JPS6034565B2 - 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
, suitable for the stereoregular polymerization of 4-methylbentene-1,3-methylbutene-1 and similar olefins,
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 Ziegler-Natta catalyst system consisting of a transition metal compound of the WA group and an organometallic compound of the first to blood groups of the periodic table. 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 non-falling 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 is A step is required to remove catalyst residue from coalescence.

In recent years, many systems comprising a reaction product of an inorganic or organic magnesium compound and a titanium or vanadium compound and an organic aluminum compound have been proposed as highly active ethylene polymerization catalysts.

Although these systems exhibit remarkable activity in the polymerization of propylene, the proportion of boiling hebutane soluble components, that is, amorphous polymers, to the total polymer produced is very large, and the steric polymerization of olefins such as propylene is difficult to achieve industrially. It is difficult to use it as it is as a specific polymerization catalyst (for example, Tokukan Sho 47-19342,
Special Publication No. 43-11305). As a solution to these problems, Hakamako Sho 52-39431, Tokuko Sho 52-3
6153 and Samurai Kaisho 48-16988 have been proposed. These methods use a solid component obtained by co-pulverizing a rust compound of a titanium halide compound and an electron donor and anhydrous magnesium halide, and an addition reaction product of trialkylaluminium and an electron donor. It is a catalyst system consisting of However, even with these methods, the proportion of boiling butane-insoluble matter in the produced polymer is still not high enough to satisfy the requirements, especially the yield of polymer per solid catalyst component is insufficient, and the production process equipment and molding machine are insufficient. The content of halogen, which causes corrosion, is high in the polymer, and the physical properties of the product are not fully satisfactory. In a previous patent application, the applicant has prepared a basic solid halogen-containing magnesium compound by reacting a solution containing organomagnesium soluble in an inert hydrocarbon medium with a tertiary alkyl halide compound as a reaction agent. We have discovered that by combining a specific solid made by contacting this with a transition metal compound such as titanium and an organometallic compound, an excellent highly active catalyst for olefin polymerization can be obtained.

The present invention is an improved method of this proposal, and is an improved method that can produce highly stereoregular olefin polymers and copolymers at high yields. That is, the present invention provides: [A] {1' {i} General formula MQMg8RIPR2q
XrYS (where Q is 0 or a number greater than 0, P'q
'r'S is 0 or a number larger than 0, p1q+r+s
=mQ128, where M is a metal element belonging to Group 1 or Blood Group of the Periodic Table, R1 and R2 are hydrocarbon groups having the same or different numbers of carbon atoms, and × and Y are the same or different. group, halogen, OR300SIR4R5R6
, NR7R8, SR9, and R3, R4, R
5, R6, R7, R8 are hydrogen atoms or hydrocarbon groups, R
9 represents a hydrocarbon group) is combined with a tertiary alkyl halide compound represented by the general formula {ii' (wherein R1o, RI1, R12 are hydrocarbon groups and Q represents a halogen). The solid obtained by the reaction is mixed with {2} one or more components selected from a titanium compound containing at least one halogen atom, a sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester; 1},
■, a solid catalyst component obtained by reacting and/or pulverizing [3]; [B] an organometallic compound; This is an olefin polymerization catalyst consisting of components [A] and [B].

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 it has high activity as described above, and
Furthermore, high stereoregularity can be obtained. The third feature of the present invention is that the particle size of the polymer is good and that a 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 catalyst of the present invention as described above are still unclear, but as shown in the examples described later, according to the present method, alkyl groups with a high surface area and reducing power can be It is believed that the active magnesium halide basic solid contained therein was synthesized.

General formula MQMg8 used in the synthesis of the solid catalyst of the present invention
RIPR is also XrYs (in the formula, Q, 8, P'q'r, s,
The organomagnesium compound (M, R1, R2, X, Y have the above-mentioned meanings) will be explained.

Although this compound is shown as an organomagnesium compound, it includes all so-called Grignard compounds of RMgX, R2Mg, and complexes of these with other metal compounds.

The hydrocarbon group represented by RI to R9 in the above formula is
an alkyl group, a cycloalkyl group or an allyl group,
Examples include methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl, etc., and RI is particularly preferably an alkyl group. R3 to R8 are not limited to hydrogen atoms. As the metal atom M, metal elements belonging to Groups 1 to M of the periodic table can be used, such as sodium, potassium, calcium, beryllium, zinc, barium, boron, aluminum, etc., but in particular aluminum, Zinc, boron, and beryllium are particularly preferred because they facilitate the production of hydrocarbon-soluble organomagnesium compounds.

The ratio of magnesium to metal atom M, 3/Q, is Q=○
Although it can be arbitrarily set including the so-called Grignard compound, hydrocarbon-soluble organomagnesium compounds having a range of preferably 0 to 10, particularly 1 to 10 are particularly preferred. Relational expression p + q + r of symbols Q, 3, p, q, r, s
+s=mQ+28 indicates the stoichiometry between the valence of the metal atom and the substituent, and is in the preferred range OS(r+s)/
(Q+8)<1.0 indicates that the sum of x and Y is greater than or equal to ◯ and smaller than 1.0 with respect to the sum of metal atoms.

A particularly preferred range is 0 to 0.8. These organomagnesium compounds or organomagnesium bodies have the general formula RIMgQ, R-Mg (RI has the above-mentioned meaning,
Q is a halogen) and an organomagnesium compound represented by the general formula MR2m or MR2m-,
, m has the above-mentioned meaning) and hexyl, heptane, cyclohexane, benzene,
In an inert hydrocarbon medium such as toluene, at room temperature to 150 qo
If necessary, this is further reacted with an alcohol, water, siloxane, amine, imine, mercaptan or dithio compound.

Furthermore, organomagnesium compounds or organomagnesium complexes include MgX2, RIMgX, MR2m, MR2m
-, day, or RIMg×, MgR room and R cost MXm-n
, or RIMgX, MgR2 and YnMXm-n (wherein M, R1, R2, X, Y are as described above, ×
, Y is a halogen, n is a number from 0 to m). Generally, organomagnesium compounds are insoluble in inert hydrocarbon media, and organomagnesium compounds where Q>○ are soluble.

In addition, even when Q=0, certain organomagnesium compounds,
For example, sec-B paid Mg and the like are soluble in hydrocarbon media, and thus compounds can also be used in the present invention to give preferable results, and these organomagnesium compounds will be described below.

R1, R2 in the general formula Mg8RIPR2qXrYS
shall be one of the following two groups (1), (b), and (m).

(1) At least one of R1 and R2 has 4 or more carbon atoms
6 is a secondary or tertiary alkyl group.

Preferably, both R1 and R2 have 4 to 6 carbon atoms, and at least one is a secondary or tertiary alkyl group. (b) R1 and R2 are alkyl groups having different numbers of carbon atoms. Preferably, RI is an alkyl group having 2 or 3 carbon atoms, and R2 is an alkyl group having 4 or more carbon atoms. (m) At least one of R1 and R2 is a hydrocarbon group having 6 or more carbon atoms.

Preferably, R1 and R2 are both alkyl groups having 6 or more carbon atoms. These groups will be specifically shown below.

In (1), as a secondary or tertiary alkyl group having 4 to 6 carbon atoms, sec-C4 is te-C4
Preferably, a secondary alkyl group is used, and sec-C4day9 is particularly preferred.

Next, in (0), the alkyl group having 2 or 3 carbon atoms is an ethyl group, or ethyl group.

Examples of the alkyl group having 4 or more carbon atoms include butyl group, amyl group, hexyl group, octyl group, and the like, with butyl group and hexyl group being particularly preferred. In (spots), hydrocarbon groups having 6 or more carbon atoms include hexyl group, octyl group, decyl group,
Examples include a phenyl group, an alkyl group is preferred, and a hexyl group is particularly preferred. It is important that the organomagnesium compound used in the present invention is soluble in a hydrocarbon medium.

Increasing the number of carbon atoms in an alkyl group makes it easier to dissolve in a hydrocarbon medium, but the viscosity of the solution tends to increase, and it is not preferable to use an alkyl group with an unnecessarily long chain from the viewpoint of handling. The above-mentioned organomagnesium compound is used as a hydrocarbon solution, but it can be used without any problem even if a small amount of a complexing agent such as ether, ester, or amine is contained or remains in the solution.

Next, the tertiary alkyl halide compound represented by the general formula (wherein R1o, RI1, R12, and Q have the meanings described above) will be explained.

The hydrocarbon group represented by R1o, RI1, and R12 in the above formula is an alkyl group, a cycloalkyl group, or an allyl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl, etc. and preferably a hydrocarbon group having 1 to 10 carbon atoms, and a particularly preferred one is a methyl group. The reaction between the organomagnesium component and the tertiary alkyl halide compound is carried out in an inert reaction medium such as hexane, hexanes, etc.
The reaction can be carried out in an aliphatic hydrocarbon such as carbon dioxide, an aromatic hydrocarbon such as benzene, toluene or xylene, an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or a mixed medium thereof.

From the viewpoint of catalytic performance, an aliphatic hydrocarbon medium is preferably used. There is no particular restriction on the reaction temperature, but in order to avoid the danger of explosive reaction accompanying the Wu-9z reaction and ensure a smooth reaction,
It is preferably carried out at 4000 or more. There is no particular restriction on the reaction ratio of the two components, but preferably 0 tertiary alkyl halide component per 1 mole of organomagnesium component.
．． 01 to 100 mol, particularly preferably 0.1 to 10
A molar range is recommended.

Regarding the reaction method, there is a simultaneous addition method (Method 2) in which two components are introduced into the reaction zone at the same time, or the organomagnesium complex component is reacted after the tertiary alkyl halide component is charged into the reaction zone in advance. There is a method (Method 3) in which the organomagnesium complex component is prepared in advance and a tertiary alkyl halide component is added (Method 3), but Methods @ and C are particularly preferred. - Law @ gives favorable results.

The composition and structure of the basic solid substance obtained by the above reaction may vary depending on the type of starting materials and reaction conditions, but based on the compositional analysis value, the basic solid substance 1 has a roughness of about 0.1 to 2.
It is estimated to be a halogenated magnesium compound containing an alkyl group with 5 mmol of Mg-C bonds. This basic solid has a large specific surface area, and B. E. T.
When measured by the method, it reaches a value of 50 to 300 w/t.
According to this method, it is possible to produce a basic solid of active magnesium halide with a high surface area, whereas conventional production was difficult.
Next, a titanium compound containing at least one halogen atom will be explained.

First, a tetravalent titanium compound containing at least one halogen atom will be explained.

Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, ethoxytitanium trichloride,
A single or a mixture of titanium halides and alkoxy halides, such as propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, and tributoxytitanium monochloride, can be used.

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. Solid solutions include solid solutions of titanium trichloride and aluminum trichloride, solid solutions of titanium tribromide and aluminum tribromide, solid solutions of titanium trichloride and vanadium trichloride, solid solutions of titanium trichloride and iron trichloride, and solid solutions of titanium trichloride and iron trichloride. Examples include solid solutions of titanium and zirconium trichloride. Among these, preferred are titanium trichloride and solid solutions of titanium trichloride and aluminum trichloride.
TIC13・1′3AIC13). The titanium compound containing at least one halogen atom used in the synthesis of this catalyst solid is a tetravalent titanium compound containing at least one halogen atom and/or a trivalent titanium halogen compound. be. 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,
Examples include benzothiophene carboxylic acid esters, phenoxathine carboxylic acid esters, benzothian carboxylic acid esters, benzothiane carboxylic acid esters, thiaxanthene carboxylic acid esters, thioindoxyl carboxylic acid esters, etc. More specifically, thiophene Methyl, ethyl, propyl, butyl and amyl-2-carboxylate, methyl, ethyl, propyl-2-carboxylate. Butyl and amyl, methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate, ethyl, methyl thiophene-2,5-dicarboxylate, ethyl, methyl 2-thhenyl acetate, butyl, propyl, butyl, 2 -Methyl thianaphthene-3-carboxylate, ethyl, methyl thianaphthene-3-carboxylate, ethyl, methyl thianaphthene-2,3-carboxylate, ethyl ethyl thianaphthene-2-carboxylate -Methyl oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenyl acetate, ethyl, methyl 3-thianaphthenyl acetate, ethyl, benzothiophene-
Methyl, ethyl, benzothiophene 2-carboxylate-3
-Methyl, ethyl, benzothiophene carboxylate-4-
Examples include methyl carboxylate, ethyl, methyl phenoxathine-1-carboxylate, ethyl, methyl phenoxathine-2-carboxylate, methyl ethyl phenoxathine-3-carboxylate, and ethyl.

More preferred are methyl thiophene 2-carboxylate, ethyl, propyl and butyl, methyl thiophene 3-carboxylate, ethyl, methyl 2-chenylacetate, ethyl, methyl 2-chenylacrylate, ethyl,
Examples include methyl and ethyl thianaphthene-2-carboxylate. Next, the oxygen-containing heterocyclic carboxylic acid ester will be explained.

Examples of oxygen-containing double ring carboxylic acid esters include furan carboxylic esters, dihydrofuran carboxylic esters, benzofuran carboxylic esters, coumaran carboxylic esters, pyran carboxylic esters, pyrone carboxylic esters, and coumarins. Examples include carboxylic 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 2,5-dicarboxylate, methyl furan-3,4dicarboxylate, methyl 4,5-dihydrofuran-2-carboxylate, ethyl, 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-
Examples include ethoxycarbonyl isocoumarin, ethyl 3-methyl-furan-2-carboxylate, ethyl isodehydroacetate, and methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate,
Ethyl, propyl, butyl, 4,5-dihydrofuran-
Methyl 2-carboxylate, ethyl, tetrahydrofuran-
Methyl 2-carboxylate, methyl coumarate, methyl coumarate, ethyl etc. give preferable results. Next, the nitrogen-containing heterocarboxylic acid esters include pyrrole carboxylic esters, indoles carboxylic esters, carbazole carboxylic esters, oxazole carboxylic esters, thiazole carboxylic esters, imidazoles carboxylic esters, and pyrazole carboxylic esters. carboxylic acid esters, pyridine carboxylic acid esters, phenanthridine carboxylic acid esters, anthrazoline carboxylic acid esters, phenanthroline carboxylic acid esters, naphthyridine carboxylic acid esters, oxazine carboxylic acid esters, thiazine carboxylic acid esters,
Examples include pyridazine carboxylic acid esters, pyrimidine carboxylic acid esters, and pyrazine carboxylic acid esters, but preferred ones include methyl, ethyl, propyl, and butyl pyrrole-2-carboxylate, and methyl, ethyl, and propyl pyrrole-3-carboxylate. and butyl, methyl pyridine-2-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-3-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-4-carboxylate, ethyl, propyl, butyl and amyl, Methyl pyridine 2,3 dicarboxylate, ethyl, methyl pyridine 2,5 dicarboxylate, ethyl, methyl pyridine 2,6 dicarboxylate, ethyl, pyridine 3
,5 Methyl dicarboxylate, ethyl, methyl quinoline-2-carboxylate, ethyl, ethyl dimethylpyrrolecarboxylate, ethyl N-methylpyrrolecarboxylate, N-carboethoxypyrrole, N-carbomethoxypyrrole, 2
Examples thereof include ethyl -methylpyridinecarboxylate, ethyl piveridine 4-carboxylate, ethyl piveridine 2-carboxylate, and ethyl pyrrolidine 2-carboxylate.

Next, the basic solid '1} obtained by the reaction of the organomagnesium component [i} and the above-mentioned tertiary alkyl halide compound [ii} is mixed with a titanium compound ■ and a sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester. The reaction and/or pulverization of {31 to obtain catalyst solid [A] will be explained.

The reaction between the basic solid and the titanium compound or the sulfur-containing, oxygen- or nitrogen-containing heterocyclic carboxylic acid ester (hereinafter referred to as the polycyclic carboxylic acid ester of the present invention) can be carried out by reacting the titanium compound or the heterocyclic carboxylic acid ester of the present application in a liquid phase or in a gas phase. Any method can be employed, such as a method of reacting in a phase [1], a method of combining a reaction in a liquid or gas phase and pulverization [2], etc.

First, the order of reaction and/or pulverization of the basic solid, the titanium compound, and the heterocyclic carboxylic acid ester of the present application will be explained.

For method [1], the basic solid, the titanium compound, and the heterocyclic carboxylic acid ester of the present invention are reacted simultaneously (synthesis method ■), or the basic solid and the titanium compound are first reacted, and then the heterocyclic carboxylic acid ester of the present application 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;
In particular, synthesis method (2) is preferred. Regarding method [2], cases in which the titanium compound is {1} tetravalent, (b) trivalent, and (m) tetravalent and trivalent are used together 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 resulting group (synthesis method ■), or first reacting the solid substance and the titanium compound, and then A method of pulverizing a solid obtained by reacting a double Qin ring carboxylic acid ester (synthesis method ■)
Alternatively, there is a method (synthesis method ①) in which the above-mentioned solid substance and the heterocyclic carboxylic acid ester of the present invention are first reacted, and then a titanium compound is reacted and the obtained 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 (D), various methods are possible for synthesizing the solid component from the three components of the basic solid, the halogen compound of trivalent titanium, and the multi-hata ring carboxylic acid ester of the present application, but the following three methods yield particularly preferable results. give. That is, a method in which the three components are co-pulverized (synthesis method ■), and a method in which the solid component and the multi-hata ring carboxylic acid ester of the present application are brought into contact in advance, and then a trivalent titanium halide is added and crushed (synthesis method ■). Alternatively, a solid component and a trivalent titanium halide are pulverized and brought into contact with each other, and then treated with the heterocyclic carboxylic acid ester of the present invention (synthesis method ①). (m), the basic solid (1}
, tetravalent titanium compound (2-1), trivalent titanium compound (2-2), and heterocyclic carboxylic acid ester [3
A method of simultaneously crushing 'li and (2-
The solid obtained by reacting 1) is treated with (3}, and (2
-2) and pulverization method (synthesis method ■), react m and rigid, and treat the resulting solid with (2-1), (2-
2) and pulverization method (synthesis method ■), m and (2-1
) with the solid obtained by reacting (2-2) and [3
Examples include a method of adding 1 and pulverizing (synthesis method ①), but synthesis method ① is preferable. Furthermore, the solid catalyst synthesized by the above method [1] and method [2] is further mixed with a tetravalent titanium compound containing at least one halogen atom [
Treatment with 4) results in increased catalyst efficiency. First, the method of further treating the solid catalyst synthesized by method [1] with the above-mentioned tetravalent titanium halide involves simultaneously reacting the basic solid, the titanium compound, and the multi-hata ring carboxylic acid ester, and then further treating the solid catalyst synthesized by method [1]. A method of treatment with a tetravalent titanium halide (synthesis method ■), in which the basic solid is reacted with a titanium compound, then the heterocyclic carboxylic acid ester of the present application is reacted, and then further treated with a tetravalent titanium halide. (synthesis method ■), a method in which the basic solid is reacted with the heterocyclic carboxylic acid ester of the present application, and then reacted with a titanium compound, and then further treated with a tetravalent titanium halide (synthesis method ■) There is.

Next, regarding the method of further treating the solid catalyst synthesized by method [2] with a tetravalent titanium halide, (1), (n), and (m) will be explained. (1
), synthesis method [2]-(1)-■, [2]-(1)
Although it is possible to treat the solid catalyst synthesized by -■ or [2]-(1)-■ with a tetravalent titanium halide, the latter two methods are more preferred.

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

In the case of (m), basic solid '1), tetravalent titanium compound (
2-1) “After simultaneously crushing the trivalent titanium compound (2-2) and the present heterocyclic carboxylic acid ester {3},
Method of treatment with tetravalent titanium halide (synthesis method■
), a method in which the solid obtained by reacting {1) and (2-1) is treated with legs, crushed together with (2-2), and then treated with a tetravalent titanium halide (synthesis method ■) , m and'
3}, the resulting solid is treated with (2-1), pulverized together with (2-2), and then further treated with a tetravalent titanium halide (synthesis method ①).

The solid obtained by reacting [1' with (2-1) and (2-
2) and '3' are added, pulverized, and then further treated with a tetravalent titanium halide (synthesis method ■), {1
) and (2-1) are treated with [3', pulverized with (2-2), and then treated with a tetravalent titanium halide (synthesis method ■), etc. Yes, but there is a method■
■■■ is preferred.

Next, the reaction between the basic solid, the titanium compound, and the polycyclic carboxylic acid ester of the present invention and/or the pulverization operation will be explained. 'i' Solid substance obtained by reacting organomagnesium component 'i} and tertiary alkyl halide compound side '1
}, or the reaction between the reaction product of this solid substance and the present invention's ring carboxylic acid ester [3' and the titanium compound (2') 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. Group 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.
It is preferable that the temperature is qo or more and the titanium compound temperature is 2 molar liters or more. 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. 'i
i} A solid substance obtained by reacting an organomagnesium component and a tertiary alkyl halide compound, or a reaction between this solid substance and a titanium compound, and a reaction with the heterocyclic carboxylic acid ester of the present application will be explained.

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 compound ring carboxylic acid ester, the reaction ratio of the two components is not particularly limited; The acid ester is 0.001 mol to 50 mol, particularly preferably 0.0 mol.
A range of 0.05 to 10 moles is recommended. When a reaction product of a solid substance and a titanium compound is reacted with the heterocyclic carboxylic acid ester of the present invention, the reaction ratio of the two components is 1 mole of titanium atom in the organomagnesium solid component, The recommended amount of ester is 0.01 mol to 100 mol, particularly preferably 0.1 mol to 10 mol. 'ii0 A method of pulverizing the solid produced by the reactions [i' to {ii'] above will be explained.

Grinding methods include rotary ball mill, vibrating pole mill,
Well-known mechanical crushing means such as an impact ball mill can be employed. The grinding time is 0.5 to 10 hours, preferably 1 to 3 hours, and the grinding temperature is 0 to 200°C, preferably 10 to 150 hours. A case will be described in which the solid component obtained by {N''i) to {5U is treated with a titanium compound of tetravalent titanium.

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, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. is preferred. Regarding the concentration of titanium compound, 2 mol/
A concentration of 〆 or higher is preferable. 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 qC or higher. Regarding the composition and cross section of the solid catalyst component obtained by the above reaction {i} to 'N',
Although it varies depending on the type of starting materials and reaction conditions, it was found from the compositional analysis that the solid catalyst contained approximately 1 to 1% by weight of titanium and was 50 to 300% solid catalyst.

[B] As the organometallic compound used as the component,
Among the compounds of Groups 1 to M of the periodic table, organic aluminum compounds are particularly preferred.

As the organoaluminum compound, general formula Yama R3oZ3
-t (wherein R1o is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, alkoxy, ailoxy, and siloxy group, and t is a number of 2 to 3. ) are used alone or as a mixture.

In the above formula, RI. The hydrocarbon group having 1 to 20 carbon atoms represented by includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tri- Hexadecyl aluminum, diethylaluminium hydride, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, dioctyl aluminum butoxide, diisobutyl aluminum octyl oxide, diethylaluminum chloride, diisobutyl aluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxy Aluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isoproprenyl, 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 hydride is particularly preferred because it achieves the highest activity.

The sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester added to the organometallic compound may be the same or different from the sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester used in the synthesis of the solid catalyst component [A]. It's okay. As for the addition method, 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 in the range of 10 mol or less, particularly preferably 1 mol or less of the sulfur-containing, oxygen-containing or nitrogen-containing polycyclic carboxylic acid ester per 1 mol of the organometallic compound. The catalyst of the present invention, in which the solid catalyst component of the present invention and one or more components selected from sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters are added to an organometallic compound, is added to the polymerization system under polymerization conditions. or may be combined in advance prior to polymerization. Particularly preferably, an organometallic compound and a sulfur-containing compound,
It is preferable to separately add the reacted oxygen- or nitrogen-containing polycyclic carboxylic acid ester and the organometallic compound to the polymerization system. The ratio of each component to be combined is 1 mmol to 3,000 mmol of the solid catalyst component 1, and the component of the organometallic compound plus the sulfur-containing, oxygen-containing or nitrogen-containing double ring carboxylic acid ester, based on the organometallic compound. Preferably, the amount is in the millimolar range. The present invention is a catalyst for highly active and highly stereoregular polymerization of olefins.

In particular, the present invention provides propylene, butene-1, bentene-1
, 4-methylbentene-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 continuous migration. 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. , olefin such as propylene in an inert atmosphere.
The polymerization can be carried out at room temperature to 15,000 ℃ by injecting 20 kg/kg. In the bulk polymerization, an olefin can be polymerized using a liquid olefin as a polymerization solvent under conditions where the olefin is a liquid, such as propylene as a catalyst. For example, in the case of propylene, the polymerization can be carried out in liquid propylene at a temperature of room temperature to 9,000 ℃ and under a pressure of 10 to 45 k9/h. On the other hand, gas phase polymerization is performed under conditions where the olefin such as propylene is a gas.
Mixing is carried out in the absence of a solvent at a pressure of 1 to 50 K9/Chu and at a temperature of room temperature to 120 C using a fluidized bed, moving bed, or competitive machine to ensure good contact between the olefin such as propylene and the catalyst. Polymerization can be carried out by other means, such as by The present invention will be explained below using examples.

In addition, the boiling n-hebutane extraction residue used in the examples means the residue obtained by extracting the polymer with boiling n-hebutane for 6 hours. Example 1 {i' Synthesis of hydrocarbon-soluble organomagnesium body
- 13.80 g of butylmagnesium and 1.90 g of triethylaluminum in 20 g with 100 g of heptane
An organomagnesium complex solution was obtained by placing the mixture in a nitrogen-substituted flask at 8,000 °C and reacting for 2 hours at 8,000 °C.

As a result of analysis, the composition of this rust body was NMg6. . (C2 day 3
) 2.9 (n-C4 days 9), 2. , and the organometallic concentration was 1.18 hol/sleeve. 'ii} Synthesis of basic solids Oxygen and moisture inside a 250 capacity flask equipped with a dropping funnel and a water-cooled reflux condenser were removed by dry nitrogen substitution, and dehydrated and dried in a nitrogen atmosphere. Butyl chloride 1 mol/butane solution 100 skin mo
1 was charged and the temperature was raised to 6,500℃.

Next, under a nitrogen atmosphere, 50 mol of the above organomagnesium complex solution was weighed into the dropping funnel. After taking safety measures by installing a protective shield between the system and the experimenter, while keeping the system at 65,000 ml, the organomagnesium solution was gradually added dropwise until the reaction proceeded smoothly and a white precipitate was formed. The mixture was added dropwise over 1 hour under the Nada Ocean while checking the temperature, and was further aged at this temperature for 1 hour to react 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 9.80 m mol of solid per night, CI
I9.50 skin mol, NO. 07 mol, alkyl group 0.65 m mol, and B. E. T.
The specific surface area measured by the method was 163 m/m. Synthesis of catalytic solid 3.0 ml of the above white solid was placed in a flask that had been purged with nitrogen, and 60% of n-hexane and 0.1 mol of ethyl thiophene-2-carboxylate/the hexane. 3.0 mol of the solution was added and reacted at 800° for 1 hour with lighting, and the solid was separated in a furnace, thoroughly washed with n-hexane, and dried.

2.5 liters of this solid and 50 ml of titanium tetrachloride were placed in a pressure-resistant container purged with nitrogen, and reacted at 130°C for 2 hours while heating. The solid was separated in a furnace, washed with n-hexane, and dried to form a solid. I got a catalyst.

As a result of analyzing this solid catalyst, the Ti content was 1.6% by weight. 'iv} Slurry polymerization of propylene '9 of 50 of the solid catalyst synthesized in 'ii0, 3.0 mol of triethylaluminum, and 1.0 mol of thiophene-2-ethyl carboxylate were dehydrated and deaerated in hexane 0.0. 8 At the same time, the inside was replaced with nitrogen and vacuum degassed 1
．． 5 I put it in the autoclave.

The internal temperature of the autoclave was maintained at 60q0, propylene was pressurized to a pressure of 5.0k9/flow, and polymerization was carried out for 2 hours while maintaining the total pressure at a gauge pressure of 4.8kg/flow, resulting in polymerized hexane-insoluble polymer 96 After that, 3.3 ml of polymerized hexane soluble material was obtained. Catalyst efficiency is 960 Tpp/hour of solid catalyst.
The titanium component, time, and propylene pressure were 11,800 ppp, and the residue obtained by extracting the polymerized hexane-insoluble polymer with boiling n-hebutane was 95.3%. The particle properties were also good, with a basket density of 0.361 m/s and a ratio of 36 to 150 mesh powder of 93%. Comparative Example 1 A solid catalyst was synthesized in the same manner as in Example 1 except that magnesium chloride was used in place of the solid material obtained by the reaction between the organomagnesium complex compound and tert-butyl chloride.

3.0 mol of ethyl thiophene-2-carboxylate was reacted with 3.0 mol of anhydrous M&12, and the resulting solid 2.
Titanium tetrachloride and titanium tetrachloride were reacted at 100 qo for 2 hours. Titanium in the solid catalyst was 0.51% by weight. 9 of this solid catalyst 400, triethylaluminum 3
．． 0 skin mol, ethyl thiophene-2-carboxylate 1
．． Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 0 mol.

Polymerized hexane uncured polymer 52 parts, hexane soluble material 10 parts
．． I got 9 nights. The boiling n-hebutane extraction residue of the polymerized hexane-insoluble polymer was 81.8%, and the catalyst efficiency was 65 tpp/tt solid catalyst/hour and 2550 tpp/tt titanium component/time/propylene pressure. Examples 2 to 11 A basic solid was synthesized in the same manner as in Example 1 using the organomagnesium components and reaction reagents shown in Table 1, and this was reacted with N-carboethoxypyrrole and titanium tetrachloride to form a solid catalyst. I got it.

Solid Catalyst 50 Female “Triethyl Aluminum 3.0 MO
l, ethyl thiophene-2-carboxylate 1.0 mol
Polymerization of propylene was carried out in a hexane solvent in the same manner as in Example 1. Table 1 shows catalyst synthesis conditions and polymerization results.
Shown below. Satoshi Example 12 AIM saddle was prepared in the same manner as in Example 1. o (C2 day 5) 2.
9 (n-C4 day 9), 2. ,, tert-butyl chloride "A group was obtained by reacting ethyl thiophene-2-carboxylate and titanium tetrachloride.

This solid 4.0 mm was heated to the steel ball 2 on the 9th side in a nitrogen atmosphere.
The powder was crushed for 5 hours in a steel mill with an internal capacity of 100 c and a vibrating ball mill at a speed of 100 jb/min or more. The Ti content of the obtained solid catalyst was 1.55% by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 50:9, 3.0 mol of triethylaluminum, and 1.0 mol of ethyl thiophene-2-carboxylate. The results are shown in Table 2. Example 13 Using the same method as Example 1 (sec-Bu), . 5
Mg(On-Bu).

．． 5, tert-butyl chloride, pyrrole-2-
Ethyl carboxylate and titanium tetrachloride were reacted to obtain a solid. This solid 3.90% and titanium trichloride (AA grade TIC1.1'3NC13 manufactured by Toyo Stoffer Co., Ltd.)
0.15 hours was ground in the same manner as in Example 11 under a nitrogen atmosphere for 5 hours. The Ti content of the obtained solid catalyst was 2.
It was 35% by weight. Slur IJ monopolymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 50:9, 3.0 mol of triethylaluminum, and 1.0 mol of ethyl furan-2-carboxylate. Table 2 shows the results.
Shown below. Example 14 In the same manner as in Example 1, and were reacted to synthesize a basic solid, and further furan-2-
Reacted with ethyl carboxylate.

Example 11 This solid 4.0 mm and titanium trichloride (AA grade manufactured by Toyo Stoffer Co., Ltd.) 0.35 mm were mixed under a nitrogen atmosphere.
It was ground for 5 hours in the same manner as above. T of the obtained solid catalyst
The i content was 1.9% by weight. This solid catalyst 50
9, triethyl aluminum 3.0 skin mol, N-
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 1.0 mol of triboethoxyvirol.

The results are shown in Table 2. Example 15 In the same manner as in Example 14, the basic solid was reacted with ethyl furan-2-carboxylate, and then the obtained solid and titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were pulverized.

The top of this solid 4.0 mm and titanium tetrachloride 60 was
After reacting for 2 hours at 3,000 °C, 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 3.05% 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 and triethylaluminum 3.0 moL N-triboethoxypyrrole 1.0 mmol.

The results are shown in Table 2. Example 16 In the same manner as in Example 12, the basic solid was reacted with ethyl thiophene-2-carboxylate, and then 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 4.09 and titanium tetrachloride 60'
After reacting for 2 hours in a 13,000-meter oven, the solid portion was isolated in a furnace, thoroughly washed with hexane, and dried to obtain a solid catalyst. Analysis of this solid resulted in 1.95% by weight
contained titanium. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 50:9, 3.0 mol of triethylaluminum, and 1.0 mol of ethyl thiophene-2-carboxylate.

The results are shown in Table 2. Table 2 Example 17 350 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 600 ml.
0, and 9 of 10 of the solid catalyst synthesized in Example 16,
1.5 mol of triethylaluminum and 0.5 mol of ethyl thiophene-2-carboxylate were added to an autoclave, and polymerization was carried out at 600° for 2 hours to obtain polypropylene 145 mol.

Catalyst efficiency is 7250 Tpp/hour solid catalyst, 372
,000 tpp/tatitan component/hour, and the n-hebutane extraction residue of the produced polypropylene was 93.1%. Example 18 Hexane solution of triethylaluminum (1 mol/night) 2.0 mol and thiophene-
Hexane solution of ethyl 2-carboxylate (lmol/〆)
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using a solution pre-mixed with 1.0 mol of solid catalyst 30 of 9 synthesized in Example 16 and 1.0 mol of triethylaluminum. 160 ml of hexane-insoluble polymer and 4.9 ml of polymerized hexane-soluble material were obtained.

The n-hebutane extraction residue of the polymerized hexane-insoluble polymer is 9
4.2%, and the catalyst efficiency was 27,400 pp/t titanium component/time/propylene pressure. Examples 19 to 24 Propylene was prepared in the same manner as in Example 1 using the solid catalyst 50x9 synthesized in the same manner as in Example 1, 3.0 mol of triethylaluminum, and 1.0 mol of the compound shown in Table 3. Slurry polymerization was carried out, and the results shown in Table 3 were obtained.

Examples 25-26 50 mg of a solid catalyst synthesized in the same manner as in Example 1,
On day 1, 1.0 mol of N-ruboethoxypyrrole and 3.0 mol of the organometallic compound shown in Table 4 were added.
Slurry polymerization of propylene was carried out in the same manner as in Table 4.
I got the result.

Table 3 Table 4 Example 27 9 of 50 solid catalysts synthesized in the same manner as in Example 1,
Using 3.0 mol of triethylaluminum and 1.0 mol of N-carpoethoxypyrrole, slurry polymerization was carried out in the same manner as in Example 1 using a propylene-ethylene mixed gas containing 2 mol% of ethylene. 100 g of a white polymer was obtained.

Example 28 Butene-1 in hexane using 500:9 of a solid catalyst synthesized in the same manner as in Example 1, 6.0 mol of triethylaluminum, and 2.0 mol of N-ruboethoxypyrrole. Polymerization was carried out in the same machine as in Example 1 to obtain a white polymer 109.

Example 29 A solid catalyst 500 female synthesized in the same manner as in Example 1,
Polymerization of 4-methylbentene-1 in hexane was carried out in the same manner as in Example 1 using 6.0 mol of triethylaluminum and 2.0 mol of N-triboethoxypyrrole, yielding 67 mol of a white polymer. I got it.

Example 30 Solid catalyst synthesized in the same manner as Example 1 50:9, triisobutylaluminum 1.0 mo
l and N-force Rubethoxypyrrole 0.1 mol
was placed in a vacuum-dried and nitrogen-substituted 1.5 autoclave with 0.8Z of dehydrated and degassed n-hexane, the internal temperature was kept at 80°C, the pressure was increased to 1.6k9/base with hydrogen, and then ethylene was added. was added, and polymerization was carried out for 1 hour while maintaining the total pressure at a gauge pressure of 4.0 k9/ground to obtain a white polymer with a weight of 48 kg.

Claims (1)

[Claims] 1 [A] (1) (i) General formula MαMgβR^1_pR
^2_qX_rY_s (where α is 0 or a number greater than 0, p, q, r, s are 0 or a number greater than 0, p
+q+r+s=mα+2β, where M is a metal element belonging to Group I to Group III of the periodic table, m is the valence of M, and R^1
, R^2 are hydrocarbon groups having the same or different numbers of carbon atoms, X and Y are the same or different groups, and halogen, O
R^3, OSiR^4R^5R^6, NR^7R^8, SR^9
represents the group R^3, R^4, R^5, R^6, R
^7, R^8 represent a hydrogen atom or a hydrocarbon group, R^9 represents a hydrocarbon group) An organomagnesium compound represented by (ii) general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula , R^1^0, R^1^1, R^1^2 are hydrocarbon groups, Q represents a halogen), (2) a solid obtained by reacting with a tertiary alkyl halide compound represented by a titanium compound containing one halogen atom,
(3) One or more selected from sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters, (1), (2), (3)
for olefin polymerization, comprising a solid catalyst component obtained by reacting and/or pulverizing [B] an organometallic compound, and one or more components selected from sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters. Catalyst 2 [A] (1) (i
), wherein α is a number greater than 0, X and Y do not contain halogen, and M is an aluminum, zinc, boron or beryllium atom, for olefin polymerization according to claim 1. catalyst. 3 [A] (1) In the organomagnesium compound of (i), α>0, 1≦β/α≦10 and (r+s)
/(α+β) ratio is 0≦(r+s)/(α+β)≦0.
8. The olefin polymerization catalyst according to claim 1 or 2, which is No. 8. 4 [A] In the organomagnesium compound of (1) (i), a secondary or tertiary alkyl group in which α is 0 and at least one of R^1 and R^2 has 4 to 6 carbon atoms. or R^1 and R^2 are alkyl groups having different numbers of carbon atoms, or R^1, R
The catalyst for olefin polymerization according to claim 1, wherein at least one of ^2 is a hydrocarbon group having 6 or more carbon atoms, and X and Y are a hydrocarbon-soluble organomagnesium compound containing no halogen. 5 [A] In the tertiary alkyl halide compound of (1) (ii), R^1^0, R^1^1, R^1^2 are C
The catalyst for olefin polymerization according to any one of claims 1 to 4, which is a hydrocarbon group of _1_ to _1_0. 6 [A] In the tertiary alkyl halide compound of (1) (ii), R^1^0, R^1^1, and R^1^2 are all methyl groups, or The catalyst for olefin polymerization according to item 5. 7 [A] The titanium compound in (2) is a tetravalent titanium compound containing at least one halogen atom, and (
The catalyst for olefin polymerization according to any one of claims 1 to 6, wherein a solid catalyst component is synthesized by reacting or reacting and pulverizing 1), (2), and (3). 8 [A] The titanium compound in (2) was a halide of trivalent titanium. (1), (2) and (3) were co-pulverized, or (1) and (3) were 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 6, which synthesizes a solid catalyst component. 9 [A] The titanium compound in (2) is (a) a titanium compound containing at least one halogen atom and (b)
A trivalent titanium halide, (1), (2)
The catalyst for olefin polymerization according to any one of claims 1 to 6, wherein a solid catalyst component is synthesized by pulverizing or pulverizing and reacting (3). 10. The catalyst for olefin polymerization according to any one of claims 1 to 9, wherein the titanium compound in [A] (2) is titanium tetrachloride and/or titanium trichloride. 11
[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 10. 12 [A] The amount of the sulfur-containing, oxygen-containing or nitrogen-containing carboxylic acid ester in (3) is contained in the solid obtained by reacting the organomagnesium compound in (1) with the tertiary alkyl halide compound. 0.00 of the number of moles of alkyl group
The catalyst for olefin polymerization according to any one of claims 1 to 11, wherein the number of moles is 1 to 50 times the amount. 1
3 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 12. 14. The catalyst for olefin polymerization according to claim 13, wherein the organoaluminum compound is trialkylaluminum or dialkylaluminum hydride. 15 [A] (1) (i) General formula MαMgβR^1_p
R^2_qX_rY_s (where α is 0 or a number greater than 0, p, q, r, s are 0 or a number greater than 0,
It has the relationship p+q+r+s=mα+2β, where M is a metal element belonging to Group I to Group III of the periodic table, m is the valence of M, and R^1
, R^2 are hydrocarbon groups having the same or different numbers of carbon atoms, X and Y are the same or different groups, and halogen, O
R^3, OSiR^4R^5R^6, NR^7R^8, SR^9
represents the group R^3, R^4, R^5, R^6, R
^7, R^8 represents a hydrogen atom or a hydrocarbon group, R^9 represents a hydrocarbon group) An organomagnesium compound represented by (ii) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula , R^1^0, R^1^1, R^1^2 are hydrocarbon groups, Q is halogen) A solid obtained by reacting with a tertiary alkyl halide compound represented by (2) at least (1) a titanium compound containing a solid halogen atom;
), (3), and then further treated with a tetravalent titanium compound (4) containing at least one halogen atom, and [B] an organic metal. A catalyst for olefin polymerization comprising a compound and one or more components selected from sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters. 16. The catalyst for olefin polymerization according to claim 15, wherein the tetravalent titanium compound containing at least one halogen atom in [A](4) is titanium tetrachloride.