JPH059240A - Production of ethylene-propylene block copolymer - Google Patents

Abstract

PURPOSE:To produce the title copolymer having an excellent balance between impact strength and stiffness and to increase the falling rate of the polymer by copolymerizing ethylene with propylene in the presence of a highly crystalline PP and a specific organosilicon compd. CONSTITUTION:Propylene is polymerized at -80 to 150 deg.C and 1-60atm. in the presence of a polymn. catalyst comprising a solid catalyst component essentially contg., Mg, Ti, a halogen, and an electron-donating compd., an organometallic compd. of a metal of the groups I, II, and III, and an organosilicon compd. having an Si-O-C bond, thus giving a highly crystalline PP. The title copolymer is produced by copolymerizing 30-95wt.% ethylene with propylene in the presence of 50-98wt.% the crystalline PP and an organosilicon compd. of the formula (wherein R<1> and R<2> are each a 1-10C hydrocarbon group, 0R<4>, 0SiR<5>3, or SiR<6>3; R<3> is a 1-10C divalent hydrocarbon group; and R<4>, R<5>, and R<6> are each a 1-10C hydrocarbon group).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a propylene-ethylene block copolymer, more specifically, a propylene-ethylene block copolymer having an excellent balance of impact resistance and rigidity and a high polymer falling speed. It relates to a method of manufacturing a coalesce.

[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, in addition to the high cost in terms of process, some additives may impair the appearance of the molded product. Although a method of improving the rigidity by a polymerization method without treatment with an additive has been proposed, the rigidity is insufficient in each case. Furthermore, polypropylene is originally
Since it has a drawback of low impact strength, a method of improving impact resistance by copolymerizing 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 for performing stepwise polymerization while changing the polymerization ratio of propylene and other olefins, that is, a method for improving the physical property balance of rigidity and impact resistance of the copolymer by performing multistage polymerization. However, even with these methods, a sufficiently excellent physical property balance cannot be obtained.

Further, the conventional polymer powder produced by block copolymerization with propylene ethylene sometimes deteriorates in slipperiness, which may cause clogging trouble in the step of transferring from the reactor. It was Therefore, it is necessary to take measures such as reducing the composition ratio of the copolymerization stage or the ethylene content, which may cause an adverse effect such that the produced polymer does not satisfy the target physical property values.

[0004]

DISCLOSURE OF THE INVENTION The present invention more effectively produces a propylene-ethylene block copolymer having an excellent balance of impact resistance and rigidity, a high polymer falling speed, and improved slipperiness. The purpose is to provide a method of doing.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by adopting a polymerization method in which a specific organosilicon compound is added at the time of copolymerization. I came to find out.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components, (B) an organometallic compound and (C) Si—O.
In the presence of a polymerization catalyst composed of an organosilicon compound having a -C bond, (1) a step of polymerizing propylene to produce a highly crystalline polypropylene (a) and (2) a step of copolymerizing propylene and ethylene (b). In the method for producing a propylene-ethylene block copolymer, the step (b) is further carried out in the presence of an organosilicon compound represented by the following general formula. is there. (D) General formula

[Chemical 2] [However, R ¹ and R ² are the same or different and have 1 to 10 carbon atoms.
Number of the hydrocarbon group, OR ^4, OSiR ₃ ⁵ or Si
R ₃ ^6, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, an R ^4, R ⁵ and R ⁶ having 1 to 10 carbon atoms each hydrocarbon radical. ] The organosilicon compound represented by these.

Solid Catalyst Component A solid catalyst component (hereinafter referred to as component A) which is one component of the catalyst used in the present invention (hereinafter referred to as catalyst of the present invention) is
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, a halogen-containing compound is contained. 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, the hydrocarbon group of R ¹ and R ² is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR group is R having 1 to 10 carbon atoms. Twelve alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups have chlorine as a halogen atom,
Examples include bromine, iodine, and fluorine.

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

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when the component A is prepared. As one example thereof, magnesium metal, halogenated hydrocarbon and an alkoxy group-containing compound 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. Examples of the hydrocarbon group 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. Hereinafter, specific examples of the alkoxy group-containing compound will be given.

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(OMe)₂,
 CH₂(OEt)₂, CH₂ClCH (OEt)₂，
CHCl₂CH (OEt)₂, CCl₃CH (OEt)
₂, CH ₂BrCH (OEt)₂, PhCH (OEt)
₂.

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

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

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

The compound of formula P (OR) when M is phosphorus₃Included in P (OMe)₃, P (OE
t)₃, P (OBu) ₃, P (OHe)₃, P (OP
h)₃.

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

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

(4) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples thereof include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters and carbonic acid esters. 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, p-tertiary 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,
Examples thereof include aromatic polycarboxylic acids such as mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

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

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

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

As the method for preparing the 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 and component 3, component 2 is contacted. A method such as contacting the components 1, 2 and 3 at the same time can be adopted. It is also possible to contact with the halogen-containing compound before contacting with component 2.

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

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of these compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetracarbon 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 the hydroxyl group in the 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
-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-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, etc. are mentioned.

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

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

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

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

A preferable method for preparing the component A in the present invention is described in JP-A-63-264607 and JP-A-58-19850.
No. 3, No. 62-146904 and the like. More specifically, (a) magnesium metal, (b) halogenated hydrocarbon, (c) general formula X _n M
A magnesium-containing solid obtained by contacting a compound of (OR) _mn (the same as the above alkoxy group-containing compound) with (d) a halogen-containing alcohol;
Then, (e) a method of bringing the compound into contact with an electron donating compound and (f) a titanium compound (JP-A-63-264607), (a) magnesium dialkoxide and (b)
After contacting a silicon halide compound having a hydrogen-silicon bond, (c) a titanium halide compound is contacted, and then (d) an electron donating compound (if necessary, further contact with a titanium halide compound). (JP-A-62-146904), (a) contacting a magnesium dialkoxide with a (b) silicon halide compound having a hydrogen-silicon bond, and then (c) contacting with an electron-donating compound. And then contacting with the (d) titanium compound (JP-A-58-198503).
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 an organoaluminum compound. The organoaluminum compound is selected from the organometallic compounds described below, which are one component of the catalyst of the present invention.

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

In 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 the compound used in preparing the component A and the Si—O—C bond or Si—N.
It is selected from organic silicon compounds having a -C bond. The component A contacted with the olefin can be washed with the above-mentioned inert medium, if necessary, and can be further dried.

Organometallic compounds Organometallic compounds (hereinafter referred to as component B) are listed in Periodic Table I.
Organic compounds of Group III to Group III metals. As the component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R _n Al
X _3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1
It is an arbitrary number within the range of ≦ n ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide, a dialkylaluminum monohydride and the like having 1 to 18 carbon atoms.
Especially preferred are alkylaluminum compounds, preferably 2 to 6 carbon atoms, or mixtures or complex compounds thereof. Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide,
Dialkyl aluminum monohalides such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monoalkyl aluminum dihalides such as isobutyl aluminum dichloride, ethyl aluminum sesquichloride, etc. Alkyl aluminum sesquihalide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide and other dialkyl aluminum monoalkoxides, dimethyl aluminum hydride, diethyl ether Aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.
Further, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include

[Chemical 3] Etc. can be illustrated.

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

Si-O-C which is one component of the catalyst of the present invention
Organosilicon compound having a bond (hereinafter referred to as component C)
Are represented by the general formula R _n Si (OR ¹ ) _4-n [wherein R is a hydrocarbon group or a halogen atom, R ¹ is a hydrocarbon group, 0 ≦
Indicates n ≦ 3. ] The compound represented by these is mentioned. The hydrocarbon group represented by R in the above general formula is an alkyl group,
Examples thereof include a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkadienyl group, a cycloalkenyl group and a cycloalkazinyl group. Examples of the halogen atom of R include chlorine, bromine, iodine and the like. Also, R
Examples of the hydrocarbon group of ¹ include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. Furthermore,
The hydrocarbon group of n R and the hydrocarbon group of R ¹ of (4-n) OR ¹ may be the same or different.

Specific examples of the component C include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane and 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,
Diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, Examples thereof include dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane and chlorophenyldiethoxysilane. Of course, the use of the organosilicon compound used in step b of the present invention described later is not limited.

The polymerization catalyst used in the present invention comprises a combination of the above component A, component B and component C. The amount of the component B used relative to the component A is usually 1 to 2,000 gram mol, particularly 20 to 50 gram mol per 1 gram atom of titanium in the component A.
0 gram mol is desirable. Further, the ratio of the component B to the component C is such that the component B is 0.1 to 40 gram atom, preferably 1 to 25 as aluminum atom, relative to 1 mol of the component C.
Selected in the range of gram atoms.

Of the propylene-ethylene block copolymer
Production Method The production method of the propylene-ethylene block copolymer includes a step of polymerizing propylene to obtain a highly crystalline polypropylene (step a) and a step of copolymerizing propylene and ethylene (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 the 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. Further, the molecular weight of the obtained polymer is 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 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 so that the ethylene content in the copolymer obtained there becomes 30 to 95% by weight, preferably 40 to 80% by weight. The copolymerization reaction can be appropriately selected from the range of 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 step b is usually 50 to 50% of that of the block copolymer.
It is 2% by weight, but is preferably 30 to 5% by weight.
The component D used in the step b together with the polymerization catalyst is represented by the above general formula.

[0044]Organosilicon compound The organosilicon compound used in the present invention (hereinafter referred to as component D)
U ) Is represented by the above general formula. In the formula, R
¹, R²Hydrocarbon groups and OR^Four, OSiR^Five ₃, Si
R⁶ ₃R in^Four, R^Five, R⁶As a hydrocarbon group of
Is an alkyl group, an alkenyl group, a cycloalkyl group,
Chloalkenyl group, cycloalkadienyl group, aryl
Groups, aralkyl groups and the like.

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

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

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

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

[Chemical 5]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

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

The amount of component D used is 0.0 per mol of component C.
It is 1 to 100 mol, preferably 0.1 to 10 mol.

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.

[0054]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-ditertiarybutyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, calcium stearate After adding 0.06% by weight of each of them to form pellets by melt-kneading, test pieces were prepared by injection molding. Flexural modulus: JIS K 7
203-1982: DuPont Impact Strength: JIS K
Compliant with 7211-1976. Also, the polymer M
FR was measured according to ASTM D-1238. In addition, the falling speed of the polymer is HOSOKAWA MICRON CORP
A POWDER TESTER was used to measure the falling speed of 100 cc of powder preheated to 110 ° C.

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 added to
Hold at 5 ° C. Then, HC (OC ₂ H
₅ ) 35.7 ml of _{3 was} added dropwise over 1 hour. After finishing the dropping
The reaction was performed at 60 ° C. for 15 minutes, the reaction product solid was washed 6 times with 300 ml of n-hexane each time, and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. 31.6 g was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, magnesium-containing solid 6.3 in a nitrogen gas atmosphere.
G and n-heptane (50 ml) were added to form a suspension, and 2,2,2-trichloroethanol (20 ml) was stirred at room temperature.
A mixed solution of (0.02 mmol) and 11 ml of n-heptane was added dropwise from a dropping funnel over 30 minutes and further stirred at 80 ° C for 1 hour. The obtained solid was filtered, washed with 100 ml of n-hexane at room temperature four times, 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. Furthermore, 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 1 each at room temperature.
Washed 7 times with 00 ml of n-hexane to give component A of 5.5 g
Got

Polymerization of Propylene In a 5 liter autoclave which had been purged with nitrogen and sufficiently dried, 31.0 mg of the component A obtained above and 0.2 liter of triethylaluminium in 1 liter of n-heptane were added. 6 ml of the solution and 6 ml of a solution containing 0.04 mol of diphenyldimethoxysilane in 1 liter of n-heptane were mixed and held for 5 minutes. Then
After 12 liters of hydrogen and 3 liters of liquid propylene were press-fitted, the first stage polymerization was carried out at an internal temperature of the autoclave of 70 ° C. 59 minutes after the start of the polymerization, n-heptane 1
0.04 mol of 2-cyclohexyl-2-l per liter
6 ml of a solution containing methyl-2-sila-1,3-dioxane
After press-in, stop the stirring of the autoclave after 1 minute,
At the same time, hydrogen and unreacted propylene were purged to adjust the internal pressure of the autoclave to 0.2 kg / cm ² · G. After a part of the first-stage polymer was collected, hydrogen was introduced into the system.

Copolymerization of Propylene and Ethylene Subsequently, propylene-ethylene copolymerization was carried out by supplying a mixed gas having a molar ratio of propylene and ethylene of 1.5. The pressure inside the vessel was kept at 6 kg / cm ² · G and copolymerization was carried out at 75 ° C for 2 hours. After completion of polymerization, purge unreacted gas,
The polymer was removed and dried. The unreacted gas contained 0.8 mol% of hydrogen. MFR of the obtained polymer
Was 11.1 g / 10 minutes. As a result of the analysis, the production amount of the polymer obtained by the copolymerization was 20%, and the ethylene content was 53%. The MFR of the polymer sampled after the completion of the first step was 29.7 g / 10 minutes. When the physical properties of the final polymer were measured, the flexural modulus was 8.12 × 10 ³ kg / cm ² , and the DuPont impact strength was 86.5 kg · cm. The polymer dropping speed was 11.1 cc / sec.

Examples 2 to 6 2-Cyclohexyl-2-methyl-2 used in place of the diphenyldimethoxysilane used in the polymerization of propylene, the organosilicon compounds shown in Table 1 and used in the copolymerization of propylene and ethylene -In the same manner as in Example 1 except that an organosilicon compound as shown in Table 1 was used instead of sila-1,3-dioxane and the amount of hydrogen was adjusted so as to obtain MFR as shown in the same table. Copolymerization of propylene was performed. The physical properties of the final polymer obtained are also shown in the table.

[Table 1]

[Table 2]

Comparative Examples 1 to 3 Copolymerization of propylene was carried out in the same manner as in Example 1 except that the organic silicon compound shown in Table 2 was used or not used. The results are shown in Table 2. From this, it is understood that the polymer of the present invention shows excellent impact resistance and rigidity in a well-balanced manner and also has improved slipperiness.

[Table 3]

[0060]

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

[Brief description of drawings]

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

Front page continuation (72) Inventor Hiroo Saito 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Inventor Takayuki Taki 1-chome, Nishitsurugaoka, Oi-cho, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute (72) Inventor Takeshi Ishihara 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside Tonen Research Institute

Claims (1)

Claims: 1. A solid catalyst component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organometallic compound and (C) a Si--O--C bond. In the presence of a polymerization catalyst composed of the organosilicon compound, propylene-comprising (1) a step (a) of polymerizing propylene to produce a highly crystalline polypropylene and (2) a step (b) of copolymerizing propylene and ethylene In the method for producing an ethylene block copolymer, the step (b) is further carried out in the presence of an organosilicon compound represented by the following general formula: A method for producing a propylene-ethylene block copolymer. (D) General formula: [However, R ¹ and R ² are the same or different and have 1 to 10 carbon atoms.
Number of the hydrocarbon group, OR ^4, OSiR ₃ ⁵ or Si
R ₃ ^6, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, an R ^4, R ⁵ and R ⁶ having 1 to 10 carbon atoms each hydrocarbon radical. ] The organosilicon compound represented by these.