JPH03174411A - Method for producing polyα-olefin - Google Patents

Abstract

PURPOSE:To obtain the title compound of high melt flow in high yields by polymerizing an alpha-olefin in the presence of a specified catalyst. CONSTITUTION:An alpha-olefin (e.g. propylene) is polymerized in the presence of a catalyst comprising a solid catalyst component essentially consisting of Mg, Ti, halogen and an electron-donating compound (e.g. di-n-butyl phthalate), an organo-metallic compound (e.g. triethylaluminum) and an ethoxylated siline compound represented by the formula: RnSi(OC2H5)4-n (wherein R is a 4-10C aliphatic hydrocarbon group; and n is 1 or 2) and having a volume of 240-500Angstrom as determined by a calculation based on quantum chemistry and an electron density of the O atoms of the ethoxy groups of 0.680-0.800 atomic unit as determined by the same calculation (e.g. t-amyltriethoxysilane).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing poly-alpha-olefins, particularly poly-alpha-olefins with high melt flow rate and a melt flow rate of 50 or more.
Concerning a method for producing olefins.

Conventional technology When producing polyα-olefin using a component containing magnesium, titanium, halogen, and an electron-donating compound as the main catalyst, the use of an organosilicon compound together with an organoaluminum compound improves the stereoregularity of the resulting polymer. . However, at the same time, this causes a decrease in the polymerization activity of the catalyst. The degree to which stereoregularity is improved and the rate to which polymerization activity is reduced vary greatly depending on the type of silicon compound used. Generally, silicon compounds having an aromatic group exhibit good performance, but there are some drawbacks.

On the other hand, in order to improve the melt flowability of a polymer, a method is generally adopted in which the melt flow rate of the polymer is increased using hydrogen, but this method usually reduces the stereoregularity of the polymer.

Recently, (A) a solid titanium catalyst component containing as essential components magnesium, titanium, a halogen, and a polyvalent carboxylic acid ester formed by contacting a magnesium compound, a titanium compound, and a polyvalent carboxylic acid ester; (B) an organic In the presence of a catalyst system formed from an aluminum compound catalyst component and (C) an organosilicon compound catalyst component represented by the general formula SiR', (OR2) =-, propylene with an MFR of 10 g/l 0 minutes or more is produced. A method for producing block copolymers has been proposed (Japanese Unexamined Patent Publication No. 6
3-27517).

However, this method is a method for producing a specific propylene block copolymer, and the MFR of the resulting copolymer is also 40g.
/ There are only examples in which the time is less than 10 minutes.

In addition, (A) component, (B) component and (C) general formula SiR'R described in the above-mentioned Japanese Patent Application Laid-Open No. 63-27517
2 (OR3) A method of polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organosilicon compound catalyst component represented by 2 is also known (JP-A-6
3-223008) In this method, even if the melt flow rate of the polymer is changed by hydrogen, the stereoregularity of the polymer is said to be less degraded. However, in this method, the organosilicon compound substantially used is a methoxy group-containing silicon compound, and the MFR of the obtained polymer is also less than 40 g/10 minutes.

Problems to be Solved by the Invention The present invention uses a catalyst in combination with an organosilicon compound that has a good effect on the melt flow rate due to hydrogen (i.e., hydrogen response) and less decreases in the stereoregularity of the polymer. It is an object of the present invention to provide a method for obtaining a poly-α-olefin with high melt fluidity in high yield.

Means for Solving the Problems The present inventors have conducted intensive research on a method for polymerizing α-olefins using a polymerization catalyst containing an organosilicon compound as one component. A specific polymerization catalyst containing an ethoxy group-containing silane compound in which the electron density of the oxygen atom of the group is in a specific range exhibits high activity and can produce polyα-olefins with high stereoregularity. The present invention was completed based on the discovery that the hydrogen response is good and that even when a large amount of hydrogen is used, the stereoregularity decreases only slightly.

Summary of the Invention That is, the present invention comprises (A) a solid catalyst component containing magnesium, titanium, a halogen, and an electron-donating compound as essential components, (B) an organometallic compound, and (C) a compound of the general formula R15i (OC21(s)i). -1 [However,
R is an aliphatic hydrocarbon group having 4 to 10 carbon atoms, and n is 1 or 2. ], the volume calculated by quantum chemical calculation is 240 to 500 people3, and the electron density of the oxygen atom of the ethoxy group is 0. The gist of the present invention is a method for producing a poly-α-olefin, which comprises polymerizing an α-olefin in the presence of a catalyst comprising an ethoxy group-containing silane compound having an atomic unit of 680 to 0.800 A, U, (atomic unit).

Solid catalyst component A solid catalyst component (which is one component of the catalyst used in the present invention)
Component A) (hereinafter referred to as component A) has magnesium, titanium, halogen, and an electron-donating compound as essential components, but these components usually include a magnesium compound, a titanium compound, an electron-donating compound, and each of the above compounds contains a halogen. In the case of a compound that does not contain a halogen-containing compound, it is prepared by contacting each with a halogen-containing compound.

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

More specifically, as the hydrocarbon group for R1 and R2, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aryl group, and as an OR group, R has 1 to 12 carbon atoms. Alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups each have chlorine,
These include 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.
MgBu2. Mgtla2゜Mg0ctz, Mg
EtBu, MgPhz, MgcyHez.

Mg(B1Ja)2. Mg(OBtL, Mg(O
Bu)z, Mg(OH8)z.

Mg(OOct)z, ug(oph)2, Mg
(Ocylle)2゜BtMgCl, Bu! JgC
1, HeMgC1, i-BuMgCI, t-BuM
gCI, PhMgC1, PhCPhC11J,
BtMgBr.

BuMgBr, PhMgBr, BuMgl,
BtOMgCIBuOMgCI, IleOMgC
I, PhOIJgCI, BtOMgBr.

BuOMgBr, BtOMgl, MgCL,
MgBrz, Mg12° 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 Hydrogen 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. ]
An example of this method is to contact the The hydrocarbon groups of X and H in the general formula of the alkoxy group-containing compound include methyl (Ma), ethyl (Bt), propyl (Pr), i
-Propyl (1-Pr) Butyl (Bu) l-Butyl (+-Bu), Hexyl (lie) Octyl (B
Alkyl groups such as ct), cyclohexyl (cyHe)
Cycloalkyl groups such as methylcyclohexyl, alkenyl groups such as allyl, propenyl, butenyl, phenyl (
Ph) iJ, aryl groups such as xylyl groups, and aralkyl groups such as phenethyl and 3-phenylpropyl.

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

■C(OMe), , C( contained in the compound formula C(OR)4 when M is carbon
OBt)-.

C(OPr), , C(OBu), , C(old-
Bu)4. C(OHe)4゜C(B0ct),'
HC(OMe) 3°tic(OBt)a, HC(OPr)3. HC(
OBu), t, HC(Olle)s.

11c(OPh)s; MeC(OMe)+, M
eC(OBt)3. Etc([]Me)BtC(OB
t)a, cyHeC(OBt)3. PhC([]
Me)a.

PhC(OBt)a, CIIzCIC(OBt)s
, MeCHBrC(OBt)s.

MeCIICIC(OBt)3; CIC(OMe)a
, CIC(OBL)3゜CIC(Oi-81)3
, BrC(OBt)s; MeCtl(OMeL, MeCtl(OBt) contained in formula X, C(OR),
z, C112C112(O.

C112(OBt)i, Cll2CICIl(OB
t)z, C11CI2[1'1l(OBt)2゜C
Cl5CH(OBt)z, CIL[]rCtl(B
[! t)2. PhCH(OBtL.

■Si(OMe) included in the compound formula Si (OR) = when M is silicon,
, 5i(OBt)n.

5i(OBu)4, 5i(Oi-Bu)a,
5i(Olle)4.

5i (B0ct), , Si (mouth Ph),: Formula X
H3i(OBt)s contained in Si(OR)3,
H3i(OBu)*, H3i(OHe)s
.

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

MeS i (OBu)s, LotS+ (OB
t)s, PhSi(OBt)3.

BtSi(OPh)a; CISiCl5i(O
, Cl5i(Oat)s.

Cl5i(OBu)s, Cl5i(OPh)s,
B(OBt)3.8([
]Bu)3°B(OHe)-, B(OPh),.

■AI(OMe)*, A included in the compound formula AI(OR)s when M is aluminum
I(B[!t)s.

81 (OPr)s, AI (old-Pr)a,
AI (OBLI)! .

^1 (Ot-Bu) s , ^1 (B118) * ,
AI(OPh)3゜■When M is phosphorus, P(OMe)s, P(O
Bt)3゜P(OBu)5. P(OHe)= , P
(OPh)=.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group 1 or Group Ma of the periodic table can also be used. The complex has the general formula MgR'[l12·n(MR
', ). The metal includes aluminum,
Zinc, calcium, etc., and R' 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' include A
IMes, AIBt3. A11-Bus, A
lPh+.

ZnMez, ZnBtz, ZnBu2. Zn
Ph2. Examples include CaBt2+CaPhz.

(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) M child-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, T-divic acid, sebacic acid, maleic acid, fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexane dicarboxylic acid 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 civalate, isobutyl pivalate, Ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, p-)methyl rulyate, p-tertiary butylbenzoic acid u-ethyl, p-ethyl anisate, α-ethyl naphthoate, α-isobutyl naphthoate, ethyl cinnamate, phthal 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, Dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, trimellitate
Ethyl, tributyl trimethylate,
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, acetic acid chloride, butyric acid bromide, 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 chloride, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, benzoyl chloride, benzoyl bromide, p- ) toluylic acid chloride, p-toluylic 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 R011.

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 carbon numbers of ■ to 12
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. .

The method for preparing component A is as follows: (1) A magnesium compound (component 1), a titanium compound (tL portion 2) and an electron-donating compound (component 3) are brought into contact in that order. ■Component 1 and component 3
Component 2 is then brought into contact. ■Ingredients 1. A method such as bringing component 2 and component 3 into contact at the same time may 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 Ila, TVa, and Va elements of the periodic table (hereinafter referred to as metal halides), and the like. 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, iodoform, 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 bromoform, methyl iodoform, 1.1.2-) dichloroethylene, 1.1.
2-) Libromoethylene, 1,1,2°2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1.
2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, chlorinated paraffin, alicyclic compounds such as chlorocyclopropane, tetrachlorocyclopenkune, hexachlorocyclopentadiene, hexachlorocyclohexane, aromatic compounds Examples include chlorobenzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, pencitrichloride, p-chloropencitrichloride, 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-chlorcatechol, 4-chloro-(m,o)-cresol, 6-chlor -(m, o
)-cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-■-naphthol, (m, o
, p)-Chlorphenol, p~chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2-
Bromoethanol, 3-bromo-l-propertool, 1
- bromo 2-propatol, 1-bromo 2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p
)-bromophenol, 4-bromoresorcin, (rn
, o, p) Fluorophenol, p-iodophenol: 2゜2-dichloroethanol, 2.3-dichloro-1-propatol, 1.3-dichloro-2-propatol, 3-chloro-1- (α-chloromethyl)-1-
Propertool, 2,3-dibrome-1-propertool,
1,3-dibromo-2propanol, 2,4-dibromophenol, 2,4-dibromo-■-naphthol: 2,
2゜2-trichloroethanol, 1.1.1-trichlor-2-propatol, β, β, β-trichloruta
rt-butanol, 2,3.4-trichlorophenol, 2.4.5-)IJ chlorphenol, 2,4.6-
Trichlorophenol 2.4.6-)ribromophenol, 2.3゜5-tribromo-2-hydroxytoluene, 2゜3.5-tribromo-4-hydroxytoluene 2
．． 2.2-) Refluoroethanol, α, α.

α-Trifluoro-m-cresol, 2,4゜6-doliodophenol: 2.3.4.6-titrachlorphenol, tetrachlorohydroquinone, tetrachlorbisphenol A, tetrabromobisphenol A, 2,
2,3.3-tetrafluoro-1-propertool, 2.
Examples include 3°5.6-titrafluorophenol and tetrafluororesorcin.

Examples of silicon halide compounds having a hydrogen-silicon bond include H3IC13+ 1I2sIC12, H3SICI+
1clIasic12, 1lc21+5sic12
, H(t-C4+1s)SiC12.

11callssicIz, H(CH3)zsic
l, It(i-Csllt)2sic1112c2
1+5slc1, H2(n-,C-H5)SICI
, H2(C6H4CH3)SiC1, H3iCI(
Examples include CaH, )z, and the like.

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

TI, Si, Ge, Sn, Pb, As,
Sb, Bi chloride, fluoride, bromide, iodide, especially BCl3, Bars, BI3
, AlCl3 , Al0r, .

GaCL, GaBra, InCIa, Tl
Cl3,5ICI4.

5nC11, 5bC1s, 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 and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic fF 2 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, (I) halogenated hydrocarbon, (c) general 2X, M (OR) a-
The magnesium-containing solid obtained by contacting n compound (same as the alkoxy group-containing compound described above) is contacted with (d) halogen-containing alcohol, and then contacted with (water) an electron-donating compound and (h) 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-
After contacting a halogenated silicon compound having a silicon bond, (3) contacting with an electron-donating compound, and then (2) contacting with 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,
It may also contain olefin polymers that form in the component upon contact with olefins. The organoaluminum compound is selected from the organometallic compounds described below that are one of the components of the catalyst used in the present invention.

Examples of olefins include ethylene, propylene, l-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. 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 the component is usually 0.1 to 100 g per g of component Al'.

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 found in the first part of the periodic table.
It is an organic compound of a group metal to a group II metal. As component B, compounds of lithium, magnesium, calcium, zinc and phosphorium can be used. Among these, organoaluminum compounds are particularly suitable. The organoaluminum compounds that can be used include the general formula It, ^1
X3-n (However, R is an alkyl group or a ryyl group,
represents a halogen atom, an alkoxy group, or a hydrogen atom, and n
is an arbitrary number in the range of 1≦n≦3. ), such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum civalide, alkyl aluminum sesquihalide,
Particularly preferred are alkyl aluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkyl aluminum monoalkoxides and dialkyl aluminum monohydrides, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, etc. dialkylaluminum monohalides, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dichloride, monoalkylaluminum cybalides such as isobutylaluminum dichloride, alkylaluminum sesquivalides such as ethylaluminum sesquichloride, etc. halide, dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethylaluminum ethoxide, diethylaluminium phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, Dialkyl aluminum hydrides such as diisobutyl aluminum hydride are mentioned. 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 (C2H5) 2
A10A1 (Calls) 2.

(C=IIs)2A10A1 (C411s)2,
Examples include (C2H5)28lNAl (C2N,)2Js.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LIAI(C2H5)4, L+AI(CJts)n
Compounds such as

Ethoxy group-containing silane compound Ethoxy group-containing silane compound used in the present invention (hereinafter referred to as component C). ) has the general formula Rn5l (OC2Hs
) 4-, , the volume of the molecule calculated by quantum chemical calculation is 240 to 500 people 3 The electron density of the oxygen atom of the ethoxy group is 0.680 to 0.80 OA, (atomic unit) It is.

Quantum chemical calculations are performed using the following method. The volume of a molecule can be calculated using the MNDO method of MOPAC, a molecular orbital method program (purchased from QCPB (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 method) CJ, Am, Chem, Sa
c., Journal of the American Chemical Society), Vol. 99, pp. 4899, 4907 (1977); Vol. 100, pp. 3607, (1978)] and V
andar Waals radius [: J, Phys, Ch
em, , (Journal of Physical Chemistry) Volume 68.

441-451 (1964)], and the electron density of the oxygen atom of the ethoxy group is calculated from the above MOPA
It was calculated by the MNDO method of C. The calculations were carried out by DEC (DIGITAL BQU-IPI, IB
NT CORPORATION) VAX 11/7
85 was used.

R in the general formula of component C is an aliphatic hydrocarbon group having 4 to 10 carbon atoms, that is, an alkyl group and an alkenyl group.

Component C is the volume of 240 to 500 people 3 determined by the above calculation method, and 0.680 to 01800 A, U.

It has an electron density of an oxygen atom of 240
~350 people 3 volume and 0.685~0.700 A, U,
It is desirable to have an electron density of .

A specific example of component C that satisfies the volume and electron density as described above is illustrated below using a chemical formula. In the formula, Me:
C11s, Bt: C2H5, Pr: C3H
? .

[1u: C4H9, Pe: [5tlz, He
: Indicates C6H13.

(n-Bu)2s+(OBt)2. (+-BuLS
i(OBt)z.

(s-Bu)2si(OBt)2. (t-Bu)2
s+(OBt)2゜[:(n-Pr)(Me)Ctl]
zsi(Oat)2. (t-Pe)zsi(OBt
)2゜[(t-Bu)CHzl s+5l(Oat)z
, [(Bt)(Me)CI!・CI+2] 2s
i(Oat)2. (n-11e)zsi(OBt)
2゜[(Bt)(Me)z C-CH2] zsi(O
Bt)z, [(t-Bu)(CI+2)2)z
si(OBt)2; (n-Pe)Si(B8t)a
.

(t-Pe)Si(OBt)8. (n-Pr) (M
e) CfiSi(OBt)s.

(t-Bu)CH, 5i(OBt)s, (Bt
) (Me)CIICII2・5i(OBt)a,
(n-He)Si(Oat)s, [(Bt)(
Me)2c・C112-3i(OBt)s, (t-
Bu)(CL)zsi(OBt)3:CIl□=CH(
CII2)!・5i(OBt)a, C112
=C1l(CL), ・5i(OBt)s, CL=C
H(Ct12)s・S+(OBt)−, CL=Cfl(
CH2)6 ・5i(OBt)s, (life
)CH=CH(CH2)3 ・5i(OBt)s:
[CHz=CH(CHz)2)zsi(OBt)z
, [CtL・CH(CH2)4]2Sl(O
at)2, [(Me)Ctl=C)ICt12]
Examples include 2si(OBtL).

The catalyst used in the present invention consists of component A, F&B, and component C, and their composition ratio is such that component B is higher than component A.
1 to 2.000 g mol, preferably 20 to 500 gram mol, per gram atom of titanium in component C, component B
o, oo i to 10 mol per 1 mol, preferably o, oi-t.

It is used to give moles.

Polymerization of α-olefin In the present invention, α-olefin is polymerized using the above catalyst to produce polyα-olefin. α-olefins have 3 to 10 carbon atoms, and specific examples include propylene, l-butene, 1-hexene,
-methyl-1-pentene and the like. Polymerization is α-
In addition to homopolymerization of olefins, it also includes random copolymerization of α-olefins and ethylene or other α-olefins.

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.

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 may be carried out continuously or batchwise, and the conditions may be those commonly used. Further, the polymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

In particular, the present invention has a melt flow rate (MFR) of 50
g/10 min or more, and the MFR can be adjusted using known molecular weight regulators, especially hydrogen.

Effects of the Invention The present invention particularly provides an MFR of 50 g/10 minutes or more, preferably 70 g/10 minutes or more, and more preferably 100 g/10 minutes.
In the production of polyα-olefins with a high MFR of more than 100%, even if a large amount of hydrogen is used as a molecular weight regulator, the butane-insoluble matter (I-(1)) remains highly stereoregular with 96% or more. , it is possible to produce polyα-olefins in high yield.Moreover, although the silane compound used in the present invention does not have an aromatic group, it has a higher yield than when a silane compound having an aromatic group is used. Shows equivalent or better catalytic performance.

EXAMPLES The present invention will be specifically explained with reference to Examples and Comparative Examples. Note that percentages (%) in the examples are based on weight unless otherwise specified.

The hebutane-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 an improved Soxhlet extractor. MFR measurements are based on ASTM-D 1238
I followed.

Example 1 Preparation of Component A Into 11 reaction vessels equipped with a reflux condenser, 8.3 g of chip-shaped metallic magnesium (purity 99.5%, average particle size 1.6 kg) and n- 250ml hexane
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
40rnl and n- of n-butylmagnesium chloride
Butyl ether solution (1,75 mol/l to 0.5 mj
2, the added suspension was kept at 55°C, and further added n-butyl ether 50rd and n-butyl chloride 38.5 if! A solution in which was dissolved was added dropwise over 50 minutes. 4 at 70°C under stirring
After carrying out the reaction for an hour, the reaction solution was maintained at 25°C.

Next, DC([]Cd1s) 3 55 was added to this reaction solution.
．． 7 me was added dropwise over 1 hour. After 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 obtain 19.0% magnesium and 28.9% chlorine. 31.6 g of magnesium-containing solid were recovered.

300- equipped with reflux condenser, stirrer and dropping funnel
2.2.2-) Lichloroethanol 20rnl (B,02 mmol) and n-heptane 1
Drop 1 ml of the mixed solution from the dropping funnel over 30 minutes,
The mixture was further stirred at 80°C for 1 hour. The obtained solid was filtered,
Washed 4 times with 100rni each of n-hexane at room temperature, and then 10017L1 each of toluene! A solid component was obtained by washing twice.

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. Under stirring, di-n-butyl phthalate 2 mj! A mixed solution of toluene and toluene 5rd was added dropwise over 5 minutes, and then stirred at 120°C for 2 hours. The resulting solid material was filtered off at 90°C and washed twice with 100ml each of toluene at 9.0°C. Furthermore, titanium tetrachloride was newly added so that the titanium tetrachloride/toluene volume ratio was 3/2, and the mixture was stirred at 120° C. for 2 hours. The obtained solid substance was filtered at 110° C. and washed seven times with each 100-hexane solution at room temperature to obtain 5.5 g of component A.

1, 51 with a propylene polymerization stirrer installed! Component A9 obtained above was placed in a stainless steel autoclave under a nitrogen gas atmosphere.
．． 7. Solution 4 containing 0.8 mol of triethylaluminum (hereinafter referred to as TBAL) in 1 liter of n-hebutane
1 ml of a solution containing 0.08 mol of t-amyltriethoxysilane in 1 ml of me and n-hebutane! Mix 5
I put in what I held for a minute. Next, hydrogen gas as a molecular weight control agent2. After pressurizing 〇- and liquid propylene 11, the temperature of the reaction system was raised to 70°C, and propylene polymerization was carried out for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder with an HI of 97.2%. The polymerization activity (Ro) of the catalyst is 25.3 kg/g-
It was component A and time. Polymer MFR is 75.9g
/10 minutes.

In addition, the volume of t-amyltriethoxysilane and the electron density of the oxygen atom of its ethoxy group were calculated as described above, and the results are shown in Table 1.

Furthermore, propylene was polymerized in the same manner as above except that the amount of hydrogen used was changed as shown in Table 1, and the results are shown in Table 1.

Examples 2 to 9 Polymerization of propylene was carried out in the same manner as in Example 1, except that the silane compounds shown in Table 1 were used instead of t-amyltriethoxysilane, and the amount of hydrogen used was as shown in Table 1. The results are shown in Table 1. In addition, the volumes and electron densities of these compounds were calculated, and the results are shown in Table 1.

Comparative Examples 1 to 7 Propylene was polymerized in the same manner as in Example 1, except that the compounds shown in Table 2 were used as silane compounds, and the amount of hydrogen used was as shown in Table 2. It is shown in Table 2. Further, the volumes of these compounds and the calculated values of the electron densities are as shown in Table 2.

Reference Examples 1 to 5 Propylene was polymerized in the same manner as in Example 1, except that the aromatic group-containing compounds shown in Table 3 were used as the silane compounds, and the amount of hydrogen used was as shown in Table 3. The results are shown in Table 3. Further, the volumes of these compounds and the calculated values of the electron densities are as shown in Table 3.

纂□−Keiichi Example silane compound volume (person 3) -nose ± honey (A, mouth.

(t-Pa) Si ([]Et) 5247,6 0.694 (n-Pe) Si (OBt) 5 247,7 0,686 (n-Pr) (Me) CH-3i (OEt) 5
(n-He) S 1 (DB t) a (s-Bu)
ssi (Oat) 2C(n-Pr) (Me)CH
I2si(OEt)zC(Et) (Ma) -C-
CH] aS+ (DEt) 2247, 8 6t8 256, 8 290, 7 2L6 0, 6898 0, 6871 0, 6870 0, 6890 0, 689 CH2=CH(CH2), ・Si (OEt) 525
9,9 0,6865 C)+2=CIl (C)+2) s・S++ (OE
t)! 293, 9 6877 2.0 2.0 25.9 28.4 26.9 29.6 97.0 96.9 97.0 97.1 86.2 96.5 72.0 78.8 25.9 96 .5 80.5 27.9 96.8 75.7 Silane compound Si (OEt) 4 MeS i (OEt) 5 EtSi (OEt) 5 n-BuSi (OEt) s (Me)2S1(OEt)2 (t- Bu) (Me) S i (OBt) 2(n
Je) isi (Il]Bt) a Volume (3 people) Table 2 Electron density (A, [1,) 204, 6 179, 3 196, 5 230, 4 154.1 205, 1 29D, 3 0.6792 0, 6845 0, 6858 0, 6846 0, 6658 0, 6799 0, 6765 2.0 2.0 2.0 2.0 20.2 95.0 12 21.5 95.2 77.1 24.4 95 .5 92.7 21.1 t0 25 26.5 29.2 95.2 95.0 89.0 39 Reference example silane compound C6H55l (OBt) s (CsHs) 2si (Oat) 2(C6H5)
(Me) Si (OMe) Second hydrogen amount <1> 2.0 2.0 2.0 24.9 96.3 27.6 95.8 17.6 96.2 85.0 21 28.9

[Brief explanation of the drawing]

No. The diagram is Flowchart illustrating the method of the invention This is a diagram.

Claims (1)

[Scope of Claims] (A) a solid catalyst component containing magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) an organometallic compound, and (C) general formula R_nSi(OC_2H_5)_4_-_
n [However, R is an aliphatic hydrocarbon group having 4 to 10 carbon atoms,
n is 1 or 2. ], the volume calculated by quantum chemical calculation is 240 to 500 Å^3, and the electron density of the oxygen atom of the ethoxy group is 0.680 to 0.800 A. U
．． A method for producing a poly-α-olefin, which comprises polymerizing an α-olefin in the presence of a catalyst comprising an ethoxy group-containing silane compound (atomic unit).