JPS5919568B2 - Olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymerization catalyst for olefins, particularly propylene, butene-1, 3-methylbutene-1, pentisol-1
The present invention relates to catalysts suitable for the stereoregular polymerization of olefins such as , 4-methylpentene-1, etc., or for the copolymerization of said olefins with ethylene or other olefins.

The Ziegler-Natsuta catalyst system, which combines a titanium halide and an organoaluminium compound, is widely used industrially as a catalyst for producing ιA stereoregular polyolefins.

When olefins such as propylene are polymerized using this catalyst system, the yield of stereoregular polymer as indicated by the fraction of boiling heptane-insoluble polymer is relatively high, but the polymerization activity is insufficient and the resulting polymer is A step to remove catalyst residue is required. Polymer Letters,. VOl3. , P
855-857, (1965), it is shown that after reacting magnesium chloride and titanium tetrachloride, triethylaluminum and optionally additives are added to polymerize propylene. It has been described that the use of an electron donor such as ethyl acetate as an agent improves the stereoregularity of the resulting polymer.

Furthermore, in Japanese Patent Publication No. 39-12105, particles of magnesium chloride, cobalt chloride, etc. are coated with titanium tetrachloride, etc., and then a metal alkyl such as triethylaluminum, diethylaluminum chloride, etc. is combined and polymerized, and ethyl acetate, etc. It has been shown that the insoluble content of the polymer can be increased by adding additives such as
It is also described that metal salts such as magnesium chloride can be used after grinding, and that novel catalysts can be prepared by adding a solution of titanium tetrachloride or the like to a supported metal salt and shaking the mixture together. There is. However, when polymerization is performed using this catalyst system, both the polymerization activity and the yield of stereoregular polymer are insufficient. In recent years, many catalyst systems have been proposed based on this catalyst system.

The present inventors have made extensive studies on the magnesium halide component, and have determined that the solid obtained by treating the magnesium halide with dialkyl sulfite is treated with titanate ester and nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester. Alternatively, the solid obtained by reacting and/or pulverizing with a hydrocarbon-based carboxylic acid ester is further added to the L-Cl bond (
A solid catalyst component (4) obtained by treatment with a compound having (L represents a specific metal), a nitrogen-containing organometallic compound,
It was discovered that a catalyst component in combination with component (8) containing a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester has excellent performance as an olefin polymerization catalyst, and the present invention was achieved.

That is, the present invention provides (A)(1)(a) magnesium halide and (b)
) Solid obtained by reacting and/or pulverizing dialkyl sulfite (2) General formula Ti (0R1), (wherein R1 is a hydrocarbon group having 1 to 20 carbon atoms.

) titanate ester (3) nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic ester or hydrocarbon carboxylic ester (1), (2). The solid obtained by reacting and/or pulverizing (3) is (4) L-X
Compounds containing bonds (L is boron, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth,
It is an element selected from mercury and tellurium, and X represents a halogen element.

) and (B) an organometallic compound and components (4) and (8) consisting of a nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester. It relates to polymerization catalysts.

The first feature of the present invention is that the resulting polymer has high stereoregularity.

As is clear from the examples below, the proportion of the stereoregular polymer in the total polymer (hereinafter referred to as the total) & in the case of polymerization of propylene in ζ hexane solvent, it is actually over 95%. reach The second feature of the present invention is that the catalyst efficiency is high per titanium and per solid catalyst component.

As is clear from the examples below, in the case of propylene polymerization in hexane solvent, 8730P-polypropylene (PP)/Fi-solid catalyst, 4160007-P
P/7-titanium is obtained and in the case of polymerization of propylene in liquid propylene (Example 8), the catalyst efficiency is 5
90000t-PP/f-titanium, 12400y-PP
/r - solid catalyst or more can be easily obtained. From the activity of the catalyst of the present invention, Ti and Cl in the polymer produced during polymerization
The contents are very low, for example 2 ppm and 55 ppm in Example 8, respectively.

This indicates the following. The polymers polymerized using the catalyst of the present invention enable a demineralization process without the need to remove catalyst residues, and are also highly stereoregular and have a low amorphous polymer content. That is, the catalyst system of the present invention has extremely high performance. The third feature of the present invention is that when hydrogen is used as a molecular weight regulator during the production of a secondary polymer, only a small amount of hydrogen is needed to obtain a commonly used molecular weight range.

The fourth feature of the present invention is that there is little scale adhesion to the reactor and other parts during polymer production.

The fifth feature of the present invention is that the particle size of the polymer is good,
It is possible to produce polymers with high bulk density.

As is clear from the examples below, the bulk density is 0.4187.
/ml or more can be easily obtained. Each component and reaction conditions used for preparing the catalyst of the present invention will be explained. First, component (A) (1) (a) magnesium halides include MgF2, MgCl2, MgBr2, MgI
Among them, MgCl2 is particularly preferred in the present invention.

Component (b) dialkyl sulfite includes dimethyl sulfite, diethyl sulfite, dipropyl sulfite, dibutyl sulfite, diamyl sulfite, and mixtures thereof.

Among these, diethyl sulfite, dipropyl sulfite, and dibutyl sulfite are preferred. The amount of dialkyl sulfite relative to magnesium halide is 0.01 to 2 dialkyl sulfites per mol of magnesium halide.
The mole amount is preferably 0.05 to 1.2 moles.

The method of treating magnesium halide (a) with dialkyl sulfite (5) will be explained separately for the case of reacting in a liquid phase and the case of pulverization.

First, when processing in the liquid phase, an inert reaction medium is used.
For example, hydrocarbon solvents such as hexane, heptane, cyclohexane, methylcyclohexane, benzene and toluene, and ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, and tetrahydrofuran can be used. The concentration of dialkyl sulfite is 0.0
It is possible to use 2 to 2.0 m01/l, but 0.05 to 1.
5m01/1 is preferable, and the X,Σ reaction temperature is not particularly limited, but is usually 10 to 180°C, and a temperature range of 50 to 130°C gives preferable results. Next, the case of pulverization will be explained.

Grinding methods include rotary ball mill, vibrating ball mill,
Known mechanical grinding means such as impact ball mills can be employed. In the case of pulverization, the dialkyl sulfite itself may be added to the magnesium halide and then pulverized, or the above-mentioned inert hydrocarbon solvent may be added together with the dialkyl sulfite and the magnesium halide and subjected to the pulverization.

It is also possible to adopt a method in which a magnesium halide is treated with dialkyl sulfite and then pulverized. The grinding time can be 0.5 to 200 hours, but usually 1 to 9 hours.
0 time is good, and there is no particular restriction on the grinding temperature, but -10~
It can be carried out at 150°C, preferably 0 to 80°C. Next, nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic acid esters or hydrocarbon carboxylic acid esters will be explained.

Examples of nitrogen-containing heterocyclic carboxylic esters include pyrolic acid carboxylic esters, indoles carboxylic esters, carbazole carboxylic esters, oxazole carboxylic esters, thiazole carboxylic esters, imidazoles carboxylic esters, and pyrazole carboxylic esters. Ester, pyridine carboxylic acid ester, phenanthridine carboxylic acid ester, anthrazoline carboxylic acid ester, phenanthroline carboxylic acid ester, naphthyridine carboxylic acid ester, oxazine carboxylic acid ester, thiazine carboxylic acid ester, pyridazine carboxylic acid ester Preferred examples include methyl ethyl pyrrole-2-carboxylate, propyl and butyl pyrrole-2-carboxylate, methyl ethyl pyrrole-3-carboxylate, propyl and butyl pyrrole, and pyridine. Methyl-2-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-3-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-4-carboxylate, ethyl, propyl, butyl and amyl, pyridine-2-carboxylate・Methyl 3-dicarboxylate Ethyl, methyl pyridine-2,5-dicarboxylate
Ethyl, methyl pyridine-2,6-dicarboxylate, methyl ethylpyridine-3,5-dicarboxylate, ethyl, methyl quinoline-2-carboxylate, ethyl, ethyl dimethylpyrrolecarboxylate, ethyl N-methylpyrrolecarboxylate, 2- Ethyl methylpyridinecarboxylate, ethyl piperidine-2-carboxylate, ethyl piperidine-4-carboxylate, ethyl pyrrolidine-2-carboxylate, L-
Proline ethyl ester, isonicotipenic acid ethyl ester, D●L-pipecolinic acid ethyl ester,
Examples include nipecotinic acid ethyl ester.

Examples of sulfur-containing heterocyclic carboxylic acid esters include thiophenes carboxylic esters, thianaphthenes carboxylic esters, isothianaphthenes carboxylic esters, benzothiophenes carboxylic esters, phenoxathiines carboxylic esters, benzothianes carboxylic esters, and thiaxanthene. Examples include thiophene-2-carboxylic acid esters, thioindoxyl-type carboxylic acid esters, and more specifically, methyl, ethyl, propyl, butyl and amyl thiophene-2-carboxylate, and thiophene-3-carboxylate.
Methyl, ethyl, propyl, butyl and amyl carboxylate, methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate, ethyl, methyl thiophene-2,5-dicarboxylate, ethyl,
2-thienyl acetate methyl, ethyl, propyl, butyl,
Methyl 2-thienyl acrylate, ethyl, methyl 2-thienylpyrupine, ethyl, methyl thianaphthene-2-carboxylate, ethyl, methyl thianaphthene-3-3-carboxylate, ethyl, methyl thianaphthene-2,3-dicarboxylate, ethyl , methyl 3-oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenyl acetate, ethyl, methyl 3-thianaphthenyl acetate, ethyl, methyl benzothiophene-2-2-carboxylate, ethyl, methyl benzothiophene-3-carboxylate, ethyl, Examples include methyl benzothiophene-4-carboxylate, ethyl, methyl phenoxathiin-1-1-carboxylate, ethyl methyl phenoxathiin-2-2-carboxylate, ethyl, methyl phenoxathiin-3-carboxylate, and ethyl. More preferred are methyl, ethyl, propyl and butyl thiophene-2-carboxylate, thiophene-3-carboxylate.
Methyl carboxylate, ethyl, methyl 2-thienyl acetate,
Examples include ethyl, methyl 2-thienyl acrylate, ethyl, methyl thianaphthene-2-carboxylate, and ethyl. Examples of the oxygen-containing heterocyclic carboxylic acid esters include heptaranes carboxylic esters, dihydrofurans carboxylic esters, benzofuran carboxylic esters, coumarans carboxylic esters, pyrans carboxylic esters,
Examples include pyrone carboxylic acid esters, coumarin carboxylic acid esters, isocoumarin carboxylic acid esters, and the like.

For example, methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate, ethyl, propyl, butyl, methyl furan-2●3-dicarboxylate, methyl furan-2,4-dicarboxylate, Methyl furan-2,5-dicarboxylate, methyl furan-3,4-dicarboxylate, methyl 4,5-dihydrofuran-2-carboxylate, methyl tetrahydrofuran-2-carboxylate, methyl coumarate (benzofuran-2-carboxylate) methyl coumarate), ethyl coumarin-2-carboxylate, methyl coumarate, ethyl, methyl comanate, ethyl, 5-hydroxy-4-ethoxycarbonylcoumarin, 4-ethoxycarbonylisocoumarin, ethyl 3-methylfuran-2-carboxylate, Examples include isodehydroacetic acid, methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate, ethyl, propyl, butyl, methyl 4,5-dihydrofuran-2-carboxylate, ethyl, Methyl tetrahydrofuran-2-carboxylate, methyl coumarate, ethyl etc. give preferable results. Examples of hydrocarbon carboxylic acid esters include ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl glopionate, ethyl n-butyrate, ethyl valerate, ethyl caproate, ethyl n-heptanoate, and oxalic acid. Di-n-butyl, monoethyl succinate, diethyl succinate, ethyl malonate, di-n-butyl maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, n-benzoate and i-Propyl, n-, i-, Sec- and tert-butyl benzoate, methylene p-toluate, ethyl p-toluate, 1-propyl p-toluate, n- and i-amyl toluate, o- Ethyl toluate, m
-ethyl toluate, methyl p-ethylbenzoate, p-
Examples include ethyl ethylbenzoate, methyl anisate, ethyl anisate, 1-propyl anisate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, methyl terephthalate, and among these, aromatic carboxylic acid esters are preferred. , especially methyl benzoate, ethyl benzoate, p
-Methyl toluate, ethyl p-toluate, methyl anisate, and ethyl anisate are preferred.

Next, the compound (A) (4) containing an L-Cl bond will be explained. In the above formula, the element represented by L is selected from boron, silicon, germanium, tin, phosphorus, antimony, bismuth, mercury, and tellurium, with silicon, germanium, and tin being more preferred. Although there are many chlorine compounds explained above, L-
Compounds with Cl bonds are those which are soluble in hydrocarbon or ethereal media, which gives favorable results.

Preferred specific compounds will be described. First, SiCl4 is mentioned as a silicon compound.

Next, as -SiCl3 type compounds, HSiCl3,
=CHSiCl3, CH3CH=CHSiCl3, and the like.

Next, as for the SiCl2 type compound, \-4-1J'O-1W)-VlV Examples include (C4H,)3SiC1.

In addition, Cl3SiCH2SiHCl2, CH3CH(SiHCl2)2, CH3CH(SiCl
3) 2nd grade etc.

Next, as chlorine compounds, germanium tetrachloride, synchrodimethylgermanium, tin tetrachloride, boron trichloride,
Examples include mercuric chloride, tellurium tetrachloride, phosphorus trichloride, antimony trichloride, etc., but among these, more preferred are silicon chloride compounds, tin tetrachloride, and germanium tetrachloride, and more particularly preferred are is the above H-Si
It is a chlorinated silicon compound containing bonds.

The above solid substance (4) and titanium compound 2), nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3) prior to treatment with a compound containing an L-Cl bond. The reaction of the above solid substance (
A method of reacting 1) with a titanium compound (2) or a heterocyclic carbo-induced ester or a hydrocarbon carboxylic acid ester (3) in a liquid phase or a gas phase [combining reaction in a liquid phase or gas phase and pulverization] Any method can be used, such as method (2) and method 3 using pulverization.

Regarding method (1), solid material (4), titanium compound (
2), a method (1) of simultaneously reacting a heterocyclic carboxylic acid ester or a hydrocarbon carboxylic acid ester (3);
Or solid substance (4) and titanium compound V! J. Method (2) of first reacting 2) and then reacting the heterocyclic carboxylic acid ester (2), or method (2) of first reacting the solid substance (1) with the heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3). There is a method (3) in which the titanium compound (2) is then reacted.

Although either method is possible, the latter two methods are preferred, and method 3 is particularly preferred. For method (2), the above solid substance (1), titanium compound (2), heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3)
A method of pulverizing the solid obtained by simultaneously reacting with fire (synthesis method 1)
), or a method in which the solid material (1) is first reacted with a titanium compound, and then a heterocyclic carboxylic acid ester or a hydrocarbon carboxylic acid ester is reacted, and the resulting solid is pulverized (synthesis method 2), or a solid material There are methods such as first reacting (1) with a heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3), and then reacting with a titanium compound (2) and pulverizing the resulting solid (synthesis method 3). .

Although either method is possible, the latter two methods are preferred, and particularly synthesis method 2 gives preferable results. For method 0], the above solid substance (1), titanized compound (2)
, a method of simultaneously pulverizing a heterocyclic carboxylic acid ester or a hydrocarbon carboxylic acid (synthesis method 1),
1) and the titanium compound (3), the heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3) is crushed.
) (synthesis method 12), after pulverizing the above solid substance (1) and heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3), adding titanium compound 2) and pulverizing. Synthesis methods 1 and 3 are preferred, with 3 being particularly preferred.

2 The above method [
The solid component synthesized by Natsio and 3 was converted into L-Cl
For the treatment with bond-containing compound (4), method C1). (2) and (3) will be explained. First, by method (1)-1, [η-2, α]-3, 2
The resulting solid component is converted into a compound containing an L-Cl bond (
b) can be adopted.

Next, a method can be adopted in which the solid components synthesized by methods 1, 2, and 2-3 are each treated with a compound (4) containing an L-Cl bond, but 3, The latter two methods are preferred.

Alternatively, a method can be adopted in which the solid components synthesized by methods (3)-1, 3-3, and [$-2] are each treated with a compound (4) containing an L-C1 bond. is preferred, and 3-3 is particularly preferred.

3. Next, the various reactions and pulverization operations described above will be specifically explained. (!) The above solid substance (
1). Or, the reaction between the reaction product of this solid substance η and the heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3) and the titanium compound 4C (odor) will be explained.

The reaction is carried out using an inert reaction medium.

Examples of the inert reaction medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Group hydrocarbons are preferred. There are no particular restrictions on the temperature during the reaction and the concentration of the titanium compound, but preferably 60°C.
At a temperature above and a titanium compound concentration of 0.0001~
2 mol/liter, more particularly preferably 0.0005
~1.5 mol/liter. Regarding the reaction molar ratio, 0.0 to 1 mole of magnesium component in the solid substance
Preferable results are obtained when the titanium compound is present in an amount of 0.01 to 2 mol, more preferably 0.01 to 1 mol.
(Ii) The reaction between the solid substance (d) 1) or the reaction product of this solid substance and the titanium compound (2) and the heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3) will be explained.

The reaction is carried out using an inert reaction medium.

As the inert reaction medium, any of the above-mentioned aliphatic, aromatic, and alicyclic hydrocarbons may be used. The temperature during the reaction is not particularly limited, but is preferably in the range of room temperature to 100°C. When reacting the solid substance (1) with the heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester (3), there is no particular restriction on the reaction ratio of the two components, but it is preferably contained in the magnesium-containing solid component. The recommended amount of heterocyclic carboxylic acid ester or hydrocarbon carboxylic acid ester is 0,001 mol to 50 mol, particularly preferably 0.005 mol to 10 mol, per gram atom of magnesium. Solid substance (1) and titanium compound (
When reacting the reaction product with 2) and the heterocyclic carboxylic ester or hydrocarbon carboxylic acid ester (3),
The reaction ratio of the two components is 0.01 mol to 100 mol, particularly preferably 0.1 mol to 10 mol of the heterocyclic carboxylic acid ester or hydrocarbon carboxylic ester per mol of titanium atom in the solid component. Range is recommended. j)
A method for pulverizing the solid produced in or by the reaction i)-{11) will be explained.

Grinding methods include rotary ball mill, vibrating ball mill,
Known mechanical grinding means such as impact ball mills 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 ℃. (1V) A case in which the solid components obtained in (1) to (g) are treated with a compound containing an L-Cl bond will be described.

The reaction is carried out either by using a reactive reaction medium or by combining the compound containing an L-Cl bond with the reaction medium.

Examples of the inert reaction medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and ether solvents. Aliphatic hydrocarbons are preferred. The concentration of the L-Cl bound gold compound is preferably 2 m01/l or more,
In particular, it is preferable to react using the L-Cl bonded gold compound itself as a reaction medium. There is no particular restriction on the reaction temperature. The composition and structure of the solid catalyst component obtained by the reactions (1) to (1V) above vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, approximately 1% of the solid catalyst component is in the solid catalyst. ~10% by weight titanium and T
It was found to be a solid catalyst containing i-0R1 bonds and having a surface area of 50 to 20 i/7. Next, as the organometallic compound used as the component (g), compounds of Groups 1 to 1 of the periodic table are preferred, and organoaluminum compounds are particularly preferred.
The organoaluminum compound has the general formula AlR2nZ
3-n (wherein, R2 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, hydrocarbyloxy group, and siloxy group, and n is a number from 2 to 3) The compounds represented by are used alone or as a mixture.

In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by R2 includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, tri-n-propylaluminum, triisopropylaluminium, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tri- Hexadecylaluminum, diethylaluminium hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminium chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydro Siloxyaluminum diethyl Ethyldimethylsiloxyaluminum diethyl, aluminum isoprenyl, etc., and mixtures thereof are recommended.

A highly active catalyst can be obtained by combining these alkyl aluminum compounds with the solid catalyst described above, and trialkyl aluminum and dialkyl aluminum hydride are particularly preferred because they achieve the highest activity.

The nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester added to the organometallic compound may be the same or different from the nitrogen-containing, sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester used in the synthesis of the solid catalyst.

Method for adding heterocyclic carboxylic acid ester The two components may be mixed in advance prior to polymerization, or may be added separately into the polymerization system. Particularly preferably, the organometallic compound and the heterocyclic carboxylic acid ester are reacted in advance, and the organometallic compound is separately added to the polymerization system.
The ratio of the two components to be combined is 0.001 to 10 mol, particularly preferably 0.01 mol, of the oxygen-containing, nitrogen-containing or sulfur-containing heterocyclic carboxylic acid ester per mol of the organometallic compound.
~1 mole.

The catalyst consisting of the solid catalyst component of the present invention and a component obtained by adding an oxygen-containing, nitrogen-containing or sulfur-containing heterocyclic carboxylic acid ester to an organometallic compound may be added to the polymerization system under the polymerization conditions, or may be added in advance to the polymerization system. They may be combined prior to polymerization.
The ratio of each component to be combined is as follows:
The amount of the component consisting of the organometallic compound and the oxygen-containing, nitrogen-containing or sulfur-containing heterocyclic carboxylic acid ester is preferably in the range of 1 mmol to 3000 mmol based on the organometallic compound. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins.

Especially around the present invention, propylene, butene-1, benzene-1,
Suitable for the stereoregular polymerization of 4-methylbenzene-1, 3-methylbutene-1 and similar olefins alone. It is also suitable for copolymerizing the olefin with ethylene or other olefins, and for efficiently polymerizing ethylene. Furthermore, in order to adjust the molecular weight of the polymer, it is also possible to add hydrogen, halogenated hydrocarbons, or organometallic compounds that tend to undergo chain transfer. As the polymerization method, usual suspension polymerization, bulk polymerization in a liquid monomer, and gas phase polymerization are possible.

Suspension polymerization involves introducing a catalyst into a reactor together with a polymerization solvent, such as an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene, or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane. , 1 to 2 olefins such as propylene under an inert atmosphere.
Polymerization can be carried out at a temperature of room temperature to 150° C. under pressure at 0 kg/CrA. In bulk polymerization, olefins can be polymerized using a liquid olefin as a polymerization solvent under conditions where the olefin, such as propylene, is a catalyst and a liquid. For example, in the case of propylene, room temperature
The polymerization can be carried out in liquid propylene at a temperature of .degree. C. and under a pressure of 10 to 45 kg/i. On the other hand, gas phase polymerization is carried out at room temperature to 120 kg/Cd in the absence of a solvent under conditions where the olefin such as propylene is a gas.
Under temperature conditions of ℃, it is possible to perform polymerization by using means such as mixing using a fluidized bed, moving bed, or a stirrer to ensure good contact between the olefin such as propylene and the catalyst. . The present invention will be explained below using examples.

The boiling n-heptane extraction residue used in the examples means the residue obtained by extracting the polymer with boiling n-heptane for 6 hours, and the melting index (MFI) & ζASTMD-
According to No. 1238, the temperature is 230℃ and the load is 2.16kg.
Measured under the following conditions. Example 1 (1) Reaction of magnesium halide and dialkyl sulfide 24.0 f of commercially available magnesium chloride, 17.5 f of dipropyl sulfide and 400 ml of n-heptane,
The mixture was placed in a 500 d container and reacted at 80° C. for 2 hours with stirring, and then the solid portion was filtered, washed with purified n-heptane, and dried to obtain solid (A-1).

(4) Synthesis of solid catalyst 18r of the above solid (A-1) was placed in a nitrogen-substituted 11 container along with 600ml of n-heptane and 15mm of ethyl thiophene-2-carboxylate, and the mixture was stirred at 80°C.
React for 1 hour, filter, wash, and dry to obtain a solid (B-
1) was obtained.

This solid 40r and tetra-n-butyl titanate 7.0mm
01, along with 25 steel balls with a diameter of 1011, and a diameter of 9.
5111 Transferred to a steel mill with a length of 100 m1,
The resulting solid was pulverized using a vibrator of 00vib/7nm or higher for 6 hours, and the resulting solid was transferred to a nitrogen-purged container, 40d of methyldichlorosilane was added, and the mixture was treated at 50°C with stirring for 2 hours, followed by purification by filtration. It was washed with n-heptane and dried to obtain a solid catalyst (S-1). As a result of analyzing this solid catalyst, the Ti content was 2.1% by weight. (III)
Slurry polymerization of propylene The above solid catalyst (S-1) 30W9, triethylaluminum 2.4mm01 and ethyl thiophene-2-carboxylate 0.877! MOL was placed in a 1.51 volume autoclave with 0.81 volume of thoroughly degassed and dehydrated hexane and the interior was vacuum dried and replaced with nitrogen, the internal temperature was kept at 60 °C, and propylene was applied to a pressure of 5.0 kg/i. The polymerization was carried out under stirring for 2 hours while maintaining the total pressure at a gauge pressure of 4.8k9/ml, and the results shown in Table 1 were obtained.

Examples 2 to 7 In the synthesis of the catalyst of Example 1, the catalyst was synthesized in the same manner as in Example 1 using the compounds shown in Table 1.
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using the following components, and the results shown in Tables 1 to 1 were obtained.

Comparative Example In the reaction of magnesium chloride and dipropyl sulfide in the synthesis of the solid catalyst of Example 1, ethyl alcohol was used in place of dipropyl sulfide, and ethyl benzoate was used in place of ethyl thiophene-2-carboxylate. After carrying out the reaction in the same manner as in 1, the solid 47 was placed in a container together with 20 ml of titanium tetrachloride and 20 ml of hebutane, and after reacting at 98°C for 2 hours, it was filtered, washed, and dried to obtain a solid catalyst (Ti content 5.0% by weight).

Claims (1)

[Scope of Claims] 1. In an olefin polymerization catalyst consisting of a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, (A) (1) (a) a magnesium halide and (b) a dialkyl sulfite are reacted and/or Or a solid obtained by pulverization (2) containing titanate ester (3) represented by the general formula Ti(CR^1)_4 (wherein R^1 is a hydrocarbon group having 1 to 20 carbon atoms). (4) L-
Nitrogen-containing solid catalyst component (B) organometallic compound obtained by treatment with a compound containing a Cl bond (L is an element selected from silicon, germanium, and tin, and X represents a halogen element) , an olefin polymerization catalyst consisting of components (A) and (B) to which a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester is added. 2. The olefin polymerization catalyst according to claim 1, wherein the dialkyl sulfite in (A)(1)(b) is diethyl sulfite, dipropyl sulfite, or dibutyl sulfite. 3. The olefin polymerization catalyst according to claim 1 or 2, wherein the amount of dialkyl sulfite used in (A)(1)(b) is 0.05 to 1.2 mol. 4 (A) (4) is a silicon compound having an R-Si-Cl bond (where R is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms) The olefin polymerization catalyst according to item 2. 5 The organometallic compound of (B) has the general formula AlR^2_nZ_3_-_n (wherein R^2 is a hydrocarbon group having 1 to 20 carbon atoms, and Z is selected from hydrogen, halogen, hydrocarbyloxy group, and siloxy group). 5. The olefin polymerization catalyst according to any one of claims 1 to 4, which is an organoaluminum compound represented by the following formula, where n is a number of 2 to 3.