JPS6010526B2 - 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 through stereoregular polymerization;
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 group WA and an organometallic compound of groups 1 to m of the periodic table. .

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 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. 43-1305). As a solution to these problems, there are
The methods described in No. 6153 and Tsubaki Seki No. 48-169 have been proposed. These methods consist of a solid component obtained by co-pulverizing a complex compound of a titanium halide compound and an electron donor and anhydrous magnesium halide, and an addition reaction product of an aluminum trialkyl compound and an electron donor. It is a catalyst system. However, even with these methods,
The proportion of boiling butane infusibles in the produced polymer is still not high enough to satisfy the requirements, especially the polymer yield per solid catalyst component is insufficient, and the halogen weight is high enough to cause corrosion of production process equipment and molding machines. The content in the coalescence is large, and the physical properties of the product are not fully satisfactory. In order to improve these points, the present inventors conducted research on various organomagnesium compounds and various reaction reagents, and as a result, the present inventors discovered a key body containing an organomagnesium compound, preferably an organomagnesium soluble in an inert hydrocarbon medium. A halogen-containing magnesium compound basic solid is produced by reacting the solution with a halogen compound such as silicon, germanium, tin, or antimony as a reaction reagent, and this is combined with a titanium compound and a sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester. A specific solid obtained by reacting and/or pulverizing the organic metal compound and a component consisting of an organometallic compound and an oxygen-containing, sulfur-containing or nitrogen-containing heterocyclic carboxylic acid ester has extremely excellent performance as a catalyst for olefin polymerization. They discovered this and arrived at the present invention. That is, the present invention provides [A] [1] River general formula MQ
Mg8R also has an R cost Metal elements belonging to Group 1 to Group m of the periodic table, R1, R2
are hydrocarbon groups having the same or different number of carbon atoms, ×, Y
are the same or different groups, OR3, OSiR4R
5R6, NR7R8, SR9, R3, R
4, R5, R6, R7, R6 represent a hydrogen atom or a hydrocarbon group, R9 represents a hydrocarbon group), (ii) the general formula LJiR8-j (wherein L is boron, silicon , germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, mercury, and tellurium, J represents a halogen atom, R〇 represents a hydrocarbon group, a represents the valence of L, and i represents 0< a solid obtained by reacting with a halogen compound represented by the number i≦a), ■ a titanium compound containing at least one halogen atom, '3} a sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid; One or more types selected from Esther~○ー,
(ii) a solid catalyst component obtained by reacting and/or pulverizing [B] an organometallic compound, and one or more components selected from a sulfur-containing, oxygen-containing or nitrogen-containing double Qin ring carbosic acid ester; .

This is an olefin polymerization catalyst consisting of [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;
Furthermore, it is possible to produce polymer powder with high density.

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
RPR cost × rYs (in the formula, Q, 8, p, q, r, s, M
, R1, R2, x, Y have the meanings described above) will be described.

This compound is shown in the form of an organomagnesium tsuba compound, but it includes all R2Mg and rust forms of these and 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 it is particularly preferable that RI is an alkyl group. Further, R3 to R8 may be 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 especially aluminum, Zinc, boron, and beryllium are particularly preferred because they facilitate the production of hydrocarbon-soluble organomagnesium keys. metal atom M
Although the ratio of magnesium to magnesium (8/Q') can be arbitrarily set, it is preferably 0 to 10, particularly 1 to 10, and particularly preferred is a hydrocarbon-soluble organomagnesium ratio. Relational expression of symbols Q, 8, p, q, r, s p ten q ten r ten s
=mQ+28 indicates the stoichiometry between the valence of the metal atom and the substituent, and the preferable range OS(r+s)/Q18)<1.0 means that Indicates that the sum is greater than or equal to 0 and less than 1.0.

A particularly preferred range is 0 to 0.8. These organomagnesium compounds or organomagnesium bodies have the general formula RIMgQ, R room Mg (RI has the above-mentioned meaning,
Q is a halogen) and an organomagnesium compound represented by the general formula M
is the above-mentioned meaning) and an organometallic compound represented by
The reaction is carried out in the dark at room temperature to 150 qo in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene, trezo, etc., and if necessary, this is further treated with alcohol, water, siloxazo, amine, imine, mercaptan or It is synthesized by reacting with a dithio compound. Furthermore, organomagnesium compounds or organomagnesium bodies are MgX2, RIN et al.
, or RIMgX, MgR2 and YnM are m−n (where M, R1, R2, ×, Y are as described above, and X
, Y is a halogen, n is a number from 0 to m). Generally, organomagnesium compounds are immovable in an inert hydrocarbon medium, and organomagnesium fins where Q>○ are soluble.

Furthermore, even when Q:0, certain organomagnesium compounds, such as sec-B uniform Mg, are soluble in hydrocarbon aqueous media, and such compounds also give favorable results when used in the present invention. The compound will be explained.

The general formula NLPR also assumes that R1 and R2 in the R cost XrYs are any one of the following two groups (1), (0), and (m).

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

Preferably, both R1 and R2 have 4 to 6 carbon atoms, and at least one of them is a secondary or tertiary alkyl group. (0) RI 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 the secondary or tertiary alkyl group having 4 to 6 carbon atoms, sec-C4 is a ratio of -C4, (C2>5>2, etc.), preferably It is a secondary alkyl group, and sec-C4day9 is particularly preferred.Next, in (b), examples of the alkyl group having 2 or 3 carbon atoms include ethyl and propyl groups, with ethyl being particularly preferred; Examples of the alkyl group having 4 or more carbon atoms include butyl group, amyl group, hexyl group, octyl group, etc., and butyl group and hexyl group are particularly preferred.

Examples of the hydrocarbon group having 6 or more carbon atoms in (m) include hexyl group, octyl group, decyl group, phenyl group, etc., and alkyl groups are preferred, and hexyl groups are 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 this tends to increase the viscosity of the solution, and it is not preferable to use an alkyl group that is longer than necessary in terms of handling. The above-mentioned organomagnesium compound is used as a hydrocarbon solution, and the solution contains a certain amount of ether, ester,
Even if a small amount of a complexing agent such as an amine is contained or remains, it can be used without any problem.

Next, the general formula LJjR8-j (where L, J, R〇, 1
, a has the above-mentioned meaning) will be explained. The element represented by L in the above formula is selected from boron, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, mercury, and tellurium, preferably boron, silicon, germanium,
Selected from tin, phosphorus, antimony, and mercury. Examples of the halogen for J include chlorine, bromine, and iodine, but chlorine is particularly preferred. The hydrocarbon group of Ro is an alkyl group, a cycloalkyl group, or an allyl group, such as methyl, ethyl, propyl, ethyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc., and preferably It is an alkyl group having 1 to 10 carbon atoms, and methyl and ethyl groups are particularly preferred. There is no particular restriction on the range of the value of j as long as 0<i≦a, but it is preferable that i is larger, and particularly preferably i
Examples include halogen compounds that do not contain Ro, where =a. There are many halogen compounds as described above, but among them, those that are easily used in the present invention are those that are soluble in hydrocarbon media or ether media, and give preferable results.

Preferred specific halogen compounds include silicon tetrachloride, trichloromethylsilane, dichlorodimethylsilane,
Germanium tetrachloride, dicyclodimethylgermane, tin tetrachloride, boron trichloride, mercuric chloride, tellurium tetrachloride,
Phosphorus trichloride, antimony trichloride, etc. are mentioned, and silicon tetrachloride, germanium tetrachloride, etc. are particularly preferred.
Tin tetrachloride includes boron trichloride, mercuric chloride, phosphorous trichloride, antimony trichloride, etc. These compounds can be used alone or as a mixture. The reaction with the compound is carried out in an “inert reaction medium, e.g.
Hexane: Aliphatic hydrocarbons such as heptane, benzene,
The reaction can be carried out in an aromatic hydrocarbon such as toluene, xylene, cyclohexane, alicyclic hydrocarbon such as methylcyclohexane, or an ether medium such as ether, tetrahydrofuran, or a mixed medium of these.In terms of catalytic performance, it is preferable to use a fatty acid. Group hydrocarbon medium is recommended. There is no particular restriction on the reaction temperature, but it is preferably carried out at 40 qC or higher in view of the reaction progress. There is also no particular restriction on the reaction ratio of the two components, but preferably organomagnesium component 1 0.01 mol to 1 mol of halogen compound component per mole
A range of 0.00 mol, particularly preferably 0.1 mol to 10 mol, is recommended. Regarding the reaction method, there is a simultaneous addition method (method
), or a method of reacting by charging the chlorosilane component in advance into the reaction zone and then introducing the organomagnesium rust component into the reaction zone. There is a method (Method/Method Q) to do this, but Methods @ and Q are preferred, with Method @ giving particularly favorable results.When the organomagnesium component is insoluble, a halogen compound is used as a reaction reagent to remove the insoluble material in the reaction zone. It is also possible to use it as a homogeneous processing reaction.

In this case as well, the conditions described above are preferred regarding temperature, molar ratio, and reaction ratio. The compositional structure of the basic solid material obtained by the above reaction may vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, approximately 0.1 to 5.5 mmol of Mg-C bonds are present per 1 g of the basic solid. It is presumed to be a halogenated magnesium compound containing an alkyl group.

This basic solid has an extremely large specific surface area, and B
．． E. T. According to the present invention, it is possible to easily produce a high surface area active magnesium balogenide basic solid, which was previously difficult to produce. Titanium compound (2) containing 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,
To propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, triptoxytitanium monochloride, etc. Titanium halides and alkoxyhalides can be used alone or in mixtures.

A preferred compound is a compound containing three or more halogens, and titanium tetrachloride is particularly preferred.Next, trivalent titanium halides will be explained.

Examples of trivalent titanium halides include titanium trichloride,
Examples include titanium tribromide and titanium triiodide, but a solid melt containing these as one component may also be used. Solid solutions include a solid solution of titanium trichloride and aluminum trichloride, a solid solution of titanium tribromide and aluminum tribromide, a solid liquid of titanium trichloride and vanadium trichloride, a solid solution of titanium trichloride and iron trichloride, and a solid solution of titanium trichloride and iron trichloride. Examples include solid solutions of titanium and zirconium trichloride. Among these, titanium trichloride, a solid solution of titanium trichloride and aluminum trichloride (
TIC13/1/3 CI3). 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. . Next, the mixed yellow, oxygen-containing to nitrogen-containing double ring carboxylic acid ester '31 will be explained.

First, the sulfur-containing polycyclic carboxylic acid esters include thiophene carboxylic acid esters, thianaphthene carboxylic acid esters, irithianaphthene carboxylic acid esters, benzothiophene carboxylic acid esters, phenoxathin carboxylic acid esters, benzothiane carboxylic acid esters, and benzothiane carboxylic acid esters. Examples include carboxylic acid esters of carboxylic acid esters, thiaxanthene carboxylic acid esters, carboxylic acid esters of thioindoxyls, etc. More specifically,
Methyl thiophene-2-carboxylate, ethyl, propyl, butyl and amyl thiophene-2-carboxylate, methyl thiophene-3-carboxylate, ethyl, propyl, butyl and amyl, methylhethyl thiophene-2,3-dicarboxylate, methyl thiophene-2,4-dicarboxylate, ethyl, Methyl thiophene-2,5-dicarboxylate, ethyl, methyl 2-thhenylacetate, ethyl, propyl, butyl, methyl 2-thenyl acrylate, ethyl, methyl 2-thenylpyruvate, ethyl, methyl thianaphthene-2-carboxylate,
Ethyl, methyl thianaphthene-3-carboxylate, ethyl, methyl thianaphthene-2,3-dicarboxylate, ethyl,
Methyl 3-oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenyl acetate, ethyl, methyl 3-thianaphthenyl acetate, ethyl, benzothiophene-2
-Methyl carboxylate, ethyl, benzothiophene-3-Methyl carboxylate, ethyl, benzothiophene-4-methyl carboxylate, ethyl, phenoxathine-1-methyl carboxylate, ethyl, phenoxathine-2-methyl carboxylate, ethyl, phenoxathine-3 -Methyl, ethyl carboxylates, etc.

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

Examples of oxygen-containing heterocyclic carboxylic acid esters include furan carboxylic esters, dihydrofuran carboxylic esters, benzofuran carboxylic esters, coumaraso 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 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 inkmarin, ethyl 3-methyl-furan-2-carboxylate, and ethyl isodehydroacetate, including methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate, and ethylpropyl furan-2-carboxylate. , butyl, 4,5-dihydrofuran-
Methyl 2-carboxylate, ethyl, tetrahydrofuran-2-carboxylate, methyl coumarate, methyl coumarate, ethyl, etc. give preferable results. Next, the nitrogen-containing polycyclic carboxylic acid esters include pyrrole carboxylic esters, indoles carboxylic esters, carbazole carboxylic esters, oxazole carboxylic esters, thiazole carboxylic esters, imidazoles carboxylic esters, Pyrazole carboxylate ester, pyridine carboxylate ester, phenanthridine carboxylate ester, anthrazoline carboxylate ester, phenanthroline carboxylate ester, naphthyridine carboxylate ester, oxazine carboxylate ester, thiazine carboxylate ester,
Examples include pyridazine carboxylic acid esters, pyrimidine carboxylic acid esters, pyrazine carboxylic esters, and preferred ones include methyl, ethyl, propyl, and butyl pyrrole-2-carboxylate, methyl, ethyl, propyl, and pyrrole-3-carboxylate. 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, pyridine 2, Methyl 3-dicarboxylate, ethyl, pyridine methyl 2,5-dicarboxylate, ethyl,
Methyl pyridine 2,6 dicarboxylate, ethyl, methyl pyridine 3,5 dicarboxylate, ethyl, methyl quinoline-2-carboxylate, ethyl dimethylpyrrolecarboxylate, N-methylpyrrole methylcarboxylate, N-carboethoxypyrrole, N -Ethyl boenatoxypyrrole 2-methylpyridinecarboxylate, Piveridine 4-
ethyl carboxylate, ethyl piverizine 2-carboxylate,
Examples include ethyl pyrrolidine 2-carboxylate.

Next, the basic solid '1} obtained by the reaction of the organomagnesium component (l) and the above-mentioned halogen compound (ii)
The following describes how to obtain a catalyst solid by reacting and/or pulverizing titanium compound (1) with one or more selected from sulfur-containing, oxygen-containing or nitrogen-containing double ring carboxylic acid esters.

In 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 present invention's millet ring carboxylic acid ester), the titanium compound or the present application's heterocyclic carboxylic acid ester is reacted with the titanium compound or the present invention's heterocyclic carboxylic acid ester in a liquid phase. Alternatively, any method can be adopted, such as a method of reacting in a gas phase [1], a method of combining a reaction in a liquid phase or a gas phase, and a pulverization reaction [2].

First, the reaction and/or pulverization order of the basic solid, the titanium compound, and the polycyclic 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 a method in which 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 (■)), or a method of first reacting the basic solid with the polycyclic carboxylic acid ester of the present application and then reacting with a titanium compound (synthesis method (■)).

Both methods are possible, but the latter two methods are preferred.
In particular, synthesis method (2) is preferred. In method [2], when the titanium compound is (1) tetravalent, (0) trivalent,
(m) The case where 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 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 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 carboxyl 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 (0), various methods are possible for synthesizing the solid component from the three components of the basic solid, the trivalent titanium halide, and the polycyclic carboxylic acid ester of the present invention, but the following three methods are particularly preferable. give. That is, a method of co-pulverizing the three components (synthesis method ■), a method of bringing the solid component into contact with the present silicone ring carboxylic acid ester in advance, and then adding a trivalent titanium halide and mechanically crushing the solid component (synthesis method Method ①), or a method (synthesis method ①) 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 multi-hata ring carboxylic acid ester of the present invention. In the case of (mountain),
A method of simultaneously crushing the basic solid {1', a tetravalent titanium compound (2-1), a trivalent titanium compound (2-2), and the present heterocyclic carboxylic acid ester {3' (synthesis method ■),
The solid obtained by reacting {1} and (2-1) is '3}
(2-3) (Synthesis method ■
), '1) and {31, and the resulting solid is (2
A method of treating with (2-1) and pulverizing with (2-2) (synthesis method ■), adding the solid obtained by reacting {1} and (2-1), (2-2) and glue. Examples include a method of pulverizing (synthesis method (2)), but synthesis method (2) is preferred.

Furthermore, by further treating the solid catalyst synthesized by the above method [1] and method [2] with a tetravalent titanium compound 4 containing at least one halogen atom, an increase in catalyst efficiency is brought about. First, the method of further treating the solid catalyst synthesized by method [1] with the tetravalent titanium halide (2) described above involves simultaneously reacting the basic solid, the titanium compound, and the monocyclic carbosic acid ester. After that, a method of further treating with a tetravalent titanium halide (synthesis method ■), reacting the basic solid with a titanium compound, and then reacting the heterocyclic carboxylic acid ester of the present application, and then further treating with a tetravalent titanium halide (synthesis method
Method of treating titanium with halogenated titanium (synthesis method ■)
There is a method (synthesis method ①) in which the basic solid is reacted with the present compound ring carboxylic acid ester, and then reacted with a titanium compound, and then further treated with a tetravalent titanium halide.

Next, regarding the method of further treating the solid catalyst synthesized by method [2] with a tetravalent titanium halide '4}, (1), (0) and (m) will be explained. In the case of (1), the synthesis method [2]-(1)-■, [2]-
Although it is possible to treat the solid catalyst synthesized by (1)-■ or (2)-(1)-■ with a tetravalent titanium halide, the latter two methods are more preferred. In the case of (0), the synthesis method [2)-(D)-■, [2
]-(b)-■, [2]-(0)-■, [2]-(0)
It is possible to further treat the solid catalyst synthesized in step 1 with a tetravalent titanium halide. In the case of (m), basic solid '1), tetravalent titanium compound (2-1))
, A method of simultaneously pulverizing the trivalent titanium compound (2-2) and the present complex carboxylic acid ester [3' and then treating it with a tetravalent titanium halide (synthesis method ■),'1}
The solid obtained by reacting with (2-1) is treated with legs,
A method of pulverizing with (2-2) and then treating with a tetravalent titanium halide (synthesis method ■), reacting {11 with [31], and treating the resulting solid with (2-1). ,(
2-2), and then further treated with a tetravalent titanium halide (synthesis method ①).

The solid obtained by reacting [11 with (2-1)] and (2-
2) and {3} are added, pulverized, and then further treated with a tetravalent titanium halide (synthesis method ■), '11
In particular, there is a method (synthesis method ■) in which the solid obtained by reacting 2-1) is treated with '3}, pulverized with (2-2), and then treated with a tetravalent titanium halide. , method■■
■■ is preferred.

Next, the reaction between the basic solid, the titanium compound, and the complex carboxylic acid ester of the present invention and/or the pulverization operation will be explained. [i) The reaction between a solid material obtained by reacting an organomagnesium component and a halogen compound, or a reaction product of this solid material and the polycyclic carboxylic acid ester of the present invention with a titanium compound will be explained.

The reaction is carried out with or without an inert reaction medium, undiluted, with 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, 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 it is preferably a temperature of 8.0 mm or higher and a titanium compound concentration of 2 moles/liter or higher. Regarding the reaction molar ratio, it is preferable to carry out the reaction in the presence of a sufficient excess amount of the titanium compound relative to the magnesium component in the solid substance to give preferable results. (i
i) The reaction between a solid substance obtained by reacting an organomagnesium component and a halogen compound, or a reaction product of this solid substance and a titanium compound, and the heterocyclic carboxylic acid ester of the present application will be explained.

The reaction is carried out using an inert reaction medium. Any of the above-mentioned aliphatic, aromatic, and alicyclic hydrocarbons may be used as the non-tritonal reaction medium. The temperature during the reaction is not particularly limited, but is preferably in the range of room temperature to 100°C. When a solid substance is reacted with the cyclic carboxylic acid ester of the present invention, the reaction ratio of the two components is not particularly limited, but it is preferable that the ester of the cyclic carboxylic acid of the present invention be reacted with 1 mol of the alkyl group contained in the organomagnesium component. Estel is 0.001
mol to 50 mol, particularly preferably 0.005 mol to 10
A molar range is recommended. When a reaction product of a solid substance and a titanium compound is reacted with the present heterocyclic carboxylic acid ester, the reaction ratio of the two components is 1 mole of titanium atom in the organomagnesium solid component to the present heterocyclic carboxylic acid The recommended amount of ester is 0.01 mol to 100 mol, particularly preferably 0.1 mol to 10 mol. (iii
' A method of pulverizing the solid produced by the reactions (i} to (ii} above) will be explained.

Grinding methods include rotary ball mill, vibrating ball 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 degrees, preferably 10 to 150 degrees. A case where the solid component obtained in (i) to oil) of (○) 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 hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. is preferable. Regarding the concentration of titanium compound, 2 mo
A concentration of 1/2 or more is preferable. There is no particular restriction on the reaction temperature, but a reaction at a temperature of 80o0 or more gives preferable results. The composition and structure of the solid catalyst component obtained by the reactions (l) to positive v) above vary depending on the type of starting materials and reaction conditions, but "from the compositional analysis value, the mass of the solid catalyst component is approximately 1 to 1. It was found that the solid catalyst contained 50-300% titanium/g.

[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 an organoaluminum compound, “general formula NR1o/L
Z-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 groups, 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. For example, "triethylaluminum" tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tridodecyl aluminum, trihexadecyl aluminum, die Chylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum ethoxide "dioctylaluminum butoxide, diisobutylaluminum octyloxide" diethylaluminum chloride "diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydro Diethyl siloxyaluminum, diethyl ethyldimethylsiloxyaluminum, diethyl aluminum siloxy, etc., and mixtures thereof are recommended.

A highly active catalyst can be obtained by combining these alkyl aluminum compounds with the solid catalyst described above, and trialkyl aluminum and dialkyl aluminum hydride are particularly preferred because they achieve the highest activity.
One or more components selected from mixed yellow, oxygen-containing, or nitrogen-containing heterocyclic carboxylic acid esters added to this organometallic compound are sulfur-containing, oxygen-containing, or nitrogen-containing esters used in the synthesis of the solid catalyst component [A]. It may be the same as or different from the rear ring carboxylic acid ester. The addition method is to mix the two components in advance prior to polymerization, or to add them separately into the polymerization system. The amount of the oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester is 10 moles or less, particularly preferably 1 mole or less.A catalyst consisting of the solid catalyst component of the present invention and a component obtained by adding the present multihata ring carboxylic acid ester to an organometallic compound. may be added to the polymerization system under polymerization conditions, or may be roughly combined in advance prior to polymerization.

Particularly preferably, the organometallic compound and the heterocyclic 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 the ingredients to be combined is
The amount of the organometallic compound plus the heterocyclic carboxylic acid ester of the present application per 1 g of the solid catalyst component is preferably in the range of 1 mmol to 3000 mmol based on the organometallic compound. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins.

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

In suspension polymerization, the catalyst is added to a reactor together with a polymerization solvent, such as an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane. olefin such as propylene under an inert atmosphere.
Polymerization can be carried out at room temperature to 150 degrees Celsius by press-fitting the polymer into a 20k9/mm soil. In bulk polymerization, olefins can be polymerized using a liquid olefin as a polymerization solvent under conditions where the olefin such as propylene is a catalyst and a liquid. For example, in the case of propylene, room temperature
The polymerization can be carried out in liquid propylene at a temperature of 0°C and a pressure of 10 to 45k9/m. On the other hand, gas phase polymerization is performed 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/kg and at a temperature of room temperature to 120 k9, it is carried out using a fluidized bed, moving bed, or flywheel to ensure good contact between the olefin such as propylene and the catalyst. Polymerization can be carried out by means such as polymerization. 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 hydrocarbon-soluble organomagnesium complex
- 13.80 g of butylmagnesium and 1.9 g of triethylaluminum were mixed with 200 g of heptane and 100 g of soil.
An organomagnesium rust solution was obtained by placing the mixture in a nitrogen-substituted flask and reacting at 8,000 ℃ for 2 hours.

As a result of analysis, the composition of this complex was NMg6. . (C2 Duke)
2.9 (n-C4 day 9), 2. , and the organometallic concentration was 1.18 hol/hole.
Oxygen and moisture inside the 0' flask were removed by dry nitrogen replacement, and 1 mol of silicon tetrachloride was removed under a nitrogen atmosphere.
/Hmol of 2 plates of hebutane solution was charged, and the temperature was raised to 70oo.

Next, under a nitrogen atmosphere, the above organomagnesium body solution 1
0 skin mol was weighed into a dropping funnel. The mixture was dropped at 70° C. over a period of 1 hour under the rope, and the reaction was further allowed to proceed at this temperature for 6 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 M crucian carp per 1 g of solid. 05h mol
, CI18.7m mol, Sjl. B.1 hmol, alkyl group 0.65 hmol. E. T
．． The specific surface area measured by the method was 187/g. (l
ii) Synthesis of catalyst solid 3.0 g 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-2h carboxylate/3.0 g of its hexane solution were added. enemy hm
Add ol and let it react for 1 hour at 80q0,
The solid was filtered out, thoroughly washed with n-hexane, and dried.

2.5 g of this solid and 50 g of titanium tetrachloride were placed in a pressure-resistant container purged with nitrogen, and reacted at 10,000 ℃ for 2 hours. The solid was separated in a furnace, washed with n-hexane, and dried. A solid catalyst was obtained. As a result of analyzing this solid catalyst, the Ti content was 2.8% by weight. G. Solid catalyst synthesized by slurry polymerization of propylene ili),
9 of 50 and triethylaluminum 3. mark h mol
, ethyl thiophene-2-carboxylate 1. 1.5 hmol of the autoclave was placed in an autoclave with 0.8 molar of dehydrated and deaerated hexane, the interior of which was replaced with nitrogen and then vacuum degassed.

The internal temperature of the autoclave was maintained at 6000℃, propylene was pressurized to a pressure of 5.0k9/m, and polymerization was carried out for 2 hours while maintaining the total pressure at 4.8k9/g, and the polymerized hexane-insoluble polymer 8 was heated. , 3.3 g of polymerized hexane soluble material was obtained. Catalyst efficiency is 84 pp nog solid catalyst/hour, 583
0 several p/g titanium component, time, and propylene pressure, and the residue obtained by extracting the polymerized hexane-insoluble polymer with boiling n-heptane was 95.4%. Particle characteristics also have a bulk density of 0.
The ratio of 355g/35 to 150 mesh powder was good at 91%. Example 2 A basic solid was synthesized in the same manner as in Example 1 using germanium tetrachloride, a substitute for silicon tetrachloride, as a reaction reagent.

This solid was reacted with ethyl furan-2-carboxylate and titanium tetrachloride in the same manner as in Example 1 to synthesize a solid catalyst. The Ti content of the catalyst solid was 3.05% by weight. 9 of this group catalyst 50 and triethylaluminum 3
．． Slurry polymerization of propylene was carried out in the same manner as in Example 1 using Hmol and N-triboethoxypyrrole to obtain 8 polymerized hexane-insoluble polymers and 2.0 polymerized hexane-soluble polymers. Got a spot.

The catalytic efficiency was 538 female pp/g titanium component/time/propylene pressure, and the residual amount after extracting the polymerized hexane-free polymer with boiling n-hebutane was 94.6%.

Comparative Example 1 A solid catalyst was synthesized in the same manner as in Example 1 using magnesium chloride instead of the solid material obtained by reacting the organomagnesium key compound with silicon tetrachloride in Example 1.

Anhydrous MgC123. Female and ethyl thiofeso-2-carboxylate3. The solid obtained by reacting 2.5 hmol of
g and 50 g of titanium tetrachloride were reacted at 100 pm for 2 hours. Titanium in the solid catalyst was 0.51% by weight.
of this solid catalyst 400, triethylaluminum 3.
h mol, ethyl thiophene-2-carboxylate 1.
Slurry polymerization of propylene was carried out in the same machine as in Example 1 using skin mol. Polymerized hexane-insoluble polymer 5, hexane-soluble 11. I got a hammer. The boiling n-heptane extraction shallowness of the polymerized hexane non-falling polymer is 80.1%, and the catalyst efficiency is 63 pp/g solid catalyst time 245 female pp/
gTitanium component, time, and propylene pressure. Example
3 (i) Synthesis of organomagnesium compound A 500-capacity flask equipped with a dropping funnel and water reflux condenser was purged with dry nitrogen, and 19.8 g of 100-200 mesh metal magnesium powder and 30 g of n-hebutane were added.
The temperature of the flask was raised to 9000 °C.

Next, 0.81 mol of n-butyl chloride was weighed into the dropping funnel and added dropwise at 90° C. over a period of 1 hour. After the reaction has started, heating is continued at 90~95°C for another 2 hours, and the gray slurry (the collective part in the slurry is n-
The slurry had a composition of BuMgCI, and the liquid portion of the slurry did not contain organic magnesium.
Next, in this slurry, sec.
0.81 mol of -butyllithium (cyclohexane solution) was gradually passed through at room temperature.

After the completion of the dropwise addition, the mixture was heated at 50°C for 2 hours, and the solid portion was removed in a furnace under a nitrogen atmosphere to obtain an organic magnesium solution. Analysis of the obtained inorganic magnesium solution revealed that it had a composition of sec-BUMgn-Bu, and the concentration of C-Mg bonds was 1.08'/so. (
ii) Synthesis of basic solid and catalyst solid A basic solid was synthesized in the same manner as in Example 1 using the above organomagnesium compound and silicon tetrachloride, and this solid was combined with N-carbethoxypyrrole and titanium tetrachloride. A solid catalyst was obtained by the reaction.

As a result of analyzing this solid catalyst, the Ti content was 2.9% by weight. 9 of this solid catalyst 50, triethyl aluminum 3. h mol, ethyl furan-2-carboxylate 1. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using hmol. Polymerized hexane-insoluble polymer 8&, hexane-soluble material 3. I got a place. The boiling n-hebutane extraction residue of polymerized hexane-insoluble polymer is 95.0%, and the catalyst efficiency is 840 p/g solid catalyst/hour, 573
The titanium component, time, and propylene pressure were 0 p/g.
Examples 4 to 12 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 ethyl thiophene-2-carboxylate and titanium tetrachloride. A solid catalyst was obtained.

Solid catalyst 50 female triethyl aluminum 3. enemy hmoI
N-carbethoxypyrrole 1. (2) Polymerization of propylene was carried out in hexane solvent in the same manner as in Example 1 using hmol. Table 1 shows catalyst synthesis conditions and polymerization results. Ship Example 13 AIM scales in the same manner as Example 1.

. (C2 day 5) 2.9 (n-C4 day 9), 2. , silicon tetrachloride tothiophene-ethyl 2-carboxylate and titanium tetrachloride were reacted to obtain a solid. This solid 4. The female was crushed for 5 hours under a nitrogen atmosphere in a steel mill with an internal volume of 100 mm containing 29 steel balls on the 9th side using a vibrating ball mill at a speed of at least 100 mm/min. The Ti content of the obtained solid catalyst was 2.85% by weight. 9 of this solid catalyst 50 and 3.0 hmol of triethylaluminum,
Ethyl thiophene-2-carboxylate 1. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using a dish mol.

The results are shown in Table-2. Example 14 Using the same method as Example 1 (sec-Bu), . 5Mg(
A solid was obtained by reacting the vessel with silicon tetrachloride, ethyl pyrrole-2-carboxylate, and titanium tetrachloride.

This solid 3.9 female and 0.15 titanium trichloride (AA grade Ti01301/3 CI3 manufactured by Toyo Stoffer Co., Ltd.)
g was pulverized for 5 hours in the same manner as in Example 11 under a nitrogen atmosphere.

The Ti content of the obtained solid catalyst was 3.65% by weight. 9 of this solid catalyst 50 and triethylaluminum 3. hmol, ethyl coumarate 1. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using cost hmol. The results are shown in Table 2. Example 15 A basic solid was synthesized by reacting silicon tetrachloride and silicon tetrachloride in the same manner as in Example 1.
It was further reacted with methyl pyridine-2-carboxylate.

This solid 4. Female and titanium trichloride (A manufactured by Toyo Stoffer Co., Ltd.)
Grade A) 0.3 flecks were crushed for 5 hours using the same method as in Example 11 under a nitrogen atmosphere. The Ti content of the obtained solid catalyst was 2.0% by weight. This solid catalyst 50 fences"
Triethyl aluminum 3. hmol, thiophene-
Butyl 2-carboxylate 1. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using hmol. The results are shown in Table 2. Example 16 In the same manner as in Example 15, the basic solid and methyl pyridine-2-carboxylate were reacted.
Next, the obtained solid and titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were ground.

This solid 4. Female and titanium tetrachloride 60M, 130q
After reacting for 2 hours at 500 ml, the solid portion was isolated by filtration, thoroughly washed with hexane, and dried to obtain a solid catalyst.
As a result of analyzing this solid, it was found that it contained 3.55% by weight of titanium.By using this solid catalyst, 9 of 50, triethyl aluminum, 3. butyl thiofeso-2-carboxylate, 1. skin mo! Slurry polymerization of propylene was carried out in the same machine as in Example 1. The results are shown in Table 2. Example 17 In the same manner as in Example 13, the basic solid was reacted with ethyl thiophene-2-day carboxylate. The solid was reacted with titanium tetrachloride.

This solid was ground in a vibrating ball mill under nitrogen atmosphere for 5 hours. Furthermore, 40 g of this solid and 60 g of titanium tetrachloride were reacted for 2 hours in a 130 qO column under a fly frame, 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 3.1% by weight of titanium. This solid catalyst 50 glue and triethylaluminum 3.

hmol, ethyl thiophene-2-carboxylate 1. Slurry polymerization of propylene was carried out in the same machine as in Example 1 using Melon hmol. The results are shown in Table 2. Table 2 Example 18 35 liters of liquefied propylene was placed in an autoclave whose interior had been replaced with nitrogen and vacuum dried, and the internal temperature was reduced to 60 q.
o and 9 of 10 of the solid catalyst synthesized in Example 17,
1.8 hmol of triethylaluminum and 0.8 hmol of ethyl thiophene-2-carboxylate were added to the autoclave, and polymerization was carried out at 60°C for 2 hours to obtain 130 g of polypropylene.

Catalyst efficiency is 6500 sheath p/g solid catalyst time, 205,
00 female pp/g titanium component/time, and the n-heptane extraction residue of the produced polypropylene was 93.0%.
Example 19 Hexane solution of triethylaluminum (lmol/night)2. hmol and thiophene-2
-Hexane solution of ethyl carboxylate (lmol/night) 1
．． A pre-mixed solution of Hmol, 9 of 30 of the solid catalyst synthesized in Example 17, and 1.9 of triethylaluminum.
Slurry polymerization of propylene was carried out in the same machine as in Example 1 using Hmol, and polymerized hexane non-falling polymer 15 was obtained.
Female, 7.9 g of polymerized hexane soluble material was obtained.

The n-heptane extraction residue of polymerized hexane-insoluble polymer is 9
4.9%, catalyst efficiency 1580 female pp/g titanium component.
time and propylene pressure. Examples 20 to 25 Solid catalyst 50 9 synthesized in the same manner as in Example 1 and triethylaluminum 3. Skin mol and compounds shown in Table 3 1. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using Kamol, and the results shown in Table 3 were obtained.

Examples 26-27 9 of 50 solid catalysts synthesized in the same manner as in Example 1,
N-carboethoxypyrrole1. mh mol and organometallic compound shown in Table 4 3. Slurary polymerization of propylene was carried out in the same manner as in Example 1 using hmol, and Table 4
I got the result.

Table 3 Table 4 Example 28 9 of 50 solid catalysts synthesized in the same manner as in Example 1,
Triethyl aluminum 3. mol, N-carbethoxypyrrole 1. Using melon hmol, slurry polymerization was carried out in the same manner as in Example 1 using a propylene-ethylene mixed gas containing 2 mol% of ethylene to obtain a white polymer.

Example 29 9 of 500 solid catalysts synthesized in the same manner as in Example 1 and 6.9 of triethylaluminum. hmol, N-benethoxypyrrole2. Polymerization of butene-1 in hexane using Hmol was carried out in the same manner as in Example 1 to obtain 105 g of a white polymer.

Example 30 A solid catalyst 500 female synthesized in the same manner as in Example 1,
Triethyl aluminum6. 5 m mol, N-force Rubethoxypyrrole 2. Polymerization of 4-methylbentene-1 in hexane using hmol was carried out in the same manner as in Example 1 to obtain white polymer 7.

Example 31 Solid catalyst 50 synthesized in the same manner as in Example 1, triisobutylaluminum 1. enemy h mol
and 0.1 mmol of N-carbethoxypyrrole and 0.8 mmol of dehydrated and degassed n-hexane were placed in an autoclave whose interior had been vacuum dried and replaced with nitrogen.
Keep the internal temperature at 80℃, pressurize to 1.6k9/ground with hydrogen,
Ethylene was then added to bring the total pressure to 4.0k9/kg.

Claims (1)

[Claims] 1 [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, 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 and R^2 are carbon atoms with the same or different numbers of carbon atoms. Hydrogen group, X, Y are the same or different groups, OR
^3, OSiR^4, R^5R^6, NR^7R^8,
Represents the group SR^9, R^3, R^4, R^5, R
^6, R^7, R^8 are water atoms or hydrocarbon groups, R
(^9 represents a hydrocarbon group) is an organomagnesium compound represented by (ii) general formula LJjR^0_a_-_j(
In the formula, L is boro, silicon, germanium, tin, lead,
An atom selected from phosphorus, arsenic, antimony, bismuth, mercury, and tellurium, J is a halogen atom, R^0 represents a hydrocarbon group, a is the valence of L, and j is a number such that 0<j≦a. (2) a titanium compound containing at least one halogen atom; and (3) a sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester. one or more species, (
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 [A] (1) In the organomagnesium compound of (i), α is a number greater than 0, and M is an aluminum, zinc, boron or beryllium atom. The catalyst for olefin polymerization according to claim 1. 3 [A] (1) The organomagnesium compound of (i) has α>0, 1≦β/α≦10 and (r+s)/(
The catalyst for olefin polymerization according to claim 1 or 2, wherein the ratio of α+β) is 0≦(r+s)/(α+β)≦0.8. 4 [A] In the organomagnesium compound of (1)(i), a secondary or tertiary alkyl in which α is 0 and at least one of R^1 and R^2 has 4 to 6 carbon atoms. group, 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, which is a hydrocarbon-soluble organomagnesium compound in which at least one of ^2 is a hydrocarbon group having 6 or more carbon atoms. 5 [A] In the halogen compound of (1) (ii),
Claim 1, wherein L is an atom selected from boron, silicon, germanium, tin, phosphorus, antimony, and mercury, and the compound is soluble in a hydrocarbon medium or an ether type medium. The catalyst for olefin polymerization according to any one of items 1 to 4. 6 [A] J in the halogen compound of (1) (ii)
The catalyst for olefin polymerization according to any one of claims 1 to 5, wherein is a chlorine atom. 7 [A] In the halogen compound of (1) (ii),
The catalyst for olefin polymerization according to any one of claims 1 to 6, wherein j=a. 8 [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 7, wherein a solid catalyst component is synthesized by reacting or reacting and pulverizing 1), (2), and (3). 9 [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. The solid catalyst component is synthesized by pulverizing the solid obtained by pulverizing (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 items 1 to 7. 10 [A] The titanium compound in (2) is (a) a tetravalent titanium compound containing at least one halogen atom, and (b) a trivalent titanium halide, and (
The catalyst for olefin polymerization according to any one of claims 1 to 7, wherein a solid catalyst component is synthesized by pulverizing or pulverizing and reacting 1), (2), and (3). 11 [A] Claim 1, wherein the titanium compound in (2) is titanium tetrachloride and/or titanium trichloride.
The catalyst for olefin polymerization according to any one of Items 1 to 9. 12 [A] The sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid ester of (3) and [B] 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, N-carbalkoxypyrrole, piperidine carboxylic acid ester, pyrrolidine carboxylic acid ester, claims 1 to 1
The catalyst for olefin polymerization according to any one of Item 1. 13 [A] The amount of the sulfur-containing, oxygen-containing or nitrogen-containing carboxylic acid ester in (3) is in the solid obtained by reacting the organomagnesium compound in (1) with a halogen compound of silicon, germanium, tin or antimony. The catalyst for olefin polymerization according to any one of claims 1 to 12, wherein the number of moles is 0.001 to 50 times the number of moles of the alkyl group contained in the catalyst. 14 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 13. 15. The catalyst for olefin polymerization according to claim 14, wherein the organoaluminum compound is trialkylaluminum or dialkylaluminum hydrand. 16 [A] (1) (i) General formula MαMgβR^1_
pR ^ 2_q A metal element belonging to Group III, m is the valence of M, R^1, R^2 are hydrocarbon groups having the same or different numbers of carbon atoms, X, Y are the same or different groups,
OR^3, OSiR^4R^5R^6, NR^7R^8
, SR^9 represents the group R^3, R^4, R^5,
R^7, R^6, R^8 are hydrogen atoms or hydrocarbon groups,
R^9 represents a hydrocarbon group) is an organomagnesium compound represented by (ii) general formula LJjR^0_a_-_j
(In the formula, L represents an atom selected from boron, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, mercury, and tellurium, J represents a halogen atom, and R^0 represents a hydrocarbon group, a is the valence of L, and j is a number such that 0<j≦a); (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) and then further treating with a tetravalent titanium compound (4) containing at least one halogen atom. , [B] An olefin polymerization catalyst comprising an organometallic compound and one or more components selected from sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters. 17. [A] The catalyst for olefin polymerization according to claim 16, wherein the tetravalent titanium compound having at least one halogen atom in (4) is titanium tetrachloride.