JPH0333106A - Catalyst for polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which can show both excellent polymerization activity and stereoregular polymerization activity without forming any noxious substance by mixing a specified solid catalyst component with an organometallic compound and a plurality of specified aromatic group-free organosilicon compounds. CONSTITUTION:A catalyst for the polymerization of an alpha-olefin comprising (A) a solid catalyst component essentially consisting of a metal oxide, Mg, TI, a halogen and an electron-donating compound [e.g. one obtained by bringing a reaction product of a metal oxide (e.g. SiO2) with a magnesium dialkoxide into contact with an electron- donating compound (e.g. carboxylic acid) and TiCl4], an organometallic compound (B) (e.g. organoaluminum compound), a dimethoxylated silane compound (C) represented by the formula (wherein R<1> and R<2> may be the same or different from each other and are each a 1-10C aliphatic hydrocarbon group) and having a volume of 150-500Angstrom <3> as determined based on quantum chemical calculation and trimethoxyhydrocarbylsilane and/or tetramethoxysilane (D). According to the above, the title catalyst which can show both polymerization activity at least as high as that of a catalyst containing a silane compound having an aromatic group and stereoregular polymerization activity without forming any noxious substance which is problematic when a silane compound having an aromatic group is used can be obtained.

Description

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

Prior Art When producing polyα-olefins using a catalyst component containing magnesium, titanium, chlorine and an electron-donating compound, the polyα-olefin has a 5i-0-C bond or has a general formula SiR'R' together with an organoaluminum compound. n(OR3)s-
It is known that when an organosilicon compound represented by
No. 56-36203, No. 57-63310, No. 58-83016, No. 62-11705, 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. It is generally known that silicon compounds having aromatic groups exhibit good performance in the polymerization of α-olefins, but depending on the intended use of the polymer, silicon compounds having aromatic groups may be harmful. .

Problems to be Solved by the Invention The present invention provides an organosilicon compound having no aromatic group, which is unlikely to be harmful even if contained in a polymer, and which is equivalent to or equivalent to an aromatic group-containing organosilicon compound. It is an object of the present invention to provide a catalyst for α-olefin polymerization that contains an organosilicon compound having the above performance as one component.

Means for Solving the Invention Generally, it is thought that there are two types of α-olefin polymerization catalysts: active species that produce isotactic polyolefins and active species that produce atactic polyolefins. Polymerization activity of isotactic polyolefin (R
1> and polymerization activity of atactic polyolefin (RA
) is the total polymerization activity (RT) and stereoregularity (H
1: 2% heptane insoluble matter) is expressed by the following formula.

The present inventors polymerized α-olefins by using a methoxy group-containing silane compound in combination with a catalyst component and an organometallic compound containing metal oxides, magnesium, titanium, halogen, and an electron-donating compound. As a result of intensive study on the relationship between R and the properties of the silane compound, we found that dimethoxydialkylsilane, trimethoxyhydrocarpylsilane and/or tetramethoxysilane having a volume of 150 to 500 people3 were used as the silanization compound. If you use
The present invention was completed based on the discovery that the object of the present invention, which is to produce polyα-olefins with high activity and stereoregularity equivalent to or higher than those of organic silicon compounds having aromatic groups, can be achieved.

Summary of the invention That is, the summary of the present invention is as follows: (A) a solid catalyst component containing a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components; (D) an organometallic compound; (C) a general formula R 'R''5I(OCH53)2C However, R1 and R2 are each the same or different carbon number 1-10
aliphatic hydrocarbon groups. α-olefin polymerization consisting of a dimethoxy group-containing silane compound represented by ] and having a volume calculated by quantum chemical calculation of 150 to 500 people, and (D) trimethoxyhydrocarpylsilane and/or (B) tetramethoxysilane. It is in the catalyst for use.

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 oxides, magnesium, titanium, halogen, and electron-donating compounds as essential components. Usually, it is prepared by contacting a metal oxide, a magnesium compound, a titanium compound, an electron-donating compound, and, if each of the above compounds contains a halogen, a halogen-containing compound.

(1) Metal oxide The metal oxide used in the present invention is an oxide of an element selected from the group of elements of Groups 1 to 2 of the Periodic Table of Elements,
Examples of them are B2O3, MgO, ^1,05,
Si, CaO1Tio2, ZnO.

Examples include ZrO, SnO, Ban, The, and the like.

Among these, 8203, MgO1A1203.5I
02, Ti port 2, Z "0. is desirable, particularly 5102 is desirable. Furthermore, composite oxides containing these metal oxides,
For example, SiOz-MgO1SiOa-AIJ*, Sin
□-h 02, SiO, -V, Q, Si mouth, -C
r, 0. , SiOz-TiOz-MgO, etc. may also be used.

These metal oxides are usually in the form of powder. The size and shape of the powder often affect the shape of the obtained olefin polymer, so it is desirable to adjust it appropriately. For the purpose of removing toxic substances before use, it is desirable to sinter metal oxides at as high a temperature as possible and handle them in a manner that prevents them from coming into direct contact with the atmosphere. Prepared by contacting.

(2) Magnesium Compound Magnesium compounds are represented by the general formula MgR'R2, where R1 and R2 are the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), or \rogen atoms. More specifically, the hydrocarbon groups of R' 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; , halogen atoms include chlorine, bromine, iodine, fluorine, etc.

Specific examples of these compounds are shown below, and in the chemical formula, Me: methyl, Bt: ethyl, Pr: probyl, Bu
Nibutyl, He:hexyl, Oct + octyl,
Ph: phenyl, cyHe dichlorohexyl, respectively.

MgMe2. MgBt*, Mg5-Prz, Mg
Bu2. MgHea.

Mg0ct2. MgBtBu, MgPh2.
MgcyHe*, Mg(OMe)z.

Mg (OBt)2. Mg (OBu)2. M
g (0)1s)2. Mg (OOct) 2゜M
g(OPh)z, Mg(OcyHe)z, BtMg
[:1. BuMgCI.

HeMgCl, i-BuMgCl, t-BuMgCl
, PhMgCl.

PhCHzMgCl, BtMgBr, BuMgBr
, PhMgBr, Bullgl.

BtOMgCI, BuOMgCI, )IeOM
gCI, Ph0MgCl.

BtOMgBr, BuOMgCI, BtOMg
CI, MgC1z, MgBr2°gL 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 carbon number of 1 to 20
m represents the valence of M, m>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)
Alkyl groups such as i-propyl (1-Pr), butyl (Bu), i-butyl (1-Bu), hexyl ()Ie), octyl (Oct), cyclohexyl (CyHe
), cycloalkyl groups such as methylcyclohexyl, alkenyl groups such as allyl, propenyl, and butenyl, aryl groups such as phenyl (Ph), )lyl, and xylyl, and aralkyl groups such as phenethyl and 3-phenylpropyl.

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

■C (OMe) contained in the compound formula C(OR) when M is carbon 4. C(
OBt) 4゜C(OPr),, C(OBu),,
C(Di-Bu)4. [:(Otle>4°C
(00ct)4. :HC(OMe) included in formula XC(OR')3 3°DC(OBt)3. tlc(O
Pr)s, HC(OBuL, HC(OPh)3゜H
C(OPh)+; MeC(OMe)a, MeC(
OBt)a, Etc(OMe)s.

etc(OBt)s, cyHec(OBt)s, P
hC(OMc)a.

PhC(OBt)s, CHaCIC(OBt),,
MeCH, BrC(OBt),.

MeCfLCIC(OBt)s; CIC(OMe)+,
CIC(OBt)s.

CIC(Di-Bu)s, BrC(OBt)s: Formula X
MeCH(OMe)z, C contained in 2C (mouth R)2
H, C11(OBtL, C112([1Me),.

CH2(OBt)z, CHzCICH(OBt)a,
CHCl2C)l(OBt)2゜CC15CH(08
t)2. CH2BrC)I(OBt)a, PhCH
(OBt)2゜■ St (OMe) contained in the compound formula Si (OR) 4 when M is silicon
4. St (OBt) 4°5i (OBu)4.
St (Oi-Bu)n, 5i(Otle)15i
(00ct)<.

S i (OPh) = :Formula XS 1(OR) 31
;l: included flst (0[Et) s.

ISi(OBu)+, ISi(OHe)3. )IS
i(OPh)3:MeSi(OMe)s, MeSi(
OBt)+, MeSi(DBu),.

BtSi(08t)s, Ph5i(OBt)3. B
tSi(OPh)a; CISiCl5i(O, Cl5i
(OBt)3. Cl5i(OBu)3゜Cl5i(O
Ph)s, Br5i(PBt)3: Formula X-5t (
OR) Me2Si(OMe)*, M included in 2
ezSi(OBt)2゜Bt2Si(OBt)z;
MeCISi(OBt)z; CHCl25IH
(OC2H5)2; [:[:1+5iH(OBt)
z; MeBrSi(OBt)2: MesSiOMe, Me+5iOBt, Mez contained in formula X3SiDR
SiOBu, Me+5iOPh.

BtsS+Obutt, Ph5S+0Bt0■ B (OBt) −, B contained in compound 2B (OR) when M is boron
(OBu) 3゜8 (OHe) 3.8 (OP h
) s.

■ AI (OMe) contained in the compound formula ^1 (OR)3 when M is aluminum 3.
AI (OBt) 3゜AI (OPr) s, ＾
1(Di-Pr)s, AI(OBLI)! , AI(Ot
-Bu)s.

AI (口He)s, ＾l　(OPh)s.

■ When M is phosphorus, P(OMe)s and P(O
Bt)s.

P(OBu)5. P(Ole)s, P(mouthP
h)s.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group 1 or Group 1IIa of the periodic table can also be used. The complex has the general formula MgR'R''・n(MR
'm). The metal includes aluminum,
Zinc, urushiram, etc., and R3 is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms.

Further, m represents the valence of the metal M, and n represents a number from 0.1 to 10. Specific examples of compounds represented by MR'm include:
AIM+33. AIBt3. A11-Bu,, A
IPha.

ZnMe2. ZnBta, ZnBu2. Z
Examples include nPha, CaBta, CaPh2, and the like.

(3) Titanium compounds Titanium compounds are compounds of divalent, trivalent, and tetravalent titanium, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichlorethoxytitanium, trichlorbutoxytitanium, 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.

(4) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides, nitriles, and aldehydes. alcoholates, alcoholates,
Examples include phosphorus, arsenic, and antimony compounds bonded to an organic group via carbon or oxygen, phosphoamides, thioethers, thioesters, carbonate esters, and the like. Among these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic acid halides, alcohols,
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, metaphthalic 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 polyhydric esters of the above-mentioned carboxylic acids can be used, and specific examples include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, and acrylic acid. Ethyl, 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, p-)methyl rulyate, p-tertiary butyl ethyl benzoate, p-ethyl anisate, α-ethyl naphthoate,
α-isobutyl naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate,
Diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate,
Examples include dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, 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, acetic acid promide, acetic 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, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexedicarboxylic acid chloride, cis-4/' cyclohexedicarboxylic acid bromide, benzoyl chloride, Benzoyl bromide, p-)ruyl acid chloride, p-toluyl bromide, p-anisyl chloride, p-anisyl bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthal Examples include acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. 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, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 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 2 carbon atoms
alkyl, alkenyl, cycloalkyl, aryl, and aralkyl, and R and R1 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,
These include butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and the like.

As for the preparation method of component A,
) and an electron-donating compound (component 4) in that order; ■ After contacting component 1 and component, component 4 and component 3;
(1) Contact components 1 and 2, and then contact components 3 and 4 at the same time. (2) Contact components 2 and 3, then contact components 4 and 1. (1) Bringing components 2 and 4 into contact, and then bringing each component 3 and component 1 into contact in that order. (2) Bringing components 2, 3, and 4 into contact at the same time, and then bringing component 1 into contact. Methods such as the following can be adopted. It is also possible to contact with a halogen-containing compound before contacting with component 3.

Examples of halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, and halides of Group 11a, IVa, and Va elements of the periodic table (hereinafter referred to as metal halides). ) etc.

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 aliphatic compounds such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride,
Carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-short ethane, methylchloroform, methylbromoform, methyliodoform, 1. 1.2-) Lichlorethylene, 1.1
゜2-Tribromoethylene, 1.1.2.2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1
．． 2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, and chlorinated paraffins; alicyclic compounds such as chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane; Benzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene,
Examples include hexabromobenzene, pencitrichloride, p-chloropencitrichlorand, 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, l
-Chlor-2-propanol, 3-chloro-1-propanol, 1-chloro-2methyl-2-propanol, 4
-Chlor-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1,
2-furopanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p)
-Chlorbenzyl alcohol, 4-chlorcatechol,
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, 0.p)-chlorophenol, p-
Chlor-alpha-methylbenzyl alcohol, lchlor-4
-Phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1
-propanol, l-bromo-2-propanol, 1-
Bromo-2-butanol, 2-bromo-p-cresol,
■-Bromo-2-naphthol, 6-bromo-2-naphthol, (m, (Lp)-bromophenol, 4-bromoresorcin, (m, o, p)-fluorophenol, p-iodophenol = 2. 2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propano-JL+, 3-90 l-(α-
Chloromethyl〉-1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-1-propanol, 2,4-dibromophenol, 2.4-dibromo-1-naphthol: 2.2.2 -Trichloroethanol, 1.1.1-) Lichlor-2-propanol, β, β
, β-trichloro-tert-phthanol, 2,3.4
-) Lichlorphenol, 2゜4.5-) Lichlorphenol, 2,4.6-) Lichlorphenol, 2,4.
6-)! J dibromophenol 2.3.5-)ribromo-2-hydroxytoluene, 2.3.5-tribromo-
4-Hydroxytoluene, 2.2.2-) Lifluoroethanol, α,α,α-trifluoro-m-cresol, 2,4.6-1-liodophenol: 2,3.4.
6-titrachlorphenol, tetrachlorohydroquinone, tetrachlorbisphenol A-tetrabromobisphenol A12°2,3.3-tetrafluoro-l
-propanol, 2,3.5.6-tetrafluorophenol, tetrafluororesorcin, and the like.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include H3LC13, H2StC1z, and H3SICI.

11cLsic1z, HC2HsSiCI2. H(
t-C411s) SiCIz.

HC, HsSiCl□, )I(CHa)zsi[:1
．． tl(i-C+L)2sic1z.

t12cJssIcI, L(n CmHs)Si[:
1. H2(CsHd:tl3)SICI.

Examples include H3+CI (C58S) 2.

As metal halides, B, 1. Ga, In,
Tl.

Si, Ge, Sn, Pb, As, Sb, old chloride, fluoride, bromide, iodide, especially B
Cl3. Bar-.

813, AlCl3. AIBrz, GaC
l3. GaBra, InCl+.

TI[:13.5iC13,5nC1s, 5bC1s
, 5bFs, etc. are suitable.

Components 1, 2, 3, and 4, and the halogen-containing compound that can be brought into contact as necessary, can be brought into contact by mixing and stirring in the presence or absence of an inert medium, or mechanically. This is done by co-grinding. Contact is 4
It can be carried out under heating at 0 to 150°C.

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.

Specific examples of the method for preparing component A in the present invention include JP-A-58-162607, JP-A-55-94909, and JP-A-55.
-115405, 57-108107, 61-
No. 21109, No. 61-174204, No. 61-17
No. 4205, No. 61-174206, No. 62-770
Examples include the method described in Publication No. 6 and the like. More specifically, ■ A method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607). A method of contacting a reaction product with a magnesium hydrocarbyl halide compound with a Lewis base compound and titanium tetrachloride (JP-A-55-94909) ■ A reaction product between a porous carrier such as silica and an alkylmagnesium compound, Method of contacting with an electron donating compound and a silicon halide compound before contacting with a titanium compound (JP-A-55-115405, JP-A No. 57-1081)
07 Publication) ■ A method of bringing a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polycarboxylic acid having a carboxyl group at the ortho position or its derivative, and a titanium compound into contact (Japanese Unexamined Patent Publication No. 174204/1984) ■ Metal oxide, alkoxy-containing magnesium compound,
Method of bringing a silicon compound having a hydrogen-silicon bond, an electron-donating compound, and a titanium compound into contact <JP-A-61-17
4205 Publication>, ■ Metal oxide, alkoxy-containing magnesium compound,
A method of bringing a halogen element or a halogen-containing compound into contact with an electron-donating compound and a titanium compound (JP-A-61
-174206 Publication) ■ A method in which a reaction product obtained by contacting a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol is brought into contact with an electron-donating compound and a titanium compound (Japanese Unexamined Patent Publication No. 61-21109) ■
A solid obtained by contacting a metal oxide, hydrocarbylmagnesium, and a hydrocarbyloxy group-containing compound (corresponding to the alkoxy group-containing compound),
A method of contacting with a halogen-containing alcohol, and further contacting with an electron donating compound and a titanium compound
No. 7706).

Among these methods, methods ① to ① are particularly desirable, and methods ① and ② are particularly preferable.

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, etc.
-Olefins may be used.

Contact with the olefin is preferably carried out in the presence of the inert medium described above. Contacting 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 g component Al.
．． 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 in contact with the olefin is
If necessary, it can be washed with said inert medium,
It can also be further dried.

The organometallic compound (hereinafter referred to as component B) is an organic compound of Groups 1 to 2 of the periodic table.

As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. The organoaluminum compound that can be used includes the general formula RnAlX5-+t (where R is an alkyl group or an aryl group, 1 to 18 carbon atoms, such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum civalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride. Particularly preferred are alkyl aluminum compounds having 2 to 6 carbon atoms, or mixtures or complexes thereof.Specifically, trialkyl aluminum compounds such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum are preferred. , dimethylaluminum chloride, diethylaluminum chloride,
Dialkyl aluminum monohalides such as diethylaluminium bromide, diethylaluminium iodide, diisobutylaluminum chloride, monoalkylaluminum such as methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, etc. alkylaluminium sesquihalides such as cybalide, ethylaluminum sesquichloride, dialkylaluminum monoalkoxides such as dimethylaluminum methoxide, diethylaluminium ethoxide, diethylaluminium phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum fethoxide, Dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, and diisobutyl aluminum hydride are exemplified. Among these,
Trialkylaluminum, particularly triethylaluminum and triisobutylaluminum, are preferred. These trialkylaluminums can also be used with other organoaluminum compounds, such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride,
It can be used in combination with ethylaluminum sesquichloride, ethylaluminum ethoxide, diethylaluminum hydride, or a mixture or complex compound thereof.

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. Such compounds include, for example (C2H3)
2A1OAI (C2H5) 2゜(C4H9)2A1
081 (C4H1l)2. (C2Hs) 2AI
Examples include N8l (C2H5)2C,R3.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as compounds such as LiA](CJs)<, Li8he(CJls)4, and the like.

Dimethoxy group-containing silane compound The dimethoxy group-containing silane compound (hereinafter referred to as component A) used in the present invention has the general formula R'R25i (OCt
It is represented by l*)i, and the volume of the molecule calculated by quantum chemical calculation is 150 to 500 people3.

Quantum chemical calculations are performed using the following method. The volume of a molecule can be calculated using the MNDO method of the molecular orbital method program MOPAC [purchased from QCPE (Quantum Chemistry Program Exchange), a non-profit organization located at Indiana University in the United States that aims to disseminate various chemistry programs. (A type of semi-empirical molecular orbital formula) [J, Am, Chem, So
c, (Journal of the American Chemical Society) vol. 99, p. 4899, p. 4907 (19
1977); vol. 100, p. 3607.

(1978)] and Van der Waals radius [J.

Phy, Chem, (Journal of Physical Chemistry) Volume 68, Pages 441-452 (19
1964)]. In addition, DE is used in the calculation.
Company C (DIGITAL B mouthpart PMBNT C0RPO
(7) VAX 11/785 manufactured by RATION) was used.

R' and R2 in the above general formula of component C have 1 to 1 carbon atoms;
10 aliphatic hydrocarbon groups, namely alkyl groups and alkenyl groups, preferably alkyl groups.

Component C has the above molecular volume, but such a compound is one in which the total number of carbon atoms in R1 and R2 in the general formula is 7 or more. In particular, a compound having a molecular volume of 200 to 3503 is desirable, and such a compound has a total number of carbon atoms of R' and R2 of 7 to 14.

A specific example of component C is "f'r) (Me) S
i (mouth Me)2. (n-Bu)(Me)Si(OM
e) t, (i-Pr)2si(OMe)2゜(n-
He)(Me)Si(OMe)a, (i-Pr)(
t-Bu)Si(OMe)z.

(n-Bu)2si(OMe)i, (l Bu)z
si(OMe)i, (s-Bu)2si(OMe)
z, (t-Bu)2Si(OMEritt, (n-C
sH++)zsi(OMe)i.

((M13)3C-('Hi)aSi(QMe)z,
C(Me)C-11-・(:fl(Me), Si(O
Me)a, [(Me)Ca12・C(Me)2]
zsi(OMe)2゜[(n-Pr) (Me) ・C
11l zsi(OMe)*, (n-11e)2s
i(OMe)z[(Me)s[”-Cz)l*) 2s
i(OMe), [(Bt)(Me)2C・CL)
Examples include aSi(OMe)w. Among these,
Especially (n-He) (Me)Si(OMe)*, (
n-Bu), Si (OMe) 2゜(i-Bu)=
Si(OMe)*, (n-Cs)1. )−3i(
Mouth Me),.

((n-Pr) (Me) ・C8) aSi(Ole
)z, (Me)+C-CL ) 2Si(OMe)
z, (n-He)aSi(mouthMe)l [(
Me), C-C2H4)S i (OMe), etc. are preferred.

Trimethoxyhydrocarpylsilane 3 R' is used. In the formula, R3 and R4 each have 1 to 10 carbon atoms.
R5 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the total number of carbon atoms in the hydrocarbon groups R3 to R5 is 3 or more.

Examples of the hydrocarbon group for R3-R5 include alkyl, cycloalkyl, aryl, and aralkyl groups, with alkyl groups and cycloalkyl groups being preferred, and alkyl groups being particularly preferred. Alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, 5e
Examples include c-butyl, pentyl, i-pentyl, hexyl, octyl, and the like.

Specific examples of trimethoxyhydrocarpylsilane (hereinafter referred to as component) include t-Bus i (OMe)
3Bt(Me)2C-3i(OMe)3. Pr(Me
)2cmSi(OMe)3゜iPr(Me)zC-3i
(OMe)s, Mc(Bt)zc-3i(OMe)+
.

Bt-Me-C8-Si(OMe)s, B
uSi(mouthMe)3+i-BuSi(OMe)s, C
sHzSi(OMe)+, i-C1-C5)IzS
i(O+.

etc.

The catalyst of the present invention uses tetramethoxysilane (hereinafter referred to as component E) in addition to the above-mentioned components, or in combination with component E instead of the other components.

The catalyst of the present invention consists of Component A, Component B, Component C, and Component E. The composition ratio thereof is such that Component B is 1 to 2.000 g mol per 1 gram atom of titanium in Component A, preferably 20 to 500 g mol, component C is 0.001 to 10 mol, preferably 0.01 to 10 mol, and/or component E is component C per 1 mol of component B.
0.1 to 10 mol, preferably 0.2 to 10 mol per mol
It is used so that it becomes 5 mol.

Polymerization of α-olefins The catalyst of the present invention is useful as a catalyst for homopolymerization of α-olefins having 3 to 10 carbon atoms or copolymerization with monoolefins or diolefins having 3 to 10 carbon atoms.
In particular, α-olefins having 3 to 6 carbon atoms, such as propylene, l-butene, 4-methyl-1-pentene, l-
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 -80°C+150°C, preferably 40 to 120°C. The polymerization pressure is, for example, 1
~60 atmospheres is sufficient. 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 may be 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 When a silane compound having an aromatic group is used, no harmful substances are generated, and the polymerization activity and stereoregularity are equal to or higher than those of a catalyst containing a silane compound having an aromatic group. Demonstrates catalytic performance that shows.

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 extruded for 6 hours with boiling n-hebutane in a modified Soxhlet extractor.

Example 1 Preparation of Component A A 200 rrdl flask equipped with a dropping funnel and a stirrer was purged with nitrogen gas. Into this flask, 5 g of silicon oxide (manufactured by DAVISONA, trade name G-952) calcined in a nitrogen stream at 200° C. for 2 hours and then at 700° C. for 5 hours and 40 g of n-heptane were added. Furthermore, a 20% n-hebutane solution of n-butylethylmagnesium (hereinafter referred to as BEM) (manufactured by Texas Alkyls, trade name MAGALA BBM > 20 rd
was added and stirred at 90°C for 1 hour.

After the suspension was cooled to 0° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-hebutane was added dropwise from the dropping funnel over 30 minutes. After the dropwise addition was completed, the temperature was raised to 50°C over 2 hours, and stirring was continued at 50°C for 1 hour. After the reaction was completed, the supernatant liquid was removed by decantation, the produced solid was washed with 60-n-hebutane at room temperature, and the supernatant liquid was further removed by decantation. This washing treatment with n-hebutane was further repeated four times.

50rn for the above solid! ! , n-hebutane was added to make a suspension, and 8.0 g of 2.2.2-)lichlorethanol was added to 10 ml of this suspension. A solution of n-hebutane was added dropwise from the dropping funnel at 25° C. over 15 minutes. After the dropwise addition was completed, stirring was continued for 30 minutes at 25°C. After the reaction is completed, at room temperature, 60rIdi! Washing was performed twice with 60 rnl of toluene and three times with 60 rnl of toluene. When the obtained solid (solid component I) was analyzed, it was found that 310236.6%, magnesium 5.1%, chlorine 3
It contained 8.5%.

10 mj' of n-heptane was added to the solid component (■) obtained above.
and 40rnl of titanium tetrachloride were added, and the temperature was raised to 90°C.
Di-n-butyl phthalate dissolved in n-hebutane 5-0.
6g was added over 5 minutes.

Thereafter, the temperature was raised to 115° C., and the mixture was reacted for 2 hours.

After the temperature was lowered to 90°C, the supernatant was removed by decantation, and 70 mjl of n-hebutane was added. Washed twice with

Additionally, 15-ml of n-hebutane and 40ml of titanium tetrachloride! was added and reacted at 115°C for 2 hours. After the reaction is completed, 60 rrtfl! of the obtained solid material is used! Washing was performed 8 times with n-hexane at room temperature.

Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of catalyst component (component A). This component A contains 3.1%
of titanium, as well as silicon oxide, chlorine and di-n-butyl phthalate.

The catalyst component A obtained above was placed in a stainless steel autoclave No. 1, 51 equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
12.2 mg, 4 ml of a solution containing 0.1 mol of triethylaluminum (hereinafter referred to as TEAL) in 1 liter of n-heptane, 0.02 mol of n- in 1 liter of n-heptane
1 ml of a solution containing hexylmethyldimethoxysilane and 1 rrl of a solution containing 0.02 mol (1,1-dimethylpropane)trimethoxysilane in 1j7 n-hebutane
were mixed and held for 5 minutes. Next, hydrogen gas 600 as a molecular weight control agent and liquid propylene 1
1! After pressurizing the reaction system, the temperature of the reaction system was raised to 70°C, and propylene was polymerized for 1 hour.

After the polymerization is completed, unreacted propylene is purged and HI 9
A 7.5% white polypropylene powder was obtained. The polymerization activity (R,) of the catalyst was 14.1 kg/g of component A. As a result, the polymerization activity (L) of isotactic polypropylene is 13.7 kg/g - The polymerization activity (RA) of component A1 atactic polypropylene is 0.35 kg
/g-component A was determined.

Also, the volume of n-hexylmethyldimethoxysilane was calculated as described above. The result was 205.2 people and 3 people.

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that (1,1-dimethylpropane)trimethoxysilane was not used. The results are shown in Table 1.

Comparative Example 2 Polymerization of propylene was carried out in the same manner as in Example 1 except that n-hexylmethyldimethoxysilane was not used.
The results are shown in Table 1.

Example 2 Instead of n-hexylmethyldimethoxysilane, di-n-
Butyldimethoxysilane, (1,1 dimethylpropane)
Propylene polymerization was carried out in the same manner as in Example 1, except that tetramethoxysilane was used instead of trimethoxysilane and the amounts used were as shown in Table 1, and the results are shown in Table 1. Ta. Further, the calculated volume of di-n-butyldimethoxysilane is shown in Table 1.

Comparative Example 3.4 Polymerization of propylene was carried out in the same manner as in Example 1, except that tetramethoxysilane or di-n-butyldimethoxysilane was not used. The results are shown in Table 1.

Example 3 Silicon oxide and BEM were brought into contact with each other in the same manner as in Example 1, except that the stirring time at 90°C for component A was 2 hours, and then the supernatant liquid was removed by decantation to produce a The solid was washed with 50-helbutane at room temperature and the supernatant liquid was removed by decantation. This washing treatment with n-hebutane was further repeated four times.

To the above solid, 20-n-heptane was added to make a suspension, and to this was added 2.2.2-) Lichloroethanol 9.6
A solution prepared by dissolving 10 g in 10 ml of n-hebutane was added dropwise from the dropping funnel at 0° C. over 30 minutes. After continuing stirring at 0°C for 1 hour, the temperature was raised to 80°C over 1 hour.
Stirring was continued at 80°C for 1 hour. After completion of the reaction, 50 mj! Washed three times with toluene to remove solids (solid components).
) was obtained.

20-toluene and 0.6 g of di-n-butyl phthalate were added to the solid component I obtained above, and the reaction was carried out at 50° C. for 2 hours. Next, 30ml of titanium tetrachloride was added, and 90ml of titanium tetrachloride was added.
After reacting for 2 hours at ℃, the resulting solid material was
Washing was performed 8 times at room temperature with f-n-hexane. Drying was performed at room temperature under reduced pressure for 1 hour to obtain 7.7 g of component A. In addition to 3.0% titanium, this component A contained silicon oxide, magnesium, chlorine, and di-n-butyl phthalate.

Polymerization of propylene Example 1 except that 13.5 mg of component A obtained above and component C and components shown in Table 1 were used, and the amounts of component C and components used were as shown in Table 1. Polymerization of propylene was carried out in the same manner as above, and the results are shown in Table 1. Further, the calculated volume of component C was as shown in Table 1.

Comparative Example 5.6 Polymerization of propylene was carried out in the same manner as in Example 3 except that a component analyzer or a component analyzer was not used. The results are shown in Table 1.

Example 4 Propylene was polymerized in the same manner as in Example 3, except that the compound shown in Table 1 was used as component C and the amount used was as shown in Table 1, and the results are shown in Table 1. It was shown to. Further, the calculated volume of the component meter was as shown in Table 1.

Comparative example? Polymerization of propylene was carried out in the same manner as in Example 4, except that no component was used, and the results are shown in Table 1.

[Brief explanation of drawings]

No. ■ The diagram is A diagram showing the preparation process of the catalyst of the present invention. It is a low chart diagram. teenager Reason Man Inside Field Akira teenager Reason Man Hagi original Ryo teenager Reason Man Cheap West Atsushi husband hand Continued Supplementary Positive book January 1.2

Claims (1)

[Scope of Claims] (A) A solid catalyst component containing a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) An organometallic compound, (C) General formula R^1R^2Si ( OHC_1_3)_2
[However, R^1 and R^2 are each the same or different aliphatic hydrocarbon groups having 1 to 10 carbon atoms. ],
A dimethoxy group-containing silane compound with a volume calculated by quantum chemical calculation of 150 to 500 Å^3, and (D) trimethoxyhydrocarpylsilane and/or (
B) An α-olefin polymerization catalyst comprising tetramethoxysilane.