Copolymer In the method for producing propylene-ethylene block copolymer, a step (step a) of polymerizing propylene to form a highly crystalline polypropylene, and copolymerizing propylene with ethylene. Step (Step b).

(1) Step a Step a) comprises polymerizing propylene in the presence of the polymerization catalyst. The polymerization reaction may be any of a gas phase and a liquid phase, and when polymerizing 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 from -80 ° C to +
It is in the range of 150C, preferably 40-120C. The polymerization pressure may be, for example, 1 to 60 atm. Adjustment of the molecular weight of the resulting polymer is performed by the presence of hydrogen or other known molecular weight regulators. In the step (a), it is desirable that the amount of the polypropylene obtained therefrom is 50 to 98% by weight, particularly 70 to 95% by weight of the block copolymer.

(2) Step b The copolymerization of propylene and ethylene is carried out in the presence of the above-mentioned polymerization catalyst and an organosilicon compound represented by the above general formula (hereinafter referred to as component D). The copolymerization is carried out by contacting and reacting propylene with ethylene such that the ethylene content in the copolymer obtained therefrom is 30 to 95% by weight, preferably 40 to 80% by weight. The copolymerization reaction can be appropriately selected from the range of polymerization conditions performed in step a, and the use of a molecular weight regulator such as hydrogen is the same as in step a. The amount of the copolymer obtained in the step b is usually 50 to 50% of the block copolymer.
It is 2% by weight, preferably 30 to 5% by weight.
Component D used together with the polymerization catalyst in step b is represented by the general formula.

[0044]Organic silicon compounds An organosilicon compound (hereinafter referred to as a component) which is one component of the catalyst of the present invention.
Minute D. ) Is represented by the above general formula. In the formula
And R¹Is aliphatic or alicyclic having 3 to 10 carbon atoms
A hydrocarbon group, preferably an alkyl group or an alkenyl group.
And an aliphatic hydrocarbon group such as
It is a kill group. In addition, the alkyl group is branched
In the case of an alkyl group, good results are often obtained. R^Two
Is an aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms
Or R^FourO. The hydrocarbon group is preferably
Cycloalkyl group, cycloalkenyl group, cycloalka
It is an alicyclic hydrocarbon group such as a dienyl group. R^FourO's R^Four
Is R¹Is equivalent to R ^ThreeIs a methyl group or ethyl
Group. x is 1 or 2, y is 0 or 1, and z is
2 or 3, and x + y + z = 4.

Hereinafter, specific examples of the component D will be listed. In addition,
In the following, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Amy = amyl, Hex = hexyl, Oct = octyl, Dec = decyl, CyPe =
Cyclopentyl, CyHe = cyclohexyl, CyPy
= Cyclopentenyl, CyPt = cyclopentadienyl, CyHy = cyclohexenyl group. The following specific examples are only for the case where R ³ is a methyl group in the above-mentioned general formula, and are omitted when the R ³ is an ethyl group. Compounds in which the methyl group of R ^{3 in} these specific examples is replaced with an ethyl group can also be mentioned as specific examples.

Compound of (R ¹ O) ₂ Si (OR ³ ) ₂ (n-PrO) ₂ Si (OMe) ₂ , (i-PrO) ₂
Si (OMe) ₂ , (t-BuO) ₂ Si (OM
e) ₂ , (s-BuO) ₂ Si (OMe) ₂ , (n-B
uO) ₂ Si (OMe) ₂ , (i-BuO) ₂ Si (O
Me) ₂ , (t-AmyO) ₂ Si (OMe) ₂ , (n
—AmyO) ₂ Si (OMe) ₂ , (n-HexO) ₂
Si (OMe) ₂ , (n-OctO) ₂ Si (OMe)
₂ , (n-DecO) ₂ Si (OMe) ₂ , (CyPe
O) ₂ Si (OMe) ₂ , (CyHeO) ₂ Si (OM
e) ₂ , (CyPyO) ₂ Si (OMe) ₂ , (CyP
tO) ₂ Si (OMe) ₂ , (CyHyO) ₂ Si (O
Me) ₂ . ○ Compound of (R ¹ O) (R ⁴ O) Si (OR ³ ) ₂ (i-PrO) (n─BuO) Si (OMe) ₂ , (n
—PrO) (t─BuO) Si (OMe) ₂ , (t−B
uO) (n─BuO) Si (OMe) ₂ , (s-Bu
O) (i─BuO) Si (OMe) ₂ , (t-Amy)
O) (n-PrO) Si (OMe) ₂ , (n-Amy)
O) (i-PrO) Si (OMe) ₂ , (n-BuO)
(T-AmyO) Si (OMe) ₂ , (s-BuO)
(S-AmyO) Si (OMe) ₂ , (i-BuO)
(N-AmyO) Si (OMe) ₂ , (t-AmyO)
(N-AmyO) Si (OMe) ₂ , (t-AmyO)
(N-HexO) Si (OMe) ₂ , (CyPeO)
(N-PrO) Si (OMe) ₂ , (CyPeO) (i
-PrO) Si (OMe) ₂ , (CyPeO) (n-B
uO) Si (OMe) ₂ , (CyPeO) (i-Bu
O) Si (OMe) ₂ , (CyPeO) (s-BuO)
Si (OMe) ₂ , (CyPeO) (t-BuO) Si
(OMe) ₂ , (CyPeO) (n-AmyO) Si
(OMe) ₂ , (CyPeO) (t-AmyO) Si
(OMe) ₂ , (CyPeO) (n-HexO) Si
(OMe) ₂ , (CyPeO) (n-OctO) Si
(OMe) ₂ , (CyHeO) (n-PrO) Si (O
Me) ₂ , (CyHeO) (i-PrO) Si (OM
e) ₂ , (CyHeO) (n-BuO) Si (OMe)
₂ , (CyHeO) (i-BuO) Si (OMe) ₂ ,
(CyHeO) (s-BuO) Si (OMe) ₂ , (C
yHeO) (t-BuO) Si (OMe) ₂ , (CyH
eO) (n-AmyO) Si (OMe) ₂ , (CyHe)
O) (t-AmyO) Si (OMe) ₂ , (CyHe)
O) (n-HexO) Si (OMe) ₂ , (CyHe
O) (n-OctO) Si (OMe) ₂ , (CyPy)
O) (n-PrO) Si (OMe) ₂ , (CyPyO)
(I-PrO) Si (OMe) ₂ , (CyPyO) (n
-BuO) Si (OMe) ₂ , (CyPyO) (i-B
uO) Si (OMe) ₂ , (CyPyO) (s-Bu
O) Si (OMe) ₂ , (CyPyO) (t-BuO)
Si (OMe) ₂ , (CyPyO) (n-AmyO) S
i (OMe) ₂ , (CyPyO) (t-AmyO) Si
(OMe) ₂ , (CyPyO) (n-HexO) Si
(OMe) ₂ , (CyPyO) (n-OctO) Si
(OMe) ₂ , (CyPtO) (n-PrO) Si (O
Me) ₂ , (CyPtO) (i-PrO) Si (OM
e) ₂ , (CyPtO) (n-BuO) Si (OMe)
₂ , (CyPyO) (i-BuO) Si (OMe) ₂ ,
(CyPtO) (s-BuO) Si (OMe) ₂ , (C
yPtO) (t-BuO) Si (OMe) ₂ , (CyP
tO) (n-AmyO) Si (OMe) ₂ , (CyPt)
O) (t-AmyO) Si (OMe) ₂ , (CyPt)
O) (n-HexO) Si (OMe) ₂ , (CyPt)
O) (n-OctO) Si (OMe) ₂ , (CyHy)
O) (n-PrO) Si (OMe) ₂ , (CyHyO)
(I-PrO) Si (OMe) ₂ , (CyHyO) (n
-BuO) Si (OMe) ₂ , (CyHyO) (i-B
uO) Si (OMe) ₂ , (CyHyO) (s-Bu
O) Si (OMe) ₂ , (CyHyO) (r-BuO)
Si (OMe) ₂ , (CyHyO) (n-AmyO) S
i (OMe) ₂ , (CyHyO) (t-AmyO) Si
(OMe) ₂ , (CyHyO) (n-HexO) Si
(OMe) ₂ , (CyHyO) (n-Oct) Si (O
Me) ₂ .

○ (R¹O) R^TwoSi (OR^Three)_TwoCompound
(I-PrO) MeSi (OMe)_Two, (I-PrO)
n-PrSi (OMe)_Two, (N-PrO) t-Amy
Si (OMe)_Two, (I-PrO) n-HexSi (O
Me)_Two, (N-BuO) MeSi (OMe)_Two, (T
-BuO) MeSi (OMe)_Two, (S-BuO) Et
Si (OMe)_Two, (I-BuO) i-PrSi (OM
e)_Two, (T-BuO) t-BuSi (OMe)_Two,
(N-BuO) s-BuSi (OMe)_Two, (T-Bu
O) n-AmySi (OMe)_Two, (N-AmyO) i
-PrSi (OMe)_Two, (T-AmyO) t-BuS
i (OMe)_Two, (T-AmyO) t-AmySi (O
Me)_Two, (T-AmyO) MeSi (OMe)_Two,
(N-AmyO) EtSi (OMe)_Two, (N-Hex
O) MeSi (OMe)_Two, (N-HexO) EtSi
(OMe)_Two, (N-HexO) i-PrSi (OM
e)_Two, (N-HexO) t-BuSi (OMe) _Two,
(N-HexO) n-HexSi (OMe)_Two, (N−
HexO) n-OctSi (OMe)_Two, (N-Oct
O) MeSi (OMe)_Two, (N-OctO) n-Oc
tSi (OMe)_Two, (I-PrO) CyPeSi (O
Me)_Two, (N-PrO) CyPeSi (OMe)_Two,
(N-BuO) CyPeSi (OMe)_Two, (I-Bu
O) CyPeSi (OMe)_Two, (S-BuO) CyP
eSi (OMe)_Two, (T-BuO) CyPeSi (O
Me)_Two, (N-AmyO) CyPeSi (OM
e)_Two, (T-AmyO) CyPeSi (OMe)_Two,
(N-HexO) CyPeSi (OMe)_Two, (N-O
ct) CyPeSi (OMe) _Two, (I-PrO) Cy
HeSi (OMe)_Two, (N-PrO) CyHeSi
(OMe)_Two, (N-BuO) CyHeSi (OMe)
_Two, (I-BuO) CyHeSi (OMe)_Two, (S−
(BuO) CyHeSi (OMe)_Two, (T-BuO) C
yHeSi (OMe)_Two, (N-AmyO) CyHeS
i (OMe)_Two, (T-AmyO) CyHeSi (OM
e)_Two, (N-HexO) CyHeSi (OMe)_Two,
(N-Oct) CyHeSi (OMe)_Two, (N-Pr
O) CyPySi (OMe)_Two, (I-PrO) CyP
ySi (OMe)_Two, (N-BuO) CyPySi (O
Me)_Two, (I-BuO) CyPySi (OMe)_Two,
(S-BuO) CyPySi (OMe)_Two, (T-Bu
O) CyPySi (OMe)_Two, (N-AmyO) Cy
PySi (OMe)_Two, (T-AmyO) CyPySi
(OMe)_Two, (N-HexO) CyPySi (OM
e)_Two, (N-Oct) CyPySi (OMe)_Two,
(N-PrO) CyPtSi (OMe)_Two, (I-Pr
O) CyPtSi (OMe)_Two, (N-BuO) CyP
tSi (OMe)_Two, (I-BuO) CyPtSi (O
Me)_Two, (S-BuO) CyPtSi (OMe)_Two,
(T-BuO) CyPtSi (OMe)_Two, (N-Am
yO) CyPtSi (OMe)_Two, (T-AmyO) C
yPtSi (OMe)_Two, (N-HexO) CyPtS
i (OMe)_Two, (N-Oct) CyPtSi (OM
e)_Two, N-PrO) CyHySi (OMe)_Two, (I
-PrO) CyHySi (OMe) _Two, (N-BuO)
CyHySi (OMe)_Two, (I-PrO) CyHyS
i (OMe)_Two, (S-BuO) CyHySi (OM
e)_Two, (T-BuO) CyHySi (OMe)_Two,
(N-AmyO) CyHySi (OMe)_Two, (T−A
myO) CyHySi (OMe)_Two, (N-HexO)
CyHySi (OMe)_Two, (N-OctO) CyHy
Si (OMe)_Two, (CyPeO) MeSi (OMe)
_Two, (CyPeO) EtSi (OMe)_Two, (CyPe
O) n-PrSi (OMe)_Two, (CyPeO) i-P
rSi (OMe)_Two, (CyPeO) n-BuSi (O
Me)_Two, (CyPeO) i-BuSi (OMe)_Two,
(CyPeO) s-BuSi (OMe)_Two, (CyPe
O) t-BuSi (OMe)_Two, (CyPeO) n-A
mySi (OMe)_Two, (CyPeO) t-AmySi
(OMe)_Two, (CyPeO) n-HexSi (OM
e)_Two, (CyPeO) n-OctSi (OMe)_Two,
(CyHeO) MeSi (OMe)_Two, (CyHeO)
EtSi (OMe)_Two, (CyHeO) n-PrSi
(OMe)_Two, (CyHeO) i-PrSi (OMe)
_Two, (CyHeO) n-BuSi (OMe)_Two, (Cy
(HeO) i-BuSi (OMe)_Two, (CyHeO) s
-BuSi (OMe) _Two, (CyHeO) t-BuSi
(OMe)_Two, (CyHeO) n-AmySi (OM
e)_Two, (CyHeO) t-AmySi (OMe)_Two,
(CyHeO) n-HexSi (OMe)_Two, (CyH
eO) n-OctSi (OMe)_Two, (CyPyO) M
eSi (OMe)_Two, (CyPyO) EtSi (OM
e)_Two, (CyPyO) n-PrSi (OMe)_Two,
(CyPyO) i-PrSi (OMe) _Two, (CyPy
O) n-BuSi (OMe)_Two, (CyPyO) i-B
uSi (OMe)_Two, (CyPyO) s-BuSi (O
Me)_Two, (CyPyO) t-BuSi (OMe)_Two,
(CyPyO) n-AmySi (OMe)_Two, (CyP
yO) t-AmySi (OMe)_Two, (CyPyO) n
-HexSi (OMe)_Two, (CyPyO) n-Oct
Si (OMe)_Two, (CyPtO) MeSi (OMe)
_Two, (CyPtO) EtSi (OMe)_Two, (CyPt
O) n-PrSi (OMe)_Two, (CyPtO) i-P
rSi (OMe)_Two, (CyPtO) n-BuSi (O
Me)_Two, (CyPtO) i-BuSi (OMe)_Two,
(CyPtO) s-BuSi (OMe)_Two, (CyPt
O) t-BuSi (OMe)_Two, (CyPtO) n-A
mySi (OMe)_Two, (CyPtO) t-AmySi
(OMe)_Two, (CyPtO) n-HexSi (OM
e)_Two, (CyPtO) n-OctSi (OMe)_Two,
(CyHyO) MeSi (OMe)_Two, (CyHyO)
EtSi (OMe)_Two, (CyHyO) n-PrSi
(OMe)_Two, (CyHyO) i-PrSi (OMe)
_Two, (CyHyO) n-BuSi (OMe)_Two, (Cy
HyO) i-BuSi (OMe)_Two, (CyHyO) s
-BuSi (OMe) _Two, (CyHyO) t-BuSi
(OMe)_Two, (CyHyO) n-AmySi (OM
e)_Two, (CyHyO) t-AmySi (OMe)_Two,
(CyHyO) n-HexSi (OMe)_Two, (CyH
yO) n-OctSi (OMe)_Two, (CyPeO) C
yPeSi (OMe)_Two, (CyPeO) CyHeSi
(OMe) _Two, (CyPeO) CyPySi (OMe)
_Two, (CyPeO) CyPtSi (OMe)_Two, (Cy
PeO) CyHySi (OMe)_Two, (CyHeO) C
yPeSi (OMe)_Two, (CyHeO) CyHeSi
(OMe)_Two, (CyHeO) CyPySi (OMe)
_Two, (CyHeO) CyPtSi (OMe)_Two, (Cy
HeO) CyHySi (OMe)_Two, (CyPyO) C
yPeSi (OMe) _Two, (CyPyO) CyHeSi
(OMe)_Two, (CyPyO) CyPySi (OMe)
_Two, (CyPyO) CyPtSi (OMe)_Two, (Cy
PyO) CyHySi (OMe)_Two, (CyPtO) C
yPeSi (OMe)_Two, (CyPtO) CyHeSi
(OMe)_Two, (CyPtO) CyPySi (OMe)
_Two, (CyPtO) CyPtSi (OMe)_Two, (Cy
(PtO) CyHySi (OMe)_Two, (CyHyO) C
yPeSi (OMe)_Two, (CyHyO) CyHeSi
(OMe)_Two, (CyHyO) CyPySi (OMe)
_Two, (CyHyO) CyPtSi (OMe)_Two, (Cy
HyO) CyHySi (OMe)_Two.

○ (R¹O) Si (OR^Three)_ThreeCompound (i-PrO) Si (OMe)_Three, (N-BuO) Si
(OMe)_Three, (S-BuO) Si (OMe)_Three, (I
-BuO) Si (OMe)_Three, (T-BuO) Si (O
Me)_Three, (T-AmyO) Si (OMe)_Three, (N−
AmyO) Si (OMe)_Three, (N-HexO) Si
(OMe)_Three, (N-OctO) Si (OMe)_Three,
(N-DecO) Si (OMe)_Three, (CyPeO) S
i (OMe) _Three, (CyHeO) Si (OMe)_Three,
(CyPyO) Si (OMe)_Three, (CyPtO) Si
(OMe)_Three, (CyHyO) Si (OMe)_Three.

Component D is used in an amount of 0.0
It is 1 to 100 mol, preferably 0.1 to 10 mol.

The method of the present invention comprises a step a and a step b. The steps a and b may be performed in order or vice versa. Alternatively, the steps a and b may be performed in parallel. A method of combining the polymers obtained in the above can be adopted, and among these, a method in which step a and step b are performed in that order is particularly advantageous and desirable in terms of the apparatus.

[0051]

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. The physical properties of the polymer were measured by adding BHT (2,6-di-tert-butyl-4) to the polymer powder.
0.18% by weight of DSTDP
0.08% by weight of (distearylthiodipropionate), 0.04% by weight of IRGANOX1010 [tetrakis- {methylene- (3,5-ditert-butyl-4-hydroxyhydro-cinnamate) methane]], calcium stearate After adding 0.06% by weight of each rate and pelletizing by melt-kneading, test pieces were prepared by injection molding. Flexural modulus: JIS K7
203-1982: Dupont impact strength: JIS K
7211-1976. Also, the polymer M
FR was measured according to ASTM D-1238. The falling speed of the polymer is HOSOKAWA MICRON CORP
Using a POWDER TESTER, the falling speed of 100 cc of powder preheated to 110 ° C. was measured.

Example 1 Preparation of Component A In a 1-liter reaction vessel equipped with a reflux condenser, a chip-shaped metal magnesium (purity: 99.000) was placed under a nitrogen gas atmosphere.
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 preactivated metallic magnesium. Next, a suspension obtained by adding 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butylmagnesium chloride (1.75 mol / l) to the metallic magnesium was added at 55 ° C.
And 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 conducting the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was added for 2 hours.
It was kept at 5 ° C. Next, HC (OC ₂ H) was added to the reaction solution.
The _{5) 3} 55.7 ml was added dropwise over 1 hour. After dropping,
The reaction was carried out at 60 ° C. for 15 minutes, and the solid produced by the reaction was washed six times with 300 ml each of n-hexane and dried under reduced pressure at room temperature for 1 hour. A magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine 31.6 g were recovered. Under a nitrogen gas atmosphere, a magnesium-containing solid 6.3 was placed in a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel.
g and n-heptane (50 ml) to give a suspension, and while stirring at room temperature, 2,2,2-trichloroethanol (20 ml).
(0.02 mmol) and 11 ml of n-heptane were added dropwise from a dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The resulting solid was filtered, washed four times with 100 ml each of n-hexane at room temperature, and twice with 100 ml each of toluene to obtain a solid component. 40 ml of toluene was added to the above solid component, and 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. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance was separated by filtration at 90 ° C and washed at 90 ° C twice with 100 ml each of toluene. Further, titanium tetrachloride was newly 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 material obtained was filtered off at 110 ° C.
After washing 7 times with 00 ml of n-hexane, 5.5 g of component A was obtained.
I got

Polymerization of Propylene In a well-dried 5 liter autoclave with a nitrogen purge, a solution containing 30.6 mg of the component A obtained above and 0.2 mol of triethylaluminum in 1 liter of n-heptane. 6 ml, and 6 ml of a solution containing 0.04 mol of diphenyldimethoxysilane in 1 liter of n-heptane were mixed and the mixture was kept for 5 minutes. Then
After pressurizing 12 liters of hydrogen and 3 liters of liquid propylene, the first-stage polymerization was performed at an internal temperature of the autoclave of 70 ° C. 59 minutes after the start of polymerization, n-heptane 1
6 ml of a solution containing 0.04 mol of diisopropoxydimethoxysilane was introduced into the liter, and the stirring of the autoclave after 1 minute was stopped. At the same time, hydrogen and unreacted propylene were purged, and the pressure in the autoclave was reduced to 0 .2 kg /
cm ² · G. After partially collecting the first-stage polymer, hydrogen was introduced into the system.

Copolymerization of Propylene and Ethylene Subsequently, a mixed gas having a molar ratio of propylene to ethylene of 1.5 was supplied to perform propylene-ethylene copolymerization. The internal pressure was maintained at 6 kg / cm ² · G, and copolymerization was carried out at 75 ° C. for 2 hours. After polymerization, purge unreacted gas,
The polymer was removed and dried. The unreacted gas contained 0.6 mol% of hydrogen. MFR of the obtained polymer
Was 11.8 g / 10 minutes. As a result of the analysis, the amount of the polymer obtained by copolymerization was 19%, and the ethylene content was 51%. The MFR of the polymer sampled after the completion of the first stage was 29.5 g / 10 minutes. When the physical properties of the final polymer were measured, the flexural modulus was 8.13 × 10 ³ kg / cm ² and the DuPont impact strength was 84.3 kg · cm. The falling speed of the polymer was 10.1 cc / sec.

Examples 2 to 4 and Comparative Examples 1 to 3 Instead of diphenyldimethoxysilane used in the polymerization of propylene, an organic silicon compound shown in Table 1 was used, and diisopropoxy used in the copolymerization of propylene and ethylene was used. With or without using the organosilicon compounds shown in Table 1 in place of dimethoxysilane, M
Propylene was copolymerized in the same manner as in Example 1 except that the amount of hydrogen was adjusted so as to obtain FR. The physical properties of the final polymer obtained are also shown in the table. This shows that the polymer of the present invention shows excellent impact resistance and rigidity in a well-balanced manner, and also has improved slipperiness.

[Table 1]

[Table 2]

[0056]

According to the method of the present invention, it is possible to more effectively produce a propylene block copolymer having an excellent balance between impact resistance and rigidity, a high polymer falling speed, and an improved slip property.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for producing a propylene-ethylene block copolymer of the present invention.

Continuing from the front page (72) Inventor Hiroo Saito 1-3-1, Nishitsurugaoka, Oimachi, Irima-gun, Saitama Prefecture Tonen Co., Ltd. (72) Inventor Takayuki Taki 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama No. 1 Tonen Co., Ltd. (72) Inventor Takeshi Ishihara 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture 1 Tonen Co., Ltd. (56) References JP-A-3-162403 (JP, A JP-A-2-173010 (JP, A) JP-A-2-77413 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (1)

(57) [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) an organosilicon compound having a Si--O--C bond. In the presence of a polymerization catalyst, a propylene-ethylene block copolymer comprising (a) a step of producing propylene by polymerizing propylene to produce a highly crystalline polypropylene and (2) a step (b) of copolymerizing propylene and ethylene. A method for producing a propylene-ethylene block copolymer, wherein the step (b) is further performed in the presence of an organic silicon compound represented by the following general formula: (D) General formula [However, R ¹ is an aliphatic or alicyclic hydrocarbon group having 3 to 10 carbon atoms, R ² is an aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms or R ⁴ O, 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 is the same as R ¹ ].