JPS595204B2 - Olefin polymerization catalyst - Google Patents

Description

Detailed Description of the Invention 10 The present invention relates to a polymerization catalyst for olefins, particularly for stereoregular polymerization of olefins such as propylene, butene-1, 3-methylbutene-1, pentisol-1, 4-methylpentene-1, or the above-mentioned polymerization catalysts. The invention relates to a polymerization catalyst suitable for copolymerizing olefins with ethylene or other olefins.

The Ziegler-Natsuta catalyst system, which combines titanium halides and organoaluminum compounds, is widely used industrially as a catalyst for the production of 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 not fully satisfactory, and the A step is required to remove catalyst residue from the polymer. Polymer Letters
, VOl, 3, P855-857, (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 when an electron donor such as ethyl acetate is used as an additive, the stereoregularity of the resulting polymer is improved.

In addition, in Japanese Patent Publication No. 39-12105, particles of magnesium chloride, cobalt chloride, etc. are coated with a compound such as titanium tetrachloride, and then a metal alkyl such as triethylaluminum, diethylaluminum chloride, etc. is combined and polymerized. , it has been described that the insoluble content of the polymer can be increased by adding additives such as ethyl acetate, that metal salts such as magnesium chloride are used after being ground, and that solutions such as titanium tetrachloride are used. It is stated that the novel catalyst can be prepared by adding . 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 metal salts, and have determined that the solid obtained by reacting and/or pulverizing a magnesium halide with a dialkyl sulfite is reacted and/or pulverized with a specific carboxylic acid compound and a titanium compound. A catalyst component that is a combination of a solid catalyst component obtained by further treating the obtained solid catalyst component with a tetravalent titanium halide and a component obtained by adding a hydrocarbon carboxylic acid ester to an organometallic compound is an olefin. It was discovered that it has excellent performance as a polymerization catalyst, and the present invention was achieved.

That is, the invention of the present application involves reacting (A) (1) (a) a magnesium halide and (b) dialkyl sulfite in an olefin polymerization catalyst comprising a magnesium halide, a titanium compound, an electron donor, and an organometallic compound. / Or solid obtained by pulverization (2) General formula Ti (
0R1) Titanium compound represented by 8X4-8 (wherein R1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and s is a number such that O<s<4) (3) General formula R2COOMgY
or R2COOAIYZ (in the formula, R2COO has 1 carbon number
~20 carboxylic acid residues, Y, Z are 0R3 or 0SiR
4R5R6, where R3, R4, R5, and R6 may be a hydrocarbon group having 1 to 20 carbon atoms, and Z may be a hydrocarbon group having 1 to 20 carbon atoms.

), which is a compound represented by (1), (2), (3
) is treated with a tetravalent titanium halide and (8) a solid catalyst component obtained by adding a hydrocarbon carboxylic acid ester to an organometallic compound. The present invention relates to an olefin polymerization catalyst consisting of (4) and (B).

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

As is clear from the Examples below, the ratio of stereoregular polymer represented by the n-heptane extraction residue is easily 95% or more. The second feature of the present invention is that the resulting polymer has good moldability.

That is, the melt fluidity of the polymer produced using the catalyst obtained according to the present invention and the consistency of the product after molding are good. 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, Mg
Examples include gI2, and mixtures containing this may also be used.

Particularly preferred in the present invention is MgCl. component(
b) Examples of the dialkyl sulfite include 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.
mol, preferably 0.05 to 1.2 mol.

The method of treating magnesium halide (a) with dialkyl sulfite (b) will be explained separately for a case of reacting in a liquid phase and a case of using 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 0.02
~20m01/l is possible, but 0.05~1.5m
01/l is preferred.

The 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 90 hours, and the grinding temperature is also not particularly limited, but it can be carried out at -10 to 150°C, preferably 0 to 80°C. The tetravalent titanium compound of component (2) has the general formula Ti(0R1)8X4-8 (wherein R1 has 1 carbon number)
~20 hydrocarbon groups, X is a halogen, and s is a number of O<s≦4).

Examples of the hydrocarbon group R1 include ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, stearyl, phenyl, cresyl, and the like, and examples of the halogen include chlorine, bromine, and iodine.
Preferred compounds include compounds where X is chlorine, titanium tetrachloride, Ti(0C2H,)8C14-S, Ti(0C3
H7)8C14-8, Ti(0C4H9)8C14-S
, etc. are mentioned as preferred compounds. Compounds where a=4, for example, Ti(0C2H5)4, Ti(0C3H
7) 4, Ti (0C4H9) 4, Ti (0C, H11)
4, Ti (0C6H13) 1, Ti (0C8H17) 4
,Ti(0C10H21)4,Ti(0C18H37)
4,Ti(02ethy1hexy1)4,Ti(0C
When 6H5)4, Ti(0C3H4.CH3)4 is used, the value of stereoregularity expressed by the n-heptane extraction residue of the resulting polymer is higher, which is preferable. General formula R2CO
OMgY or R2COOAlYZ (in the formula, R2COO is a carboxylic acid residue having 1 to 20 carbon atoms, Y and Z are 0R3,0
It is a group selected from SiR4R5R6.

) (hereinafter referred to as a carboxylic acid compound) will be explained. Aliphatic as R2COO
Alicyclic or aromatic hydrocarbon carboxylic acid residues, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, palmitic acid, stearic acid, oxalic acid, succinic acid, malonic acid, maleic acid acid, acrylic acid,
Examples include carboxylic acid residues such as methacrylic acid, benzoic acid, toluic acid, p-ethylbenzoic acid, anisic acid, p-ethoxybenzoic acid, hydroxybenzoic acid, and aminobenzoic acid, but preferred ones include benzoic acid and toluic acid. acid, p
- Carboxylic acid residues such as ethylbenzoic acid, anisic acid, and p-ethoxybenzoic acid are mentioned.

Y and Z are 0R3, or 0SiR4, R5R6
As a compound represented by 0CH3,0C2H5,0
C3H7・0C4H9・0C5H11・0C6H11・
0C6H13, 0C6H5, α￥鿇a rabbit, etc. are also 0Si
(CH3)3,0Si(CH3),C,H,,OSiC
H3(C,H,)2,-Si(C2H5)3,-Si(
CH3), (C6H,),0SiH2CH3,0SiH
(CH3)2,0SiH2C21-[5,0SiH(C
2H5)2,0SiH(C6H5),,0SiH(CH
3) (C6H,), etc.

Z may be a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, and phenyl, but include ethyl, propyl, butyl, Aliphatic hydrocarbon groups such as amyl are preferred. The above fixed substance (1), titanium compound (2)
The solid obtained by reacting and/or pulverizing the carboxylic acid compound (3) is treated with a tetravalent titanium halide.

Examples of this compound include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, and preferred compounds are tetrahalides, especially titanium tetrachloride. give favorable results.

The reaction between the immobilizing substance (1) and the titanium compound (2) or the carboxylic acid compound (3) involves the reaction between the immobilizing substance (1) and the titanium compound (2) or the carboxylic acid compound (3) in a liquid phase or a gas phase. Any method can be adopted, such as a method of reacting in a 1x liquid phase or gas phase and a method of combining pulverization (2), and a method of pulverization (3).

Regarding method (1), method (1) in which solid substance (1), titanium compound (2), and carboxylic acid compound (3) are simultaneously reacted, or solid substance (1) and titanium compound (2) are simultaneously reacted.
) is first reacted, and then the carboxylic acid compound (3) is reacted (2), or the solid substance (1) and the carboxylic acid compound (3) are reacted, and then the titanium compound (2) is reacted.
) There is a method (3) of reacting.

Which one? Methods are also possible, but the latter two methods are preferred, and method 3 is particularly preferred. For method (2), the above solid substance (1), titanium compound (2), carboxylic acid compound (
3) and pulverizing the solid obtained by simultaneously reacting them (synthesis method 1), or the above solid substance (1) and the titanium compound (
2) and then react with a carboxylic compound to pulverize the solid obtained (synthesis method 2), or react the solid substance (1) with the carboxylic acid compound (3), and then react with the titanium compound (2). ) is a method of pulverizing the solid obtained by reacting (
There is a synthesis method 3).

Although either method is possible, the latter two methods are preferred, with Synthesis Method 3 giving particularly favorable results. For method (3), the solid substance (1), the titanium compound (2),
A method in which the carboxylic acid compound (3) is simultaneously crushed (synthetic method 1), a method in which the fixed substance (1) and the titanium compound (2) are crushed, and then the carboxylic acid compound (3) is added and crushed (synthetic method) 2). After pulverizing the fixed substance (1) and the carboxylic acid compound (3), the titanium compound (2) is added and further pulverized (synthesis method 3). Preferably, 3 is particularly preferable.

Regarding the method of further treating the solid synthesized by the above method (1), method (2) and method (3) with tetravalent titanium halide (4), method (1) and method (2)
] will be explained.

First, a method can be adopted in which each of the solid catalyst components synthesized by methods (1]-1, (1]-2, and (1]-3) is treated with a tetravalent titanium halide (4).

Next, a method can be adopted in which the solid catalyst components synthesized by methods (2]-1, [2]-2, and (2]-3 are each treated with a tetravalent titanium halide (4). However, the latter two methods are preferable.Also, methods (3]-1, [3]-
2 and (3]-3, respectively, can be treated with a tetravalent titanium halide (4), but the former two are preferred, especially (3]-3).
is preferred.

Next, the various reactions and pulverization operations described above will be specifically explained. (1) The above solid substance (1), or a solid obtained by reacting and/or pulverizing the solid substance (1) and the carboxylic acid compound (3), and a titanium compound (2).
).

The reaction is carried out using an inert reaction medium or without an inert reaction medium, using the undiluted titanium compound itself as the 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. 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 0.000
It is carried out at 5 to 1.5 mol/liter. Regarding the reaction molar ratio, 0.
Preferably, the reaction is carried out in the presence of 0.001 to 2 mol, more preferably 0.01 to 1 mol, of the titanium compound.
(4) The above solid substance (1), or a reaction product of this solid substance (1) and a titanium compound (2), and a carboxylic acid compound (
3) The reaction with and/or pulverization will be explained. The reaction is carried out using an inert reaction medium, in which the carboxylic acid compound (
3) is carried out using a substance that solubilizes. 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 carboxylic acid compound (3), there is no particular restriction on the reaction ratio of the two components, but preferably carboxylic acid is added to 1 mole of the magnesium component contained in the solid substance (1). Acid compound 0.001~
A range of 50 mol, particularly preferably from 0.005 to 10 mol, is recommended. Solid substance (1) and titanium compound (2)
When reacting the solid material obtained by reaction and/or pulverization with carboxylic acid compound (3), the reaction ratio of the two components is as follows:
The recommended amount of the carboxylic acid compound is 0.01 to 50 mol, particularly preferably 0.05 to 10 mol. When pulverization is used instead of the above reaction, a reaction medium may or may not be used, and the reaction temperature and reaction ratio are the same as when using reaction. (11!) A method for pulverizing the solid produced in or by the reactions (1) to (1;) above 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 ℃. 0V) A case in which the solid components obtained in (1) to (111) are treated with a tetravalent titanium halide will be described.

The reaction is carried out using an inert reaction medium or using the titanium compound itself as 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 titanium compound is preferably 2 mol/liter or more, and it is particularly preferable to react using the titanium compound itself as a reaction medium. There is no particular restriction on the reaction temperature, but 80
Preferable results are obtained when the reaction is carried out at a temperature of 0.degree. C. or above.
The composition and structure of the solid catalyst component obtained by the reactions (1) to QV) above vary depending on the type of starting materials and reaction conditions, but from the compositional analysis value, the solid catalyst contains approximately 1 to 100% Surface area with weight% titanium 50~2
It turned out to be a solid catalyst of 0T1/fl.

Next, as the organometallic compound used as the component (B), 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 AlRKZ3
-n (wherein R7 is a hydrocarbon group having 1 to 20 carbon atoms,
Z is a group selected from hydrogen, halogen, hydrocarbyloxy, and siloxy, and n is a number from 2 to 3.

) are used alone or as a mixture. In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by R7 includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminium, trin-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tridecylaluminum, Hexadecyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum ethoxide,
Diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isobrenyl, etc., and these A mixture is 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.

Examples of the hydrocarbon carboxylic acid ester added to the organometallic compound include ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, ethyl n-butyrate, ethyl valerate, ethyl caproate, n-heptane. Ethyl acid, di-n-butyl oxalate, monoethyl succinate, diethyl succinate, ethyl malonate, di-n-butyl maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate,
n- and i-propyl benzoate, n-, i-benzoate
, Sec-, and tert-butyl, methyl p-toluate, ethyl p-toluate, 1-propyl p-toluate, n- and i-amyl toluate, ethyl o-toluate, m-ethyl toluate, p - Methyl ethylbenzoate, ethyl p-ethylbenzoate, methyl anisate, ethyl anisate, 1-propyl anisate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, methyl terephthalate, etc. Aromatic carboxylic acid esters are preferred, particularly methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-toluate,
Methyl anisate and ethyl anisate are preferred.

The hydrocarbon carboxylic acid ester may be added by mixing the two components prior to polymerization, or by adding them separately into the polymerization system.

Particularly preferably, the organometallic compound and the hydrocarbon carboxylic acid ester are reacted in advance and the organometallic compound is separately added to the polymerization system. The ratio of both components to be combined is 0.001 to 10 mol, particularly preferably 0.01 to 1 mol, of the hydrocarbon carboxylic acid ester per 1 mol of the organometallic compound. The catalyst consisting of the solid catalyst component of the present invention and a component obtained by adding a hydrocarbon carboxylic acid ester to an organometallic compound may be added to the polymerization system under polymerization conditions, or may be combined and mixed in advance before polymerization. It may also be supplied within the system.

The ratio of the organic metal compound and the hydrocarbon carboxylic acid ester to the solid catalyst component 19 is preferably in the range of 1 mmol to 3000 mmol based on the organic metal compound. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins.

In particular, the present invention provides propylene, butene-1, benzene-1
, 4-methylbenzene, 1,3-methylbutene-1 and similar olefins are suitable for stereoregular polymerization 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. by injecting 0 kg/CTii under pressure. In the bulk polymerization, olefins can be polymerized under conditions where the olefin, such as propylene, is a catalyst and a liquid olefin is used as a polymerization solvent. For example, in the case of propylene, room temperature
The polymerization can be carried out in liquid propylene at a temperature of 0.degree. C. and under a pressure of 10 to 45 k9/. On the other hand, gas phase polymerization is performed under conditions where the olefin such as propylene is a gas, at a pressure of 1 to 50 kgr in the absence of a solvent, and at room temperature to 120°C.
Under these temperature conditions, polymerization can be carried out by means such as mixing using a fluidized bed, moving bed, or a stirrer so that the olefin catalyst such as propylene can come into good contact with the polymer. 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 (MF'I) is according to ASTM
According to No. D-1238, temperature 230℃, load 2.161
It was measured under the condition of <g. Example 1(i)
Reaction of magnesium halide and dialkyl sulfide Commercially available magnesium chloride 209, diethyl sulfide 149 and n-heptane 400d were mixed in a volume of 50
The mixture was placed in a 0 ml 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 a solid (A-1).

(Ii) Synthesis of magnesium benzoate hydrocarbyl oxide 138.09 of di-n-butylmagnesium and 19.09 of triethylaluminum were placed in a 22 flask purged with nitrogen, along with 12 of n-heptane, and reacted with stirring at 80°C for 2 hours. After that, NBuOH was added in an equimolar amount to the organic metal and reacted to obtain an organic magnesium complex solution.

The organometallic concentration was 1.25 m01/l. 100 mm01 of this organomagnesium complex was weighed into a nitrogen-substituted container, and an ether solution of benzoic acid (0.1 m01/l
) into 100mm0I with stirring at 80°C for 30 minutes, and after further reacting at 90°C for 1 hour, the solid portion (
As a result of isolation and analysis of B-1), (C6H5α°C).
．． It was found that it was a solid with a composition of 98Mg1.0 (0n-Bω1.1. (Synthesis of 110 solid catalyst (
Solid (A-1) synthesized in 1) 4.0f! and (4)
The solid (B-1) 1.09 synthesized in was placed in a steel mill with a diameter of 95 uj and a length of 100 mm together with 25 steel balls with a diameter of 10 mm, and after pulverizing with a vibrator of 1000 vib / Min or more for 10 hours. , n-butoxytrichlortitanium 6mm01 was added and further pulverization was continued. After 5 hours, the obtained solid (C11) was transferred to a nitrogen-purged container, 25ml titanium tetrachloride was added, and the mixture was treated at 130°C for 2 hours with stirring. After that, the solid was filtered, washed with purified n-heptane, and dried to obtain a solid catalyst (S-1).

As a result of analyzing this solid catalyst, the Ti content was 20% by weight.
It was hot. 0V) Slurry polymerization of propylene The above solid catalyst (S-1) 30~, triethylaluminum 24 [NnlOl and p-toluic acid ethyl 0.8
Hexane 0.81 with n1n101 sufficiently degassed and dehydrated
At the same time, the inside was vacuum dried and replaced with nitrogen, with a capacity of 1.51
into an autoclave, maintain the internal temperature at 60℃, pressurize propylene to a pressure of 5kg/(7it, and increase the total pressure to 4.8k).
Polymerization was carried out for 2 hours while maintaining the gauge pressure at ~g/~ to obtain 1259 polymerized hexane-insoluble polymers and 2.29 polymerized hexane soluble polymers.

The catalyst efficiency was 208,0009-PP/9-titanium, and the n-heptane extraction residue of the polymerized hexane-insoluble polymer was 96.8%. Example 2 Liquefied propylene 3 was placed in a 1.51 autoclave that had been sufficiently purged with nitrogen and vacuum dried.
509 was introduced, the internal temperature was maintained at 60°C, 10~ of the solid catalyst synthesized in Example 1, and 1.8 m of triethylaluminum were introduced.
m01 and 0.6 mm01 of ethyl p-toluate were added and polymerization was carried out at 60°C for 2 hours with stirring to obtain polypropylene 1269.

The catalyst efficiency was 630,0009-PP/9-titanium and the n-heptane extraction residue of this polymer was 95.8%. Examples 3 to 5 In the synthesis of the solid catalyst of Example 1, the solid catalyst was synthesized in the same manner as in Example 1 except that the compounds shown in Table 1 were used in place of the benzoic acid used in the synthesis of the carboxylic acid compound. Slurry polymerization of propylene was carried out using the synthesis method, Table-1
I got the result.

Comparative Example 1 In the synthesis of the solid catalyst of Example 1, all procedures were carried out in Example 1 except that ethyl alcohol was used instead of diethyl sulfite and titanium tetrachloride was used instead of n-butoxytrichlorotitanium. Synthesis of solid catalyst and slurry polymerization of propylene were carried out in the same manner as in Table-
1 result was obtained.

Comparative Example 2 A solid catalyst was synthesized in the same manner as in Example 1 except that titanium tetrachloride was used in place of n-butoxytitanium trichloride and magnesium benzoate hydrocarpyl oxide was not used. A catalyst was synthesized and slurry polymerization of propylene was carried out, and the results shown in Table 1 were obtained.

Example 6 The solid (A-1) synthesized in Example 1 (1) was synthesized in the same manner, and 49 thereof was ground for 5 hours using the same grinder as in Example 1 to obtain aluminum benzoate diethoxide 1. After adding 29 and further grinding for 4 hours, adding 6 mm of n-butoxytitanium trichloride and continuing grinding for 5 hours, the solid was transferred to a nitrogen-purged container, 35 ml of titanium tetrachloride was added, and the mixture was stirred at 130℃ for 2 hours. After the treatment, the solid was filtered, washed with purified n-hexane, and dried to obtain a solid catalyst.

As a result of analyzing this solid catalyst, the Ti content was 2.1% by weight. 15 mg of this solid catalyst, 1.8 mm of triethylaluminum, and 0.1 mm of ethyl p-toluate.
Propylene pressure is 9.8k in gauge pressure using 6mm01
g/C77t, hydrogen gas phase partial pressure 0.11<9/C
! Slurry polymerization of propylene was carried out in the same manner as in Example 1, except that the polymerized hexane-insoluble polymer 1
289, polymerized hexane soluble material 3.89 was obtained.

The n-heptane extraction residue of polymerized hexane-insoluble polymer is 9
6.3%, catalyst efficiency 4060009-PP/9-titanium, bulk density 0.4269/~, melting index ZO9/1
It was 01 Min. Example 7 Butene-1 was polymerized according to Example 1 using 200η of the solid catalyst synthesized in Example 1, 4.6n1n101 of triethylaluminum, and 1.2[Tl[NOl] of ethyl p-toluate. 47 g of polymer was obtained.

Example 8 200η of the solid catalyst synthesized in Example 1, 4.6 plates of triethylaluminum, and 1.6 plates of ethyl p-toluate.
Using 2 mm01, 4-methylbenzene-1 was polymerized according to Example 1 to obtain 40 g of a white polymer.

Example 9 Using the solid catalyst 30TI9 synthesized in Example 1, triethylaluminum 2.4rI1jn01 and ethyl p-toluate 0.8mm01, a propylene-ethylene mixed gas containing 2 mol% ethylene was used instead of propylene. Polymerization was carried out in the same manner as in Example 1 to obtain white polymer 1279.

Example 10 Solid catalyst 60TI synthesized in Example 1! 9
, triisobutylaluminum 1.0mm01 and p
-Thoroughly degas 0.1n1n101 of ethyl toluate.
Place it in a vacuum-dried and nitrogen-substituted 1.51 autoclave with 0.8e of dehydrated n-hexane, and bring the internal temperature to 8.
Keep it at 0℃ and hydrogen at 1.6k9/CTl! Then, ethylene was added to make the total pressure 4.0 kg/c:Rit.

Claims (1)

[Scope of Claims] 1. In an olefin polymerization catalyst comprising a magnesium halide, a titanium compound, an electron donor, and an organometallic compound, A(1)(a) a magnesium halide and (
b) Solid obtained by reacting and/or pulverizing dialkyl sulfite (2) General formula Ti(OR^1)_sX_4_-
__s (wherein R^1 is a hydrocarbon group having 1 to 20 carbon atoms,
is a halogen, and s is a number such that 0<s≦4) (3) General formula R^2COOMgY or R^2C
OOAlYZ (in the formula, R^2COO is a carboxylic acid residue having 1 to 20 carbon atoms, Y and Z are OR^3 or OSiR^4R
^5R^6, however, R^3, R^4, R^5, R^6
is a hydrocarbon group having 1 to 20 carbon atoms, and Z is a hydrocarbon group having 1 to 20 carbon atoms.
may be a hydrocarbon group. ), which are (1), (2), (3
(4) A solid catalyst component obtained by treating the solid obtained by reacting and/or pulverizing (4) with a tetravalent titanium halide (B) Obtained by adding a hydrocarbon carboxylic acid ester to an organometallic compound An olefin polymerization catalyst consisting of components (A) and (B). 2. The olefin polymerization catalyst according to claim 1, wherein the dialkyl sulfite 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) The titanium compound of (2) has the general formula Ti(OR
The olefin polymerization catalyst according to claim 1 or 2, which is ^1)_4. 5. The olefin polymerization catalyst according to any one of claims 1 to 4, wherein the titanium compound in (A)(4) is titanium tetrachloride. 6 The organometallic compound of (B) has the general formula AlR^7_n
Z_3_-_n (wherein, R^7 is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, halogen, hydrocarbyloxy,
It represents a group selected from siloxy groups, and n is a number from 2 to 3. ) The olefin polymerization catalyst according to any one of claims 1 to 5, which is an organoaluminum compound represented by: