JPH0480208A - Catalyst component for alpha-olefin polymerization - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

BACKGROUND OF THE INVENTION Catalyst components for alpha-olefin polymerization containing magnesium, titanium, halogens and electron-donating compounds are known.

If the particle strength of the catalyst component is low, the polymer produced by polymerization will be destroyed and pulverized. A typical method for preventing this is so-called prepolymerization, in which the catalyst component is brought into contact with the olefin in advance, and the resulting polymer is incorporated into the catalyst component to increase the strength of the catalyst component particles. By adding an electron-donating compound such as a silicon compound during this prepolymerization, the particle strength is improved and the final polyα-
Attempts have also been made to increase the stereoregularity of olefins.

However, the addition of an electron-donating compound during prepolymerization usually
This brings about effects such as a decrease in catalyst activity or deterioration of catalyst performance during storage.

In addition, as silicon compounds used during prepolymerization, compounds with aromatic groups are often used from the viewpoint of performance, but silicon compounds with aromatic groups may be harmful depending on the purpose of the polymer. There is.

Problems to be Solved by the Invention The present invention aims to increase the strength of catalyst particles, improve the stereoregularity of the obtained polymer, maintain high catalyst activity, and prevent deterioration of catalyst performance during storage.

Means for Solving the Problems As a result of intensive research, the present inventors found that if a specific compound is used as the silicon compound added during prepolymerization, the performance is equivalent to or better than that of an organic silicon compound having an aromatic group. The present invention was completed based on the discovery that a poly-α-olefin can be obtained using the method described above, and that the object of the present invention can be achieved.

The gist of the invention, that is, the gist of the present invention is to combine (A) a solid component containing magnesium, titanium, halogen, and an electron-donating compound as essential components with (B) an organoaluminum compound and (C) a general formula [provided that R1 and R2 is the same or different hydrocarbon group having 1 to 10 carbon atoms, OR', 03iR; or 5iRfi,
R3 is a divalent hydrocarbon group having 1 to 10 carbon atoms;
4, R5 and R6 are each a hydrocarbon group having 1 to 10 carbon atoms. ] A catalyst component for α-olefin polymerization which is brought into contact with (D) an olefin in the presence of an organosilicon compound represented by the formula.

Solid component The solid component (hereinafter referred to as "component") used in the present invention has magnesium, titanium, halogen, and an electron-donating compound as essential components, but such components usually contain a magnesium compound, a titanium compound, and an electron-donating compound. When the compound and each of the above compounds does not have a halogen, it is prepared by contacting each with a halogen-containing compound.

(1) Magnesium Compound A magnesium compound is represented by the general formula MgR'R'. In the formula, R1 and R2 represent the same or different hydrocarbon group, OR group (R is a hydrocarbon group), or a halogen atom.

More specifically, the hydrocarbon groups for R1 and R2 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, and 7JL.

Examples of the alkyl group and the OR group include an alkyl group, cycloalkyl group, aryl group, and aralkyl group in which R has 1 to 12 carbon atoms, and examples of the halogen atom include chlorine, bromine, iodine, and fluorine.

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

MgMez, MgBtz, Mg1-Pr2.
MgBuz, Mgfle2゜Mg0ct2,
MgEtBu, MgPL, MgcyH
ez.

Mg(OMe>z, Mg(OEt)z, Mg(
OBu)2. Mg(Otle)2゜Mg(OOct)
2, Mg(OPh)a, Mg(OcyHe)2
.

BtMg[:], BuMgCI, He
MgCl, i-BuMgCl, tBuMgC]
, PhMgC1, PhCHJgCl,
EtMgBrBuMgBr, PhMgBr
, BuMgl, EtOMgCI.

BuOMgCI, He0MgCl, P
h0MgCl, EtOMgBr.

BuOMgBr, BtOMgl, Mg
CIz, MgBr5, MgL.

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

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

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

C(OMe) contained in the compound formula C(OR) when 0M is carbon.4. C([
]Et)-.

C(OPr)= , C(OBu), , C(Oi−
Bu)4. C(Otle)=C(00ct) 4:
HC(OMe) contained in the formula XC(OR) 3
3゜HC(OEt)3, H[:(OPr)3
, IIC(OBu)3, HC(Olle)3
H[l' (OPh) 3: MeC (OMe) 3.
MeC(0εtL+, Etc(OMe)+.

Etc(OEt)s, cyHe[:(OBt)
3 PhC (mouth Me) 3 PhC (OBt) 3.
Ct12CIC(OBt)3. Me[:HBrC(
Kano t)aMeCHCIC(OBt)3; Cl[l
:(OMe)3 , [:IC(OEt)3CIC(
Oi-Bu)3. BrC(OBt)3: Formula X, C(O
MeCH (OMe) contained in R)2 2. MeC
tl (OEt) 2. [:H2(OLIe) 2
CL(OBB, , [l:lI201cH(Kanot
), , [:HCL[:H(ClTo02.

CCl3[:H(OBt)2, [:HJrCtl
(OEt)-, PhCH(Kanot)2.

Si (OMe) contained in the compound formula Si (OR) when 0M is silicon
4, Si(OBt) 4Si(OBu)<
, 5i(Oi-Bu)4, 5i(Otle),
.

Si (00ct) 4, Si (OPh) 4
: H3i (O
Bt) 3, H3i (OBu) -, 1Isi
(Old (e)3H3i(OPh)+; MeSi(O
Me)3. MeSi(DEL)3MeSi(OBu)
+ , BtSi(OEt)+ , Ph5i(OEt
)3゜BtSi(OPh)+ ; CISiCl5i(
O,Cl5i(OEt)3°Cl5i(OBu)3.
Cl5i(OPh)3. Br5i(OEt)3: Formula %
Formula %) ): [] B (Ko t) contained in the compound formula B (OR) when 0M is boron3. [1(OB
IJ)3B (OHe) 3. B (OPh) s.

To the compound formula when 0M is aluminum] (OR) sl Containing AI (OMe)
3, 8l (Oat) 3Al(OPr)3,
AI(Oi-Pr)= , 8] (OBu)
3AI (Ot-Bu)3, Al(O)Ie)
3. AI (OPh) 3゜P(OMe)3 contained in the compound formula P (OR)3 when 0M is phosphorus. P(O
Et)3゜P(OBu)3. P(OHe), , P
(OPh)=.

Furthermore, as the magnesium compound, a complex with an organic compound of a metal (M) of Group 1 or Group Ia of the periodic table can also be used. The complex has a Gohan style 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. As a specific example of the compound represented by MR3,
1Mes, AIEj3. Ali Bu3.
8IPh3ZnMe2, ZnEtz,
ZnBu2, ZnPhz, Ca[1Lz
Examples include CaPh2.

(2) Titanium compounds Titanium compounds are compounds of divalent, trivalent, and tetravalent titanium, and examples thereof include titanium tetrachloride, titanium tetrabromide, titanium trichloroethquine, titanium trichlorobutoxy, and titanium dichlorjetoxy. Titanium, dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortryptoquine titanium, tetrabutoxytitanium, titanium trichloride and the like can be mentioned. 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 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 thereof include aromatic polycarboxylic acids such as carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellidic acid, hemimellitic acid, trimellidic 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, cyclohexanecarboxylic acid Ethyl, methyl benzoate, ethyl benzoate, methyl p-)rulyate, ethyl p-tertiary butylbenzoate, 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, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate , dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate,
Examples include 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, acetic acid iodide, and pivaline. Acid chloride, pivalic acid chloride, acrylic acid chloride, acrylic acid furomide,
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 chloride, 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 chloride, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, benzoyl chloride, benzoyl bromide, p- ) tolyic acid chloride, p-toluic acid chloride, p-anisyl acid chloride, p-anisic acid bromide, α-
Examples include naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic 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 methazol, ethanol, propatool, isoproptool, butanol, isobutanol, pentanol, hexanol, octatool, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol,
These include xylenol, ethylphenol, isopropylphenol, p-ternary-butylphenol, n-octylphenol, and the like. Ethers are represented by the general formula ROR'. In the formula, R and R' are alkyl, alkenyl, cycloalkyl, aralkyl, and aralkyl having 1 to 12 carbon atoms, and R and R' may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisomethyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, etc. .

The preparation method for the components is as follows: ■ Magnum compound (component 1), titanium compound (component 2), and electron-donating compound (component 2).
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 Group 11a, TVa, and Va elements of the periodic table (hereinafter referred to as metal halides). 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 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-fromethane, 1,2-short ethane, methylchloroform, methylbromoform, methyliodoform, 1. 1.2-) dichloroethylene, 1.1
．． 2-tribromoethylene, 1. 1. 22-tetrachloroethylene, pentachloroethane, hexachloroethane, hexachloroethane, n-propyl chloride,
1.2-dichloropropane, hexachloropropylene,
Octachloropropane, decabromobutane, chlorinated paraffin; alicyclic compounds such as chlorocyclopropane, tetrachlorocyclobencune, hexachlorocyclopentadiene, hexachlorocyclohexane; aromatic compounds such as chlorobenzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene,
Examples include hexabromobenzene, bensitrichloride, p-chloropenecitrichloride, and the like. Not only one kind but also two or more kinds of these compounds may be used.

As a hao/y'n-containing alcohol, - any 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. means a compound that has been 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-1-7' lovanol, 1-10-2-methyl-2-propatur, 4
-Chlor-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro1.2
-propanediol, 2-chlorocyclohexanol,
4-Chlorobenzhydrol, (m,o,p)-chlorobenzyl alcohol, 4-chlorcatechol, 4-chloro-(m,o)-cresol, 6-chloro-(mO)
-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-di0-ruthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1 brmo 2-propatool, 1-brmo 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-dichloroethanol, 2. 3-';') chloro-1-propatol, 1,3-dichloro-2-propatol, 3-chloro-1-(α-chloromethyl)-1-propatol,
2.3-sifurome-1-propatur, 1.3-dibromo-2-propatol, 2.4-dibromophenol, 2.
4-dibromo-1-naphthol: 2,2゜2-trichloroethanol, 1,1.1-)lichlor-2-propatol, β, β, β-trichlor-tert-butanol, 2,3.4-)lichlor Phenol, 2,4.5-)
IJ dichloroethanol 2,4.6-)lichlorphenol, 2.4.6-)ribromophenol, 2.35-
) IJ dibromo 2-hydroxytoluene, 2°3.
5-) Ribromo-4-hydroxytoluene, 2.2.2
−) Refluoroethanol, α, α.

α-Trifluoro-m-cresol, 2.4°6-triiodophenol: 2,3,4.6tetrachlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A, 7-trabromobisphenol A, 2.
2,3.3 Tetrafluoro-1-propertool, 2.3
Examples thereof include 5.6-titrafluorophenol and tetrafluororesorcinol.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include H3iCIs, H2SiCl2. H3SiCl
.

HCH35ICI2, 1lc2H5sIcI2
, H(t-CaHs)S+[:lz.

11CaHsSiCI2, H(CH3)zsic
l, H(i-C3H7)2si[:I.

H2c2H5sic1, L(n-CJs)Si
C1,112(Cr,1IacHi)SiC1,1(S
Examples include ICI (C61(5)2).

Metal halides include B, AI, Ga, I
n.

TI, Si, Ge, Sn, Pb, As,
Examples include chlorides, fluorides, bromides, and iodides of Sb and Bi, especially (2B[1,1,, BBr3. Bi3.
AlCl3. 8lBr3゜Gaels, GaBr
5, InCl+, TlCl3.5IC14.

5nCI4. SbCls, 5bFs, 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, octane, saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, aromatic M hydrocarbons such as benzene, toluene, xylene, etc. can be used.

The preferred preparation method for the components 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, (c) general formula XhM(OR), -,
A magnesium-containing solid obtained by contacting a compound (same as the alkoxy group-containing compound described above) with (
A method of contacting 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.

Organoaluminum compound The organoaluminum compound (hereinafter referred to as component B) is:
General formula R,,^1x3-o (where, R is an alkyl group or an aryl group, χ is a halogen atom, an alkoxy group, or a hydrogen atom, and the number is any number in the range of 1≦n≦3.) For example, trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride having 1 to 18 carbon atoms, preferably carbon number 2 to 6
Alkylaluminum compounds or mixtures or complexes thereof are particularly preferred. Specifically, trialkyl aluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum,
Dialkyl aluminum monohalides such as dimethyl aluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dichloride, ethyl aluminum dichloride, ethyl aluminum diiodide, Monoalkylaluminum dihalides such as isobutylaluminum dichloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride,
Dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethylaluminium ethoxide, diethyl aluminum phenoquine, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide,
Dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, and diisobutyl aluminum hydride are exemplified. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum.

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 the formula, the hydrocarbon group of R', R2 and OR', O3
+Rffi, R' in S+R'r, R5
, +76 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkagenyl group, an aryl group, an aralkyl group, and the like.

Alkyl groups include methyl, ethyl, propyl, ]-
Propyl, butyl, l-butyl, S-butyl, t-butyl, ryo-myl, ]-amyl, t-7-myl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and alkenyl groups include vinyl, allyl, propenyl, etc. , 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl,
1-dekenyl, 1-methyl-1-pentenyl, 1-methyl-1-heptenyl, etc., as cycloalkyl groups,
Cyclopentyl, cyclohexyl, methylcyclohexyl groups, etc., cycloalkenyl groups include cyclopentenyl, cyclohexenyl, methylcyclohexenyl groups, etc., and cycloalkagenyl groups include cyclopentagenyl, methylcyclopentagenyl, Examples of the aryl group include phenyl, tolyl, xylyl, etc., and examples of the aralkyl group include benzyl, phenethyl, 3-phenylpropyl, and the like.

Further, R3 in the above general formula is a divalent hydrocarbon group, and specific examples include groups represented by the following general formula.

In the above, m is 1 to 10, n, p.

q is 2 to 8, respectively.

Specific examples of the groups (1) to (2) above are as follows.

[:2Hs ■ C, /[:8%C1 c, /CH.

0H Pa・C1 CH/CH・C11,\c1 (2 Component C is usually a rogene atom) and a compound represented by the general formula % are combined with a compound such as pyridine, quinoline, etc. Either the compound represented by the general formula R'R25i(OR7)2 (R7 is a hydrocarbon group) and the compound represented by the Gohan formula HOR'Ko are reacted in the presence of a dehydrohalogenating agent or in the presence of an acid or base catalyst. It can be synthesized by the reaction described below.

Prepolymerization The prepolymerization of the solid component (component A) is carried out by contacting it with an olefin in the presence of an organoaluminum compound (component B) and an organosilicon compound (component C).

In addition to ethylene, the olefins include propylene, 1-
α of butene, 1-hexene, 4-methyl l-pentene, etc.
-Olefins may be used.

The prepolymerization is preferably carried out in the presence of the above-mentioned inert medium. Prepolymerization is usually carried out at a temperature of 100°C or lower, preferably -30°C to +30°C, more preferably -20°C to +1°C.
It is carried out at a temperature of 5°C. The polymerization method may be either a batch method or a continuous method, or may be carried out in multiple stages of two or more stages. When carrying out multi-stage polymerization, it is natural that the polymerization conditions can be changed in each stage.

Component B has a concentration in the prepolymerization system of 50 to 500 mmol/1. It is preferably used in an amount of 80 to 200 mmol/1, and per 1 gram atom of titanium in component A, 4
~50,000 mol, preferably 6 to 1,000 mol.

Component C has a concentration in the prepolymerization system of 1 to 100 mmol/
1. It is preferably used at a concentration of 5 to 50 mmol/l.

Olefin polymer is incorporated into component A through prepolymerization, and the amount of polymer is 0.1 to 2 per 1 g of component A.
00g, particularly preferably 0.5 to 50g.

The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but washing is particularly desirable from the viewpoint of preventing storage deterioration of the catalyst component. After washing, it may be dried if necessary.

In addition, when storing catalyst components, it is desirable to store them at as low a temperature as possible, from -50°C to +30°C, especially from 20°C to
A temperature range of +5°C is recommended.

Polymerization of α-olefins The catalyst component of the present invention obtained as described above can be combined with an organometallic compound and, if necessary, an electron-donating compound to carry out homopolymerization of α-olefins having 3 to 10 carbon atoms. It is useful as a catalyst for copolymerization with other monoolefins or diolefins having 3 to 10 carbon atoms, but especially α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl- It exhibits extremely excellent performance as a catalyst for the homopolymerization of 1-pentene, 1-hexene, etc., or the random and block copolymerization with each other and/or with ethylene.

The organometallic compound that can be used is an organic compound of a metal from Group 1 to Group II of the periodic table. As such compounds, 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 is appropriately selected from compounds used in the prepolymerization of the solid component (component A), and trialkylaluminum, particularly triethylaluminum and triisobutylaluminum, are preferred. 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 (C2H5)2^
10AI (C21(S) 2 .

(C,l19)2A10A](C,H8)2, (
Examples include C2H5), AINAI(C2H5)22Hs, and the like.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LiA1(CzHs)< , LiA](CJ+s)n
Compounds such as

Examples of electron-donating compounds that can be combined with the catalyst component and organometallic compound of the present invention as needed include the compound used in preparing the component A and the organosilicon compound ( In addition to being appropriately selected from component C), electron-donating compounds made of organic silicon compounds other than the silicon compounds and electron-donating compounds containing heteroatoms such as nitrogen, oxygen, oxygen, and phosphorus can also be used. It is.

Specific examples of organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra(p-methylphenoxy)silane, tetrabenzyloxysilane, methyltrimethoxysilane, and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane Silane, isobutyltriisobutoxysilane, vinyltriethoxysilane, trimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyljethoxysilane, diethyldiisobutoxy Silane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyljethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, diphenyldibutoxysilane, dibenzyljetoxysilane Examples include toxysilane, divinyldiphenoxysilane, diethyljethoxysilane, diethylzinclyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

Specific examples of electron-donating compounds containing heteroatoms include:
Examples of compounds containing a nitrogen atom include 2゜2.6.6-titramethylpiperidine, 2.6=dimethylpiperidine, 2.
6-diethylpyrrolidine, 2.6-diisopropylpyrrolidine, 2.6-dibutyl-4-methylpiperidine, 1.2.2.6.6-pentamethylpiperidine, 2.
2.5.5-Tetramethylpyrrolidine, 2゜5-dimethylpyrrolidine, 2.5-diethylpyrrolidine, 2.5-
Diisopropylpyrrolidine, 1.2.2.5.5-pentamethylpyrrolidine, 2.2. ．． 5-) Dimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-
Methylpyridine, 2.6-dimethylpiperidine, 2.6
- Butylpyridine, l, 2.4-trimethylpiperidine, 2.5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinamide, benzoic acid amide, 2-methylpyrrole, 2.5-dimethylvirol,
Imidazole, toluic acid amide, pentonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc. are compounds containing a sulfur atom.
Thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methylmercaptan, ethylmercaptan, isopropylmercaptan, butylmercaptan,
Diethyl thioether, diphenyl thioether, methyl benzenesulfonate, methyl sulfide, ethyl sulfide, etc. are compounds containing an oxygen atom, such as tetrahydrofuran, 2-methyltetrahydrofuran, 3-
Methyltetrahydrofuran, 2methyltetrahydrofuran, 2,2,5.5tetraethyltetrahydrofuran,
2,2.55-tetramethyltetrahydrofuran, 2.
2゜6.6-Titraethyltetrahydropyran, 22.
6.6-Titrahydrobilane, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, 0-tolyl-t-butyl ketone, methyl 2
．． 6-di-t-butylphenylketone, 2-ethyl furalate, 2-isoamyl furalate, methyl 2-furalate, 2-
Propyl furalate etc. are compounds containing phosphorus atoms,
Examples include triphenylphosphine, tributylphosphine, triphenylphosphite, tribenzylphosphite, diethylphosphate, diphenylphosphine, and the like.

Two or more types of these electron-donating compounds may be used. Further, these electron-donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with an organometallic compound in advance.

The amount of organometallic compound used for the catalyst component of the present invention is:
Usually 1 to 2.0% per gram atom of titanium in the catalyst component.
000 gmol, especially 20 to 500 gmol.

The ratio of the organometallic compound to the electron donating compound is selected within the range of 0.1 to 40, preferably 1 to 25 gram atoms of the organometallic compound based on aluminum per mole of the electron donating compound.

The polymerization reaction of α-olefins may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, n-phthane, isobutane, n-pentane, isopentane, hexane,
It can be carried out in inert hydrocarbons such as heptane, octane, cyclohexane, benzene, toluene, xylene and in liquid monomers. Polymerization temperature is usually -80℃~+
The temperature is 150°C, preferably in the range of 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 is
The reaction may be carried out continuously or batchwise, and the conditions may be those commonly used. Moreover, the copolymerization reaction may be carried out in one step,
It may be done in two or more stages.

Effects of the Invention By adopting the above-mentioned configuration, the present invention can improve the strength of the catalyst component, and the catalyst component maintains high activity in the (co)polymerization of α-olefin.
A catalyst component that exhibits high stereoregularity and is particularly washed exhibits an excellent effect of suppressing deterioration of performance during storage of the catalyst.

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 H1), 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 components 8.3 g of chip-shaped metallic magnesium (purity 99.5%, average particle size 1.6 mm) and n-hexane were placed in 11 reaction vessels equipped with a reflux condenser under a nitrogen gas atmosphere. 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
A suspension containing 0.5 mol/A of n-butyl ether solution (1.75 mol/A) of n-butylmagnesium chloride was kept at 55°C, and further 50 ml of n-butyl ether was added.
A solution prepared by dissolving 38.5 ml' of n-butyl chloride in No. 12 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.

Then, )I[:(OCJS)3 55.
7 mff was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was carried out at 60°C for 15 minutes, and the reaction product solid was washed 6 times with 300% of n-hexane and dried under reduced pressure at room temperature for 1 hour to give a concentration of 19.0% magnesium and 28.9% chlorine. 31.6 g of magnesium-containing solid containing % were recovered.

300- equipped with reflux condenser, stirrer and dropping funnel
6.3 g of magnesium-containing solid and 50 ml of n-hebutane were placed in a reaction vessel under a nitrogen gas atmosphere. to make a suspension, and while stirring at room temperature, a mixed solution of 2.2.2-) Lichloroethanol 20-(0.02 mmol) and n-hebutane 11- was added dropwise from the dropping funnel over 30 minutes. , further 80
The mixture was stirred at ℃ for 1 hour. The resulting solid was filtered off and stored at room temperature.
-Wash 4 times with 100rnP each of hexane, and 100ml each of toluene! A solid component was obtained by washing twice.

To the above solid component was added 40% of toluene, further titanium tetrachloride was added so that the volume ratio of titanium tetrachloride/toluene was 372, and the temperature was raised to 90°C. Under stirring, diphthalate n
A mixed solution of 2-butyl and 5 toluene was added dropwise over 5 minutes, and then stirred at 120°C for 2 hours. The obtained solid substance was filtered at 90°C and diluted twice with 100 ml of toluene at 90 °C.
Washed at 0°C. Furthermore, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride/toluene was 3/2,
The mixture was stirred at 120°C for 2 hours. The obtained solid substance was
Separated by filtration at 0°C and diluted with 100 d of n-hexane at room temperature for 7
After washing twice, 5.5 g of component A was obtained.

In a 500-mm reactor equipped with a prepolymerization stirrer, 2.4 g of the component A obtained above and (hereinafter referred to as "T") were added under a nitrogen gas atmosphere.
■Abbreviated as -ri. ) in n-hebutane solution (2,0 mol/l) and 2-cyclohexyl-2-methyl-2-silar 1,3-dioxane L and CMR3 with concentrations of 100 μIJ mol/1 and 10 mmol, respectively. /l and stirred for 5 minutes. Next, after reducing the pressure in the system, propylene gas is continuously supplied to
Polymerization was carried out for 0 minutes. After the polymerization was completed, the gaseous propylene was purged with nitrogen gas, and the mixture was washed with 100-hexane three times each.
The solid phase portion was washed at room temperature. Furthermore, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of prepolymerization was 13.9 g per 1 g of component A.

Note that CMR3 was prepared as follows. 150 ml of dry ether was placed in a reaction vessel and cooled on ice. to this,
A mixture of 47.5 g of cyclohexylmethyldichlorosilane and 100 g of dry ether and 18.8 g of 1,3-propanediol 1 40 g of pyridine and 1 g of dry Jx-Til
00 mt' of the mixture was added dropwise while stirring. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The formed precipitate is filtered,
By distilling the filtrate, 319.9 g of CMR was obtained.

The boiling point was 83°C/0.1 mmHg.

Examples 2 to 4 In the prepolymerization of Example 1, the first
The organosilicon compounds shown in the table can also be used as TIBAL or TI.
Prepolymerization of component A was carried out in the same manner as in Example 1, except that triethylaluminum (TEAL) was used in place of BAL at the concentrations shown in Table 1, and the prepolymerization conditions were as shown in Table 1. , the catalyst components were prepared.

Comparative Example 1 A catalyst component (component A) was prepared in the same manner as in Example 1, except that prepolymerization was not performed.

Comparative Example 2 In the prepolymerization of Example 1, component A was prepolymerized in the same manner as in Example 1, except that no organosilicon compound was used and the prepolymerization conditions were as shown in Table 1. was prepared.

Comparative Example 3 In the prepolymerization of Example 1, dimethyldimethoxysilane was used instead of CMR3O, and the prepolymerization conditions were changed to the first
A catalyst component was prepared by prepolymerizing component A in the same manner as in Example 1, except that the procedure was as shown in the table.

Reference Examples 1 and 2 Same as Example 1 except that in the prepolymerization of Example 1, diphenyldimethoxysilane or phenyl)IJ ethoxysilane was used instead of CMR3, and the prepolymerization conditions were as shown in Table 1. Prepolymerization of the components was carried out in the same manner to prepare catalyst components.

Application Example 1 A solution of TEAI in n-heptane (
0.1 mol/1) yl/- of 2 companies and CMR3 and a butane solution (0.01 mol/1) 2- were mixed and held for 5 minutes. Next, 600 rnl of hydrogen gas as a molecular weight control agent and 11 liquid propylene were pressurized, and then the temperature of the reaction system was raised to 70°C. After charging 40 mg of the catalyst component obtained in Example 1 to the reaction system, propylene polymerization was carried out for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder with Hl of 97.2%. The amount of polypropylene produced (CE) per gram of component A/hour was 49.2 kg.

Application Examples 2 to 7 The catalyst components obtained in Examples 2 to 4 are used in place of the catalyst components obtained in Example 1, and the electron donating compounds shown in Table 2 are used in place of CMR3. Polymerization of propylene was carried out in the same manner as in Application Example 1, except that no polymer was used, and the results are shown in Table 2.

Application Examples 8 to 15 In place of the catalyst component obtained in Example 1, the catalyst components obtained in Comparative Examples 1 to 3 and Reference Example 1.2 were used, and CMR
Polymerization of propylene was carried out in the same manner as in Application Example 1, except that the electron donating compound shown in Table 2 was used instead of 3, and the results are shown in Table 2.

Application example catalyst component Comparative example 1 No. electron donation :H3) :2H3 n-C3LS+(OC2H5: C3H75+ (QC2Hs) To U :)+3)s ]CH3) C6H5Si (OC2H5) 3 L CH3 52,8 26,1 31,7 22.5" 32.4 35.4 16.8 33.4 28.1 92.0 93.0 96.7 93.6 65.1 93.5 86.3 97.2 97.0

[Brief explanation of drawings]

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

Claims (1)

[Claims] (A) A solid component whose essential components are magnesium, titanium, halogen, and an electron-donating compound, (B) an organoaluminum compound, and (C) a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1 and R^2 are the same or different carbon numbers 1 to 1
0 hydrocarbon groups, OR^4, OSiR^5_3 or S
iR^6_3 and R^3 are divalent hydrocarbon groups having 1 to 10 carbon atoms, and R^4, R^5 and R^6 are each hydrocarbon groups having 1 to 10 carbon atoms. ] A catalyst component for α-olefin polymerization which is brought into contact with (D) an olefin in the presence of an organosilicon compound represented by the following.