JPS6142511A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To polymerize an olefin efficiently into an excellent polymer, by using a catalyst comprising a specified organomagnesium component, an H-Si-Cl bond-containing silicon compound, an electron donor, a transition metal compound and an organometallic compound. CONSTITUTION:A catalyst is obtained from (i) a solid catalyst component obtained by reacting a Ti compound or the like with a solid obtained by reacting 0.05-20mol, per mol of C-Mg bond, of an alcohol or the like with a solid obtained by reacting 1mol of an organomagnesium of formula I (wherein M is Al or the like, R<1-2> are each a hydrocarbon, X and Y are each OR<3> or the like, R<3-8> are each H or a 1-10C hydrocarbon, and R<9> is a 1-10C hydrocarbon) or a component obtained by reacting this organomagnesium with an electron donor with 0.01-100mol of an H-Si-containing chlorosilane of formula II (wherein R<10> is a 1-10C hydrocarbon) and further treating this product with titanium halide or the like and (ii) an organometallic compound component. An olefin is polymerized by using the above obtained catalyst.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a method for polymerizing olefins using a novel catalyst, and more specifically, a method for polymerizing olefins using a novel catalyst, and more specifically,
The present invention relates to a method for polymerizing olefins using a catalyst comprising a silicon compound containing an f'L=si-CL bond, an electron donor, a transition metal compound, and an organometallic compound.

<Prior art> As the polymerization of olefin #I, elements Nos. - V of the periodic table
The so-called Chevesey catalyst system, which consists of a transition metal compound of Group IA and an organometallic compound of Groups 1 to 2 of the Periodic Table of the Elements, is known, but in recent years, non-ta-gnesium compounds and titanium have been used as highly active olefin polymerization catalysts. or a catalyst system consisting of a vanadium compound or even an electron donor, such as Pol 7mer Letters Vol. 3
P 855, or Japanese Patent Publication No. 39-12105, etc., on the other hand, #(
Many reeling yarns have been proposed. In the case of organomagnesium-based catalysts, for example, in Japanese Patent Publication No. 46-31968, when an aluminum halide compound, a titanium compound, and an organomagnesium compound are mixed, flukanol, alkenol, or alkanolade is used before, during, or after mixing. A method is described in which fulkenes are polymerized at 110° C. or higher by adding alkanolades, carboxylic acids, carboxylic acid esters or salts, aldehydes or ketones.

Furthermore, Japanese Patent Publication No. 50-32270, Japanese Patent Publication No. 50-32270,
3-46799, JP 50-95382, JP 55-58207, JP 57-205
Proposals such as Japanese Patent Application Laid-open No. 407 and Japanese Patent Application Laid-Open No. 57-205409 have also been made.

Also, Japanese Patent Publication No. 56-43046, Equity [57-95
Publication No. 67, Japanese Patent Application No. 14940/1983, Japanese Patent Application No. 1983
In Japanese Patent Application No. 2-64006, Japanese Patent Application No. 52-67303, Japanese Patent Application No. 52-68834, active organic magnesium obtained by reacting an organomagnesium component with H-8i-C/, bond-containing chlorosilane is disclosed. We are proposing an olefin polymerization catalyst using a solid material containing.

<Problems to be Solved by the Invention> Although these catalyst systems exhibit excellent performance, they are still insufficient as industrial catalysts.

<Problem f: Means and action for solving the problem> The present authors have proposed an organomagnesium component, cF/I-silane with H-S 1 to Ct bonded gold, an electron donor compound, a transition metal compound, and an organometallic compound. As a result of extensive research on polymerization methods using catalyst systems using compounds, we discovered an excellent method for polymerizing olefins.

Therefore, the present invention provides: CA) (1) (1) (a) General formula MaM3βR'p
R”qXrYsC In the formula, M is Al, Zn, B, Be, L
i atom, R'', R'' are the same or different C□~C
□. The hydrocarbon groups, X and Y are the same -i lt is different1
R', Ha0 Keni Rut table b L/, R3, R
'l R''IR',R'#iζ8 is 1 ton of water
It is a hydrocarbon group of 'ak child or C□~CIO 12
11 is a C~C1° hydrocarbon group, α≧O2β>
Oe p −q # r @ 8≧0, m is the valence of M, p+q+r+B=mα+2β, 0=(r+s)/(
The relationship is α+β)≦1. ), or (- and (b) react with an electron donor returned from an ether, thioether, ketone, aldehyde, carboxylic acid or derivative thereof, alcohol, thioalcohol, amino/ (it) general formula H, Si "bR" 4-(a+b)
(In the formula, a, b are numbers larger than 0, a+bL, 4, O(
a≦2, RIO represents a hydrocarbon group having 1 to 20 carbon atoms)
．． 01 to 100 mol in the presence or absence of an inorganic carrier selected from the following: (1) inorganic oxide, (11) inorganic carbonate, silicate, sulfate, (Ill) inorganic hydroxide, 0v )(i) to (lit), double salt, solid solution or mixture, per mole of C-Mg bond contained in the solid formed by reaction, (2) 0.0 of alcohol and/or thioalcohol.
The solid obtained by reacting 5 to 20 mol, (3) titanium compound, vanadium compound, zirconium compound,
A 1- and 2-body catalyst component introduced by reacting a component of 1s or more selected from honeycomb compounds and their mixtures or reactants, Sansha #further (
4) Titanium tetrahalide compound! A solid catalyst component CB) an organometallic compound component obtained by processing a component selected from aluminum halides, silicon halides, and tin/SS chlorides, which consists of [A] and CB) The organomagnesium component used in this application is an olefin polymerization method in which a catalyst is brought into contact with an olefin.
My7R”pR”qXrY,s (wherein, M is At*Z
ntBsBe, Li atom, R1 and R2 are the same or different C1~; hydrocarbon group, X and Y are the same or different OR'', 08iR'R'R', NR'R
"e SR' e]-S represents a group, R3r
R' t R' t R'#R' * R' is hydrogen or Cyu~□. is a hydrocarbon group, and R9 is C8-
C engineering. is a hydrocarbon group with α≧0. β>O, p.

q + r p 8 m≧O1m is the valence of M, p + q
+y+6=mα+2βe o =< r+s )/(α
+β)≧1. ) can be used.

Although this compound is shown as a complex compound of organomagnesium, it includes all of R, Mg, and complexes of these with other metal compounds. R in the above formula
The hydrocarbon group represented by R9 is an alkyl group,
a cycloalkyl group or an aryl group, for example,
Methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl groups, etc.
In particular, R1 is preferably an alkyl group. Also 1
3 to R8 are hydrogen atoms.

As the metal atom M, a six-element gold Ai element belonging to Group 1 to Group II of the periodic table can be used, for example, sodium,
Potassium, Cal7cum, Beryllium, Zinc, Barium,
Examples include boron, aluminum, lithium, etc., and aluminum, zinc, boron, beryllium, and lithium are particularly preferred because they facilitate the formation of hydrocarbon-soluble organomagnesium complexes.

The ratio β/α of magnesium to the metal atom M can be set arbitrarily, but is preferably 0 to 10, particularly 9.5 to
Particularly preferred are hydrocarbon soluble organomagnesium complexes in the range 10.

Symbols α, β, pe qer #! Relational expression of I p+q
+r+B=mα+2β indicates the chemical nature of the metal atom Q) valence and substituent, and is in a preferable range (1=(r
+s)/(α+β)≦1. o is X for the sum of metal atoms
Indicates that the ratio of the sum of Y and Y is greater than or equal to 0 and less than 1.0. A particularly preferred range is 0 to 0.8.

These organomagnesium compounds or organomagnesium complexes have the general formula RMgQ, R, jutg (R has the above meaning and Q is a halogen)''!: The organomagnesium compound shown and the general formula MRm or M
An organometallated compound represented by Rm-IH (M, R, and m have the meanings described above) was heated to ~150°C in an inert hydrocarbon medium such as hexa/, heptane, cyclohexane, benzene, toluene, etc. If necessary, this is further reacted with an alcohol, water, siloxane, amine, imine, mercaptan or dithio compound. Furthermore, the organomagnesium compound or organomagnesium complex is MgX2. RMg
X and MRml MRm-0H, or RMgX, M
gR1 and RnMX, -.

or RMgX, MgR2 and YnIvixm-n (
In the formula, M, R.

X, Y are as described above, including the case where X, Y are )10 gen, and n is 0 to mf)'? In general, organomagnesium compounds are inert in an inert hydrocarbon medium, whereas organomagnesium complexes where α>0 are soluble.

Also, certain 41"f magnesium compounds with α=O, such as see-Bu2Mg#, are soluble in hydrocarbon media, and such compounds have also been used in the present invention with favorable results, and hereinafter these organomagnesium compounds are soluble in hydrocarbon media. The compound will be explained.

General formula 'g/R'PR'' (lXrYs Vc and Hl
, R2 is the following three groups (I), (II),
(I[).

(I) At least one of R1 and R'' has 4 carbon atoms
-6 is a secondary or tertiary alkyl group. Preferably, R1 and B2 are both carbon atoms @4 to 6,
At least one of them is a secondary or tertiary alkyl group.

(I[) R1 and R2 are alkyl groups having different numbers of carbon atoms. Preferably, R1 is an alkyl group having 2 carbon atoms, fc is an alkyl group having 3 carbon atoms, and R2 is an alkyl group having 4 or more carbon atoms.

(I[) At least one of R'tR2 is a hydrocarbon group having 6 or more carbon atoms. Preferably R2R2
are both alkyl groups having 6 or more carbon atoms.

Hereinafter, these groups will not be specifically shown, but examples of secondary or tertiary alkyl groups having 4 to 6 carbon atoms in o(I)VC include 5ee-c4H,', tert-C4Hg
h, preferably a secondary alkyl group, sea
-C, H, are particularly preferred. Next, in (■), examples of the alkyl group having 2t or 3 carbon atoms include ethyl group and propyl group, and ethyl group is preferable.
Examples of the above alkyl groups include butyl group, amyl group, hexyl group, octyl group, etc., with butyl group and hexyl group being particularly preferred. In (III), examples of the hydrocarbon base layer having 6 or more atoms include hexyl group, octyl group, tecyl group, phenyl group, etc., with alkyl groups being preferred, and hexyl group being particularly preferred.

It is essential that the organomagnesium compound used in the present invention be soluble in a hydrocarbon medium. Increasing the number of carbon atoms in an alkyl group makes it easier to dissolve in a hydrocarbon medium, but the viscosity of the solution tends to increase, and it is not preferable to use an alkyl group with an unnecessarily long chain from the viewpoint of handling.

The above-mentioned magnesium compound is used as a hydrocarbon solution, but it can be used without any problem even if a trace amount of a complex compound such as ether, ester, or amine is contained or remains in the solution. can. It is also possible to use an organomagnesium halide as the organomagnesium component.

In the general formula, α=o, β”1 + (1=o + r
The organomagnesium halide represented by =x will be explained.

This compound is a so-called Grignard compound and is generally synthesized by reacting magnesium with an organic halide in an ether solution, but it is also known to carry out the reaction in a hydrocarbon medium in the absence of ether. Yes, you can use both.

Examples of these include, for example, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n- or 1so-propylmagnesium chloride, n-1 or 1so-propylmagnesium bromide, n- or 1ao-propylmagnesium iodide, n-butylmagnesium chloride, n-butylmagnesium bromide, n-butylmagnesium iodide, 1so-, 5ee- or tert-butylmagnesium chloride, 180 "-e 5ee-tirui tert-butylmagnesium bromide, 180-1
Compounds such as 15ee- or tert-butylmagnesium iodide, n-amylmagnesium chloride, ■-amylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, octylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, and These ether complexes can be mentioned. Examples of these ether compounds include various ether compounds such as dimethyl ether, diethyl ether, diimpropyl ether, dibutyl ether, diallyl ether, tetrahydro-7rane, dioxane, and anisole.

The electron donor (b) to be reacted with the hydrocarbon-soluble organomagnesium component (a) will be explained.

For ethers of the general formula ROR', R and R' are aliphatic, aromatic and cycloaliphatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, octyl, dodecyl Examples include hydrocarbon groups such as , cyclohexyl, phenyl, and benzyl.

Also for the thioether R8R', R and R' are aliphatic, aromatic and cycloaliphatic hydrocarbons, such as methyl, ethyl, propyl, buty, amyl, hexyl,
Examples include hydrocarbon groups such as cyclohexyl and phenyl.

For the ketone RCOR', R and R' are aliphatic, aromatic and cycloaliphatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl, etc., but especially dimethyl ketone. /, diethyl ketone, etc. are preferred.

Regarding aldehydes, aliphatic, aromatic and cycloaliphatic aldehydes are also used.

As the carboxylic acid or derivative thereof, carboxylic acid carboxylic acid anhydride, carboxylic acid ester, carboxylic acid halide, and carboxylic acid amide are used.

Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid,
Examples include maleic acid, acrylic acid, benzoic acid, toluic acid, and terephthalic acid.

Examples of the carbo/acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, chloric anhydride, maleic anhydride, benzoic anhydride, heptatalic anhydride, and the like.

Examples of carboxylic acid esters include methyl and ethyl formate, methyl acetate, ethyl, propyl, methyl propionate, ethyl, propyl, butyl, ethyl butyrate, ethyl valerate, ethyl caproate, ethyl n-hebutanoate, dibutyl oxalate, Ethyl succinate, ethyl malonate, cyphthyl maleate, acrylic, methyl rulate, ethyl acrylate, methyl methacrylate, methyl benzoate, amyl, propyl, butyl, methyl toluate, ethyl, propyl,
Butyl, amyl, methyl and ethyl p-ethylbenzoate, methyl anisate, ethyl, propyl and butyl,
Examples include methyl p-ethoxybenzoate and ethyl p-ethoxybenzoate.

As the carboxylic acid chloride, acid chlorides are preferred, and examples thereof include acetyl chloride, propionyl chloride, butyryl chloride, succinyl chloride, benzoyl chloride, and toluyl chloride.

Examples of the carboxylic acid amide include dimethylformamide, dimethylacetamide, dimethylglobionamide, and the like.

Examples of alcohols include methyl alcohol, ethyl alcohol, flobyl alcohol, methyl alcohol, amyl alcohol, hexyl alcohol, phenol, cresol, etc. 5ee-amyl alcohol, tert-
Secondary, tertiary or aromatic alcohols such as amyl alcohol, 8cc-hexyl alcohol, phenol, O, m, p-cresol are preferred.

Examples of the thioalcohol include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, phenyl mercaptan, etc., but secondary, tertiary or aromatic thio alcohols are preferred.

Examples of the amine include aliphatic, alicyclic and aromatic amines, but secondary to tertiary amines such as trialkylamine, triphenylamine, pyridine and the like give preferable results.

For the reaction of a hydrocarbon-soluble organomagnesium component with an electron donor, the reaction may be carried out in an inert reaction medium such as an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, cyclohexane,
Dilution of alicyclic hydrocarbons such as methylsulfate and hexane can be carried out in a mixed solvent of these. Regarding the reaction order, there are three methods: adding the VC electron donor to the organomagnesium component (■), adding the organomagnesium component to the electron donor (■), and adding both at the same time (■). Can be used.

The reaction ratio between the hydrocarbon-soluble organomagnesium component and the electron donor is 1 mol or less of the electron donor per 1 mol of the organomagnesium component, preferably 0.05 to 0.0.
It is 8 moles.

Next, the general formula HaSIC1bR”, −(a+B) (
In the formula, a.

b, 5i-H denoted by
The bond-containing chlorosilane compound will be explained.

The hydrocarbon group represented by RIO in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, such as methyl, ethyl, propyl, butyl,
Examples include amyl, hexyl, decyl, cyclohexyl, phenyl, etc., preferably alkyl groups having 1 to 10 carbon atoms, and lower alkyl groups such as methyl, ethyl, and propyl are particularly preferred □ The values of a and b are as follows: a a b )
Ol, 4 bL-4,0 (a42, 0.5
4a41.5 is preferred.

These compounds include H8Ct3* H8i Ct
, CH=CH2l cz2C2H5* H8i C1~
2n -C3H7, H8i cz, i -C3H7*
H8i Ct2n -C,H,* H8i C4C,H
, t H, Si CL2 (4-CL-C.

H4), [8i C120H= CH2-H8L C
L2 CH2C6H6-H8i Cj2(i-C□.H
, ) , H81Ct, OH, CH=CH2+ H2St
CzCH,.

H2,Si CHCH2e H8i ('L(CH3)
2 #H8i CtCH3(i-C3I-I7)
+IIS i CLCH3 (Ce Hs), H8
i CL (C2H5)! -H3i CL (C@
H5)2, etc., and a chlorosilane compound consisting of a mixture of these compounds and a compound selected from these compounds is used, and trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, etc. are preferred. , tricrotasilane, and monomethyldichlorosilane are particularly preferred.

When using a silicon compound that does not contain 5L-H bonds,
No favorable results are obtained.

The reaction between the organomagnesium component (1) and the chlorosilane compound (1) will be described below.

The reaction between an organomagnesium compound or an organomagnesium lead body and a chlorosilane compound can be carried out using an inert reaction medium, such as a fatty acid such as hexane or heptane, a hydrocarbon such as benzene, toluene, xylene, an aromatic hydrocarbon such as cyclohexane, The reaction can be carried out in an alicyclic hydrocarbon such as methylschifftetrahexane, an ether medium such as ether or tetrahydrofuran, or a mixed medium thereof. In terms of catalyst performance, aliphatic hydrocarbon media are preferred. The reaction temperature can be from 20 to 150°C, but in view of the progress of the reaction, it is preferably carried out at a temperature higher than the boiling point of chlorosilano or higher than 40°C. There is no particular restriction on the reaction ratio of the two species, but usually 0.01 to 1 part of chlorosilane is used per mole of magnesium component.

It is preferably in the range of 1 to 10 mol, particularly preferably 0.2 to 5 mol, of chlorsila yhE per 1 mol of the organomagnesium component.

Regarding the reaction method, there is a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted (method ①), or a chlorosilane component is charged into the reaction zone in advance, and then an organomagnesium component is introduced into the reaction zone. There is a method of reacting (method @), or a method of preparing the organomagnesium component in advance and adding the chlorosilane component (method θ), but the latter two are preferable, and particularly method [Co.] gives preferable results. .

The reaction of components (1) and (II) can also be carried out in the presence of an inorganic carrier. As the inorganic carrier, the following can be used.

(1) Inorganic oxide, (11) Inorganic carbonate, silicate, sulfate, (Ill) Inorganic hydroxide, Double salt, solid solution or mixture consisting of (lv) (1) to Qll), Specifications of the inorganic carrier Examples include silica, silica alumina,
Alumina, alumina, magnesia, doria, titania, zirconia, calcium phosphate, barium sulfate, calcium sulfate, magnesium silicate, magnesium/calcium/aluminum silicate) ((Mg-Ca)O
・At203 ・5Si02 'nH2O], potassium aluminum silicate (x2o-, m, o3・6Si02
], Mica [R20・3At20.・6Si02・220), magnesium iron silicate [(Mg, Fe)28
104), aluminum silicate (At203.810.
), calcium carbonate, etc., and particularly preferably silica or silica/alumina. The specific surface area of the inorganic carrier is preferably 20 m''/t or more, particularly preferably 90!+1''/f or more.

Next, regarding component (2) to be reacted with the solid, component (1)
) -(+) -Alcohols and thioalcohols used as (b) are used.

When alcohol is used, the effect of hydrogen as a molecular weight regulator during polymerization is good. In particular, C1 to C8 straight chain alcohols are particularly preferred.

Next, the amount of component (2) used is the amount of C- contained in component (1).
The amount is 0.05 to 20 mol, preferably 0.1 to 10 mol, particularly preferably 0.2 to 8 mol, per mol of Mg bond.

The reaction between the solid substance (1) obtained by reacting the organomagnesium component and the chlorosilane compound and the component (2) will be described.

The reaction is carried out in the presence or absence of an inert medium. As the inert medium, any of the aforementioned aliphatic, aromatic or alicyclic hydrocarbons may be used. There is no particular restriction on the temperature during the reaction, but the reaction is preferably carried out between room temperature and 200°C. Regarding the method of reacting solid (1) and component (2), there is a method (p) in which component (2) is added to solid material (1) in a suspended state (fluid state). Method (2) of adding υ and method (III) of adding both at the same time can be considered, but methods (υ and (II)
I) Preferably 0 solid component (2) t-It is also possible to treat with an acid such as a dialkyl aluminum halide after the reaction.

Note that even after the solid substance (1) is reacted with component (2), the content of hydrocarbon groups contained in the solid substance decreases slightly, but it is important that the content remains constant. The titanium compound, vanadium compound, zirconium compound, and honeycomb compound to be reacted with the solid substance reacted with component (2) will be explained. Titanium, vanadium, zirconium, hafnium halogenated el, oxyhalides, alkoxyhalides, alkoxides and mixtures thereof are used.

As a titanium compound, the general formula Ti (OR town 8X4-1
A titanium compound represented by the compound represented by l is used. In the formula, S is a number satisfying O≦S≦4; i) The hydrocarbon group having 1 to 20 carbon atoms represented by R11 includes methyl, ethyl, h, and 1so-propyl, n-#11
10-1 Bee- and tert-butyl, n+.

115G -z Sec -e and tert-amyl, neo-pentyl, hexyl, 2-ethylhexyl,
heptyl, octyl, decyl, undecyl, dodecyl,
Aliphatic hydrocarbon groups such as tridecyl, tetradecyl, hexitedecyl, octadecyl, allyl, cyclohexyl, 2
Examples include alicyclic hydrocarbon groups such as -methylcyclohexyl and cyclopentyl, aromatic hydrocarbon groups such as phenyl, cresyl, xylyl, and naphthyl, but aliphatic hydrocarbon groups are preferred. It is possible to use a mixture of two or more titanium compounds selected from the above.

Examples of the halogen represented by X include chlorine, bromine, and iodine, with chlorine being preferred.

As a vanadium compound, VCt4. VOC23+V
OCt2(On-C,H,) r VOCl(On-C
4H,) #VO(On-C4H,)3°VCLs(
OCz Hs ) etc. are used, and VCt, , VOC
l is preferred.

As a zirconium compound, ZrCl2゜Zr (O
n-C4Hg)4eZr (OCIH,), v
Zr (OCzHs), tZr (On-Pr
)4*ZrO(CH3Coo)2 etc. are used.

Hafnium compounds include Hf C14* Hf (
0nBu )4 eHf (OPr )4 or the like is used.

For the reaction between a solid substance and a titanium compound, etc., an inert reaction medium is used, or in the case of a titanium compound, etc., gold is used as a reaction medium. Examples of the inert reaction medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexyl and methylcyclohexyl. preferable. There is no particular restriction on the reaction temperature, but it is preferably carried out in the range of room temperature to 150°C.

A mixture or reactant of a titanium compound, a vanadium compound, a zirconium compound, and a hafnium compound will be explained.

As for the mixture, two or more types of compounds may be mixed in a large amount, or two or more types of compounds may be mixed in the presence of a solid substance. The mixing is preferably carried out in diluted form in an inert solvent such as a hydrocarbon solvent, but it is also possible to use two or more components as a medium.

Regarding the reactants, two or more compounds are used by reacting them in advance, but it is also possible to use a hand grinding machine such as a zero-ball mill, which allows the reaction to be carried out in the presence or absence of an inert hydrocarbon solvent. be. As the pulverization method, well-known mechanical pulverization means such as a rotary ball mill, a vibrating ball mill, and an impact ball mill can be employed. The grinding time is 0.5 to 100 hours, preferably 1 to 30 hours, and the grinding temperature is 0 to 200°C, preferably 10 to 150°C.

It is also possible to add an organometallic compound during the reaction of the solid substance with the titanium compound, vanadium compound, zirconium compound, or no-funium compound, or before or after the reaction. As the organometallic compound to be present when the solid substance and the titanium compound are reacted, an organoaluminum compound or an organomagnesium compound can be used. The organoaluminum compound and t and te have the general formula AtR'tZs
-t (in the formula, 10 is a hydrocarbon group having 1 to 10 carbon atoms, 2 is) Sogen, hydrocarbyloxy group, siloxyg,
A group selected from hydrogen s, where t represents a number satisfying 1≦t≦3. ) and a mixture of organoaluminum compounds selected therefrom,
Reactants can be used.

Preferred organic aluminum compounds include triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, trimybutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, imprenylaluminum, Diethylaluminium hydride, diisobutylaluminum rhamnohydride, diethylaluminium chloride, di-l propylaluminum chloride, di-n-propylaluminum chloride, diisobutylaluminum chloride,
Sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, hep-propylaluminium chloride, sesqui-n-propylaluminum chloride, ethylaluminum dichloride, n-
Examples include propylaluminum dichloride, i-propylaluminum dichloride, butylaluminum dichloride, diethylaluminum bromide, diethylaluminium iodide, and mixtures thereof.

The solid catalyst component thus obtained has an extremely large surface area as indicated by the so-called BET specific surface area, has a high olefin polymerization activity, and has excellent particle properties of the resulting polymer.
It has great characteristics such as excellent copolymerizability.

Although it is not clear what mechanism this feature is based on, it is thought to be based on the use of an active organomagnesium-containing solid obtained by the reaction of a specific magnesium component and H-8t-CL bonded gold-containing chlorosilane.

It is more preferable that the solid catalyst thus obtained is treated with a component selected from a quaternary titanium compound, an aluminum halide, a silicon halide, and a tin halide.

As the titanium tetrahalide compound, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and mixtures thereof are used.

Examples of aluminum halides include aluminum trichloride, ethyldichloraluminum, methyldichloraluminum, propyldichloraluminum, methyldichloraluminum, ethylaluminum sesquichloride, diethylaluminum chloride, aluminum tribromide, ethylaluminum dipromide, Examples include aluminum trichloride and ethylaluminum diiodide, and mixtures thereof can also be used.

As the silicon halide and tin halide, silicon tetrahalide, monoalkyl tin halide, tin tetrahalide, etc. are preferred. Particularly preferred compounds are
They are alkylaluminum dichloride, alkylaluminum sesquichloride, dialkylaluminum chloride, silicon tetrachloride, and tin tetrachloride.

Regarding the treatment with these compounds 11, they can be used themselves as reaction solvents or can be treated in inert solvents. The amount used in the treatment is not particularly limited, but it is at least 1 gram, o, oos per liter of the solid catalyst component.
000 mol or less is preferable.

Although the solid catalyst of the present invention is useful as a catalyst for olefin polymerization as it is, it becomes an even more excellent catalyst when combined with a specific metal compound.

The specific metal compound is preferably a compound of Groups 1 to 1 of the periodic table, particularly a complex containing an organoaluminium compound and an organomagnesium compound.

The organoaluminum compound has the general formula ALR" t
Z 5-t (wherein, R11 is a carbon ai -20tv
A compound represented by a hydrocarbon group (2 is a group selected from hydrogen, halogen, alkoxy, allyloxy, or siloxy group, and t is a number from 2 to 3) is used as a compound or compound. In the above formula, the number of carbon atoms represented by RIO is 1 to
The 20 hydrocarbon groups include aliphatic hydrocarbons, aromatic hydrocarbons, and Bd cyclic hydrocarbons.

゛ These compounds t-Specifically, for example, triethylaluminum, tri-normalpropylaluminum, triisobutylaluminum, tri/#-v
/l/l/Butylaminium hydride, isobutylaluminum, trihexylaluminum, trioctylaluminum, triethylaluminum, tridodecylaluminum, trihexadecylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide , diisobutylaluminum ethoxide, dioctylaluminum ester, diisobutylaluminum octerosilane, -diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, a 7v minium isoprenyl, etc., and mixtures thereof are recommended.

A highly active catalyst can be obtained by combining these alkylaluminum compounds with the solid catalyst described above, and bamboo trialkylaluminum and dialkyl aluminum hydrides are preferred because they achieve the highest activity.

As a complex containing organomagnesium, the above-mentioned general formula M
It is a complex represented by α-cho/R”pR”qXrYs.

α, β*p+q, r, azMi1. Although R'', X, and Y have already been described, since a hydrocarbon-soluble complex is desirable, β/α is preferably O, S to 10, and a complex in which %KM is aluminum is preferred.

The solid catalyst component and the organometallic compound may be added into the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. Also, the ratio of both components to be combined is as follows: solid catalyst l
It is preferable to use the organometallic compound in an amount of 1 to 3000 mmol relative to t.

Olefins that can be polymerized using the catalysts of the invention are alpha olefins, especially ethylene. Furthermore, the catalyst of the present invention can also be used for highly stereoregular polymerization of propylene by combining electron donor treatment as described above. It is also possible to use ethylene or propylene to polymerize in the coexistence of monoolefins such as propylene, butene-1, and hexene-1, and dienes such as butadiene and imprene, and furthermore, to polymerize dienes. It is.

As the polymerization method, usual suspension polymerization, solution polymerization, gas phase polymerization, and high pressure polymerization (approximately 3000 kg/cri or less) are possible.

The catalyst is introduced into the reactor together with a polymerization solvent, e.g., an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, and an inert atmosphere. 1 to 300 ethylene or propylene below
The polymerization may be carried out at a temperature ranging from room temperature to 300° C., but is not limited in any way by these examples. In addition, MI in the examples represents melt index, and from ASTM D-1238K, temperature 1
9 (Ic, measured under the conditions of 7 at a load of 2.16).

PR means the quotient obtained by dividing the value measured at a temperature of 190°C and a load of 21.6 Kf by MI, and is one of the measures of molecular weight distribution.
or propylene) pressure I Kg/al and the amount of polymer produced 2.

Example 1 (1) Synthesis of organomagnesium component Metallic magnesium powder 502 was weighed out in a flask with a volume of 1zt under a nitrogen atmosphere, 30 mmot of butoxyaluminum dichloride and 310 mm of n-octane were added, and the temperature was raised to 100°C. Shilhi. n-butyl chloride 1
mot, butyl bromide 1 mot and n-octane 0
．． 7 tons of bath liquid was added dropwise over about 2 hours while stirring, and after the addition was completed, the reaction was continued with stirring for an additional 1 hour. As a result of separating the solid part in the furnace and analyzing the F liquid, it was found that the Mg g1 degree was 0.
87 mot/l, At concentration 0, 017 mot/L 400 ml of this P solution was weighed into an It flask, and 140 ml of n-dibutyl alcohol was added under stirring at 0°C.
mot was added, and the mixture was further stirred and reacted at 30° C. for 1 hour.

As a result of analyzing this reaction solution, the composition AtMga (Cz
Hs)s (n-C4Hg)1゜(on-c4H,),
. and the compound concentration was 0.87 mot/L.

(2) Synthesis of a solid substance by reaction with a chlorosilane compound A 2-t capacity flask equipped with a dropping funnel and a condenser was sufficiently degassed and dried, and trichlorosilane (H
8i CL3) 1 mob/L IIF) n -
Charge 1 mot of heptane solution, and add 0.5 mot of the above organomagnesium complex solution from the dropping funnel while keeping it at 65°C.
mot was added dropwise over 1 hour, and the mixture was further reacted at 65°C for 1 hour with stirring. Washing with Hexa/5 times was performed by decantation to obtain a solid material slurry. As a result of separating and drying this solid and analyzing it, it was found that Mg 9.22 per solid 1
mmot, CL 19.14 mm0t# St 1
．． It contained 68 mmot + 0.67 mmot of alkyl groups.

(3) Synthesis of solid catalyst The slurry containing the above solid 201 was reacted with 100 ml of butyl alcohol + 2 t of n-hexane at 80° C. for 1 hour under stirring in a pressure-resistant container purged with nitrogen, and
The supernatant was removed by decantation and further washed twice with 300 Wlt of n-hexane.

This slurry was kept at 10°C, 20 mmot of tetra-n-butoxytitanium was introduced, and the slurry was allowed to react by pressing for 30 minutes.Then, the temperature was raised to 60°C, the reaction was carried out for 2 hours, and after cooling, the supernatant was removed by decanting. After washing twice with 300-hexane, a hexane solution of titanium tetrachloride (
2mo4/l) 300tne was added thereto, and the mixture was reacted at 130°C for 2 hours with stirring. After the reaction was completed, the supernatant was removed by decanting, and 300 g of hexane was added. The titanium contained in the solid lf was 2.6% by weight.

(4) Polymerization of ethylene The solid catalyst component 5η synthesized in (3) and triinobutylaluminum 0.25 mmoA were dehydrated and degassed together with n-hexane 800-, and the inside was dehydrated and dried to form 7'C1,5.
t Introduced into an autoclave, butene-1, 120 mmo
t, raise the internal temperature to 80℃, and add 0.8Kg of hydrogen.
The mixture was pressurized at a pressure of /c#t and then ethylene was added to give a total pressure of 4.6 Ky7a/l.

Polymerization was carried out for 1 hour while maintaining the total pressure at a gauge pressure of 4.0 to 7/2 by replenishing ethylene, resulting in polymer 172
I got 1. Catalyst efficiency is 1320 Ky-PE/1~Ti
, MI was 1.4f/10-. The bulk density of the polymerized powder was 0.48 f/d, and the 105-149 fi powder was 91 wt or more.

Examples 2 to 4 Polymerization of a solid substance, a solid catalyst, and ethylene was carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used. The results are shown in Table 1.

Effects below: The first feature of the present invention is that the catalyst efficiency is high per gram of titanium per catalyst. 1320 for Example 1
~-PE/g-Ti and 34400 g-PE/g-
A solid catalyst component is obtained at °C.

The second feature of the present invention is that the obtained polymer particles have a large bulk density. ! 5 In the case of turbidity polymerization, (Example 1
) 0.48 f/art is obtained.

The third feature of the present invention is that only a small amount of hydrogen is needed as a molecular weight regulator during polymerization.

The fourth feature of the present invention is that the copolymerization effect during olefin copolymerization is good. Shown in the Examples.

The characteristic feature of the present invention is that the olefin polymer or olefin copolymer has a good hue.

The sixth feature of the present invention is that the molecular weight distribution of the polymer is widened.

Claims (1)

[Claims] 1 [A] (1) (i) (a) General formula M_αMg_βR^
1_pR^2_qX_rY_s (where M is Al, Zn
, B, Be, Li atom, R^1, R^2 are the same or different hydrocarbon groups of C_1 to C_1_0, X, Y are the same or different OR^3, OSiR^4R^5R^6,
NR^7R^8, SR^9, representing a halogen group,
R^3, R^4, R^5, R^6, R^7, R^8 are hydrogen atoms or C_1 to C_1_0 hydrocarbon groups,
R^9 is a hydrocarbon group of C^1 to C_1_0, and α≧
0, β>0, p, q, r, s≧0, m is the valence of M, p
+q+r+s=mα+2β, 0≦(r+s)/(α+β
)≦1. ) Organomagnesium 1
moles, or (a) and (b) ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof;
Alternatively, 1 mol of a component reacted with an electron donor selected from alcohol, thioalcohol, and amine, and (ii) general formula HaSiCloR^1^0-(a+b)
(In the formula, a, b are numbers larger than 0, a+d≦4, 0<a
≦2, R^1^0 represents a hydrocarbon group having 1 to 10 carbon atoms) H-Si bonded gold-containing chlorosilane compound 0
．． 01 to 100 mol in the presence or absence of an inorganic carrier selected from the following (i) inorganic oxide (ii) inorganic carbonate, silicate, sulfate (iii) inorganic hydroxide (iv) (i) A double salt, solid solution or mixture consisting of (iii). (2) 0.0% alcohol and/or thioalcohol per mole of C-Mg bonds contained in the reacted solid;
A solid catalyst component obtained by reacting a solid obtained by reacting 05 to 20 moles with one or more components selected from (3) titanium compounds, vanadium compounds, zirconium compounds, hafnium compounds, and mixtures or reactants thereof. , and further (4) a solid catalyst component [B] an organometallic compound component obtained by treatment with a component selected from a titanium tetrahalide compound, an aluminum halide, a silicon halide, and a tin halide, Olefin polymerization method 2 in which a catalyst consisting of A] and [B] is brought into contact with an olefin, [A] 0.1 to 10 mol of component (2) per 1 mol of C-Mg bond in the solid of (1) Olefin polymerization method 3 according to claim 1, [A] A patent in which component (2) is present in an amount of 0.2 to 8 moles per mole of C-Mg bond in the solid of (1). Olefin polymerization method 4 according to claim 1, general formula M_αMg_βR^1_pR^2_qX_r
In the organomagnesium component represented by _Ys, M
Claim 1 in which is Al, B, Zn or Be
Olefin polymerization method 5 according to any one of Items to Items 3, general formula M_αMg_βR^1_pR^2_qX_r
In the organomagnesium component represented by Y_s, α>
0, 0.5≦β/α≦10, 0≦(r+s)/(α+β
)≦0.8, a method 6 for polymerizing an olefin according to any one of claims 1 to 4, comprising a solid and a component selected from a titanium compound, a vanadium compound, a zirconium compound, and a hafnium compound. Olefin polymerization method 7 according to any one of claims 1 to 5, wherein the reaction is carried out in the presence of an organometallic compound, a titanium compound, a vanadium compound, a zirconium compound, a hafnium compound, or a mixture thereof. The method for polymerizing an olefin according to any one of claims 1 to 6, wherein the component (3) selected from the reactants is a titanium compound or a component containing a titanium compound.