JPS608002B2 - Catalyst for polymerization of olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly active and highly stereoregular polymerization catalyst for olefins.

In particular, the present invention provides propylene, butene-1, bentene-1
, 4-methylbentene-1, 3-methylbutene-1 and similar olefins in a stereoregular manner,
It is also suitable for copolymerizing the olefin with ethylene or other olefins. Periodic table W~
It is well known that stereoregular polymers can be obtained by contacting an olefin with a Chigfu-Natta catalyst system consisting of a transition metal compound of Group A of There is.

In particular, combinations of titanium halides and organoaluminum compounds such as triethylaluminum or diethylaluminum chloride are widely used industrially as stereoregular polyolefin polymerization catalysts. When olefins such as propylene are polymerized using this catalyst, a boiling hebutane-insoluble polymer, that is, a stereoregular polymer, can be obtained in a fairly high yield, but the polymerization activity is not fully satisfactory, and the resulting polymer A step is required to remove catalyst residue from the catalyst.

In recent years, many methods have been proposed using Grignard reagents or decomposition products thereof as highly active ethylene polymerization catalysts.

For example, a method of reducing titanium tetrachloride with a Grignard reagent (Tsubaki Seki No. 46-4393), a method of reacting magnesium, a monohalogenated hydrocarbon, and titanium tetrachloride (Japanese Unexamined Patent Publication No. 17585-1985), and a method of reducing titanium tetrachloride with a Grignard reagent. A method of reacting hydrogen halide and reacting this with titanium tetrachloride (Japanese Patent Publication No. 47-41676), or a method of reacting a Grignard reagent with aluminum halide or silicon halide, and reacting this with a titanium compound ( Special Seki Sho 52-74686) etc. have been proposed. As is clear from the comparative examples described later, these systems exhibit remarkable activity in the polymerization of propylene, but the proportion of boiling hebutane solubles, that is, amorphous polymer, to the total polymer produced is extremely large. industrially, it is difficult to use it as it is as a stereospecific polymerization catalyst for olefins such as propylene. Also, Special Publication No. 52-39431, Special Publication No. 52-361
53 and Japanese Patent Publication No. 48-16988, a solid component obtained by co-pulverizing a tsuba compound of a titanium halide compound and an electron donor and an anhydrous magnesium halide, a trialkylaluminium, and an electron donor. A catalyst system consisting of a donor and an addition reaction product.

However, even with these methods, the proportion of butane insolubles in boiling polymers is still not high enough to satisfy
In particular, the yield of polymer per solid catalyst component is insufficient, the content of halogen in the polymer is high, which causes corrosion of manufacturing process equipment and molding machines, and the physical properties of the product are not fully satisfactory. As a result of intensive studies on these points, the present inventors reacted a Grignard reagent with a chlorosilane compound containing an Si-day bond as a reaction reagent to produce a solid halogen-containing magnesium compound, which was then combined with a titanium compound and a sulfur-containing compound. A specific solid obtained by reacting and/or pulverizing an oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester is combined with an organometallic compound to form a component consisting of a yellow, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester. It has been discovered that the combination of these has extremely excellent performance as an olefin polymerization catalyst, and the present invention has been achieved.

That is, the present invention provides: [A][1}(i) An organomagnesium compound represented by the general formula RIMgX (wherein RI is an alkyl group or aryl group having 1 to 20 carbon atoms, and X represents a halogen atom)
, the general formula HasIC1bR4-(zu) (wherein, a
, b is a number larger than 0, and R represents a hydrocarbon group. a solid component obtained by reacting and/or crushing one or more titanium compounds selected from sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters; This is an olefin polymerization catalyst comprising an organometallic compound and one or more components selected from sulfur-containing, oxygen-containing, or nitrogen-containing enocyclic carboxylic acid esters.

The first feature of the present invention is that the catalyst efficiency per titanium metal and per catalyst solid component is extremely high.

The second feature of the present invention is that in addition to the above-mentioned high activity, high stereoregularity can also be obtained.

The third feature of the present invention is that the particle size of the polymer is good,
Another advantage is that polymer powder with high bulk density can be produced.

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 when hydrogen is used as a molecular weight regulator during polymer production, only a small amount of hydrogen is required.

The essential factors behind the surprising performance of the present invention as described above are still unclear, but as shown in the examples described below, according to this method, alkyl groups with high surface area and reducing power can be It is believed that the active magnesium halide basic solid contained therein was synthesized.

General formula RIMgX used in the synthesis of the solid catalyst of the present invention
The organomagnesium compound (wherein R1 and X have the above-mentioned meanings) will be explained.

This compound is a so-called Grignard compound, and is generally synthesized by reacting magnesium with an organic halide in an ether solution, but it is also known that the reaction can be carried out in hydrocarbon soot in the absence of ether. Both can be used. Examples of these include, for example, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n- or iso-propylmagnesium chloride, n-
- or iSo-propylmagnesium bromide, n- or jSo-propylmagnesium iodide, n-butylmagnesium chloride, n-butylmagnesium bromide, n-butylmagnesium iodide, sec
- or tert-butylmagnesium chloride, s
ec or te-butylmagnesium bromide, s
Compounds such as ec- or rt-butylmagnesium iodide, n-amylmagnesium chloride, n-amylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, octylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, and These Able complexes can be mentioned.

Examples of these ether compounds include various ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diallyl ether, tetrahydrofuran, dioxane, and anisole. Next, the general formula HasiC
The Si-bond-containing chlorosilane compound represented by 1bR4-(a+b) (wherein a, b, and R have the above-mentioned meanings) will be described. The hydrocarbon group represented by R in the above formula is an alkyl group, a cycloalkyl group, or an allyl group, and examples thereof include methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, and phenyl groups. Preferred are alkyl groups having 1 to 10 carbon atoms, and lower alkyl groups such as methyl and ethyl groups are particularly preferred. For the range of values of a and b, a>0
There is no particular restriction as long as b > 0 and a + b S4, but
Preferably 0<a<2. These compounds include HSiC13, HSiC12CH3, HSiC12 (
C2 day 5), HSiC12 (n-C3 day 7), HSiC
12 (i-C4 ratio), HSiC12 (C6 day 5), HS
iC12 (CH=CH2), HSiC12CH2 (C6
W), HSiC1 (CH3)2, HSiC1 (C2 public)
2, HSiC1 (CH3) (C6 day 5), HiroSICIC
A chlorosilane compound in which a single compound, a mixture, or a mixture partially containing these compounds, such as H3, Hi2SIC12 (C2 Hi5), is used, preferably 0<a<2, and R is a lower alkyl group, For example, trichlorosilane HSiC13, monomethyldichlorosilane HSi
C12CH3, diethylchlorosilane HSiC1 (C2
Day 5) 2nd grade is used.

As can be seen from Example 1 and Comparative Examples 1, 2, and 3,
When using a silicon compound that does not contain a Si-day bond,
No favorable results are obtained. The reaction between the Grignard reagent and the chlorosilane compound can be carried out using an inert reaction medium, such as an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, or an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane. The reaction can be carried out in a hydrocarbon, an ether medium such as ether or tetrahydrofuran, or a polymerization medium thereof.

In terms of catalyst performance, aliphatic hydrocarbon media are preferred. There is no particular restriction on the reaction temperature, but it is preferably 40qC in terms of reaction progress.
The above will be implemented. There is no particular restriction on the reaction ratio of the two components, but it is preferably in the range of 0.01 to 100 mol, particularly preferably 0.1 mol to 10 mol, of the chlorosilane component per 1 mol of the organomagnesium component.

Regarding the reaction method, there is a simultaneous addition method (Method ①) in which one component is introduced into the reaction zone at the same time and reacted), or the chlorosilane component is charged into the reaction zone in advance, and then the organomagnesium lead component is introduced into the reaction zone. (Introduction)) A method of reacting (Method @), or a method of preparing the organomagnesium component in advance and adding the chlorosilane component (Method Q)
), but methods @ and Q are preferred.

The composition and structure of the solid substance '1} obtained by the above reaction may vary depending on the type of starting materials and reaction conditions, but
Based on the composition analysis value, the stiffness of solid substance 1 is about 0.1 to 2.5
It is presumed to be a halogenated magnesium compound containing an alkyl group with millimole of Mg-C bonds.

This solid substance has an extremely large specific surface area, and B
．． E. T. Measurements using the method show high values of 100 to 300 per unit. Compared to conventional magnesium halide solids, the solid materials of the present invention have a very high surface area;
Another major feature is that it is an active halogenated magnesium compound containing an alkyl group with reducing power. Next, a titanium compound containing at least one halogen atom will be explained.

The titanium compound is a tetravalent titanium compound containing at least one halogen atom and/or a trivalent titanium halogen compound.

Thousand-valent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, ethoxytitanium trichloride,
Titanium compounds such as propoxytitanium trichloride, propoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride, etc.

Genides and alkoxy halides may be used alone or in mixtures. Preferred compounds are those containing three or more halogens, and titanium tetrachloride is particularly preferred.
Next, the trivalent titanium halide will be explained.

Examples of trivalent titanium halides include titanium trichloride,
Examples include titanium tribromide and titanium triiodide, but a solid solution containing these as one component may also be used. Examples of the solid solution include a solid melt of titanium trichloride and aluminum trichloride, a solid melt of titanium tribromide and aluminum tribromide, a solid solution of titanium trichloride and vanadium trichloride, a solid solution of titanium trichloride and iron trichloride, Examples include solid solutions of titanium trichloride and zirconium trichloride. Among these, titanium trichloride, a solid solution of titanium trichloride and aluminum trichloride (
TIC13・1'Matsu IC13). Next, the sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester will be explained. First, the sulfur-containing heterocyclic carboxylic acid esters include thiophene carboxylic acid esters, thianaphthene carboxylic acid esters, isothianaphthene carboxylic acid esters, benzodithiophene carboxylic acid esters, phenoxathine carboxylic acid esters, and benzothiane carboxylic acid esters. ester, penzothian carboxylic acid ester, thiaxanthene carboxylic acid ester, thioindoxyl carboxylic acid ester, etc. More specifically, thiophene-2-carboxylic acid methyl'k, ethyl, propyl, butyl and amyl, Thiophene-3
- 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, methyl 2-thhenylacetate , ethyl, propyl, butyl, methyl 2-chenyl acrylate, ethyl, methyl 2-chenylpyruvate, ethyl, methyl thianaphthene-2-carboxylate, ethyl, methyl thianaphthene-3-carboxylate, ethyl, thianaphthene 2,3-dicarboxylate Methyl acid, methyl 3-oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenyl acetate, ethyl, 3
-Thianaphthenyl methyl acetate, ethyl, methyl benzothiophene-2-carboxylate, ethyl, methyl benzothiophene-3-carboxylate, ethyl, methyl benzothiophene-4-carboxylate, ethyl, phenoxathiin-1
-Methyl, ethyl carboxylate, phenoxathiin-2-
Examples thereof include methyl carboxylate, ethyl carboxylate, methyl phenoxathiine-3-carboxylate, and ethyl carboxylate.

More preferred are methyl, ethyl, propyl and butyl thiophene 2-carboxylate, thiophene-2-carboxylate.
Methyl 3-carboxylate, ethyl, methyl 2-thenyl acetate, ethyl, methyl 2-thenyl acrylate, ethyl,
Examples include methyl and ethyl thianaphthene-2-carboxylate. Next, the oxygen-containing ring carboxylic acid ester will be explained.

Examples of oxygen-containing heterocyclic carboxylic acid esters include furan carboxylic esters, dihydrofuran carboxylic esters, benzofuran carboxylic esters, coumaran carboxylic esters, pyran carboxylic esters, pyrone carboxylic esters, and coumarin carboxylic esters. Examples include acid esters, ink marine 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-2,4-dicarboxylate, Methyl 5-dicarboxylate, methyl furan-3,4-dicarboxylate, methyl 4,5-dihydrofuran-2-carboxylate, ethyl, methyl tetrahydrofuran-2-carboxylate, methyl coumarate (methyl benzofuran-2-carboxylate), Ethyl coumaran-2-carboxylate,
Methyl coumarate, ethyl coumarate, methyl coumarate, ethyl,
5-hydroxy-4-ethoxycarbonyl coumarin, 4
Examples include -ethoxycarbonyl isocoumarin, 3-methyl-furan-2-carboxylic acid ester, ethyl isodehydroacetate, and methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate, ethyl, propyl, butyl, Methyl 4,5-dihydrofuran-2-carboxylate, ethyl tetrahydrofuran-2-carboxylate, methyl coumarate, methyl coumarate, ethyl etc. give preferable results. next,
Examples of nitrogen-containing heterocyclic carboxylic acid esters include pyrrole carboxylic esters, indoles carboxylic esters, carbazole carboxylic esters, oxazole carboxylic esters, thiazole carboxylic esters, imidazole carboxylic esters, and pyrazole carboxylic esters. ester, pyridine type carboxylic acid ester, phenanthridine type carboxylic acid ester, anthrazoline type carboxylic acid ester, phenanthroline type carboxylic acid ester, naphthyridine type carboxylic acid ester, oxazine carboxylic acid ester, thiazine type carboxylic acid ester, pyridazine type carboxylic acid ester , pyrimidine carboxylic acid esters, and pyrazine carboxylic acid esters, but preferred ones include methyl, ethyl, propyl, and butyl pyrrole-2-carboxylate, methyl, ethyl, propyl, and butyl pyrrole-3-carboxylate, and pyridine-2-carboxylate. - Methyl, ethyl, propyl, butyl and amyl carboxylate, methyl pyridine-3-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, N-methyl Ethyl pyrrolecarboxylate, 2-
Examples include ethyl methylpyridinecarboxylate, ethyl piveridine 4-carboxylate, ethyl piveridine 2-carboxylate, and ethyl pyrrolidine 2-carboxylate.

Next, a basic group (1') obtained by the reaction of a Grignard reagent with a chlorosilane compound, a titanium compound {2} and a sulfur-, oxygen-, or nitrogen-containing heterocarboxylic acid ester (hereinafter referred to as the present heterocyclic carboxylic acid ester) )
The method of obtaining a catalyst solid by reacting and/or pulverizing contact with the catalyst will be explained.

The reaction between the basic solid and the titanium compound or the heterocyclic carboxylic acid ester of the present application is a method in which the titanium compound or the heterocyclic carboxylic acid ester of the present application is reacted in a liquid phase or a gas phase [1]
Any method can be adopted, such as the method [2] that combines a reaction in a liquid phase or a gas phase and a pulverization reaction. First, the order of reaction and/or pulverization of the basic solid with the titanium compound and the heterocyclic carboxylic acid ester of the present application will be explained.

Regarding method [1], there is a method in which the basic solid, the titanium compound, and the present heterocyclic carboxylic acid ester are reacted simultaneously (synthesis method ■), or the basic solid and the titanium compound are first reacted, and then the present heterocyclic carboxylic acid ester is reacted. There is a method of reacting (synthesis method (2)), or a method of first reacting the basic solid with the heterocyclic carboxylic acid ester of the present invention and then reacting with a titanium compound (synthesis method (2)). Although either method is possible, the latter two methods are preferred, and synthesis method (2) is particularly preferred. For method [2], the titanium compound is (1)
The case of tetravalence, (0) the case of trivalence, and (m) the case of using both tetravalence and trivalence will be described.

In the case of (1), a method of simultaneously reacting the basic solid, a titanium compound, and the heterocyclic carboxylic acid ester of the present invention and pulverizing the solid obtained (synthesis method ■), or first reacting the solid substance and the titanium compound and then further A method of pulverizing a solid obtained by reacting a polycyclic carboxylic acid ester (synthesis method ■)
Alternatively, there is a method (synthesis method ①) in which the above-mentioned solid substance is first reacted with the multi-hata ring carboxylic acid ester of the present invention, and then a titanium compound is reacted, and the resulting solid is pulverized.

Although either method is possible, the latter two methods are more preferable, and particularly synthesis method (1) gives preferable results. In the case of (b), various methods are possible for synthesizing the solid component from the three components of the basic solid, the trivalent titanium halide, and the enomoto ring carboxylic acid ester of the present application, but the following three methods yield particularly preferable results. give. That is, a method of co-pulverizing the three components (synthesis method ■), a method of bringing the solid component into contact with the heterocyclic carboxylic acid ester of the present application in advance, and then adding a trivalent titanium halide and mechanically crushing it (synthesis method (2), or a method (synthesis method (2)) in which a solid component and a trivalent titanium halide are mechanically crushed and brought into contact with each other, and then treated with the enomoto ring carboxylic acid ester of the present invention. In the case of (m), a method (synthesis method ■),'1}
Treating the solid obtained by reacting with (2-1) with glue,
Method of crushing together with (2-2) (synthesis method ■), {1)
The solid obtained by reacting the leg with (2-1) is treated with
Method of crushing together with (2-2) (synthesis method ■), {1}
A solid obtained by reacting (2-1) with (2-2)
Examples include a method of adding and pulverizing (3) (synthesis method ①), but synthesis method ① is preferable.

Further, when the solid catalysts synthesized by the above methods [1) and [2] are further treated with a tetravalent titanium compound [4] containing at least one halogen atom, an increase in catalytic efficiency is brought about.

First, the solid catalyst synthesized by method [1] is further
The above method of treating with tetravalent titanium halide is as follows:
A method in which the basic solid, the titanium compound, and the heterocyclic carboxylic acid ester of the present invention are simultaneously reacted, and then further treated with a tetravalent titanium halide (synthesis method ■); A method in which a carboxylic acid ester is reacted and then further treated with a tetravalent titanium halide (synthesis method ■), a basic solid is reacted with the present heterocyclic carboxylic acid ester, and then a titanium compound is reacted. After that, there is a method of further treating with a tetravalent titanium halide (synthesis method ①).

Next, a method of further treating the solid catalyst synthesized by method [2] with a tetravalent titanium halide will be described in (1), (b), and (m) below. (1)
In the case of , synthesis method [2]-(1)1■, [2]-(1)-
It is possible to treat the solid catalyst synthesized by (1) or (2)-(1)-(2) with a tetravalent titanium halide, but the latter two methods are more preferred.

In the case of (b), synthesis method [2]-(0)-■, [2]-(
It is possible to further treat the solid catalyst synthesized by b)-■, [2]-(b)-■, and [2]-(0)-■ with a tetravalent titanium halide.

In the case of (m), the basic solid '1}, the tetravalent titanium compound (
2-1), a method in which the trivalent titanium compound (2-2) and the heterocyclic carboxylic acid ester of the present application are simultaneously pulverized and then treated with a tetravalent titanium halide (synthesis method ■);
1} and (2-1) are treated with [3}, pulverized together with (2-2), and then treated with a tetravalent titanium halide (synthesis method ■), '11 and '3}, the resulting solid is treated with (2-1), pulverized with (2-2), and then further treated with a tetravalent titanium halide (synthesis method). ■).

The solid obtained by reacting '1' with (2-1) and (2-
2) and a method of adding glue, pulverizing it, and then treating it with a tetravalent titanium halide (synthesis method ■), [1' and (2)
There are methods such as treating the solid obtained by reacting 1-1) with glue, pulverizing it with 2-2, and then treating it with a tetravalent titanium halide (synthesis method ■), and method ■■ ■■ is preferred. Next, the reaction of the basic solid with the titanium compound and the heterocyclic carboxylic acid ester of the present invention and/or the pulverization operation will be explained. (i) The reaction between a titanium compound and a solid substance obtained by reacting a Grignard reagent with a chlorosilane compound, or a reaction product of this solid substance and the compound cylindrical carboxylic acid ester of the present invention will be explained.

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 temperature of the titanium compound, but preferably 80°C.
The reaction is carried out at a temperature of 0 or more and the titanium compound temperature is 2 molar liters or more, or using the undiluted titanium compound itself as a reaction medium. Regarding the reaction molar ratio, preferred results are obtained when the reaction is carried out in the presence of a sufficient excess amount of the titanium compound relative to the magnesium component in the solid substance. {ii) The reaction between a solid material obtained by reacting a Grignard reagent and a chlorosilane compound, or a reaction product of this solid material and a titanium compound, and the polycyclic carboxylic acid ester of the present application will be described.

The reaction is carried out using an inert reaction medium. As the inert reaction medium, any of the aforementioned aliphatic, aromatic, and alicyclic hydrocarbons may be used. The temperature during the reaction is not particularly limited, but is preferably in the range from room temperature to 10,000 ℃. When a solid substance is reacted with the present heterocyclic carboxylic acid ester, the reaction ratio of the two components is not particularly limited, but preferably the present heterocyclic carboxylic acid ester is reacted with respect to 1 mole of alkyl group contained in the solid substance. is recommended to be in the range of 0.001 mol to 50 mol, particularly preferably 0.005 mol to 10 mol. When a reaction product of a solid substance and a titanium compound is reacted with the polycyclic carboxylic acid ester of the present invention, the reaction ratio of the two components is as follows: acid ester 0
．． 01 mol to 100 mol, particularly preferably o. 1 mole ~
A range of 10 moles is recommended. ``ii) Above (i)~
A method for pulverizing the solid produced by the reaction (ii) will be explained.

Grinding methods include rotary ball mill, vibrating ball mill,
Well-known mechanical crushing means such as an impact pole mill can be employed. The grinding time is 0.5 to 10 field hours, preferably 1 to 3 field hours, and the grinding temperature is 0 to 200 qo, preferably 10 to 15,000 qo. (i) Skin - The case where the solid component obtained in step (ii) is 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 hexa)/heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Hydrocarbons are preferred. Regarding the concentration of titanium compound, 2 mol
A concentration higher than 1' is preferable. There is no particular restriction on the reaction temperature, but a reaction temperature of 8,000 or higher gives preferable results. Regarding the composition and structure of the solid catalyst component obtained by the reactions (i) to (M) above,
Although it varies depending on the type of starting material and reaction conditions, it was found from the compositional analysis that it was a solid catalyst containing approximately 1 to 1% by weight of titanium in the solid catalyst.

[B] As the organometallic compound used as the component,
Among the compounds of the first to blood groups of the periodic table, organoaluminum compounds are particularly preferred.

The organoaluminum compound has the general formula NRlotZ
-t (wherein R1o is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group, and t 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 R1o 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, diisobutyl aluminum hydride, diethylaluminum ethoxide, diisobutyl aluminum ethoxide, dioctyl aluminum butoxide, diisobutyl aluminum octyl oxide, diethylaluminium chloride,
Diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydroxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminumisoprenyl, etc., and mixtures thereof are recommended.

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

The present heterocyclic pseudocarboxylic acid ester added to the organometallic compound may be the same or different from the present heterocyclic carboxylic acid ester used in the synthesis of the solid catalyst component. The addition method is
The two components may be mixed in advance prior to polymerization, or
They may be added separately into the polymerization system. The ratio of the two components to be combined is 10 mol or less, particularly preferably 1 mol or less, of the present heterocyclic carboxylic acid ester per 1 mol of the organometallic compound. The solid catalyst component of the present invention and the catalyst consisting of an organometallic compound and the polycyclic carboxylic acid ester component of the present invention may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization.

Particularly preferably, the organometallic compound and the complex moat carboxylic acid ester of the present invention are reacted in advance, and the organometallic compound is separately added to the polymerization system. The ratio of each component to be combined is 1 mmol to 3000 mmol based on the organic metal compound for the solid catalyst component 1, and the organic metal compound plus the present enocyclic carboxylic acid ester. preferable. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins. In particular, the present invention relates to propylene. ten-1, bentene-1, 4-methylbentene-1,
Suitable for stereoregular polymerization of 3-methylbutene-1 and similar olefins alone. and copolymerizing the olefin with ethylene or other olefins;
Furthermore, it is suitable 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 for the polymerization method,
Usual suspension polymerization, bulk polymerization in liquid monomers, and gas phase polymerization are possible. Suspension polymerization involves polymerizing a catalyst (e.g., aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane).
Polymerization can be carried out at a temperature from room temperature to 15,000 ℃ by introducing an olefin such as propylene into a reactor under an inert atmosphere at a rate of 1 to 20 k9/cm. 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, 10 to 45 kg/c at room temperature to 90 qo.
The polymerization can be carried out in liquid propylene under pressures such as On the other hand, gas phase polymerization is carried out under conditions where the olefin such as propylene is a gas, in the absence of a solvent, at a pressure of 1 to 50 k9/h, and at a temperature of room temperature to 120 pm. In order to achieve good contact, polymerization can be carried out by means such as a fluidized bed, a moving bed, or mixing using a hawk machine. 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. Example 1 (i) Synthesis of organomagnesium compound A 500-volume flask equipped with a dropping funnel and a water-cooled reflux condenser was purged with dry nitrogen, and 14.6 minutes of 100-200 mesh metal magnesium powder was added. 6 mol), 363 g of n-hebutane, and a small piece of iodine were charged, and the flask was heated to 95°C.

Next, a mixture of 0.5 mol of n-butyl chloride and 0.5 mol of di-n-butyl ether was weighed into the dropping funnel, and
The mixture was added dropwise at ~100°C over 2 hours under pressure. During the dropwise addition, the color of iodine disappears and the reaction begins. After the dropwise addition was completed, heating was continued at 90 to 100° C. for another 4 hours, and the mixture was allowed to settle down, and the top solution was taken out in nitrogen. As a result of analyzing this liquid, it was found to be a magnesium butyl ether dibutane solution having a composition of n-BUM or 1, and the organic metal concentration was 0.73 mol/solution. (ii) Capacity 500 with base solids synthesis addition funnel and water-cooled reflux condenser
Oxygen and moisture inside the flask were removed by dry nitrogen substitution, and the above n-B mountain MgCI was removed under a nitrogen atmosphere.
100 mmol of a butane solution was added to the butane coordination compound, and the temperature was raised to 8,000 ℃.

Next, under a nitrogen atmosphere, trichlorosilane (HSiC13
) lmol/100 mmol of the butane solution was weighed into the dropping funnel.

The mixture was added dropwise over a period of 1 hour at 80q○ under Nada gas, and further aged at this temperature for 1 hour, allowing the reaction to proceed for a total of 2 hours.

The resulting hydrocarbon-insoluble white precipitate was isolated, washed with hexane and dried to yield a white basic solid. As a result of analyzing this solid, it was found that Mg9.05wmol, C
I 18.7 mol, Sil. 55 mmol, alkyl group 0.58 mmol, B. E. T. The specific surface area measured by the method was 187 mm. Synthesis of catalytic solid 3.0 mm of the above white solid was placed in a flask that had been sufficiently purged with nitrogen, and 60% of n-hexane and 0.1 mol of ethyl thiophene-2-carboxylate/3.0 mm of its hexane solution were added.
ol was added thereto, and the mixture was reacted at 80 q○ for 1 hour with the light turned on. The solid was separated in a furnace, thoroughly washed with n-hexane, and dried.

2.5 liters of this solid and 50 liters of titanium tetrachloride were placed in a pressure vessel purged with nitrogen, and heated at 13,000 ℃ for 2 hours.
After reacting for an hour, the solid was separated by furnace and washed with n-hexane.
A solid catalyst was obtained by drying. As a result of analyzing this solid catalyst, the Ti content was 2.8% by weight. Others Solid catalyst 50c synthesized by propylene slurry polymerization oii)
, 3.0 mmol of triethylaluminum, and 1.0 mmol of ethyl thiophene-2-carboxylate were dehydrated,
The interior of the autoclave was replaced with nitrogen and then vacuum degassed for 1.5 hours with 0.8 hours of deaerated hexane.

Maintaining the internal temperature of the autoclave at 600℃, propylene was pressurized to a pressure of 5.0k9/kg, and polymerization was carried out for 2 hours while maintaining the total pressure at 4.8k9/kg, resulting in a polymerized hexane-free polymer. After 94 days, 3.4 times of polymerized hexane soluble material was obtained. Catalyst efficiency is 940 pp/t solid catalyst/hour, 6
640 pp' of titanium content, time, and propylene pressure, and the residue obtained by extracting the polymerized hexane-insoluble polymer with boiling n-hebutane was 95.1%. The particle properties were also good, with a bulk density of 0.365 m/m and a ratio of 35 to 150 mesh powder of 94%. Example 2 Instead of the butane solution of the n-BUMgCI butyl ether coordination used in Example 1, a n-butylmagnesium chloride dibutyl ether solution synthesized by reacting n-BuCI with metal magnesium in a butyl ether solution was used, and other solutions were used. A solid catalyst was synthesized in the same manner as in Example 1.

As a result of analysis of this solid catalyst, the Tj content was 5.1% by weight. Slurry monopolymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 50:9, 3.0 moles of triethylaluminum, and 1.0 moles of N-carboethoxypyrrole, and the polymerized hexane was unmelted. 100 ml of polymer and 3.7 ml of polymerized hexane soluble material were obtained. The catalytic efficiency was 1000 Tpp/unit solid catalyst/hour, 3920 Tpp/unit titanium component/hour/propylene pressure, and the remaining volume after extracting the polymerized hexane-insoluble polymer into boiling n-hebutane was 95.3%. Ta. Example 3 (i) Synthesis of organomagnesium compound A 500-capacity flask equipped with a dropping funnel and a water-cooled reflux condenser was purged with dry nitrogen, and 100 to 200 mesh metal magnesium powder 20.0 mm and 20.0 mm was added to butane. 30
The flask was heated to 9,000 ℃.

Next, 0.81 mol of n-butyl chloride was weighed into the dropping funnel and added dropwise at 90:00 over a period of 1 hour while condensing. After the reaction started, Isoazusa was continued for 2 hours at 90-960°C, and then the solid portion was washed in a furnace, washed with hexane, and dried. As a result of analyzing the solid, it had a composition of n-B mountain MgCI. (ii) Synthesis of basic solids In a pressure-resistant container purged with nitrogen, 150 mmol of the above organomagnesium compound and 1 mol of monomethyldichlorosilane (HSiC12/C ratio)/100 mmol of sohebutane solution were charged, and the mixture was heated to 7000 m After reacting for 2 hours, the solid portion was filtered, washed with hexane, and dried to obtain a basic solid.

"ii) Synthesis and polymerization of catalyst solid A catalyst solid was synthesized in the same manner as in Example 1 using the above basic solid.

The Ti content of the catalyst solid was 2.61% by weight, and the specific surface area was 118 mm/h. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 50 mol of this solid catalyst, 3.0 mol of triethylaluminum, and 1.0 mol of ethyl furan-2-carboxylate. 80 ml of polymer and 2.6 ml of polymerized hexane soluble material were obtained. The catalyst efficiency was 6130 pp/t titanium component/time/propylene pressure, and the residual weight when the polymerized hexane-insoluble polymer was extracted with boiling n-heptane was 94.8%. Comparative Example 1 100 mmol of n-butylmagnesium chloride dibutyl ether solution synthesized in the same manner as in Example 2 was charged into a pressure-resistant capacity purged with nitrogen, and the temperature was raised to 40 oo.

HCI gas is generated by dropping HX04 into NaCI,
This is n-BUMgCI. Bubbling into dibutyl ether solution gave 8.8 g of a white solid. Using this solid, in the same manner as in Example 1, ethyl thiophene-2-carboxylate,
A solid catalyst was synthesized by reacting with titanium and titanium tetrachloride.

The Ti content of the catalyst solid was 0.6% by weight. This solid catalyst 100/9, triethyl aluminum 3.0 mm
ol, ethyl thiophene-2-carboxylate 1.0 mmo
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 1.

Polymerized hexane-insoluble polymer 17. Hexane-soluble material 2.
I got 5 nights. The catalytic efficiency was 85 tpp/t solid catalyst/hour, 2500 tpp't titanium component/time/propylene pressure, and the residual amount after extracting the polymerized hexane-free polymer with boiling n-heptane was 84.1%. Ta. Comparative Example 2 In the same manner as in Example 2, using silicon tetrachloride (SIC14) instead of trichlorosilane as a reaction reagent, n
-Butylmagnesium chloride/dibutyl ether solution was reacted, and this solid was reacted with titanium tetrachloride to obtain a solid catalyst.

The Ti content of the solid catalyst was 7.5% by weight.

This solid catalyst 50:9 and triethylaluminum 2.4
Slurry polymerization of propylene was performed in the same manner as in Example 1 using skin mol. After polymerization, the slurry was treated by adding a large amount of methanol to obtain Polymer 45. The polymer was fluffy and had a poor powder particle shape, and the bulk density of the polymer was as low as 0.22 poly/dielectric. Catalyst efficiency is 1200 taps
p' titanium component, time, and propylene pressure, and the residue obtained by extracting the polymer with boiling n-heptane was 68.1%. Comparative Example 3 A small amount of iodine was added to powdered magnesium and titanium tetrachloride, heated to 90°C in n-hebutane medium, n-butyl chloride was added, and the mixture was reacted for 3 hours.

The produced brown-black solid was washed and dried to obtain a solid catalyst. As a result of analyzing this solid catalyst, the Ti content was 8.3
It was 0% by weight.

50mg of this solid catalyst and 2.4mg of triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using mmol.

After polymerization, a large amount of methanol was added to treat the slurry to obtain Polymer 52. The catalyst efficiency was 1250 pp/t titanium component/time/propylene pressure, and the residue obtained by extracting the polymer with boiling n-hebutane was 48.8%.
Example 4 In the same manner as in Example 1, ethylmagnesium chloride/ethyl ether coordination was reacted with a butane solution and monomethyldichlorosilaso (HSiC12.CH3), and this solid was reacted with ethyl furan-2-carboxylate and A solid was obtained by reaction with titanium chloride.

This solid 4.0 mm was heated to 1000 Vib in a steel mill with an internal volume of 100 flow containing 23 solid steel balls of 9 ◇ under a nitrogen atmosphere.
The mixture was pulverized for 5 hours using a vibrating ball mill at a speed of 1/min or more. The Ti content of the obtained solid catalyst was 2.92% by weight. This solid catalyst 50 female and triethyl aluminum 3
．． 0 mmol, N-ruboethoxypyrrole 1.0 m
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using OL.

The results are shown in Table 1. Example 5 In the same manner as in Example 2, a solution of ethylmagnesium chloride in tetrahydrofuran was reacted with trichlorosilane, and this solid was reacted with N-rboethoxypyrrole and titanium tetrachloride to obtain a solid.

3.90% of this solid and 0.1% of titanium trichloride (AA grade TIC13/1/3NC13 manufactured by Toyo Stoffer Co., Ltd.)
5 hours under a nitrogen atmosphere in the same manner as in Example 4. The Ti content of the obtained solid catalyst was 5.75% by weight. 9 of 50 of this solid catalyst, 3.0 mol of triethylaluminum, 1.0 M ethyl coumarate
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using mol. The results are shown in Table 1. Example 6 In the same manner as in Example 3, a suspension of phenylmagnesium chloride in n-hebutane was reacted with trichlorosilane to synthesize a basic solid, which was further reacted with methyl pyridine-2-carboxylate.

4.09 g of this solid and 0.35 g of titanium trichloride (AA grade, manufactured by Toyo Stofa Co., Ltd.) were pulverized for 5 hours in the same manner as in Example 4 under a nitrogen atmosphere. Ti of the obtained solid catalyst
The content was 2.01% by weight. Table 1 shows the results of slurry polymerization of propylene in the same manner as in Example 1 using this solid catalyst 50:9, 3.0 mmol of triethylaluminum, and 1.0 mmol of butyl thiophene-2-carboxylate. Example 7 In the same manner as in Example 6, the basic solid and methyl pyridine-2-carbosoate were reacted, and then the obtained solid and titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were pulverized.

. After reacting this group of 4.0% with 60% of titanium tetrachloride for 2 hours at 13,000 degrees Celsius, the solid portion was isolated by filtration, thoroughly washed with hexane, and dried to obtain a solid catalyst. . Analysis of this solid revealed that it contained 3.2% by weight of titanium. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 50:9, 3.0 mmol of triethylaluminum, and 1.0 mmol of butyl thiophene-2-carboxylate.

The results are shown in Table 1. Example 8 In the same manner as in Example 4,
Reacting the basic solid with ethyl furan-2-carboxylate,
Next, the obtained solid was reacted with titanium tetrachloride.

This solid was ground in a vibrating ball mill under nitrogen atmosphere for 5 hours. Furthermore, this solid 4.0 liters and titanium tetrachloride 60 liters were reacted for 2 hours at 13,000 yen under the ocean, and the solid portion was isolated by filtration, thoroughly washed with hexane, and dried to obtain a solid catalyst. . Analysis of this solid revealed that it contained 3.35% by weight of titanium. Example 1 Using this solid catalyst 9 of 50, 3.0 mmol of triethylaluminum, and 1.0 mmol of N-carboethoxypyrrole,
Slurry polymerization of propylene was carried out in the same manner.

The results are shown in Table 1. Table 1 Example 9 350 ml of liquefied propylene was placed in an autoclave whose interior had been replaced with nitrogen and vacuum dried, and the internal temperature was brought to 60 ml.
00, and 9 of 10 of the solid catalyst synthesized in Example 8,
1.5 mmol of triethylaluminum and 0.5 mmol of nitrogen oxide pyrrole were added to the autoclave, and polymerization was carried out at 6000 for 2 hours to obtain 155 mmol of polypropylene.

Catalyst efficiency is 7750 Tpp/day solid catalyst/hour, 231
000 Tpp/Tatitan component/hour, and the n-hebutane extraction residue of the produced polypropylene was 93.1%. Example 10 Synthesis in Example 8 with a pre-mixed solution of 2.0 mol of a hexane solution (lmol/〆) of triethylaluminum and 1.0 mmol of a hexane solution (mol/〆) of N-polyethoxypyrrole 9 of 30 solid catalysts,
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 1.0 mmol of triethylaluminum, and 173 of the polymerized hexane infusible polymer and 5 of the polymerized hexane soluble material were obtained.
．． I got 4 nights.

The n-hebutane extraction residue of polymerized hexane-insoluble polymer is 9
4.7%, and the catalyst efficiency was 17,200 Tpp/Tatitanium component, time, and propylene pressure. Examples 11 to 16 A propylene slurry was prepared in the same manner as in Example 1 using 9 of 50 of the solid catalyst synthesized in the same manner as in Example 1, 3.0 mol of triethylaluminum, and 1.0 mmol of the compound shown in Table 3. Polymerization was carried out and the results shown in Table 2 were obtained.

Examples 17-18 9 of 50 solid catalysts synthesized in the same manner as in Example 1 and 1.0 of N-triboethoxypyrrole
mmol and 3.0 mmol of the organometallic compound shown in Table 3
Slurry polymerization of propylene was carried out in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Table 2 Table 3 Example 19 9 of 50 solid catalysts synthesized in the same manner as in Example 1,
Slurry polymerization was carried out in the same manner as in Example 1 using 3.0 mmol of triethylaluminum and 1.0 mmol of N-carbethoxypyrrole using a propylene-ethylene mixed gas containing 2 mol% of ethylene to obtain white polymer 104. I got the evening.

Example 20 Example 1 Polymerization of putene-1 in hexane using 9 of 500 solid catalyst synthesized in the same manner as in Example 1, 6.0 mmol of triethylaluminum, and 2.0 mmol of N-carboethoxypyrrole In the same manner as above, a white polymer 93 was obtained.

Example 21 Preparation of 4-methylbentene-1 in hexane using 9 of 500 solid catalysts synthesized in the same manner as in Example 1, 6.0 mmol of triethylaluminum, and 2.0 mmol of N-triboethoxypyrrole. Polymerization was carried out in the same machine as in Example 1 to obtain 71 white polymers.

Example 22 50 pieces of solid catalyst synthesized in the same manner as in Example 1, 1.0 mmol of triisobutylaluminum, and 0.1 mol of N-carbethoxypyrrole were mixed with 0.8 mol of n-hexane, which was dehydrated and degassed. At the end of the day, the inside was vacuum dried and replaced with nitrogen, then placed in an autoclave for 1.5 days, keeping the internal temperature at 80:00, pressurized with hydrogen to 1.6 kg/kg, and then adding ethylene to reduce the total pressure. 4.0k9/carp.

Claims (1)

[Scope of Claims] 1 [A] (1) (i) An organomagnesium compound represented by the general formula R^1MgX (wherein R^1 has 1 to 1 carbon atoms)
20 alkyl group or aryl group, X represents a halogen atom), (ii) general formula H_aSiCl_bR_4
A solid obtained by reacting with a Si-H bond-containing chlorosilane compound represented by _-_(_a_+_b_) (where a, b are numbers larger than 0, a+b≦4, and R represents a hydrocarbon group), ( 2) a titanium compound containing at least one halogen atom; (3) one or more selected from sulfur-containing, oxygen-containing, or nitrogen-containing heterocyclic carboxylic acid esters;
A solid catalyst component obtained by reacting and/or pulverizing (1), (2), and (3), [B] an organometallic compound, and a sulfur-containing, oxygen-containing, or nitrogen-containing heterocyclic carboxylic acid ester. A catalyst for olefin polymerization comprising one or more components. 2. The catalyst for olefin polymerization according to claim 1, wherein in the Si-H bond-containing chlorosilane compound of [A](ii), the value of a is 0<a<2. 3 [A] Claim 1, wherein the titanium compound in (2) is a tetravalent titanium compound and/or a trivalent titanium halide containing at least one halogen atom.
The catalyst for olefin polymerization according to item 1 or 2. 4. The catalyst for olefin polymerization according to claim 3, wherein the titanium compound in [A] (2) is titanium tetrachloride and/or titanium trichloride. 5 [A] The titanium compound in (2) is a tetravalent titanium compound containing at least one halogen atom, and (1
), (2) and (3) to synthesize a solid catalyst component by reacting or reacting and pulverizing the catalyst for olefin polymerization according to any one of claims 1 to 4. 6 [A] The titanium compound in (2) is a trivalent titanium halide, and (1), (2) and (3) are co-milled, or (1) and (3) are reacted. By pulverizing the solid obtained by grinding (2) or by treating the solid obtained by co-pulverizing (1) and (2) with (3),
The catalyst for olefin polymerization according to any one of claims 1 to 4, which synthesizes a solid catalyst component. 7 [A] The titanium compound of (2) is (a) at least 1
a tetravalent titanium compound containing halogen atoms, and (b) a trivalent titanium halide, comprising (1)
, (2) and (3), or by pulverizing and reacting to synthesize a solid catalyst component, the catalyst for olefin polymerization according to any one of claims 1 to 4. 8 [A] (3) and [B] sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester is a thiophene carboxylic acid ester, a furocarboxylic acid ester, a coumaric acid ester, a pyrrole carboxylic acid ester or a pyridine carboxylic acid ester The catalyst for olefin polymerization according to any one of claims 1 to 7, which is an acid ester. 9 [A] The amount of the sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester in (3) is determined in the solid obtained by reacting the organomagnesium compound in (1) with the Si-H bond-containing chlorosilane compound. The catalyst for olefin polymerization according to any one of claims 1 to 8, wherein the number of moles is 0.001 to 50 times the number of moles of the alkyl group contained. 10 The organometallic compound [B] has the general formula AlR^1^0_tZ_3_-_t (in the formula, R^1^0
is a hydrocarbon group of C_1_ to_2_0, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group, and t is a number of 2≦t≦3). A catalyst for olefin polymerization according to any one of claims 1 to 9. 11. The catalyst for olefin polymerization according to any one of claims 1 to 9, wherein the organometallic compound [B] is trialkylaluminum or dialkylaluminum hydride. 12 [A] (1) (i) R^
An organomagnesium compound represented by 1MgX (wherein R
^1 is an alkyl group or aryl group having 1 to 20 carbon atoms,
(X represents a halogen atom), (ii) general formula H_a
SiCl_bR_4_-_(_a_+_b_) (in the formula,
a, b are numbers larger than 0, a+b≦4, R represents a hydrocarbon group) A solid obtained by reacting with a Si-H bond-containing chlorosilane compound, (2) at least 1
a titanium compound containing halogen atoms, (3) one or more of (1), (2), and (3) selected from sulfur-containing, oxygen-containing, or nitrogen-containing heterocyclic carboxylic acid esters. A solid catalyst component obtained by pulverization and further treatment with a tetravalent titanium compound (4) containing at least one halogen atom, [B] an organometallic compound, and a sulfur-containing, oxygen-containing or nitrogen-containing compound. A catalyst for olefin polymerization comprising one or more components selected from heterocyclic carboxylic acid esters. 13. The catalyst for olefin polymerization according to claim 12, wherein the four titanium compounds containing at least one halogen atom in [A] (4) are titanium tetrachloride.