JPH06136030A - Production of propylene-ethylene block copolymer - Google Patents

Abstract

PURPOSE:To obtain a propylene-ethylene block copolymer useful for molded articles, etc., having excellent luster and rigidity by copolymerizing propylene with ethylene in the presence of a specific polymerization catalyst under a specified condition. CONSTITUTION:(i) Propylene is copolymerized with ethylene to produce a copolymer having 0.01-10wt.% ethylene content, (ii) propylene is copolymerized with ethylene to produce a copolymer having 30-95wt.% ethylene content and (iii) a homopolymer of ethylene is produced in the presence of a polymerization catalyst comprising (A) a solid catalyst component composed of a metal oxide, magnesium, titanium, a halogen and an electron donative compound as essential components, (B) an organometallic compound and (C) an organosilicon compound of the formula [R<1> is 1-10C hydrocarbon or R<7>3Si (R<7> is 1-10C hydrocarbon); R<2> is 1-10C hydrocarbon or R<8>O (R<8> is R<7>); R<3> is 1-10C hydrocarbon or R<9>O (R<9> is R<7>); R<4> and R<5> are R<7>; R<6> is 1-10C hydrocarbon, OR<10> or SiR<11>3 (R<10> and R<11> are R<7>), etc.] to give the objective block copolymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a propylene-ethylene block copolymer. For more details,
The present invention relates to a method for producing a propylene-ethylene block copolymer having a good balance of gloss and rigidity by using a specific polymerization catalyst.

[0002]

2. Description of the Related Art Highly crystalline polypropylene is widely used because of its excellent rigidity, heat resistance and surface gloss. However, because of the drawback of low impact strength, several methods have been proposed to improve impact resistance. For example, a method is known in which a small amount of ethylene is added to propylene to carry out random copolymerization. However, according to this method, the rigidity, which is a characteristic of polypropylene, is significantly reduced. As a method for obtaining polypropylene having an excellent balance of impact resistance and rigidity, a method of producing a so-called prolene-ethylene block copolymer, which is a combination of a step of homopolymerizing propylene and a step of copolymerizing propylene and ethylene Is being done. However, although this method improves the balance between impact resistance and rigidity, this time the surface gloss, which is an inherent property of polypropylene, is impaired. In recent years, various added values have been required as the applications of polypropylene have expanded, and depending on the field of application, not only mechanical properties but also the beauty of appearance such as good surface gloss is an important factor that affects product value. It often becomes a factor.

In order to improve the balance between such mechanical properties and surface glossiness, a small amount of ethylene is added to the propylene homopolymerization step in the recent production of a propylene-ethylene block copolymer to obtain propylene. The method of performing copolymerization has come into practice. However, when this method is used, the surface gloss is improved, but the rigidity is not improved as expected, and the use thereof may be limited depending on the intended use of the copolymer.

[0004]

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

[0005]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention achieved the object of the present invention by copolymerizing with a polymerization catalyst containing a specific organic silicon compound as an essential component. The present invention has been completed by finding out that

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

[Chemical 2][However, R¹Is a hydrocarbon group having 1 to 10 carbon atoms or
R⁷ ₃Si, R²Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁸O, R³Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁹O, R^FourAnd R^FiveHave the same or different carbon numbers 1 to 1
0 hydrocarbon groups, R⁶Is a hydrocarbon having 1 to 10 carbon atoms
Group, OR^TenOr SiR¹¹ ₃And R ⁷~ R¹¹Is the same
It is a hydrocarbon group having 1 to 10 different carbon atoms. 〕so
Existence of polymerization catalyst consisting of represented organosilicon compound
Below, (1) Copolymerize propylene and ethylene to produce ethylene
Propylene and ethylene with a content of 0.01 to 10% by weight
Steps (a) and (2) for producing the copolymer of
Copolymerized with ethylene to give an ethylene content of 30 to 95 weight
% Copolymer of propylene and ethylene
(B) and (3) a step of producing a homopolymer of ethylene
Propylene-ethylene block copolymer consisting of (c)
Manufacturing method.

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
A metal oxide, magnesium, titanium, a halogen and an electron donating compound are essential components. Such components are usually a metal oxide, a magnesium compound, a titanium compound and an electron donating compound. In the case of the compound which does not exist, it is prepared by bringing the halogen-containing compounds into contact with each other.

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

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

Specific examples of these compounds are shown below, and in the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show. MgMe ₂ , MgEt ₂ , Mgi-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 the component A is prepared. As an example thereof, a compound containing magnesium metal, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1-2
0 hydrocarbon group, M is boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m
Indicates the valence of M, m> n ≧ 0. ] The method of making it contact is mentioned. X in the general formula of the alkoxy group-containing compound
Examples of the hydrocarbon group for R and R include methyl (Me), ethyl (Et), propyl, (Pr), i-propyl (i-P).
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHe), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. Alkenyl group, phenyl (Ph), tolyl, aryl group of xylyl group, phenethyl, aralkyl such as 3-phenylpropyl, and the like. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Specific examples of the alkoxy group-containing compound will be given below.

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

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

Compound in which M is boron B (OEt) ₃ , B (OB 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 .

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 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, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols and ethers are preferably used.

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

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

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

Alcohols are represented by the general formula 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.

The ethers are represented by the general formula ROR ¹ . In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, 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,
Examples include diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole and ethyl phenyl ether.

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

As the halogen-containing compound, halogenated hydrocarbon, halogen-containing alcohol, silicon halide compound having hydrogen-silicon bond, Group IIa, 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 include 2-chloroethanol and 1-chloro-
2-propanol, 3-chloro-1-propanol, 1
-Chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6
-Chlor-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-
Chlorbenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-
(M, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol,
Chlorhydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p)
-Chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6
-Chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2-butanol,
2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p)-
Bromphenol, 4-bromoresorcin, (m, o,
p) -fluorophenol, p-iodophenol: 2,
2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-
Chlor-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1- Naphthol: 2,2,2-
Trichloroethanol, 1,1,1-trichloro-2-
Propanol, β, β, β-trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,
4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol,
2,3,5-tribromo-2-hydroxytoluene,
2,3,5-tribromo-4-hydroxytoluene,
2,2,2-Trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetra Chlorbisphenol A, tetrabromobisphenol A, 2,2
3,3-tetrafluoro-1-propanol, 2,3
5,6-tetrafluorophenol, tetrafluororesorcin, etc. may be mentioned.

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

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

The components 1, 2, 2, 3 and 4, and optionally a halogen-containing compound which can be optionally contacted are mixed and stirred in the presence or absence of an inert medium, This is done by mechanical co-milling. The contact can be performed under heating at 40 to 150 ° C.

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

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

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

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

Further, the component A may further contain an olefin polymer produced in the component A by contacting with an olefin in the presence of an organoaluminum compound. The organoaluminum compound is selected from the organometallic compounds described below, which are one component of the catalyst of the present invention.

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

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

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

It is also possible to use an organoaluminum compound in which two or more aluminum atoms are bound to each other through an oxygen atom or a nitrogen atom. 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, diethylzinc and the like, and LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Organosilicon Compound The organosilicon compound which is one component of the catalyst of the present invention (hereinafter referred to as component C) is represented by the above general formula. In the formula, the hydrocarbon group represented by R ^{1 to} R ¹¹ is an alkyl group,
Examples thereof include an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group and an aralkyl group.

As the alkyl group, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl and the like, cycloalkyl groups such as cyclopentyl, cyclohexyl and methylcyclohexyl groups, and cycloalkenyl groups such as cyclopentenyl. , A cyclohexenyl group, a methylcyclohexenyl group, etc., a cycloalkadienyl group, a cyclopentadienyl group, a methylcyclopentadienyl group, an indenyl group, etc., and an aryl group, a phenyl group, a tolyl group, a xylyl group, etc. Examples of the alkyl group include benzyl, phenethyl and 3-phenylpropyl groups. For R ⁴ and R ⁵ , especially methyl,
The ethyl group is preferred.

Specific examples of the component C will be listed below. In addition,
R ¹ / R ² / R ³ // OR ⁴ / OR ⁵ / R ⁶
Is displayed. In the following, Me = methyl and Et =
Represents ethyl, Pr = propyl, Bu = butyl, Amy = amyl, Hex = hexyl.

1) R¹, R²And R³Is a hydrocarbon group
And R⁶Is OR^TenIn case of [R¹And R ²And R³Is the same
R at the time of one¹, R¹And R²R are the same when¹ ₂/ R³
And OR ^Four, OR^FiveAnd OR^TenWhen is the same, OR^FourWhen,
OR^FourAnd OR^FiveAre the same (OR^Four)₂/ OR^TenToso
Display each. ) Me // OMe, Me // OEt, Et // OMe, Et // O
Et, Me₂/ N-Pr // OMe, Me₂/ N-Pr //
OEt, Me₂/ T-Bu // OMe, Me₂/ T-Bu
// OEt, Et₂/ Me // OMe, Et₂/ Me // OE
t, Me // (OMe)₂/ OEt, Me // (OMe)₂
/ Oi-Pr, Me // (OMe)₂/ Ot-Bu, Me
// (OMe)₂/ On-Hex, Et // (OMe)₂/
Oi-Pr, Me₂/ T-Bu // (OMe)₂/ Ot-
Bu, Et₂/ Me // (OMe) ₂/ On-Hex.

2) R¹Is R⁷ ₃Si, R²And R³But
R is a hydrocarbon group⁶Is OR^TenIn case of [R²And R³Are the same
When is R⁷ ₃Si / R² ₂And OR^Four, OR^FiveAnd OR
^TenWhen is the same, OR^FourAnd OR^FourAnd OR^FiveWhen are the same
(OR^Four)₂/ OR^TenAre displayed respectively. ] Me₃Si / Me₂// OMe, Me₃Si / Me₂// O
Et, Et₃Si / Me₂// OMe, Et₃Si / Me
₂// OEt, Me₃Si / Et₂// OMe, Me₃Si
/ Et₂// OEt, Et₃Si / Et₂// OMe, Et
₃Si / Et₂// OEt, Me₃Si / Me / Et // O
Me, Et₃Si / Me / Et // OEt, Me₃Si /
Et / i-Pr // OEt, Et₃Si / Me / t-Bu
// OMe, Me₃Si / Me₂// (OMe)₂/ Ot-
Bu, Me₃Si / Me₂// (OEt)₂/ On-He
x, Et₃Si / Me₂// (OMe)₂/ Os-Am
y, Me₃Si / Me / Et // (OMe)₂/ Ot-B
u, Et₃Si / Me / Et // (OEt)₂/ On-H
ex, Et₃Si / Me / i-Pr // (OEt)₂/ T
-Bu, Et₃Si / Me / t-Bu // (OMe)₂/
Os-Amy.

3) R¹, R²And R³Is a hydrocarbon group
And R⁶Is a hydrocarbon group [R¹, R²And R³Is the same
R at the time of one¹And R¹And R²R are the same when¹ ₂/ R
³And OR^FourAnd OR^FiveAre the same (OR^Four)₂/ R⁶
Are displayed respectively. ] Me // (OMe)₂/ Me, Me // (OEt)₂/ M
e, Me // (OMe)₂/ Et, Me // (OEt)₂/
Et, Me // (OMe)₂/ I-Pr, Me // (OE
t)₂/ I-Pr, Me // (OMe)₂/ T-Bu, M
e // (OEt)₂/ T-Bu, Me // (OMe)₂/ N
-Bu, Me // (OEt)₂/ N-Bu, Me // (OM
e)₂/ S-Bu, Me // (OEt)₂/ S-Bu, E
t // (OMe)₂/ Me, Et // (OEt)₂/ Me,
Et // (OMe)₂/ I-Pr, Et // (OEt)₂/
i-Pr, Me₂/ N-Pr // (OMe)₂/ Me, M
e₂/ N-Pr // (OEt)₂/ Me, Me₂/ T-B
u // (OMe)₂/ Et, Me ₂/ T-Bu // (OE
t)₂/ Et, Me₂/ N-Bu // (OEt)₂/ M
e, Me₂/ N-Bu // (OEt)₂/ Me, Me₂/
n-Hex // (OMe)₂/ Me, Me₂/ N-Hex
// (OEt)₂/ Me, Me₂/ S-Amy // (OM
e)₂/ Me, Me₂/ S-Amy // (OEt)₂/ M
e, Me // (OMe)₂/ Cyclopentyl, Me // (O
Me)₂/ Cyclopentadienyl.

4) R¹Is R⁷ ₃Si, R²And R³But
Hydrocarbon group, R⁶Is a hydrocarbon group [R²And R
³R are the same when⁷ ₃Si / R¹ ₂And OR^FourAnd OR^Five
Are the same (OR^Four)₂/ R⁶Are displayed respectively
It ] Me₃Si / Me₂// (OMe)₂/ Me, Me₃Si
/ Me₂// (OEt) ₂/ Me, Et₃Si / Me₂//
(OMe)₂/ I-Pr, Et₃Si / Me₂// (OM
e)₂/ N-Hex.

[0049] 5) R ^1, R ² and R ³ is a hydrocarbon group, when if R ⁶ is a SiR ¹¹ ₃ [R ^1, R ² and R ³ are identical and R ^1, R ¹ and R ² R ¹ ₂ / R but when the same
^{When 3} is the same as OR ⁴ and OR ^5, (OR ⁴ ) ₂ / S
iR ¹¹ ₃ is displayed respectively. ] Me // (OMe) ₂ / SiMe ₃ , Me // (OEt) ₂
/ SiMe ₃ , Me // (OMe) ₂ / SiEt ₃ , Et
// (OMe) ₂ / SiMe ₃ , Et // (OEt) ₂ / S
iMe ₃ , Et // (OMe) ₂ / SiEt ₃ , Et //
(OEt) ₂ / SiEt ₃ , Me ₂ / n-Pr // (OM
e) ₂ / SiMe ₃ , Me ₂ / t-Bu // (OMe) _{2
/ SiMe 3, Et 2 / i} -Pr // (OEt) 2 / Si
Et ₃ .

6) R¹Is R⁷ ₃Si, R²And R³But
Hydrocarbon group, R⁶Is SiR¹¹ ₃In case of [R²And R
³R are the same when⁷ ₃Si / R² ₂And OR^FourAnd OR^Five
Are the same (OR^Four)₂/ SiR¹¹ ₃And display respectively
To do. ] Me₃Si / Me₂// (OMe)₂/ SiMe₃, Me
₃Si / Et₂// (OMe)₂/ SiMe₃, Me₃S
i / Me₂// (OEt)₂/ SiMe₃, Me ₃Si /
Me₂// (OMe)₂/ SiEt₃, Me₃Si / Me
/ Et // (OEt)₂/ SiMe₃, Et₃Si / Et
₂// (OEt)₂/ SiMe₃, Et₃Si / Et₂//
(OEt)₂/ SiEt₃, Me₃Si / Me / n-B
u // (OEt)₂/ SiMe₃.

7) When R ¹ and R ² are hydrocarbon groups, R ³ is R ⁹ O, and R ⁶ is OR ¹⁰ [when R ¹ and R ² are the same, R ¹ ₂ / R ⁹ O, When OR ⁴ , OR ⁵ and OR ¹⁰ are the same, OR ⁴ and when OR ⁴ and OR ⁵ are the same (O
R ⁴ ) ₂ / OR ¹⁰ is displayed. ] Me ₂ / MeO // OMe, Me ₂ / MeO // OEt, M
e ₂ / EtO // OMe, Me ₂ / EtO // OEt, Me
_{2 / i-PrO // OMe,} Me 2 / i-PrO // OE
_{t, Me 2 / t-BuO} // OMe, Me 2 / t-BuO
_{// OEt, Me 2 / n-} HexO // OMe, Me 2 / n
-HexO // OEt, Et ₂ / MeO // OMe, Et ₂
/ MeO // OEt, Me / t-Bu / MeO // OMe,
Me / t-Bu / MeO // OEt, (i-Pr) ₂ / M
eO // OMe, (i-Pr) ₂ / MeO // OEt, Me
/ S-Amy / MeO // OMe, Me / s-Amy / M
eO // OEt, Me ₂ / MeO // (OMe) ₂ / OE
t, Me ₂ / MeO // (OEt) ₂ / Ot-Bu, Me
_{2 / EtO // (OMe) 2} / On-Hex, Me 2 / E
tO // (OEt) ₂ / Oi-Pr, Et ₂ / MeO //
(OMe) ₂ / OEt, Et ₂ / MeO // (OEt) ₂
/ Ot-Bu, Et ₂ / EtO // (OMe) ₂ / On-
_{Hex, Et 2 / EtO // (} OEt) 2 / Oi-Pr,
Me / t-Bu / MeO // OMe / OEt / Oi-P
r, Et / i-Pr / EtO // OMe / OEt / On-
Amy.

8) When R ^{1 is} R ⁷ ₃ Si, R ² is a hydrocarbon group, R ³ is R ⁹ O, and R ⁶ is OR ¹⁰ [OR ⁴ , O
When R ⁵ and OR ¹⁰ are identical to the OR ^4, OR ⁴ and OR
^{When 5} is the same, it is displayed as (OR ⁴ ) ₂ / OR ¹⁰ . ] Me ₃ Si / Me / MeO // OMe, Me ₃ Si / Me
/ MeO // OEt, Me ₃ Si / Me / EtO // OM
e, Et ₃ Si / Et / MeO // OMe, Et ₃ Si /
Me / EtO // OMe, Et ₃ Si / Me / MeO // O
Et, Et ₃ Si / Et / EtO // OEt, Me ₃ Si
/ T-Bu / MeO // OMe , Et 3 Si / i-Pr /
EtO // OEt, Me ₃ Si / Me / MeO // (OM
e) ₂ / Ot-Bu, Me ₃ Si / Et / MeO // (O
Et) ₂ / On-Pr, Me ₃ Si / Et / EtO //
(OEt) ₂ / Oi-Pr, Et ₃ Si / Me / MeO
// (OEt) ₂ / Oi-Pr, Et ₃ Si / Et / Et
O // (OEt) ₂ / Oi-Pr, Et ₃ Si / Me / E
tO // (OMe) ₂ / Os-Amy.

9) R¹And R²Is a hydrocarbon group, R³But
R⁹O, R⁶Is a hydrocarbon group [R¹And R²Is the same
R at the time of one¹ ₂/ R⁹O and OR^FourAnd OR^FiveAre the same
Time is (OR^Four)₂/ R⁶Are displayed respectively. ] Me₂/ MeO // (OMe)₂/ Me, Me₂/ MeO
// (OEt)₂/ Me, Me₂/ EtO // (OMe)₂
/ Me, Me₂/ EtO // (OEt)₂/ Me, Me₂
/ I-PrO // (OMe)₂/ Me, Me₂/ I-Pr
O // (OEt) ₂/ Me, Me₂/ S-BuO // (OM
e)₂/ Me, Me₂/ S-BuO // (OEt)₂/ M
e, Me₂/ T-AmyO // (OMe)₂/ Me, Me
₂/ T-AmyO // (OEt)₂/ Me, Me₂/ N-
HexO // (OMe)₂/ Me, Me₂/ N-HexO
// (OEt)₂/ Me, Et₂/ MeO // (OMe)₂
/ Me, Et₂/ MeO // (OEt)₂/ Me, Me /
n-Pr / MeO // (OMe)₂/ Et, Me / n-P
r / MeO // (OEt)₂/ Et, Me / t-Bu / M
eO // (OMe)₂/ Me, Me / t-Bu / MeO //
(OEt)₂/ Me, Me₂/ MeO // (OMe)₂/
Et, Me₂/ MeO // (OEt)₂/ Et, Me₂/
MeO // (OMe)₂/ I-Pr, Me₂/ MeO //
(OEt)₂/ I-Pr, Me₂/ MeO // (OMe)
₂/ T-Bu, Me₂/ MeO // (OEt)₂/ T-B
u, Me₂/ MeO // (OMe)₂/ Cyclohexyl,
Me₂/ MeO // OMe / OEt / Et, Me₂/ Et
O // OMe / OEt / t-Bu, Et₂/ MeO // OM
e / OEt / i-Pr, Me / t-Bu / MeO // OM
e / OEt / Me, Et / i-Pr / EtO // OMe /
OEt / n-Hex.

10) R¹Is R⁷ ₃Si, R²Carbonized water
Base, R³Is R⁹O, R⁶Is a hydrocarbon group [OR
^FourAnd OR^FiveAre the same (OR^Four)₂/ R⁶Is displayed
It ] Me₃Si / Me / MeO // (OMe)₂/ Me, Me
₃Si / Et / MeO // (OMe)₂/ Me, Me₃S
i / Et / EtO // (OMe)₂/ Me, Me ₃Si /
Et / EtO // (OEt)₂/ Et, Et₃Si / Me
/ MeO // (OMe)₂/ Me, Et₃Si / Et / M
eO // (OMe)₂/ Me, Et₃Si / Et / EtO
// (OMe)₂/ Me, Et₃Si / Et / EtO //
(OEt) ₂/ Et, Me₃Si / Et / MeO // (O
Et)₂/ T-Bu, Et₃Si / Me / EtO // (O
Me)₂/ S-Bu, Me₃Si / Me / MeO // OM
e / OEt / Me, Et₃Si / Et / MeO // OMe
/ OEt / i-Pr.

11) R¹And R²Is a hydrocarbon group, R³
Is R⁹O, R⁶Is SiR¹¹ ₃In case of [R¹And R²But
R when same¹ ₂/ R⁹O and OR^FourAnd OR^FiveAre the same
At the time of (OR^Four)₂/ SiR¹¹ ₃Are displayed respectively
It ] Me₂/ MeO // (OMe)₂/ SiMe₃, Me₂/
EtO // (OMe)₂/ SiMe₃, Me₂/ MeO //
(OEt)₂/ SiMe₃, Me₂/ MeO // (OM
e)₂/ SiEt₃, Et₂/ MeO // (OMe)₂/
SiMe₃, Et ₂/ EtO // (OMe)₂/ SiMe
₃, Et₂/ MeO // (OMe)₂/ SiEt₃, Et
₂/ EtO // (OEt)₂/ SiEt₃, Me / Et /
MeO // (OEt)₂/ SiMe₃, Me / Et / Et
O // (OMe)₂/ SiEt₃, Me / t-Bu / Et
O // (OMe)₂/ SiMe₃, Et / s-Amy / M
eO // (OEt)₂/ SiMe₃, I-Pr / n-Bu
/ MeO // (OMe)₂/ SiEt₃, Me / Et / M
eO // OMe / OEt / SiMe₃, Et / t-Bu /
MeO // OMe / OEt / SiEt₃.

12) R¹Is R⁷ ₃Si, R²Carbonized water
Base, R³Is R⁹O, R⁶Is SiR ¹¹ ₃In case of [OR
^FourAnd OR^FiveAre the same (OR^Four)₂/ SiR¹¹ ₃When
indicate. ] Me₃Si / Me / MeO // (OMe)₂/ SiM
e₃, Me₃Si / Et / MeO // (OMe)₂/ Si
Me₃, Me₃Si / Me / EtO // (OMe)₂/ S
iMe₃, Et₃Si / Me / MeO // (OMe)₂/
SiMe₃, Et₃Si / Et / MeO // (OMe)₂
/ SiMe₃, Et₃Si / Et / EtO // (OMe)
₂/ SiMe₃, Et₃Si / Me / MeO // (OM
e)₂/ SiEt₃, Et₃Si / Et / EtO // (O
Et)₂/ SiEt₃, Me₃Si / Me / MeO // O
Me / OEt / SiMe₃, Et₃Si / Et / EtO
// OMe / OEt / SiMe₃.

13) R ¹ is a hydrocarbon group and R ² is R
^{When 8} O and R ³ are R ⁹ O and R ⁶ is OR ¹⁰ , [when R ⁸ O and R ⁹ O are the same, R ¹ / (R ⁸ O) ₂ and OR ⁴ ,
And OR ⁴ when OR ⁵ and OR ¹⁰ are the same, OR ⁴ and O
When R ⁵ is the same, it is displayed as (OR ⁴ ) ₂ / OR ¹⁰ . ] Me / (MeO) ₂ // OMe, Me / (MeO) ₂ // O
Et, Et / (MeO) ₂ // OMe, Et / (MeO)
₂ // OEt, Me / (EtO) ₂ // OMe, Me / (E
tO) ₂ // OEt, Me / (n-PrO) ₂ // OMe,
Me / (n-PrO) ₂ // OEt, Me / (MeO) /
(T-BuO) // OMe, Me / (MeO) / (t-B
uO) // OEt, Me / (MeO) ₂ // (OMe) ₂ /
Ot-Bu, Me / (MeO) ₂ // (OEt) ₂ / Oi
-Pr, Me / MeO / t-BuO // (OMe) ₂ / O
n-Hex, Et / EtO / i-PrO // (OEt) ₂
/ Oi-Bu, Me / EtO / n-BuO // OMe / E
tO / On-Hex.

14) R¹Is R⁷ ₃Si, R²Is R
⁸O, R³Is R⁹O, R⁶Is OR^TenIn case of [R⁸O and
And R⁹R when O is the same⁷ ₃Si / (R⁸O)₂And O
R^Four, OR ^FiveAnd OR^TenWhen is the same, OR^FourAnd OR^Four
And OR^FiveAre the same (OR^Four) ₂/ OR^TenAnd that
Displayed. ] Me₃Si / (MeO)₂// OMe, Me₃Si / (E
tO)₂// OMe, Me₃Si / (MeO)₂// OE
t, Et₃Si / (EtO)₂// OMe, Et₃Si /
(MeO)₂// OEt, Et₃Si / (EtO)₂// O
Et, Me₃Si / (n-PrO)₂// OMe, Et₃
Si / EtO // i-PrO // OEt, Me ₃Si / Me
O / n-BuO // OMe, Me₃Si / (MeO)₂//
(OMe) ₂/ Ot-Bu, Me₃Si / (EtO)₂
// (OMe)₂/ On-Hex, Et₃Si / (Me
O)₂// (OEt)₂/ Oi-Pr, Me₃Si / Me
O / t-BuO // (OMe)₂/ Os-Amy, Et₃
Si / EtO / i-PrO // OMe / OEt / On-H
ex.

15) R¹Is a hydrocarbon group, R²Is R
⁸O, R³Is R⁹O, R⁶Is a hydrocarbon group
[R⁸O and R⁹R when O is the same¹/ (R⁸O)
₂And OR^FourAnd OR^FiveAre the same (OR^Four)₂/ R
⁶Are displayed respectively. ] Me / (MeO)₂// (OMe)₂/ Me, Me / (M
eO)₂// (OEt) ₂/ Me, Et / (MeO)₂//
(OMe)₂/ Me, Et / (EtO)₂// (OEt)
₂/ Me, i-Pr / (MeO)₂// (OMe)₂/ M
e, i-Pr / (MeO)₂// (OEt)₂/ Me, n
-Bu / (MeO)₂// (OMe)₂/ Me, n-Bu
/ (MeO)₂// (OEt)₂/ Me, Me / (n-P
rO)₂// (OMe)₂/ Me, Me / (n-PrO)
₂// (OEt)₂/ Me, Me / (s-BuO)₂//
(OMe)₂/ Me, Me / (s-BuO)₂// (OE
t) ₂/ Me, Me / MeO / n-HexO // (OM
e)₂/ Me, Me / MeO / n-HexO // (OE
t)₂/ Me, Et / (MeO)₂// (OMe)₂/ E
t, Et / (MeO)₂// (OEt)₂/ Et, vinyl
/ (MeO)₂// (OMe)₂/ Vinyl, vinyl / (E
tO)₂// (OEt)₂/ Vinyl, Me / (MeO)₂
// OMe / OEt / Me, Me / (EtO)₂// OMe
/ OEt / Et, Et / (EtO)₂// OMe / OEt
/ Me, Et / (EtO)₂// OMe / OEt / Et,
Me / MeO / EtO // OMe / OEt / Et, Et /
MeO / EtO // OMe / OEt / Et.

16) R¹Is a hydrocarbon group, R²Is R
⁸O, R³Is R⁹O, R⁶Is SiR¹¹ ₃In case of [R⁸
O and R⁹R when O is the same¹/ (R⁸O)₂And OR
^FourAnd OR^FiveAre the same (OR^Four)₂/ SiR¹¹ ₃When
Display each. ] Me / (MeO)₂// (OMe)₂/ SiMe₃, Me
/ (MeO)₂// (OEt)₂/ SiMe₃, Me /
(MeO)₂// (OMe)₂/ SiEt₃, Et / (M
eO)₂// (OMe)₂/ SiMe₃, Et / (Et
O)₂// (OMe) ₂/ SiMe₃, Et / (MeO)
₂// (OEt)₂/ SiMe₃, Et / (MeO)₂//
(OMe)₂/ SiEt₃, Et / (EtO)₂// (O
Et)₂/ SiEt₃, Me / MeO / EtO // OMe
/ OEt / SiMe₃, Et / MeO / EtO // OMe
/ OEt / SiEt₃, I-Pr / (MeO)₂// (O
Me) ₂/ SiMe₃, N-Bu / (MeO)₂// (O
Me)₂/ SiEt₃, Me / (s-BuO)₂// (O
Et)₂/ SiMe₃, Vinyl / (MeO)₂// OMe
/ OEt / SiMe₃.

17) R ¹ is R ⁷ ₃ Si, R ² is R
⁸ O, R ³ is R ⁹ O, and R ⁶ is SiR ¹¹ ₃ [R ⁸
When O and R ⁹ O are the same, R ⁷ ₃ Si / (R ⁸ O)
_{When 2} is the same as OR ⁴ and OR ⁵ and OR ^10, (OR
⁴ ) Display as ₂ / SiR ¹¹ ₃ , respectively. ] Me ₃ Si / (MeO) ₂ // (OMe) ₂ / SiM
e ₃ , Me ₃ Si / (EtO) ₂ // (OMe) ₂ / Si
Me ₃ , Me ₃ Si / (MeO) ₂ // (OEt) ₂ / S
iMe ₃ , Me ₃ Si / (MeO) ₂ // (OMe) ₂ /
SiEt ₃ , Me ₃ Si / (EtO) ₂ // (OEt) ₂
/ SiEt ₃ , Et ₃ Si / (MeO) ₂ // (OMe)
₂ / SiEt ₃ , Et ₃ Si / (EtO) ₂ // (OE
t) ₂ / SiEt ₃ , Me ₃ Si / MeO / EtO //
(OMe) ₂ / SiMe ₃ , Me ₃ Si / (EtO) ₂
// OMe / OEt / SiMe ₃ , Et ₃ Si / MeO /
EtO // (OMe) ₂ / SiMe ₃ , Et ₃ Si / Me
O / EtO // OMe / OEt / SiEt ₃ .

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

Of the propylene-ethylene block copolymer
Production method In the production method of the propylene-ethylene block copolymer, propylene and ethylene are copolymerized to give an ethylene content of 0.
A step of producing a copolymer of propylene and ethylene of 01 to 10% by weight (step a), a copolymer of propylene and ethylene to produce a copolymer of propylene and ethylene having an ethylene content of 30 to 95% by weight. It comprises a step (step b) and a step of producing an ethylene homopolymer (step c). (1) Step a Step a consists of copolymerizing propylene and ethylene in the presence of the polymerization catalyst. The copolymerization reaction may be either a gas phase or a liquid phase, and in the case of polymerizing in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane,
It can be carried out in an inert hydrocarbon such as benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to + 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. The copolymerization is carried out by contacting and reacting propylene with ethylene so that the ethylene content in the copolymer obtained there will be 0.01 to 10% by weight, preferably 0.1 to 5% by weight. It In step a, the copolymer obtained there is 40 to 98% by weight of the block copolymer,
In particular, it is desirable that the content be 70 to 90% by weight.
Further, in this step, the melt flow rate (MFR) of the copolymer obtained is preferably 0.01 to 200 g / 10 minutes, particularly preferably 0.1 to 100 g / 10 minutes.

(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 regulator such as hydrogen can also be selected in step a.
Is the same as in. The amount of the copolymer obtained in step b is 50 to 1% by weight of the block copolymer, especially 30 to
It is preferably 5% by weight. Further, in the step b, the MFR of the obtained copolymer is 0.001 to 150 g / 10.
Min, particularly 0.01 to 100 g / 10 min.

(3) Step c The production of an ethylene homopolymer is carried out in the presence of the above-mentioned polymerization catalyst.
Below, it is carried out by polymerizing ethylene. Echire
The polymerization reaction of the polymerization is carried out in step a or step b.
It is selected from the range of conditions. Also, control the molecular weight of hydrogen, etc.
The use of the agent is the same as in the case of step a and step b. Process
The ethylene homopolymer obtained in step c is the block copolymer.
50 to 1% by weight of the body, especially 30 to 5% by weight is desired
More preferably, the MFR of the homopolymer is 10 ^-8~ 150g
/ 10 minutes, especially 10^-6~ 100g / 10min is desired
Good

The method of the present invention comprises steps a, b and c. In addition to the serial method in which the three steps are performed in an arbitrary order, the three steps are performed in parallel and the polymers obtained in each step are combined. Method can be adopted,
Among these, the method of performing step a, step b, and step c in that order is advantageous and desirable in terms of the apparatus. The block copolymer thus obtained has a concentration of 0.001-1.
Have an MFR of 50 g / 10 min, but preferably 0.0
It is 1 to 100 g / 10 minutes.

[0067]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-ditertiarybutyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, calcium stearate After adding 0.06% by weight of each of them to form pellets by melt-kneading, a test piece was prepared by injection molding. Flexural modulus: JIS K
According to 7203-1982. The MFR of the polymer is A
It was measured according to STM D-1238. Furthermore, for the polymer gloss, a sheet with a thickness of 2.0 mm is used
According to K 7105-1981, the incident angle and the light receiving angle were each measured at 60 °.

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

Copolymerization of propylene and ethylene Into a 5 liter autoclave which had been purged with nitrogen and sufficiently dried, 41.4 mg of component A obtained above and 0.6 liter of triethylaluminum in 1 liter of n-heptane were contained. 0.0 in 4 ml of solution and 1 liter of n-heptane
3 ml of a solution containing 8 mol of 1,1-dimethoxy-1,2,2,2-tetramethyldisilane was mixed and held for 5 minutes. Next, 9.5 liters of hydrogen and 3 liters of liquid propylene were injected under pressure, the internal temperature of the autoclave was raised to 70 ° C., and a fixed amount of ethylene was continuously supplied to carry out the first-stage polymerization (step a). After 1 hour, unreacted propylene, ethylene, and hydrogen were purged to set 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. Subsequently, in the second-stage polymerization (step b), a mixed gas having a molar ratio of propylene and ethylene of 2: 3 was supplied to maintain the internal pressure at 6 kg / cm ² -G, and the propylene was heated at 75 ° C. for 40 minutes for 40 minutes. And ethylene were copolymerized. After completion of the polymerization, the unreacted gas contained 0.7 mol% of hydrogen. After removing the unreacted gas, a small amount of polymer was collected. Further, hydrogen and ethylene gas were introduced, and the third stage polymerization (step c) was carried out at 75 ° C. for 1 hour and 30 minutes. As a result of the analysis, the MFR of the polymer sampled after the completion of the first-stage polymerization was 29.
It was 9 g / 10 minutes, and the ethylene content was 1.1% by weight. After the completion of the second-stage polymerization, the MFR of the sampled polymer was 18.9 g / 10 minutes, the amount of the polymer obtained by the second-stage copolymerization was 8%, and the content of ethylene was 46%. It was The MFR of the final polymer was 6.8 g / 10 minutes, and the production amount of the polymer obtained by the third-stage polymerization was 17%. The flexural modulus of the final polymer was 8.52 kg / cm ² . The gloss was 81.0%.

Examples 1 to 5, Comparative Examples 1 and 2, 1,1-dimethoxy-used as Component C of the polymerization catalyst
Instead of 1,2,2,2-tetramethyldisilane, the organosilicon compounds shown in Tables 1 and 2 were used, and the hydrogen content was adjusted so that the MFRs shown in Tables 1 and 2 were obtained. Copolymerization of propylene and ethylene was carried out in the same manner as in Example 1. The physical properties of the final polymer obtained are also shown in Tables 1 and 2.

[0071]

[Table 1]

[Table 2]

[0072]

By the method of the present invention, a propylene-ethylene block copolymer having an excellent balance of rigidity and glossiness can be obtained.

[Brief description of drawings]

FIG. 1 is a drawing showing the relationship between the flexural modulus and the gloss of the block copolymers obtained in Examples of the present invention and Comparative Examples.

FIG. 2 is a flow chart diagram illustrating the method of the present invention.

Front page continuation (72) Inventor Kunihiko Imanishi 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Corporation Research Institute (72) Inventor Satoshi Ueki 1-3-chome Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute (72) Inventor Hiroo Saito 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside Tonen Research Institute

Claims (1)

[Claims] 1. A metal oxide, magnesium, titanium
Solids containing halogen, an electron-donating compound and
Body catalyst component, (B) organometallic compound and (C) general formula:[However, R¹Is a hydrocarbon group having 1 to 10 carbon atoms or
R⁷ ₃Si, R²Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁸O, R³Is a hydrocarbon group having 1 to 10 carbon atoms
Kuha R⁹O, R^FourAnd R^FiveHave the same or different carbon numbers 1 to 1
0 hydrocarbon groups, R⁶Is a hydrocarbon having 1 to 10 carbon atoms
Group, OR^TenOr SiR¹¹ ₃And R ⁷~ R¹¹Is the same
It is a hydrocarbon group having 1 to 10 different carbon atoms. 〕so
Existence of polymerization catalyst consisting of represented organosilicon compound
Below, (1) Copolymerize propylene and ethylene to produce ethylene
Propylene and ethylene with a content of 0.01 to 10% by weight
Steps (a) and (2) for producing the copolymer of
Copolymerized with ethylene to give an ethylene content of 30 to 95 weight
% Copolymer of propylene and ethylene
(B) and (3) a step of producing a homopolymer of ethylene
Propylene-ethylene block copolymer consisting of (c)
Manufacturing method.