JPH06145235A - Catalyt for polymerizing alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst, composed of a specific solid catalyst component, a specified organosilicon compound and a specific organometallic compound, excellent in polymerization activity, capable of producing a highly stereoregular polymer in high yield and useful for propylene, etc. CONSTITUTION:The objective catalyst is composed of (A) a solid catalyst component consisting essentially of a metallic oxide such as B2O3 magnesium such as dimethylmagnesium, titanium such as titanium tetrachloride, a halogen and an electron donative compound, (B) an organometallic compound such as trimethylaluminum and (C) an organosilicon compound of the formula [R<1> is monovalent cyclic substituent group having (thio)ether bond in the ring; R<2> is 1-10C hydrocarbon; R<4>O (R<4> is 3-10C hydrocarbon), etc.; R<3> is methyl or ethyl; x is 1 or 2; y is O or 1; z is 2 or 3; (x+y+z) is 4]. Furthermore, the blending ratio of the components (A) to (C) are preferably as follows: the component (B) in an amount of 20-500g mol based on 1g-atom titanium in the component (A) and the component (C) in an amount of 0.01-1.0mol based on 1mol component (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for .alpha.-olefin polymerization.

[0002]

2. Description of the Related Art When a poly .alpha.-olefin is produced by using a catalyst component containing magnesium, titanium, chlorine and an electron donating compound, S is used together with an organoaluminum compound.
having an i-O-C bond or having the general formula SiR ¹ R ² _n
It is known that when an organosilicon compound represented by (OR ³ ) _3-n (n = 0 to 2) is used, the stereoregularity of the resulting polymer is improved (for example, JP-A-54-946).
No. 90, No. 56-36203, No. 57-63310
No. 58-83016, No. 62-11705, etc.).

However, contrary to the improvement in stereoregularity, the polymerization activity may be reduced to less than half that in the case where the organosilicon compound is not used, and the relationship between the improvement in stereoregularity and the decrease in polymerization activity is as follows. Depends on the type of organosilicon compound.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymerization catalyst which maintains high stereoregularity and exhibits high polymerization activity in the polymerization of α-olefins.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted diligent research on a catalyst component containing magnesium, titanium, a halogen and an electron-donating compound, and an organosilicon compound to be combined with an organoaluminum compound, and as a result, found that a specific organic compound was obtained. The present invention has been completed by finding that the object of the present invention can be achieved by using a silicon compound.

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] [Wherein R ¹ is a monovalent cyclic substituent having an ether or thioether bond in the ring, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O-, R ⁵ ₃ Si- or R ⁶ ₃
SiO-, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3, x +
y + z = 4, R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by

Solid Catalyst Component The solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, contains metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components. Such components are usually prepared by bringing a metal oxide, a magnesium compound, a titanium compound and an electron donating compound into contact with each other, and in the case where each of the above compounds does not have a halogen, a halogen-containing compound.

(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, 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 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.

Contact with component 1, component 2 and component 3 and component 4, and optionally with a halogen-containing compound, which may be contacted, is carried out in the presence or in the absence of an inert medium.
Mixing and stirring, but 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, R ¹ is a monovalent cyclic substituent having an ether or thioether bond in the ring. However, the substituent having a lactone structure is excluded. Such a substituent has the formula —C _n H
It is represented by _2n-2m-1 Y _l . In the above formula, Y is an oxygen atom or a sulfur atom. n is a number of 2 to 20, preferably 3 to 7. m is a number of 0 to 10, preferably 0 to 5. However, 2m <n. l is a number of 1 to 5, preferably 1 to 2. n + 1 is 3 to 25, preferably 4 to 7. Specific examples of R ^{1 will be} given below. In the following example, Y is an oxygen atom,
Also in the case of a sulfur atom, the structure in which O in the following example is replaced with S is adopted. Hereinafter, the respective groups are referred to as RA, RB, RC, etc.

[0043]

[Chemical 4]

[Chemical 5]

Among the above-mentioned substituents, a substituent having an ether bond in the ring is particularly desirable.

R ² in the above general formula of the component C is C 1-10 hydrocarbon group, R ⁴ O, R ⁵ ₃ Si or R 2.
⁶ ₃ SiO is shown, R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms. Examples of these hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups and aralkyl groups. 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 and decyl groups. However, as the alkenyl 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.

The component C is exemplified below. In the following,
Codes such as [RH] and [RP] are in the general formula of the component C.
R¹Me is methyl and Et is et
Cyl, Pr are propyl, and Bu is a butyl group.
You [RH]₂Si (OMe)₂, [RH] (i-Pr
O) Si (OMe)₂, [RP] (i-PrO) Si
(OMe)₂, [RS] (t-Bu) Si (OM
e) ₂, [RS] (Me₃SiO) (OMe)₂; [R
H] (Me₃SiO) Si (OEt)₂, [RH] (i
-Pr) Si (OEt)₂, [RQ] (i-PrO) S
i (OEt)₂, [RS] (Me₃SiO) Si (OE
t)₂, [RS] (t-Bu) Si (OEt)₂; [R
H] Si (OMe)₃, [RS] Si (OMe)₃，
[RV] Si (OMe)₃; [RH] Si (OE
t)₃, [RS] Si (OEt)₃, [RP] Si (O
Et)₃.

The catalyst of the present invention comprises component A, component B and component C, the composition ratio of component B is 1 to 2,000 gmol 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.

Polymerization of α-Olefin The catalyst of the present invention is a homopolymerization of α-olefin having 3 to 10 carbon atoms or another monoolefin or 3 to 10 carbon atoms.
Useful as a catalyst for the copolymerization with diolefins, especially α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene,
It exhibits extremely excellent performance as a catalyst for homopolymerization of 1-hexene or the like or for random and block copolymerization with the above α-olefins and / or ethylene.

The polymerization reaction may be carried out in a gas phase or a liquid phase. When the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in inert hydrocarbons and in liquid monomers. The polymerization temperature is usually -80 ° C to +1.
It is in the range of 50 ° 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. Further, the amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually selected in the range of up to 30% by weight, particularly 0.3 to 15% by weight based on the α-olefin. The polymerization reaction by the catalyst system according to the present invention is carried out in a continuous or batch reaction,
The conditions may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

[0050]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. The heptane-insoluble matter (hereinafter abbreviated as HI) showing the ratio of the crystalline polymer in the polymer is
6 with boiling n-heptane in a modified Soxhlet extractor
It is the remaining amount when time is extracted.

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.

Component A obtained above was placed in a 1.5-liter stainless steel autoclave equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
13.0 mg, 4 ml of a solution containing 0.8 mol of triethylaluminum in 1 liter of n-heptane and 4 ml of a solution containing 0.08 mol of bis (oxacyclopent-3-yl) dimethoxysilane in 1 liter of n-heptane. 1m
1 was mixed and kept for 5 minutes. Then, 600 ml of hydrogen gas as a molecular weight controlling agent and 1 liter of liquid propylene were injected under pressure, and then the temperature of the reaction system was raised to 70 ° C. to polymerize propylene for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain white polypropylene powder having a HI of 96.8%. Polymerization activity is 16.7k
It was g / g · component A.

Examples 2 to 5 and Comparative Examples 1 and 2 Example 1 except that the organosilicon compounds shown in Table 1 were used as the component C instead of bis (oxacyclopent-3-yl) dimethoxysilane. Polymerization of propylene was carried out in the same manner, and the results are shown in Table 1.

[0054]

[Table 1]

[0055]

The catalyst of the present invention exhibits high polymerization activity while maintaining high stereoregularity in the polymerization of α-olefins.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing a catalyst of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Ishihara 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Inventor Takayuki Takigaoka, Nishitsugaoka, Oi-cho, Saitama Prefecture 3-3-1 Tonen Co., Ltd. Research Institute (72) Inventor Hiroo Saito 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. A solid catalyst component comprising (A) a metal oxide, magnesium, titanium, a halogen and an electron-donating compound as essential components, (B) an organometallic compound and (C) a general formula: [Wherein R ¹ is a monovalent cyclic substituent having an ether or thioether bond in the ring, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O-, R ⁵ ₃ Si- or R ⁶ ₃
SiO-, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3, x +
y + z = 4, R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms. ] The catalyst for alpha-olefin polymerization which consists of an organosilicon compound represented by these.