JPS595603B2 - 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 a polymerization catalyst suitable for stereoregular polymerization of olefins such as , 4-methylpentene-1, etc., or for copolymerizing the above 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. P01ymerLe ters,
In V01, 3, p855-857 (1965),
It has been shown that after reacting magnesium chloride and titanium tetrachloride, triethylaluminum and optionally additives are added to polymerize propylene. In this case, an electron donor such as ethyl acetate is used as an additive. It is described that the stereoregularity of the resulting polymer is improved.

Furthermore, 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 has been stated that the parent catalyst can be prepared by adding the catalyst to a carrier metal salt and shaking the mixture together.

However, even when polymerization is performed using this catalyst system, both the polymerization activity and the yield of stereoregular polymers are still insufficient.

In recent years, many catalyst systems have been proposed based on the above-mentioned catalyst systems, but none have been found to be satisfactory in terms of both polymerization activity and stereoregular polymer yield.

As a result of intensive studies on titanium compounds, the present inventors have discovered that a magnesium halide obtained by reacting and/or pulverizing a magnesium halide or dialkyl sulfite with a specific titanium compound and/or
Alternatively, a solid catalyst component obtained by pulverization, or a solid catalyst component obtained by further treating this with a tetravalent titanium halide, an organometallic or organometallic compound, and a hydrocarbon carboxylic acid ester or a heterocyclic carbon A catalyst made by combining a component with an acid ester added,
It was discovered that it has excellent performance as a catalyst for olefin polymerization, and the present invention was achieved. That is, the first invention of the present invention provides (Al (1) a solid obtained by reacting and/or pulverizing a magnesium halide or a magnesium halide and a dialkyl sulfite and ~20 hydrocarbon groups, X is a halogen , n represents a number such that O>n≦2) and a solid catalyst component obtained by reacting and/or pulverizing a compound represented by It is an olefin polymerization catalyst comprising a component to which a heterocyclic carboxylic acid ester is added, and the second invention of the present invention is CA) (1) Reaction and/or pulverization of a magnesium halide or a magnesium halide and a dialkyl sulfite. The solid obtained by
- 1 - 1 - 1 hee-kei-n (in the formula,
R1 and R2 each represent a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents a number of O (n≦2). ) An olefin polymerization catalyst consisting of a solid catalyst component obtained by treatment with a tetravalent titanium halide and a component obtained by adding a hydrocarbon carboxylic acid ester or a heterocyclic carboxylic acid ester to an 8 organometallic compound or an organometallic compound. be.

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 flowability of the polymer produced using the catalyst obtained by the present invention and the finish of the product after molding are good. In addition, when a heterocyclic carboxylic acid ester is used as the main component, in addition to the above characteristics, when hydrogen is used as a molecular weight regulator during polymer production,
It has the characteristics that only a small amount of hydrogen is required to obtain a molecular weight range commonly used, and that there is little scale adhesion to the reactor and other parts during polymer production.

Each component and reaction conditions used for preparing the catalyst of the present invention will be explained below.

First, as a magnesium halide, MgF2
, MgCl, , MgBr2, and MgI2, and mixtures containing these may also be used.

Particularly preferred in the present invention is MgCl2. next,
The use of a magnesium halide reacted with dialkyl sulfite and/or pulverized further increases the effects of the present invention.

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 for treating a magnesium halide with dialkyl sulfite will be explained separately for the case of reacting in a liquid phase and the 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, toluene, diethyl ether, dipropyl ether, dibutyl ether. Ether solvents such as 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.
5 m01/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 for pulverization, or the above-mentioned inert hydrocarbon solvent may be added to the dialkyl sulfite and the magnesium halide for pulverization. . Alternatively, a method may be adopted 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 not particularly limited, but it can be carried out at -10 to 150°C, and 0 to 80°C.
is preferred. Component (2) has the general formula Ti(0-R1-COOR)NX4-n (wherein, Rl
,R! The titanium compound represented by (and n has the above-mentioned meaning) will be explained.

Examples of the hydrocarbon group represented by R1 include aliphatic, aliphatic, aromatic hydrocarbon groups, and their halogen-substituted hydrocarbon groups, and examples of the hydrocarbon group represented by R2 include methyl, ethyl, propyl, Examples include hydrocarbon groups such as butyl, pentyl, hexyl, heptyl, cyclohexyl, phenyl, and benzyl.

Specific compounds include glycolic acid methyl ester and ethyl ester residues, oxypropionate methyl ester and ethyl ester residues, α-hydroxyisobutyric acid methyl ester and ethyl ester residues, α-
hydroxy n-monobutyrate methyl and ethyl ester residues, DL-β-hydroxybutyrate methyl and ethyl ester residues, ricinoleate methyl and ethyl residues,
Methyl, ethyl o-, m-, p-hydroxybenzoate,
Propyl, butyl residues, methyl and ethyl oxytoluate residues, methyl and ethyl oxydimethylbenzoate residues, methyl and ethyl gallate residues, methyl and ethyl chlorooxybenzoate residues, methyl and ethyl dichlorogallate residues Among them, R1 is an aromatic hydrocarbon group, and o-, m-, p-hydroxybenzoic acid methyl residues and o-, m-, p-hydroxy Propyl benzoate residue, o-, m-. A titanium compound (2) having a butyl p-hydroxybenzoate residue, a methyl oxytoluate residue, an ethyl oxytoluate residue, etc. gives preferable results. Examples of the halogen represented by X include chlorine, bromine, and iodine, with chlorine being preferred. n is Okun
<． The number is 2, but 0.1×n×1 is preferable. Reacting the solid substance (1) with the titanium compound (2) and/or
Alternatively, the tetravalent titanium halide (3) to be treated with the solid obtained by pulverization includes titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride. Mention may be made of chloride, preferred compounds are tetrahalides, with titanium tetrachloride giving particularly favorable results. The solid substance (1) and the titanium compound (2) are reacted and/or pulverized.
The effects of the present invention can be obtained by carrying out 2) when it is liquid or soluble in a solvent.

A more preferable result can be obtained by further pulverizing the obtained solid. In addition, the above solid substance (1)
The method of pulverizing the titanium compound (2) and the titanium compound (2) also gives favorable results. 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.

Inert reaction media include, for example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, chlorobenzene, dichlorobenzene, etc. Examples include halogenated hydrocarbon solvents. In addition, in the case of pulverization, a reaction medium may or may not be used, and the solid substance (1) and the titanium compound (
The molar ratio of 2) is 0.0001 to 2 mol, preferably 0.0001 to 2 mol, per 1 mol of magnesium component in the solid substance (1).
0005-1 mol, more preferably 0.001-0.
It is 5 moles.

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. A case where the solid component obtained above is further treated with a tetravalent titanium halide (3) will be described.

The reaction is carried out using an inert reaction medium or 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,
In particular, it is preferable to react using the titanium compound itself as a reaction medium. Although there is no particular restriction on the reaction temperature, preferable results are obtained when the reaction is carried out at a temperature of 80° C. or higher. The composition and structure of the solid catalyst component obtained by the above reaction will vary depending on the type of starting materials and reaction conditions, but from the compositional analysis value, approximately 1 to 10
Surface area containing 50 to 20 i/f of titanium by weight%! It turned out to be a solid catalyst.

Next, as the organometallic compound used as the main component, 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 AlR7nZ
32n (wherein R7 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, hydrocarbyloxy, 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 R7 includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tridecylaluminum, hexadecyl aluminum,
Diethylaluminium hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminium chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethyl Siloxyaluminum 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.

A hydrocarbon carboxylic acid ester may be added to the organometallic compound, and examples of the hydrocarbon carboxylic acid ester include ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, n-propyl ester, etc. Ethyl butyrate, ethyl valerate, ethyl caproate, ethyl n-heptanoate, di-n-butyl oxalate, monoethyl succinate, diethyl succinate, ethyl malonate, di-n maleate
-butyl, 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, ethyl m-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.

Further, a heterocyclic carboxylic acid ester may be added to the organometallic compound, and examples of the heterocyclic carboxylic acid ester include nitrogen-containing, sulfur-containing, or oxygen-containing heterocyclic carboxylic ester.

Examples of nitrogen-containing heterocyclic carboxylic esters include pyrrole 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 Examples include acid esters, pyrimidine carboxylic acid esters, pyrazine carboxylic acid esters, and specifically preferred ones include methyl pyrrole-2-carboxylate, ethyl, propyl and butyl pyrrole-3-carboxylate, methyl pyrrole-3-carboxylate, and ethyl pyrrole-3-carboxylate. , propyl and butyl, methyl pyridine-2-carboxylate, ethyl, propyl, butyl and amyl, pyridine-3-
Methyl carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-4-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-2,3-dicarboxylate, ethyl, methyl pyridine-2,5-dicarboxylate, Ethyl, methyl pyridine-2,6-dicarboxylate, ethyl, methyl pyridine-3,5-dicarboxylate, ethyl, methyl quinoline-2-carboxylate, ethyl,
Ethyl dimethylpyrrolecarboxylate, ethyl N-methylpyrrolecarboxylate, ethyl 2-methylpyridinecarboxylate, ethyl piperidine-2-carboxylate, ethyl piperidine-4-carboxylate, ethyl pyrrolidine-2-carboxylate, ethyl L-proline Examples include ester, isonicotipenic acid ethyl ester, D,L-pipecolinic acid ethyl ester, nipecotinic acid ethyl ester, and the like.

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. carboxylic acid esters, thioindoxyl carboxylic acid esters, etc., more specifically, methyl, ethyl, propyl, butyl and amyl thiophene-1-2-carboxylate, methyl, ethyl, propyl thiophene-3-carboxylate. , butyl and amyl,
Methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate, ethyl, methyl thiophene-2,5-dicarboxylate, ethyl, methyl 2-thienylacetate, ethyl, propyl, butyl, 2- Methyl thienyl acrylate, ethyl, methyl 2-thienylpyrupine acid, ethyl, methyl thianaphthene-2-carboxylate, ethyl, methyl thianaphthene-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-carboxylate, ethyl, methyl benzothiophene-3-carboxylate, ethyl, methyl benzothiophene-4-4-carboxylate, ethyl, phenoxathiin-1-1-carboxylate, ethyl, methyl benzothiophene-3-carboxylate 2
-Methyl, ethyl carboxylate, phenoxathiin-3-
Examples include methyl carboxylate and ethyl carboxylate.

More preferred are methyl, ethyl, propyl and butyl thiophene-2-carboxylate, methyl thiophene-3-carboxylate, ethyl, methyl 2-thienyl acetate, ethyl, methyl 2-thienyl acrylate, ethyl, thianaphthene-2-carboxylate. -Methyl carboxylate, ethyl etc. Examples of oxygen-containing complex carboxylic acid esters include furan carboxylic esters, dihydrofuran carboxylic esters, benzofuran carboxylic esters,
Examples include coumarans carboxylic esters, pyrans carboxylic esters, pyrones carboxylic esters, coumarins carboxylic esters, isocoumarins carboxylic 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 2,5-dicarboxylate, Methyl furan-3,4-dicarboxylate, Methyl 4,5-dihydrofuran-2-carboxylate, Methyl tetrahydrofuran-2-carboxylate, Methyl coumarate (Methyl benzofuran-2-carboxylate) ) Ethyl coumaran-2-carboxylate, methyl coumarate, ethyl, methyl comanate, ethyl 5-hydroxy-4-ethoxycarbonylcoumarin, 4-ethoxycarbonylisocoumarin, ethyl 3-methylfuran-2-carboxylate, isodehydroacetic acid Examples include methyl, ethyl, propyl, butyl furan-2-carboxylate,
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. The method for adding the hydrocarbon carboxylic acid ester or the heterocyclic carboxylic acid ester is as follows:
The components may be mixed or added separately to the polymerization system.

Particularly preferably, the organometallic compound and the hydrocarbon carboxylic acid ester or 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 to 1 mol, of the hydrocarbon carboxylic acid ester or the heterocyclic carboxylic ester per 1 mol of the organometallic compound.

A catalyst consisting of the solid catalyst component of the present invention and an organometallic compound or a component (g) in which a hydrocarbon carboxylic acid ester or a heterocyclic carboxylic acid ester is added to an organometallic compound is added to the polymerization system under polymerization conditions. Alternatively, they may be combined and mixed in advance and supplied into the polymerization system.

The ratio of the organometallic compound or the component obtained by adding a hydrocarbon carboxylic acid ester or a heterocyclic carboxylic acid ester to an organometallic compound is 1f! of the solid catalyst component (A)! On the other hand, it is preferably carried out in a 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.

In particular, the present invention provides propylene, butene-1, benzene-1
, 4-methylbenzene-1,3-methylbutene-1 and similar olefins alone in a stereoregular manner. 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 uses a catalyst as a polymerization solvent, such as an aliphatic hydrocarbon such as hexane, heptane, benzene, toluene,
An aromatic hydrocarbon such as xylene and an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane are introduced into a reactor together with an olefin such as propylene under pressure of 1 to 20 Vd under an inert atmosphere, and the temperature is from room temperature to 150°C. Polymerization can be carried out with 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, it is
The polymerization can be carried out in liquid propylene at a temperature of 0.degree. C. and under a pressure of 10 to 45 kg/d. On the other hand, gas phase polymerization is carried out under conditions where the olefin such as propylene is a gas, at a pressure of 1 to 50 kg/Cd in the absence of a solvent, from room temperature to 1 kg/Cd.
Under a temperature condition of 20°C, polymerization can be carried out by mixing with a fluidized bed, a moving bed, or a stirrer, etc., so that the olefin such as propylene and the catalyst are in good contact with each other. . The present invention will be explained below using examples.

In addition, 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) is according to ASTMD.
-1238, temperature 230℃, load 2.16kg
Measured under the following conditions. Example 1 (1) Synthesis of titanium compound 50 mm01 of titanium tetrachloride (toluene solution) was added dropwise to a toluene solution of ethyl o-hydroxybenzoate under stirring at 40° C. over 30 minutes in a nitrogen atmosphere.

The dropwise addition generated heat and white smoke, and the reaction was continued at 60° C. for 1 hour, followed by filtration, washing, and drying to obtain solid (A-1). Analysis of this solid resulted in Ti(0-ku○〉)1.
It had a composition of 0C1,p, and no -0H absorption peak was detected in the infrared absorption spectrum.

() Synthesis of solid catalyst 4.09 obtained by drying commercially available anhydrous magnesium chloride at 300°C for 8 hours under reduced pressure, and 0.5129 of titanium compound (A-1) synthesized by (:), 10 m 1 g in diameter.
With 25 steel balls, diameter 95u, length 100mm
The solid catalyst (S-
As a result of analyzing 1), the Ti content was 1.7% by weight.

(11!) Slurry polymerization of propylene 80 mg of the above solid catalyst (S-1), 2.4 mm of triethylaluminum and 0.8 m of ethyl p-anisate
m01 was placed in an autoclave with a capacity of 1.51 which had been thoroughly purged with nitrogen and dried under vacuum, together with 0.811 l of purified hexane, the internal temperature was maintained at 60°C, propylene was pressurized to a pressure of 5 kg/Cit, and the total pressure was reduced to 4. Polymerization was carried out for 2 hours while maintaining the gauge pressure at 8 kg/Cd, and the results shown in Table 1 were obtained.

Example 2 20f1 of commercially available magnesium chloride, 149 diethyl sulfide and 400d of n-heptane were mixed in a capacity of 500W.
The mixture was placed in a container II and reacted at 80° C. for 2 hours with stirring, and then the solid portion was filtered and purified.

- Washed with heptane and dried to obtain solid (A-2).
In the synthesis of the solid catalyst of Example 1, the above solid (A-2) 4.09% was used instead of dried magnesium chloride.
A solid catalyst was synthesized in the same manner as in Example 1, except that a solid catalyst was used, and slurry polymerization of propylene was performed to obtain the results shown in Table 1. Example 3 The solid catalyst (S-1) 29 obtained in Example 1 was placed in a container purged with nitrogen, 20 d of titanium tetrachloride was added, and the mixture was heated for 130 min with stirring.
After treating at °C for 2 hours, the solid was filtered, washed with purified n-heptane, and dried to obtain a solid catalyst (S-3).

This solid catalyst is 50T! If, triethylaluminum 2
．． 4mm02 and ethyl p-toluate 0.8mm0
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using Example 1, and the results shown in Table 1 were obtained. Example 4 Solid catalyst (S-2) 2f obtained in Example 2! was placed in a nitrogen-purged container, 18d of titanium tetrachloride was added, and the mixture was heated under stirring for 13 minutes.
After treatment at 0 °C for 2 h, the solid was filtered and the purified n-
The solid catalyst (S-4) was obtained by washing with heptane and drying.

Slurry polymerization of propylene was carried out in the same manner as in Example 3, and the results shown in Table 1 were used in Example 5. In place of the titanium compound obtained from ethyl m-hydroxybenzoate, a titanium compound obtained from ethyl m-hydroxybenzoate was used. A solid catalyst was synthesized in the same manner as in Example 4, and slurry polymerization of propylene was performed using ethyl pyridine-3-carboxylate in place of ethyl p-toluate, and the results shown in Table 1 were obtained.

Example 6 A solid catalyst was synthesized in the same manner as in Example 4, except that a titanium compound obtained from methyl o-hydroxybenzoate was used in place of the titanium compound obtained from ethyl o-hydroxybenzoate. Slurry polymerization of propylene was performed using ethyl furan-2-carboxylate in place of ethyl toluate, and the results shown in Table 1 were obtained.

Comparative Example 1 A solid catalyst was synthesized in the same manner as in Example 1 except that titanium tetrachloride was used in place of the titanium compound in the synthesis of the solid catalyst in Example 1, slurry polymerization of propylene was performed, and the results shown in Table 1 were obtained. I got it.

Comparative Example 2 Commercially available anhydrous magnesium chloride was heated to 300 ml under reduced pressure.
59, which had been dried at 70° C. for 8 hours, was placed in a nitrogen-substituted container with 5 mm 0 of ethyl o-hydroxybenzoate and 100 a of toluene, and reacted at 70° C. for 2 hours.

The solid portion was filtered, washed and dried to obtain a solid (AH-2). This solid 49 and titanium tetrachloride 361 were combined with 25 steel balls with a diameter of 10 nm, a diameter of 95 mm, and a length of 10011.
The solid catalyst was placed in a steel mill and pulverized for 5 hours using a vibrator of 1000 vib/Mm or more, and slurry polymerization of propylene was performed using the obtained solid catalyst to obtain the results shown in Table 1.

Example 7 The solid (A-2) synthesized in Example 2 was synthesized in the same manner, and the solid 49 was ground for 5 hours using the same grinder as in Example 1, and 0-hydroxy A titanium compound synthesized using ethyl benzoate was added and pulverized for another 5 hours. The obtained solid was transferred to a nitrogen-purged container, and 8a of titanium tetrachloride and 15 ml of heptane were added and heated at 110°C.
After stirring for 2 hours at
I got it.

This solid catalyst 30η and triethylaluminum 1.8m
m01 and ethyl thiophene 2-carboxylate 0.6m
Using m01, set the propylene pressure to 9.8 kg/gage pressure.
(1-JmoV!, and the gas phase partial pressure of hydrogen is 0.1kf!/d
Propylene slurry polymerization was carried out in the same manner as in Example 1 except for charging, and polymerized hexane-insoluble polymer 152f
5.51 of polymerized hexane soluble material was obtained.

The n-heptane extraction residue of polymerized hexane-insoluble polymer is 9
6.4%, catalyst efficiency is 317,000! -pnku titanium, bulk density is 0.383f! /d, melting index is 7.09/
It had 10 fins. Example 8 Liquefied propylene 3509 was introduced into a 1,511 autoclave that had been sufficiently purged with nitrogen and vacuum dried, and the internal temperature was adjusted to 60°C.
20 η of the solid catalyst synthesized in Example 3, 1.8 mm of triethylaluminum and 0.6 mm of ethyl p-toluate were added, and polymerization was carried out at 60 °C for 2 hours with stirring to obtain polypropylene 1589.

The catalyst efficiency is 5270009-Pp-9-titanium;
The n-heptane extraction residue of this polymer was 93.3%. Example 9 Slurry polymerization of propylene was carried out in the same manner as in Example 1 using the solid catalyst 50W9 synthesized in Example 3 and 0.8 mm of triethylaluminum, and hexane-insoluble polymer 155' and hexane-soluble polymer 10.69 were obtained. Obtained.

The n-heptane extraction residue of the hexane-insoluble polymer is 92.
It was 8%. Example 10 Using 200 mg of the solid catalyst synthesized in Example 3, 4.6 mm of triethylaluminum, and 1.2 mm of ethyl p-toluate, butene-1 was polymerized according to Example 1, resulting in a white polymer of 449 I got it.

Example 11 200r of solid catalyst synthesized in Example 3! Polymerization of 4-methylbenzene-1 was carried out in accordance with Example 1 using 4.6 mm01 of triethylaluminum and 1.2 mm01 of p-ethyl anisate to obtain a white polymer 349.

Example 12 Using the solid catalyst 50T11f synthesized in Example 3, 2.4 mm of triethylaluminum, and 0.8 mm of ethyl p-toluate, a propylene-ethylene mixed gas containing 2 mol% of ethylene was used instead of propylene. The polymerization was carried out in the same manner as in Example 1 to obtain a white polymer 309.

Example 13 Solid catalyst 80WII synthesized in Example 3! , n-hexane 0.81<! :＼Vacuum drying and nitrogen substitution 1.
Place it in a 51 autoclave and keep the internal temperature at 80℃.
1 hydrogen.

Pressurize to 6 kg/Cd, then add ethylene to bring the total pressure to 4.01<f! /Cllt.

Claims (1)

[Scope of Claims] 1 [A] (1) A solid obtained by reacting and/or pulverizing a magnesium halide or a magnesium halide and a dialkyl sulfite, and (2) a solid obtained by the general formula Ti(O-R^1- COOR^2)_nX_4_-_n
(In the formula, R^1 and R^2 each have 1 to 20 carbon atoms.
A solid catalyst component obtained by reacting and/or pulverizing a compound represented by a hydrocarbon group, X is a halogen, and n is a number 0<n≦2; and [B] an organometallic compound or an organometallic compound. An olefin polymerization catalyst consisting of a hydrocarbon carboxylic acid ester or a heterocyclic carboxylic acid ester. 2 [A] (1) A solid obtained by reacting and/or pulverizing a magnesium halide or a magnesium halide and a dialkyl sulfite, and (2) a general formula Ti (O-R^1-COOR^2) _nX_4_=_n
(In the formula, R^1 and R^2 each have 1 to 20 carbon atoms.
A solid obtained by reacting and/or pulverizing a compound represented by a hydrocarbon group, X is a halogen, and n is a number 0<n≦2 is further treated with (3) a tetravalent titanium halide. and [B] an organometallic compound, or the organometallic compound is a hydrocarbon carboxylic acid ester or a heterocyclic carboxylic acid ester.