JPH047304A - Alpha-olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To increase the activity in alpha-olefin polymn. by compounding a solid catalyst component contg. Mg, Ti, a halogen, and an electron-donating compd. with an organometallic compd. and a specific organosilicon compd. CONSTITUTION:An Mg compd., a Ti compd., an electron-donating compd., and, if necessary, a halogen compd. are brought into contact with each other to give a solid catalyst component contg. Mg, Ti, a halogen, and the electron- donating compd. The catalyst component is compounded with an organometallic compd. of a metal of the group I, II, or III in an amt. of 1-2000 gram mol based on one gram atom of Ti in the catalyst component and an organosilicon compd. of the formula (wherein R<1>, R<4>, and R<5> are each a 1-10C hydrocarbon group; R<2> is R<1> or R<6>O; R<3> is R<1> or R<7>O; R<6> and R<7> are each R<1>; and (x) is 2 or 3) in an amt. of 0.001-10mol based on one mol of the organometallic compd.

Description

[Detailed description of the invention] The present invention relates to a catalyst for α-olefin polymerization.

Prior Art When producing polyα-olefins using catalyst components containing magnesium, titanium, chlorine and electron-donating compounds, they contain 5i-0-C bonds together with organoaluminum compounds, or the general formula % formula % organic It is known that the use of silicon compounds improves the stereoregularity of the resulting polymer (for example,
No. 4-94690, No. 56-36203, No. 57-6
No. 3310, No. 58-83016, No. 62-1170
5 etc.).

However, despite the improvement in stereoregularity, the polymerization activity may be reduced to less than half of that when no organosilicon compound is used, and the relationship between the improvement in stereoregularity and the decrease in polymerization activity is Depends on the type of. Also, Ti
, a solid component containing Mg and /% rogen as essential components, an organic aluminum unit, and 5i-0-C or 5i-N
A method for producing α-olefin polymers using a catalyst made of an organosilicon compound that does not contain -C bonds has also been proposed (Japanese Patent Application Laid-Open No. 62-201904), but the polymerization performance of the catalyst used there is by no means satisfactory. It's not something you do.

Problems to be Solved by the Invention An object of the present invention is to provide a polymerization catalyst that maintains high stereoregularity and exhibits high polymerization activity in the polymerization of α-olefins.

Means for Solving the Problems The present inventors have conducted intensive research on catalyst components containing magnesium, titanium, norogen, and electron-donating compounds, and organosilicon compounds to be combined with organoaluminum compounds, and have found that 5i- The present invention was completed by discovering that the object of the present invention can be achieved by using specific organosilicon compounds having 0-3i and 5i-0-C bonds.

Summary of the Invention That is, the summary of the present invention is as follows: (A) a solid catalyst component containing magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) an organometallic compound, and (C) a general formula [where R' , R' and R5 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, R2 is a hydrocarbon group having 1 to 10 carbon atoms or R'[l, R3 is a hydrocarbon group having 1 to 10 carbon atoms,
X is 2 or 3, and R6 and R7 are the same or different hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by the following.

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 magnesium, titanium, halogen, and an electron-donating compound as essential components, and such components usually include a magnesium compound, It is prepared by contacting a titanium compound, an electron-donating compound, and a halogen-containing compound when each of the above compounds does not have a halogen.

(1) Magnesium Compound Magnesium compounds are represented by the general formula MgR'R''. In the formula, R' and R2 represent the same or different hydrocarbon group, OR group (R is a hydrocarbon group), or \rogen atom. More specifically, the hydrocarbon groups of R1 and R2 are:
As the OR group, R is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms; , chlorine atoms include chlorine, bromine, iodine, fluorine, etc.

Specific examples of these compounds are shown below, and in the chemical formula, Me-methyl, [: x tyl, Pr: propyl, Bu nibbutyl, He: hexyl, Oct: octyl, Ph:
phenyl and cyHe dichlorohexyl are respectively shown.

MgMe2. MgBtz, Mgi Pr2,
MgBua, MgHez.

Mg0ctz, MgBtBu, MgPh2.
Mgcy)fez.

Mg(OMe)z, Mg(OBt)2. Mg(O
Bu)2. Mg(OHe)z.

Mg (00ct)2. Mg([1Ph)2. Mg(
OcyHe)z.

BtMgCl, BuMgCl, HeMgCl,
i-BuMgCl, t-BuMgCl, PhM
gC1, PhCHJgCl, BtMgBr.

BuMgBr, PhMgBr, BuMgl,
BtOMgCI.

BuOMgCI, He0MgCl, Ph0Mg
Cl, BtOMgBr.

BuOMgBr, BtOMgl, MgC1,,
MgBr2. MgL.

The above magnesium compound can also be prepared from metallic magnesium or other magnesium compounds when preparing component A.

Examples include metallic magnesium, halogenated hydrocarbons, and alkoxy group-containing compounds of the general formula , M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is the valence of M, and rri>n≧0. ] is mentioned. As the hydrocarbon groups of X and R in the general formula of the alkoxy group-containing compound,
Methyl (Me) Ethyl (Bt) Propyl (Pr
), 1-propyl (1-Pr) butyl (Bu) i-
Alkyl groups such as butyl (1-Bu) hexyl (He) octyl (0ct), cyclohexyl (cyHe
Examples include cycloalkyl groups such as methylcyclohexyl, alkenyl groups such as allyl, propenyl and butenyl, aryl groups such as phenyl (Ph))lyl and xylyl groups, and aralkyl groups such as phenethyl and 3-phenylpropyl.

Among these, alkyl groups having 1 to 10 carbon atoms are particularly desirable. Specific examples of alkoxy group-containing compounds are listed below.

C(OMe) contained in the compound formula C(OR) when 0M is carbon.4. C (mouth Bt) 4°C (OPr) 4. C(OBLI)4,
C(Di-Bu)4. C(OHe).

C(00ctL: HC(OMe) contained in the formula XC(OR)3.

HC(OBt)3. HC(OPr)-, HC(OBu
)3. HC(Kano e)3゜HC(OPh)+; M
eC(OMe)3, MeC(OEt)3, Etc(
OMe)3゜BtC(OEt>3, cyHeC(OE
it)a, PhC(OMe):+.

PhC(OBt)a, ChzCIC(OEt)3
．． MeCHBrC([]Bt)3゜MeCHCIC
(OBt)s: CIC(DMe)+, CI
C(OBtL.

CIC (Di-Bu)3. BrC(OBt)s; MeCH(OMe)2 contained in formula X, C(OR),
MeCH(OBt)2, CH2(OMe)2.

CHz(OBt)2. C11, CICH (OBtL
, CHCl2CH(OBt)a.

CC15Ctl(OBt)z, CHJrCH(O
Et)z, PhCH(OBt)z.

Sl(OMe) 4 contained in the compound formula 5i (OR) when 0M is silicon,
3t (OBt) 4゜3i (OBu) 4.5i (Di
-Bu)4.5i(OHe)4°5i(00ct)4.
5i(OPh),: H3i(OBt)s included in formula X5i(OR)s, tlsi(OBu)a,
)lsi([]He)s.

H3i(OPh)s; MeSi(OMe)s,
MeSi(OBt)s.

MeSi([1Bu)s, BtSi(OBt)a
, Ph5i(OBt)s.

BtSl(OPh)s; CISiCl5i(O,C
l5i(Out)s.

CIS+(OBu)a, Cl5l(OPh)s,
B(OBt)3.8(O
Bu)s.

B(OHe)s, B(OPh) 3゜AI(OMe) contained in the compound formula AI (OR) when 0M is aluminum! l,
AI(OBt)3゜AI(OPr)a, AI(O
IPr)s, AI(OBu)s.

AI(Ot-Bu)a, AI(OHEri!, A
I((]Ph)s.

P(OMe)s contained in the compound formula P (OR) s when 0M is phosphorus, P
(OBt)s.

P(DBu)s, P(Otle)s, P(OP
h) s.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group Ⅰ or Group 1I [a of the periodic table] can also be used. The complex has the general formula MgR'R2.n (M
R3,). Examples of the metal include aluminum, zinc, calcium, etc., and R3 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 a number from 0.1 to 10. A specific example of a compound represented by MR' is ^
IMea, AIBt3. A11-Bu+, A
lPb5.

ZnMea, ZnBt2. ZnBu2. ZnP
hz, CaBt2.

Examples include CaPh2.

(2) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorjetoxytitanium. , dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride, and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

(3) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic esters and the like.

Among these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic acid halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, and crotonic acid, malonic acid, and succinic acid. , aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid ,
Alicyclic carboxylic acids such as cis-4-methylcyclohexene-1,2-dicarboxylic acid, aromatic monomers such as benzoic acid, toluic acid, anisic acid, p-tert-butylbenzoic acid, naphthoic acid, and cinnamic acid. Examples include aromatic polycarboxylic acids such as carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellidic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and mellitic acid.

As the carboxylic acid anhydride, acid anhydrides of the above-mentioned 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, isobutyl pivalate, acrylic. Ethyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl conophosphate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, adipine Diisobutyl acid, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, benzoin Methyl acid, ethyl benzoate, methyl p-)rulyate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate , monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, terephthalic acid Examples include dibutyl, diethyl naphthalate, dibutyl nactate, triethyl trimellidate, tributyl trimellidate, tetramethyl pyromellitate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above-mentioned carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide,
Acrylic acid iodide, methacrylic acid chloride, methacrylic acid iodide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid promide,
Succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid chloride, maleic acid chloride, maleic acid chloride, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride , tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, l-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, benzoyl chloride, benzoyl bromide , p-toluic acid chloride, p-toluic acid bromide,
p-Anisyl chloride, p-anisyl bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid Dichloride is mentioned.

Monoalkyl halides of dicarboxylic acids such as monomethyl adipate chloride, monoethyl maleate chloride, monomethyl maleate, and butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH.

In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms.

Specific examples include methanol, ethanol, propatool, isoproptool, butanol, isobutanol, pentanol, hexanol, octatool, 2-
These include ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol, and the like. Ethers have the general formula ROR
' In the formula, R and R' have 1 to 12 carbon atoms.
alkyl, alkenyl, cycloalkyl, aryl, and aralkyl, and R and R' may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, etc. .

As for the preparation method of component A, ■ a magnesium compound (component 1), a titanium compound (component 2) and an electron-donating compound (
Component 3) is contacted in that order. (2) After component 1 and component 3 are brought into contact, component 2 is brought into contact. ■Ingredients 1. Ingredient 2
A method such as bringing Component 3 and Component 3 into contact at the same time can be adopted.

It is also possible to contact with a halogen-containing compound before contacting with component 2.

Examples of halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, halides of elements of group Na, rVa, and Va of the periodic table (hereinafter referred to as metal halides), etc. can be mentioned.

Examples of halogenated hydrocarbons include mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of these compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoborum, carbon tetrachloride, carbon tetrabromide, Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-short ethane,
Methyl chloroform, methyl bromovolum, methyl chloroform, l, 1.2-) dichloroethylene, 1.1.
2-) Libromoethylene, 1.1,2°2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1.
2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, chlorinated halafine, and alicyclic compounds such as chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexachloride, and aromatic compounds. Examples of the compounds include chlorobenzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, pensitrichloride, p-chlorobencitrichloride, and the like. Not only one kind but also two or more kinds of these compounds may be used.

A halogen-containing alcohol refers to a compound in which one or more hydrogen atoms other than the hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in the molecule are substituted with a halogen atom. do. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, with chlorine atoms being preferred.

Examples of these compounds include 2-chloroethanol, 1
-Chlor-2-propatur, 3-chlor-1-propatur, 1-chloro-2-methyl-2-propatur, 4
-Chlor-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1
, 2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m,o,p)-chlorobenzyl alcohol, 4-chlorocatechol, 4-
chloro-(m,o)-cresol, 6-chloro-(m,
o)-Cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m,
o,p)-Chlorphenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2
-bromoethanol, 3-bromo-1-propertool,
1-bromo-2-propatol, 1-bromo-2-butanol, 2-bromo-p-cresol, l-bromo-2-
naphthol, 6-bromo-2=naphthol, (m, o,
p)-bromophenol, 4-bromoresorcin, (m
, o, p) Fluorophenol, p-iodophenol:
2゜2-dichloroethanol, 2.3-dichloro-1-
Propatool, 1,3-dichlor-2-propatool,
3-chloro-1-(α-chloromethyl)-1-propatol, 2,3-dibromo-1-propatol, 1,3-
Dibromo-2-propatol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2゜2
-trichloroethanol, 1.1.1-)dichloro-2
-Proper tool, β, β, β-trick, loroutert
-butanol, 2.3.4-) dichlorophenol, 2
, 4.5-) dichlorophenol, 2,4.6-) dichlorophenol, 2.4.6-) ribromphenol,
2,3゜5-tribromo-2-hydroxytoluene, 2
゜3.5-)! J bromo-4-hydroxytoluene, 2
．． 2.2-) Refluoroethanol, α, α.

α-Trifluoro-m-cresol, 2,4°6-doliodophenol: 2,3.4.6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A, tetrabromobisphenol A, 2.
2.3.3 ~ Tetrafluoro-1-propertool, 2.
Examples include 3°5.6-tetrafluorophenol and tetrafluororesorcin.

Examples of silicon halide compounds having a hydrogen-silicon bond include H3iC1+, H2S1C1□, H3SICI
.

HCLSi[:lz, 1lc2Hssic12.
H(t-CJs)SiC12゜)IC6HsSiC1z
, H([:H3)2sic1, 11(i-CJi
)zsicIH2CJsSiC1,Hz(n-C,)I
s) SiCI H2 (C61(4CH3)SiC1,
Examples include H3ICI(CsHs)z.

Examples of metal halides include B, AI, Ga, and In.

TI, Si, Ge, Sn, Pb,
As, Sb, Bi chloride, fluoride, bromide,
Mention may be made of iodides, especially BCl3, BBr3.
BI3, AlCl3, ^IBra.

GaC15, GaBr+, InC15, TlCl3
, 5IC14.

5nC1, 5bC1s, SbF5, etc. are suitable.

Ingredient 1. Components 2 and 3, and the halogen-containing compound that can be brought into contact as necessary, are brought into contact by mixing and stirring in the presence or absence of an inert medium, and by mechanical co-pulverization. Ru. 40-150 contacts
It can be carried out under heating at ℃.

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

A preferred method for preparing component A in the present invention is disclosed in Japanese Patent Application Laid-open No. 63
-264607, 58-198503, 62-
This method is disclosed in Japanese Patent No. 146904 and the like. More specifically, ■ (a) metallic magnesium, (b) halogenated hydrocarbon, (viii) general formula X, M (OR) m-
A magnesium-containing solid obtained by contacting n compound (same as the alkoxy group-containing compound) (d) with a halogen-containing alcohol, and then (e) an electron-donating compound and (h) a titanium compound. (Japanese Unexamined Patent Publication No. 63-264607), ■ (a) Magnesium dialkoxide and (b) hydrogen-
After contacting a halogenated silicon compound having a silicon bond, (c) contacting a halogenated titanium compound, and then (
d) A method of contacting with an electron-donating compound (further contacting with a halogenated titanium compound if necessary) (Unexamined Japanese Patent Publication No. 6
2-146904) ■ (a) Magnesium dialkoxide and (b) hydrogen-
A method of contacting a halogenated silicon compound having a silicon bond, (c) contacting an electron-donating compound, and then (d) contacting a titanium compound (JP-A-58-19850)
Publication No. 3).

Among these, method (2) is particularly desirable.

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

In addition, component A further comprises, in the presence of an organoaluminum compound,
Olefin polymers formed in component A upon contact with olefins may also be included. The organoaluminum compound is selected from the organometallic compounds described below that are one of the components of the catalyst of the present invention.

Examples of olefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and other α-
Olefins can be used.

Contact with the olefin is preferably carried out in the presence of the inert medium described above. The contact is usually carried out at a temperature of 100°C or less, preferably -10°C to +50°C. The amount of olefin polymer contained in component A is usually 0 per gram of component A.
．． It is 1-100g.

In the contact between component A and the olefin, an electron-donating compound may be present together with the organoaluminum compound. The electron-donating compound is selected from among the compounds used in preparing component A. Component A that has been in contact with the olefin can be washed with the above-mentioned inert medium, if necessary, or further dried.

Organometallic compoundsOrganometallic compounds (hereinafter referred to as component B) are listed in No.■ of the periodic table.
It is an organic compound of a group metal to a group II metal. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. As organoaluminum compounds that can be used, general formulas R, AlX3
-, (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 an arbitrary number in the range of 1≦n≦3), For example, trialkyl aluminum, dialkyl aluminum monohalide, 1,000 alkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride having 1 to 1 carbon atoms.
Particularly preferred are alkylaluminum compounds having 8, preferably 2 to 6 carbon atoms, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride dialkylaluminum monohalides such as methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, monoalkylaluminum cybarides, alkylaluminum sesquihalides such as ethylaluminum sesquichloride , diethyl aluminum ethoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dialkyl aluminum monoalkoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl Examples include dialkyl aluminum hydrides such as aluminum hydride. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum. In addition, these trialkylaluminums may be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or mixtures or complex compounds thereof. Can be used in combination with etc.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include (C2)15)-
^10AI (C2H5) 2.

(C4H8)2^10^1(C,L)2 , (C,
Examples include H5)2AINAI(C2Hs)22H5.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc. 1A1(CzHs)a, LiA1(CJ+s)t
Compounds such as

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In this formula, the hydrocarbon group of R'-R' and OR', OR'
Examples of the hydrocarbon groups R' and R' in include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Alkyl groups include methyl, ethyl, propyl, i-
Propyl, butyl, i-butyl, S-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and alkenyl groups include vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-dekenyl, 1-methyl-1-pentynyl, 1-methyl-1-hebutenyl, etc., cycloalkyl groups include cyclopentyl, cyclohexyl, Examples of aryl groups include methylcyclohexyl, phenyl, tolyl,
Xylyl group etc., aralkyl group includes benzyl,
Examples include phenethyl and 3-phenylpropyl groups.

Among these, aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups are preferred, and alkyl groups are particularly preferred. Furthermore, among the hydrocarbon groups for R4, methyl and ethyl groups are most desirable.

Furthermore, in the general formula, OR' and R2 are R60,
It is preferable that the number of alkoxy groups represented by R'[] is 4 or less in total, and when the number is 4, at least one of the alkoxy groups is a methoxy group. is particularly desirable. Further, it is particularly desirable that the number of alkoxy groups is at most three.

Component C is usually a compound represented by the general formula R'R'R35iOH and a compound represented by the general formula (R'(]) X++5tR53-X
It can be synthesized by reacting the compound represented by in the presence of an amine compound.

Specific examples of component C will be listed below. In addition, in the following, Me=methyl, Bt-ethyl, Pr-propyl, Bu
=butyl, Amy-amyl, and Hex-hexyl, respectively.

OR'R'R35iO3i(OR')-, R
2, When R3 is a hydrocarbon group (R'/R"/R'10R
'

However, when R', R2 or R3 are the same, R'.

It is displayed as R'2/R' etc. ) Mea/OMe, Me3/OBt, B
t3/OMe, Bta/OBt, Me
z/ n-Pr/ OMe, Me2/ n-Pr
/OBt.

Me2/t BuloMe, Me2/t-B
uloBt, Bta/Me/OMe, B
t2/ Me/ OBt 0OR'R'R'5iO3i
(OR')2R5, where R'' and R3 are hydrocarbon groups (R'/R2/R310R'/R').

However, when R', R' or R3 are the same, R'3,
It is displayed as R'2/R3, etc. )Me+10Me
/Me, Mes/[]Bt /Me, Me+1
0Me/Bt, Me310Bt/Bt, M
e310Me/1-Pr.

Me+ 10Et/1-Pr, Mes
loMe/1-Bu, Me310Bt
/1-Bu, MesloMe /n-Bu,
MealoBt/n-Bu, Mes/OM
e/5-Bu, Me3/OBt/5-
Bu.

Bt+ /[]Me /Me, Bt310Bt /M
e, Bts/[1Me/ 1-Pr, Btslo
Bt/1-Pr, Me2/n-n-Pr1O/M
e, Mez/n-Pr/DBt/Me, Mez
/l-BuloMe /Bt, Me2/1-Bul
oBt/Bt, Me2/n-BuloBt
/ Me, Me2/ n-Bu/ OBt /
Me, Me2/nHex 10Me/
Me, Me2/n-Hex/mouthBt/Me
.

Me2/s-Amy 10Me/Me, Me2/
It is expressed as s-^my10Bt/Me 0 0R'R'R'5iO3i (OR'),
When R2 is a hydrocarbon group and R3 is R'0 (R'/R2/
It is indicated as R'010R'. However, when R' and R'' are the same, it is displayed as Rl.) Mez /Men 10Me, Me2/MeO1
0Bt, ME! 2/EtO10Me, Mea/
BtO10Bt, Me2/1-PrO10Me,
Me2/ 1-PrO10Bt, Mez/
t-BunloMe, Me2/1-Bun 10
Et, Me2/nJIexO10Me, M
e2/n-HexOloBt, Btz/Men
10Me.

Bt2/MeO10Bt, Me/1-Bu/MeO1
0Me, Me/1-Bu/Men 10Bt,
(i-Pr)z/Men 10Me.

(i-Pr)2 /Men 10Bt, Me/s-
Amy /Men 10Me, Me/s-Amy
/MeO/DEt.

○R'R2R35iO3i (OR') When represented by 2R5, where R2 is a hydrocarbon group and R3 is R'0 (R'/R
'/R6010R' Indicated as /R5. However, R1 and R2
When they are the same, R12 is displayed. ) Mez /Men 10Me /Me, Mez/M
en 10Bt/Me, Mez/BtO10Me
/Me, Me2/EtD 10Bt/Me,
Me2/ 1-PrO10Me /Me, Me2/
1-PrOloBt/Me, Mez/5-Bu
n10Me/Me, Me2/5-BuO/
OBt/Me, Mez/t-AmyO/
OMe/Me.

Mez/t-AmyO/OBt/Me,
Me2/n-Hex[I/OMe/Me, M
ea/n-HexO/OBt/Me, Bt
z/ MeOloMe /Me, Bt2/ Men
10Bt/Me, Me/n-Pr/Men
10Me/Bt, Me/n-Pr/
Men 10Bt/Bt, Me/1-Bu
/Men 10Me /Me, Me/1-Bu/
Men 10Bt/Me, Me2/MeO10M
e/Bt.

Me2/Men' 10Bt/Bt, Me2/
MeOloMe/iPr, Me2/Men
10ut/1-Pr, Me2/MeO10Me
/1-Bu, Me2/MeO10Bt /1
-Bu○R'R2R'5iO3i (OR') 3, when R2 is R'0 and R3 is R70 (R'/R
It is indicated as '0/R'010R'. However, when R6 and Rff are the same, (R'0)2 is displayed. ) Me/ (MeO)zloMe, Me/ (MeO
)210Bt, Bt/(MeO), 10Me,
Bt/ (Men)210Bt, Me/ (BtO
)+/DMe, Me/(BtO)210Bt,
Me/ (n-PrO)aloMe, Me/ (
n-PrD) 10Bt, Me/(Men)/
(t-BuO)10Me, Me/(Men)
/ (t-Bun) / OEt 00R'R2R'5
iO3i(OR')zR5, R2 is R60,
When R' is R'0 (R'/R'0 /R'010R'
/R'. However, when R6 and R7 are the same, (R
'0)2 is displayed. ) Me/ (Men) 2/ OMe/ Me, Me
/ (Men) 2/ OBt/Me, Bt/
(Men) 2/ OMe/ Me, Bt/ (
Btu) 210Bt/Me, 1-Pr/(M
eO)210Me/Me, 1-Pr/(Men)
2/ OBt/ Me, n-Bu/ (Men)
2/ OMe/ Me.

n-Bu/ (Men) 2/ OBt/ Me,
Me/(n-PrO)2/OMe/Me,
Me/ (n-PrO) 2/ DBt/ Me
, Me/(sBuO)z 10Me/Me,
Me/(S-BLIO)210Bt/Me.

Me/Men/n-HexO/DMe/Me
, Me/ Men/ n-Hexn/ OBt/
Me, Bt/ (Men) 2/ OMe/ B
t, Bt/(Men) 2/OBt/Bt
, vinyl/ (Men) 2/ OMe/vinyl, vinyl/ (Bto) 2/ ogt/vinyl The catalyst of the present invention consists of component A, component B, and component C. 1 to 2,000 gram mol, preferably 20 to 500 gram mol per gram atom of titanium in A, component C 0.001 to 1 mol of component B
It is used in an amount of 10 mol, preferably 0.01 to 1.0 mol.

Polymerization of α-olefins The catalyst of the present invention can be used for the homopolymerization of α-olefins having 3 to 10 carbon atoms or other monoolefins or other monoolefins having 3 to 10 carbon atoms.
It is useful as a catalyst for copolymerization with other diolefins, but especially α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1
It exhibits extremely excellent performance as a catalyst for the homopolymerization of hexene, etc., or the random and block copolymerization of the above α-olefins and/or with ethylene.

The polymerization reaction may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, inert carbonization of normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually in the range of -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 also be controlled by the presence of hydrogen or other known molecular weight regulators. Further, the amount of other olefin to be copolymerized with the α-olefin in the copolymerization is usually selected within the range of 30% by weight, particularly from 0.3 to 15% by weight based on the α-olefin. The polymerization reaction using the catalyst system according to the present invention is carried out in a continuous or batchwise reaction, and the conditions may be those commonly used. Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

Effects of the Invention The catalyst of the present invention can produce a highly stereoregular polymer in high yield in the polymerization of α-olefins.

EXAMPLES The present invention will be specifically explained by examples and application examples. Note that percentages (%) in the examples are based on weight unless otherwise specified.

The heptane insoluble content (hereinafter abbreviated as HI), which indicates the proportion of crystalline polymer in the polymer, is the residual amount when extracted with boiling n-hebutane for 6 hours using a modified Soxhlet extractor.

Example 1 Preparation of Component A Chip-shaped metallic magnesium (purity 99.5%,
average particle size 1.6 mm) 8.3 g and n-hexane 250
After stirring at 68°C for 1 hour, magnesium metal was taken out and dried under reduced pressure at 65°C to obtain preactivated magnesium metal.

Next, n-butyl ether 1
40 ml of n-butyl ether solution (175 mol/β) of n-butylmagnesium chloride was added and the suspension was kept at 55°C, and further 5 ml of n-butyl ether was added.
A solution in which 38.5 mi' of n-butyl chloride was dissolved in 0 ml was added dropwise over 50 minutes. After carrying out the reaction at 70°C for 4 hours with stirring, the reaction solution was maintained at 25°C.

Next, HC(DC2H5)3 55.7 was added to this reaction solution.
m17 was added dropwise over 1 hour. After dropping, heat at 60℃ for 1
The reaction was carried out for 5 minutes, and the reaction product solid was mixed with 3 each of n-hexane.
00ml 6 times and dried under reduced pressure at room temperature for 1 hour to recover 31.6 g of a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine.

300m equipped with reflux condenser, stirrer and dropping funnel
6.3 g of a magnesium-containing solid and 50 mff of n-heptane were put into a reaction vessel under a nitrogen gas atmosphere to form a suspension, and while stirring at room temperature, 20 ml (0.02 mmol) of 2.2.2-)lichloroethanol was added. ) and n-heptane 1
The mixed solution of 1- was added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80°C for 1 hour. The obtained solid was separated by filtration, washed four times with each 100+ nl of n-hexane at room temperature, and further washed twice with each 100 nl of toluene to obtain a solid component.

40 ml of toluene was added to the above solid component, and further titanium tetrachloride was added so that the titanium tetrachloride/toluene volume ratio was 372, and the temperature was raised to 90°C. While stirring, add 2 ml of di-n-butyl phthalate! A mixed solution of 5- and toluene was added dropwise over 5 minutes, and the mixture was stirred at 120°C for 2 hours. The resulting solid material was filtered at 90°C and washed twice with 100°C of toluene at 90°C. Furthermore, titanium tetrachloride was newly added so that the titanium tetrachloride/toluene volume ratio was 372, and the mixture was stirred at 120° C. for 2 hours. The solid material obtained was filtered off at 110°C and 100 ml each at room temperature! The mixture was washed seven times with n-hexane to obtain 5.5 g of component A.

Component A 11 obtained above was placed in a stainless steel autoclave No. 1, 51 equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
．． 4■ Solution 4 containing 0.1 mol of triethylaluminum (hereinafter referred to as TEAL) in 11 n-hebutane
rnI! and 0.04 mol of 1. in n-hebutane 11.
1.1-rn of a solution containing 1-)rimethoxy-3,3,3-)limethyldisiloxane (hereinafter referred to as SOTMS)
1 was mixed and held for 5 minutes. Next, after pressurizing 600 ml of hydrogen gas and 11 liquid propylene as a molecular weight control agent, the reaction system was heated to 70°C and 1
Polymerization of propylene was carried out for hours. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder with an HI of 97.3%.

The polymerization activity of the catalyst was 23.5 kg/g of component A.

Incidentally, SOTMS was prepared in the following manner. That is, 0.450 moles of trimethylsilanol, 0.451 moles of tetramethoxysilane, and 20.6 moles of n-butylamine were placed in a 300-trilo flask. J mol was added and heated and stirred at 80°C for 1 hour under a nitrogen atmosphere. After the reaction was completed,
SOTMS was obtained by distillation. The boiling point was 144°C.

Examples 2 to 8 Propylene polymerization was carried out in the same manner as in Example 1, except that the organosilicon compounds shown in Table 1 were used instead of SOTMS, and the results are shown in Table 1.

Comparative Examples 1 to 4 Propylene was polymerized in the same manner as in Example 1, except that the compounds shown in Table 1 were used as organosilicon compounds, and the results are shown in Table 1.

Table 1 example Example 1 〃〃〃2 〃〃3 〃〃4 〃〃5 〃〃6 7 〃〃8 Comparative example 1 〃〃〃2 〃〃3 〃〃4 organosilicon compounds MeStO3' (OMe).

Me2 (Mero 5iO3i (OMe) 2MeMe
sSiO3' (OMe) 2MeMeaSi(lS'
([]OBt sMesSiO3' (OMe) 2
i-PrBtsSiO3' (OMe) a Mea(BtO)SiOSi(OBt)sNew (M
en) 5iO3i (OMe) s Polymerization activity
Hl (g/g・Component A) (%) 23.5 25.7 30.3 24.8 32.4 30.8 23.6 21.8 97.3 97.1 96.6 96.8 97 .0 97.1 95.1 96.5 MesSiO3iMes MezSi (OMe) 2 MeJSiO3iHMe2 (i-Pr) aH3iO3iH (i-Pr) 221
．． 8 18.2 20.5 24.9 80.1 84.2 59.4 62.8 Example 9 Preparation of component A 170 g of commercially available magnesium jetoxide was added to a tube with a diameter of 12 m.
Stainless steel (SOS 316) with an internal volume of 1.21 m and containing 400 balls made of stainless steel (SO3316)
The mixture was placed in a manufactured mill pot under a nitrogen gas atmosphere, and the mill pot was attached to a shaker, and the mixture was shaken and contacted for 2 hours at an amplitude of 10Ill11 and a rotation speed of 142 Orpm, to obtain a pulverized product (I).

200 equipped with reflux condenser, dropping funnel and stirrer
The glass reactor in step d is sufficiently purged with nitrogen gas. In this reactor, 8.3 g of pulverized material (I) and 42 m of n-hebutane were added.
After adding ff, a mixed solution of 14.9 g of trichlorosilane and 301111 n-hebutane was added dropwise from the dropping funnel over 30 minutes while stirring at room temperature, and then the mixture was added at 65°C for 4 hours.
Stir for hours. The resulting solid was filtered off at 65°C and diluted twice each with 100 g of n-hebutane at room temperature and 100 g of toluene at room temperature.
After washing by stirring and pressing for 10 minutes each three times, a toluene slurry of the reaction solid (I) was obtained.

T1Cl□51- was added to a toluene slurry consisting of 8.5 g of reaction solid (I) and 26 rnl of toluene, and the internal temperature was raised to 80°C over 20 minutes. After the temperature was raised, di-n-butyl phthalate was added. A mixed solution consisting of 1.7 g and 8 toluene was added dropwise over 15 minutes using a dropping funnel. Thereafter, the temperature was further raised to 115°C, and the mixture was stirred at the same temperature for 2 hours. After removing the supernatant liquid by decantation, washing was performed twice by stirring at a temperature of 90° C. for 10 minutes using 100% toluene. Next, add 21 m of new toluene
1,251 ml' of TIC was added, and the mixture was stirred at 115°C for 2 hours.

The obtained solid substance was filtered at 115°C, and 100 ml of each
was washed eight times with n-hebutane at room temperature to obtain a hebutane slurry of component A.

Polymerization of propylene Propylene was produced in the same manner as in Example 1, except that triisobutylaluminum was used in place of the organosilicon compound shown in Table 2 of component A1 obtained above and TEAL, and the polymerization temperature was 80°C. Polymerization was carried out and the results are shown in Table 2.

Examples 10 to 12 Propylene was polymerized in the same manner as in Example 9, except that the compounds shown in Table 2 were used as organosilicon compounds, and the results are shown in Table 2.

Comparative Examples 5 to 7 Propylene was polymerized in the same manner as in Example 9, except that the compounds shown in Table 2 were used as organosilicon compounds, and the results are shown in Table 2.

Examples Example 9 Comparative Example 5 Table 2 Organosilicon compounds MesSiOSi(OBt)s MeaSiOSi (OMe) s Me(Men) asiOsi (OMe) aMeM
e(Btmouth) asiOsi (OBt)zMeMesS
i (Oflt) 5 (Btu) 5siOsi (OBt) s(Si-0
).

Polymerization activity Hl (g/g/component A) (%) 29.6 96.1 36.2 97.0 25.3 96.4 21.5 94.8 16.4 93.7 14.7 90.8 37.4 67.9

[Brief explanation of the drawing]

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

Claims (1)

[Claims] (A) Solid catalyst component containing magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) Organometallic compound, and (C) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R^1, R^4 and R^5 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, and R^2 is a hydrocarbon group having 1 to 10 carbon atoms.
hydrocarbon groups or R^6O, R^3 has 1 or more carbon atoms
10 hydrocarbon groups or R^7O, x is 2 or 3, R^6 and R^7 are the same or different carbon numbers 1 to 1
There are 10 hydrocarbon groups. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by: