JPS608003B2 - Catalyst for polyolefin production - Google Patents

Description

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

In particular, the present invention provides propylene, butene-1, bentene-1
, 4-methyl-2-pentene-1, 3-methylbutene-1, etc., and copolymerizing the above-mentioned olefins with ethylene or other olefins. A stereoregular polymer is produced by bringing an olefin into contact with a Ziegler-Natta catalyst system consisting of a transition metal compound of Groups W to A of the Periodic Table of the Elements and an organometallic compound of Groups 1 to M of the Periodic Table of the Elements. In particular, a combination of titanium halide and an organoaluminum compound such as triethylaluminum or diethylaluminum chloride is used industrially as a catalyst for the production of stereoregular polyolefins.

When olefins such as propylene are polymerized using this catalyst, the proportion of boiling hebutane-insoluble polymers, i.e., stereoregular polymers, is quite high, but the polymerization activity is not satisfactory, and the resulting polymer A step to remove catalyst residue is necessary.

In recent years, many catalyst systems comprising reaction products of inorganic or organic magnesium compounds and titanium or vanadium compounds, and organic aluminum compounds have been proposed as highly active catalysts for ethylene polymerization. Although these catalyst systems exhibit remarkable activity for the polymerization of propylene, the proportion of stereoregular polymers in the total polymer is low, making them difficult to use in industry for the production of stereoregular polymers of olefins such as propylene. That is extremely difficult. (For example, JP-A-47-19
342, Special Publication No. 43-11305) As improvements to these, Special Publication No. 52-39431, Special Publication No. 52-36153
The method described in Japanese Patent Application Laid-open No. 48-16988 has been proposed. These methods consist of a solid catalyst 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 aluminum trialkyl and an electron donor. It is a catalyst system. However, even with these methods, the proportion of stereoregular polymer in the produced polymer is still not high enough to satisfy the requirements, the polymer yield per solid catalyst component is insufficient, and the catalyst residue during polymerization, especially The high content of halogen causes problems such as corrosion of manufacturing process equipment and molding machines.
The physical properties of the product are also not fully satisfactory. The inventors of the present invention have found that it is necessary to improve these points.
After reacting a chlorosilane compound containing a bond as a reaction agent to produce a halogen-containing magnesium compound solid, and reacting and/or pulverizing this with a titanium compound and a carboxylic acid or its derivative, or further producing tetravalent titanium. It was discovered that a catalyst consisting of a solid obtained by reacting with a halide, a sulfur-containing or oxygen-containing double ring carboxylic acid ester, and an organoaluminium compound has extremely excellent performance as an olefin polymerization catalyst, and the present invention was achieved based on this discovery. did.

That is, the present invention provides the following: [A]'1}(i) General formula MQMg6RipR2q (wherein M is aluminum, zinc, boron or beryllium atom, R1 and R2 are the same or different carbon numbers 1 to 20
hydrocarbon soluble organomagnesium represented by the following formula: hydrocarbon group, Q≧0, 8>0, p, q>0, m is the valence of M, 8/Q≧0.1, p+q=mQ+23 The components are represented by (ii) the general formula HasiC1bR4-(a+b)(
In the formula, a, b are numbers larger than 0, a+bS4, R represents a hydrocarbon group having 1 to 20 carbon atoms)
A solid obtained by reacting with a chlorosilane compound containing a bond,
■ Titanium compounds containing at least one halogen atom, [3] carboxylic acids or derivatives thereof (however,
(excluding sulfur-containing heterocyclic carboxylic acid esters), or above [1}
, ■, a solid catalyst component obtained by reacting and/or pulverizing {3}, and [B] a component consisting of an organometallic compound and a sulfur- or oxygen-containing square ring carboxylic acid ester, and [A]. This is a catalyst for producing polyolefin consisting of [B].

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

As is clear from the examples below, in the case of polymerization of propylene in liquid propylene, the catalyst efficiency is more than 309,500 pp/tertitanium component/hour and 6,500 pp/tertitanium component/hour. The second feature of the present invention is
In addition to having high activity as described above, high stereoregularity can also be obtained. The value of the present invention is 94.2%.
A third 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 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 the particle size of the polymer is good and that polymer particles with a high degree of clarity can be produced.

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

{1} General formula MQMgBR1pR (in the formula, 8,
(p, q, M, R1, R2 have the above-mentioned meanings) This organomagnesium component is shown as a complex compound of organomagnesium, but R2Mg and these This includes all types of flanges with other metal compounds.

In the above formula, the hydrocarbon group represented by RI to R2 is
An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, such as methyl, ethyl, propyl,
Butyl, amyl, hexyl, decyl, cyclohexyl,
Examples include phenyl groups, and RI is particularly preferably an alkyl group. As M, aluminum, zinc, boron, or beryllium atoms are preferable because they facilitate the formation of a hydrocarbon-soluble organomagnesium body.

When used as a catalyst component in the present invention, an organomagnesium lead body or compound that is soluble in an inert zero-hydrocarbon solvent is preferred.

When Q > 0 in the above formula, this organomagnesium rust body has a ratio of magnesium to metal atom M of 3/hi = 0.
．． 1 or more, preferably 0.5 or more, particularly preferably 1 to
It is 10. These organomagnesium rust compounds have the general formula RIMgQ, R-chamber Mg (RI has the above meaning,
Q represents a halogen) and an organometallic compound represented by the general formula MR (M, R2, m have the above-mentioned meanings) in hexane, heptane, cyclohexane, benzene, toluene. It is synthesized by reacting in an inert hydrocarbon solvent such as at room temperature to 150 qo.

Furthermore, MgX2, RIMgX and M old express, MR etc., or RIMgX, MgR season and R house MXmh (in the formula,
M, R1, and R2 are as described above, x represents a halogen, and n is a number from 0 to m).

Generally, organomagnesium compounds are insoluble in inert hydrocarbon media, but organomagnesium compounds where Q>0 are soluble, and in the present invention, hydrocarbon-soluble complexes are preferred. give.

As the organomagnesium component, when Q=0 in the above formula, that is, MgR1pR2q (in the formula, R1, R2
, p, and q have the above-mentioned meanings).

In the above formula, R1 and R2 are assumed to be in any of the following three cases.

[A] When at least one of R1 and R2 is a secondary to tertiary alkyl group having 4 to 6 carbon atoms.

[o} When RI and R2 are alkyl groups having different carbon numbers. (1) When at least one of RI and R2 is a hydrocarbon group having 6 or more carbon atoms.

Preferably, R1 and R2 are in any of the following three cases.

When both R. and R2 have 4 to 6 carbon atoms, and at least one is a secondary to tertiary alkyl group.

(2) When RI is an alkyl group having 2 to 3 carbon atoms and R2 is an alkyl group having 4 or more carbon atoms.

Both R1 and R2 are alkyl groups Z having 6 or more carbon atoms
If it is.

These groups will be specifically shown below.

{In A and (A'), the secondary or tertiary alkyl group having 4 to 6 carbon atoms is sec-C4day9
, tert-C4 is one CH (C2 day 5) 2, one C (C
2 days 5) (C ratio) 2, J-CH (C melon) (C 4 days 9),
1CH (C2 day 5) (C3 day 7), -C (C ratio) 2 (C
3 days 7), 1C(CH3)(C2 days 5) 2, etc. are used, preferably secondary alkyl groups, and sec-C4 days 7 are particularly preferred. In (b'), examples of the alkyl group having 2 to 3 carbon atoms include ethyl and propyl, with ethyl being particularly preferred. Examples of the alkyl group having 4 or more carbon atoms include butyl, amyl, hexyl, octyl and the like, with butyl and hexyl being particularly preferred. Shiichi and (ha'
), examples of the hydrocarbon group having 6 or more carbon atoms include hexyl, octyl, decyl, phenyl, etc., with alkyl groups being preferred, and hexyl being particularly preferred. Examples of such organomagnesium compounds include:
sec-C44) 2Mg, (grap rt-C4) 2Mg
, n-C4 Mr.-Mg-C2 Duke, n-C4 day 91 Mg-s
ec-C4 ratio, n-C4 day 9-Mg-sec-C4 day 9
, n-C4 days 91 Mg one day C4 days 9, n-C6 days, 31 Mg one C2 days 5, n one C8 days, 7-Mg-C2 public, (n-C6 days, 3) 2 Mg , (n-C8 days, 7) 2M
g, (n-C, pan-2,)2Mg, and the like. next,
General formula HasjC1bR4-(a+b) (wherein a, b
, R has the above-mentioned meanings) will be described. The hydrocarbon group represented by R in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, such as methyl, ethyl, propyl, butyl, amyl, hexyl,
Examples include decyl, cyclohexyl, phenyl, etc., preferably an alkyl group having 1 to 10 carbon atoms, methyl,
Lower alkyl groups such as ethyl and propyl are particularly preferred.
The values of a and b are a, b > 0, a + b mi 4, and preferably 0 < a mi 2. These compounds include HS
iC13, HSiC12CH3, HSiC12C2day5, HSiC12n-C3day7, HSiC12i-
C3 day 7, HSiC12n-C4 day 9, HSiC12C
6 days 5, HSiC12 (4-CI-C 6 days 4), HSi
C12CH=CH2, HSiC12CH2C6&, H
SiC12 ( 1 C,.

day 7), HSiC12CH2CH = CH2,
Day 2 SICIC is , Day 2 SICIC 2 Day 5, HSiC
1 (C ratio) 2, HSiCICH3 (i-C3 day 7), H
SiCICH3 (C6 &), HSiC1 (C2 day 5) 2
, HSiC1 (C6day5)2, etc., and chlorosilane compounds consisting of these compounds and mixtures with compounds selected from these compounds are used, including trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, etc. Chlorosilane and the like are preferred, and trichlorosilane and monomethyldichlorosilane are particularly preferred. As is clear from the Examples and Comparative Examples described later, when a silicon compound containing no Si-day bond is used, favorable results cannot be obtained.

The reaction between the organomagnesium component (i) and the chlorosilane compound (ii) will be described below.

The reaction between an organomagnesium compound or an organomagnesium compound and a chlorosilane compound can be carried out using an inert reaction medium, such as an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, benzene, toluene, xylene, etc. The reaction can be carried out in aromatic hydrocarbons such as cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, ethers, phenolic media such as tetrahydrofuran, or a mixed medium thereof. In terms of catalyst performance, aliphatic hydrocarbon media are preferred.
Although there is no particular restriction on the reaction temperature, it is preferably carried out at 40 qo or higher in view of the progress of the reaction. There is no particular restriction on the reaction ratio of the two components, but it is preferably in the range of 0.01 to 100 mol, particularly preferably 0.1 mol to 1.0 mol, of the chlorosilane component per 1 mol of the organomagnesium component.

Regarding the reaction method, there is a simultaneous addition method (method ①) in which two components are introduced into the reaction zone at the same time and reacted, or the chlorosilane component is charged into the reaction zone in advance, and then the organomagnesium complex component is introduced into the reaction zone. There is a method of reacting (Method @), and a method of preparing the organomagnesium key component in advance and adding the chlorosilane component (Method Q).
However, the latter two are preferred, and method @ gives particularly favorable results.

When the organomagnesium compound is insoluble, it is also possible to use a chlorosilane compound as a reaction agent for a heterogeneous treatment reaction in the reaction zone.

In this case as well, the conditions described above are preferable regarding temperature, molar ratio, and reaction ratio. The composition and structure of the solid substance obtained by the above reaction (corresponding to Preconception 1) may vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, the stiffness of Solid Substance 1 is approximately 0.1 It is estimated to be a halogenated magnesium compound containing an alkyl group with ~2.5 mmol of Mg-C bonds.

This solid substance has an extremely large specific surface area, and B
．． E. T. Measurements using the method show high values of 100 to 300 degrees. Compared to conventional magnesium halide solids, the solid materials of the present invention have a very high surface area;
Another major feature is that it is an active magnesium-containing solid containing an alkyl group with reducing power. Next, a tetravalent titanium compound containing at least one halogen atom {
2 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, trivalent titanium halide (2) 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.

The solid lacquer includes a solid solution of titanium trichloride and aluminum trichloride, a solid melt of titanium tribromide and aluminum tribromide,
Examples include solid solutions of titanium trichloride and vanadium trichloride, solid solutions of titanium trichloride and iron trichloride, and Sonoko bodies of titanium trichloride and zirconium trichloride. Among these, preferred are titanium trichloride and a solid solution of titanium trichloride and aluminum trichloride (TIC13.1/3NC13). Next, carboxylic acid or its derivative [3} will also be explained.

Carboxylic acids or derivatives thereof include aliphatic, cycloaliphatic and aromatic saturated and unsaturated mono- and polycarboxylic acids, their acid halides, acid anhydrides, and esters, including sulfur-containing polycyclic carpons. Excludes acid esters.

Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, acrylic acid, benzoic acid, toluic acid, and terephthalic acid. Acid, toluic acid is preferred.

Examples of carboxylic acid halides include acetyl chloride, propionyl chloride, n-butyryl chloride, isobutyryl chloride, succinyl chloride, penzoyl chloride, tolyl chloride, and among these, aromatic carboxylic acid halides such as penzoyl chloride and tolyl chloride Acid halides are particularly preferred. Examples of carboxylic anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, toluic anhydride, anisic anhydride, and phthalic anhydride. Among these, benzoic anhydride, toluic anhydride, and anisic anhydride are preferred. Examples of carboxylic acid esters include ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, n-ethyl acetate, ethyl claurate, ethyl caproate, n-ethyl hebutanoate, and di-oxalate. -butyl, monoethyl succinate, diethyl succinate, ethyl malonate, di-n-butyl maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, n- and i-propyl benzoate , n-, 1-, sec-, and rt-butyl benzoate, methyl p-tolylate, ethyl p-tolylate,
p-propyl toluate, n- and i toluate
-amyl, o-ethyl toluate, m-ethyl toluate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate, methyl anisate, ethyl anisate, i and n-propyl anisate, methyl p-ethoxybenzoate, p −
There are ethyl ethoxybenzoate, methyl terephthalate, etc., and among these, aromatic carboxylic acid esters are preferred, particularly methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, and anisic acid. Ethyl is preferred.

A method for synthesizing the solid component obtained by reacting and/or pulverizing the solid substance {1}, titanium compound (2), and carboxylic acid or its derivative [3} will be described below.

The reaction with the above-mentioned solid substance {1), titanium compound ■, carboxylic acid Z or its derivative {3-} is carried out by a method of reacting a titanium compound or carboxylic acid or its derivative in a liquid phase or a gas phase [1], or a liquid phase reaction. Alternatively, any method can be employed, such as the method [2] that combines a reaction in a gas phase and a pulverization reaction.

Regarding Z method [1], a method in which a solid substance, a titanium compound, and a carboxylic acid or its derivative are reacted simultaneously (■), or a method in which a solid substance and a titanium compound are first reacted, and then a carboxylic acid or its derivative is reacted. (■) Alternatively, there is a method (■) in which two solid substances are first reacted with a carboxylic acid or a derivative thereof, and then a titanium compound is reacted. Although either method is possible, the latter two methods are preferred, and method (2) is particularly preferred. Method〔
Regarding 2], the case where the titanium compound is (1) 24-valent, (b) trivalent, and (m) the case where tetravalent and trivalent titanium compounds are used together will be described.

In the case of (1), the solid obtained by simultaneously reacting the solid substance, a titanium compound, a carboxylic acid or a derivative thereof can be pulverized (synthesis method A method of pulverizing a solid obtained by reacting an acid or its derivative (synthesis method ■)
Alternatively, there is a method in which the above-mentioned solid substance is first reacted with a carboxylic acid or a derivative thereof, and then the solid obtained by reacting with a titanium compound is pulverized (synthesis method ①).

Although either method is possible, the latter two methods are more preferable, and particularly synthesis method (1) gives preferable results. In the case of (b), various methods are possible for synthesizing the solid component from the three components of the solid substance, trivalent titanium halide, and carboxylic acid or carbosic acid derivative, but the following three methods are particularly preferable. give. In other words, a method in which the three components are co-pulverized (synthetic method ■), a method in which the solid component is brought into contact with a carboxylic acid or a carboxylic acid derivative in advance, and then a trivalent titanium halide is added and mechanically crushed (synthetic method (2), or a method (synthesis method (2)) in which a solid component and a trivalent titanium halide are brought into mechanical crushing contact and then treated with a carboxylic acid or a carboxylic acid derivative. In the case of (m), a method of simultaneously pulverizing the solid component m, the tetravalent titanium compound '2}, the trivalent titanium compound (3}, and the carboxylic acid or its derivative [41 (synthesis method ■), '1 A method of treating the solid obtained by reacting - and '21 with ■ and pulverizing it together with '3} (synthesis method ■), (
A method of treating the solid obtained by reacting 1- and {41 with '2} and crushing it together with glue (synthesis method ■), {1) and ■
Examples include a method of adding and pulverizing the solid obtained by reacting [3} and ■ (synthesis method ■), but synthetic method ■
is preferred.

The first feature of the present invention can be achieved 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 even further increase in catalyst efficiency is achieved.

First, the method of further treating the solid catalyst synthesized by method [1] with the above-mentioned tetravalent titanium halide involves simultaneously reacting the above-mentioned solid substance, titanium compound, carboxylic acid or its derivative, and then further A method of treatment with a tetravalent titanium halide (synthesis method ■), in which the above solid substance is reacted with a titanium compound, then a carboxylic acid or its derivative is reacted, and then further treated with a tetravalent titanium halide. (synthesis method ■), and a method in which the above solid substance is reacted with a carboxylic acid or a derivative thereof, and then reacted with a titanium compound, and then further treated with a tetravalent titanium halide (synthesis method ■). .

Next, methods (1), (0) and (m) of further treating the solid catalyst synthesized by method [2] with a tetravalent titanium halide will be explained.

In the case of (1), synthesis method [2]-(1)-■, [2]-[
It is possible to treat the solid catalyst synthesized by 1) 1) or 2) 1(1)-2 with a tetravalent titanium halide, but the latter two methods are more preferred.

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

In the case of (m), basic solid {1}, tetravalent titanium compound'
2}, a method in which a trivalent titanium compound [3) and a carboxylic acid or its derivative ■ are simultaneously ground and then treated with a tetravalent titanium halide (synthesis method ■), {1} and {
The solid obtained by reacting 2) was treated with '4} and t3
} and then treated with a tetravalent titanium Z halide (synthesis method ■), the solid obtained by reacting [1} and '4} is treated with ■, and then crushed with [31] After that, a method of treating with a tetravalent titanium halide (synthesis method ■), adding the solid obtained by reacting '1} and ■ and {3; and t4), and grinding Z, further A method of treating titanium with a halide (synthesis method)
), a method in which the solid obtained by reacting [1} and ■ is treated with {4}, crushed with {3}, and then treated with a tetravalent titanium halide (synthesis method ■), etc. Method■、■、
■ and ■ are preferably 2.

Next, the reaction and/or pulverization of the solid substance with the titanium compound, carboxylic acid or carboxylic acid converter will be explained.

(i) Organomagnesium component and chlorosilane compound 2
The reaction between a solid material obtained by reacting a solid material, or a reaction product of this solid material with a carboxylic acid or a derivative thereof, and a titanium compound 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 concentration of the titanium compound, but preferably at a temperature of 8000 °C or higher,
The reaction is carried out using the titanium compound itself as a reaction medium, and the concentration of the titanium compound is 2 mol/liter or more, or the titanium compound itself is not diluted. Regarding the reaction molar ratio, preferred results are obtained when the reaction is carried out in the presence of a sufficient excess amount of the titanium compound relative to the magnesium component in the solid substance. (ii) The reaction between a solid substance obtained by reacting an organomagnesium component and a chlorosilane compound, or a reaction product of this solid substance and a titanium compound, and a carboxylic acid or its derivative 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 of room temperature to 100°C. When reacting a solid substance with a carboxylic acid or its derivative, the reaction ratio of the two components is not particularly limited, but preferably the carboxylic acid or its derivative is reacted with respect to 1 mole of the alkyl group contained in the organomagnesium-containing solid component. is 0.001 mol to 50 mol, particularly preferably 0.001 mol to 50 mol.
A range of 0.005 to 10 moles is recommended. When reacting a reaction product of a solid substance and a titanium compound with a carboxylic acid or its derivative, the reaction ratio of the two components is as follows:
The recommended amount of carboxylic acid or its derivative 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 described in (i) to 3 above in the presence or absence of a reaction reagent will be explained.

Grinding methods include rotary ball mill, vibrating ball mill,
Known mechanical grinding means such as impact ball mills can be employed. The grinding time is 0.5 to 10 hours, preferably 1 to 3 field hours, and the grinding temperature is 0 to 200°C, preferably 10 to 15,000°C. The case where the solid component obtained in G (i) to Gii) 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 preferred. The concentration of the titanium compound is preferably 2 mol/or more, and it is also preferable to react using the titanium compound itself as a reaction medium. Although there is no particular restriction on the reaction temperature, preferable results are obtained when the reaction is carried out at a temperature of 80 qo or higher. The composition and structure of the solid catalyst component obtained by the reactions (i) to W above vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, approximately 1 to 1% by weight of the solid catalyst. It was found to be a solid catalyst containing titanium and having a surface area of 50 to 300 w/m.

The organometallic compounds used as the ZO [B] component include those listed in the first part of the periodic table.
Among compounds of group 0 to 0, organoaluminum compounds are particularly preferred. The organoaluminum compound has the general formula AIR
Imitation 3-t (in the formula, R1o is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group, and t is a number of 2 to 3) ) is used alone or as a mixture. In the above formula, the number of carbon atoms represented by R1o is 1 to 2
The hydrocarbon group 0 includes aliphatic hydrocarbons, aromatic dihydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminum, 2-trin-nbutylaluminum, triisoptylaluminium, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecyl Aluminum, trihexadecylaluminum, diethylaluminium hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminium chloride, di3isobutylaluminum chloride, dimethylhydrosiloxy Recommended are aluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isoprenyl, etc., and mixtures thereof.

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

Examples of sulfur-containing heterocyclic carboxylic acid esters added to organometallic compounds include thiophene carboxylic esters, thianaphthene carboxylic esters, isothianaphthene carboxylic esters, benzothiophene carboxylic esters, phenoxathine carboxylic esters, and benzothiane carboxylic esters. ester, benzothiane carboxylic acid ester, thiaxanthene carboxylic acid ester, thioindoxyl carboxylic acid ester, etc. More specifically, thiophene-2-carboxylic acid methyl, ethyl, propyl, butyl and amyl, thiophene-3-carboxylic acid Methyl, ethyl, propyl, butyl and amyl, methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate,
Ethyl, methyl thiophene-2,5-dicarboxylate, ethyl, methyl 2-thhenylacetate, ethyl, propyl, butyl, methyl 2-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,
Methyl benzothiophene-2-carboxylate, ethyl, methyl benzothiophene-3-carboxylate, ethyl, methyl benzothiophene-4-carboxylate, ethyl, methyl benzothiophene-1-carboxylate, ethyl, phenoxathine-2-carboxylic acid Examples include methyl, ethyl, methyl phenoxathine-3-carboxylate, and ethyl. More preferred are methyl thiophene-2-carboxylate, ethyl, propyl and butyl, methyl thiophene-3-carboxylate, ethyl, methyl 2-thhenyl acetate, ethyl, methyl 2-thhenyl acrylate, ethyl, methyl thianaphthene-2-carboxylate, Examples include ethyl. Next, the oxygen-containing double ring carboxylic acid ester will be explained. Examples of oxygen-containing polycyclic carboxylic acid esters include furan type carboxylic acid esters, dihydrofuran type carboxylic acid esters, benzofuran type carboxylic acid esters, coumaran type carboxylic acid esters, pyran type carboxylic acid esters, pyrone type carboxylic acid esters, and coumarin. Examples include carboxylic acid esters of carboxylic acid esters, inkmarine carboxylic acid esters, and the like.

For example, methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate, ethyl, propyl, butyl, methyl furan-213-dicarboxylate, methyl furan-2,4-dicarboxylate,
Methyl furan-2,5-dicarboenate, furan-3.
Methyl 4-dicarboxylate, methyl 4,5-hydrofuran-2-carboxylate, ethyl, tetrahydrofuran-2-
Methyl carboxylate, methyl coumarate (benzofuran-
methyl 2-carboxylate), ethyl coumaran-2-carboxylate, methyl coumarate, ethyl coumarate, methyl comanate,
Examples include ethyl, 5-hydroxy-4-ethoxycarbonylcoumarin, 4-ethoxycarbonylisocoumarin, ethyl 3-methylfuran-2-carboxylate, isodehydroacetic acid, and methyl furan-2-carboxylate, ethyl Propyl, butyl, methyl furan-3-carboxylate, ethyl, propyl, butyl, methyl 415-dihydrofuran-2-carboxylate, ethyl, methyl tetrahydrofuran-2-carboxylate, 2-methyl coumarate, methyl coumarate, ethyl etc. give favorable results. The organometallic compound and the sulfur- or oxygen-containing heterocyclic carboxylic acid ester may be added by mixing the two components in advance, or by adding the three components separately into the polymerization system.

Favorable results can be obtained if a metal compound previously reacted with a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester and an organometallic compound are separately added to the polymerization system. The ratio of the sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester to the organometallic compound is 1 mol or less, particularly preferably 0.9 mol, of the sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester to 1 mol of the organic trimetallic compound. It is as follows. The ratio of each catalyst component to be combined is 191 to 191 for the solid catalyst component, and 1 to 3,000 for the component consisting of the organometallic compound and the sulfur-containing to tetraoxygen-containing heterocarboxylic acid ester based on the organometallic compound.
A millimolar range is preferred.

The present invention is a highly active and highly stereoregular polymerization catalyst for olefins.

In particular, the present invention provides propylene, phthene-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 chain transfer. As the polymerization method, usual suspension polymerization, bulk polymerization in a liquid monomer, and gas phase polymerization are possible.

Suspension polymerization involves using a catalyst in a reactor 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.
It can be press-fitted into a 20k9/mt and polymerization can be carried out at a temperature of nitrogen temperature to 150 oo. 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 000° C. and under a pressure of 10 to 45 k9' streams. 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' and a temperature of room temperature to 12,000 ℃ using a fluidized bed, a moving bed, or a hawk 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 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 rust 138.0 g of di-n-butylmagnesium and 19.0 g of triethylaluminum were placed in a nitrogen-substituted flask together with 1 portion of n-heptane, and heated at 80 qC. 2 hours,
The reaction was carried out while stirring to obtain an organomagnesium body solution.

Analysis of this complex revealed that the composition was AIMg6. . (C2
Day 5)2. o (n-C4 ratio), 2. , and the organometallic concentration was 1.25 mol/sleeve. (ii) Synthesis of magnesium-containing solid materials by reaction with chlorosilane compounds In a well degassed and dried flask with 2 volumes, 1 mol of trichlorosilane (HSiC13) is added to a solution of 1. Add hol and add 500 mmol of the above organomagnesium enantiomer solution to 1 qo while maintaining the temperature at 65 qo.
The mixture was added dropwise over a period of time, and the mixture was further reacted at 65 qo for 1 hour under reduced pressure.

The produced white solid Z was filtered, washed with n-hexane, and dried to obtain 42.5 g of white solid substance (A-1). As a result of analyzing this solid material, it was found that M chicks per night. 1
6 mmol, CII 9.20 mmol, 1.70 units mo
1, alkyl group 0.58 mmol, B.
E. T. The specific surface area measured by Z method was 269 mm. ``ii) Synthesis of solid catalyst In a nitrogen-substituted container, 20 mmol of the above solid was added together with 600 mmol of n-hexane and 15.0 mmol of ethyl benzoate, and reacted at 8,000 ℃ for 21 hours while shaking to form a solid. (B-1) was obtained.

Weighed 18 kg of this solid together with 300 kg of titanium tetrachloride into a pressure-resistant container purged with nitrogen, and reacted it under a rope at 130 Qo for 2 hours. S-1) was obtained. As a result of analyzing this solid catalyst 2, the Ti content was 2.2% by weight. 9 of 80 of the solid catalyst synthesized on the propylene slurry polymerization side of G, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl thiophene-2-carboxylate, together with 0.8 mmol of hexane that had been sufficiently degassed and dehydrated. Place in an autoclave with a capacity of 1.5 vacuum dried and replaced with nitrogen, and bring the internal temperature to 60o.
o, pressurize propylene to a pressure of 5.0 k9/min, and polymerize for 2 hours while maintaining the total pressure at a gauge pressure of 4.8 kg'.
6.6 ml of polymerized hexane soluble material was obtained.

Catalyst efficiency is 9060 terpp/unit - titanium component/hour/
The n-heptane extraction residue 4 of the polymerized hexane non-falling polymer was 96.2%. The particle properties were good, with a high density of 0.36 ta' and a ratio of 91% of particles of 35 to 150 mesh. Example 2 (i) Synthesis of hydrocarbon-soluble organomagnesium body 138.0 g of di-butylmagnesium and 19.0 g of triethylaluminum were placed in a nitrogen-substituted flask together with n-heptane, and heated at 80 qC for 2 g. The reaction was allowed to take place over time, and an organic magnesium solution was obtained.

As a result of analyzing this rust body, the composition was found to be AIM saddle. o (C2 day 5) 2.9 (n-C4), 2. , and the organometallic concentration was 1.20 mmol/sleeve. (ii) Synthesis of a magnesium-containing solid material by reaction with a chlorosilane compound In a well degassed and dry volume 2 flask was added 1 mol of dichloromethylsilane (HSiCH3CI2)/1 mol of its solution in n-hebutane. Prepare blood 01, and while maintaining it at 65 qo, add 500 mmo of the above organomagnesium solution.
1 was added dropwise over 1 hour, and the mixture was further reacted at 6500 for 1 hour.

The produced white solid was separated by furnace, washed with n-hexane, and dried to obtain a white solid substance (A-2) with a weight of 42.6 mm. As a result of analyzing this solid substance, it was found that Mg9.1 per solid substance per evening
8 skin m. I, CI19, 20 m. I, m of Si1.70. I, containing 0.60 mol of alkyl groups,
B. E. T. The specific surface area measured by the method was 261/h. Gii) Synthesis of solid catalyst In a nitrogen-substituted container, 600 g of n-hexane and 1 g of ethyl toluate were added.
Add 20 moles of the above solid together with 5.0 mol, drop it over 1 hour at 8,000 mol while shaking, and then add 6,500 mol.
The mixture was allowed to react under the conditions of Azusa Azusa for 1 hour.

The produced white solid was separated by furnace, purified with n-hexane, and dried to obtain a white solid substance (B-2). This solid 180 mm was weighed out in a pressure-resistant container purged with nitrogen, along with 300 mm titanium tetrachloride, and reacted for 2 hours at 130 mm under a heated atmosphere. C-2) was obtained. Next, this solid (C-2) 4.0 mm was transferred together with 25 steel balls with a diameter of 10 mm into a steel mill with a diameter of 95 mm and a length of 100 mm, and a vibrator of 1000 Vib/min or more was placed. The mixture was pulverized for 5 hours to obtain a solid catalyst (S-2).

As a result of analyzing this collective catalyst, the Ti content was found to be 2. It was box weight%. ``W'' In the same manner as in Example 1, using 50 parts of the solid catalyst (S-2) synthesized in a propylene slurry polymerization dish, 2.4 mmol of triethylaluminum, and 0.8 mol of ethyl thiophene-2-carboxylate. Slurry polymerization of propylene was carried out, polymerizing hexane infusible polymer 153, polymerizing hexane soluble polymer 5.
I got 8 evenings.

The catalyst efficiency was 13,300 terpp/tertitanium component, time, propylene pressure, and n of the polymerized hexane-insoluble polymer.
- Hebutane extraction residue was 95.0%. Example 3
In the synthesis of the solid catalyst in Example 2, a solid catalyst (S
-2-1) Take 2.0 titanium tetrachloride and 30 titanium tetrachloride into a pressure-resistant container purged with nitrogen, and react under the mound at 13,000 for 2 hours.The solid portion is then filtered, refined, and dried to form a solid catalyst. As a result of analyzing this solid catalyst obtained (S-3), T
j content was 2.1% by weight.

Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 9 of 30 of the above solid catalyst (S-3), 2.4 mol of triethylaluminum, and 0.8 mmol of ethyl thiophene-2-carboxylate, and polymerized hexane-insoluble polymer. After 135 days, 3.4 times of polymerized hexane soluble material was obtained.

The catalyst efficiency was 21,400 pp/tertitanium component/time/propylene pressure, and the n of the polymerized hexane-insoluble polymer
-Hebutane extraction residue was 96.8%. Example 4 350 liters of liquefied propylene was introduced into the autoclave which had been thoroughly purged with nitrogen and dried under vacuum, and the internal temperature was brought to . 6
000 and the solid catalyst (SH3) synthesized in Example 3
9 of 10, 1.6 mmol of triethylaluminum and 0.6 mmol of ethyl thiophene-2-carboxylate were added to an autoclave, and polymerization was carried out at 6,000 for 2 hours under a heated atmosphere to obtain polymer 130.

The catalyst efficiency is 309,500 terpp per tertitanium component/hour, and the residual solution of this polymer after extraction with n-hebutane is 94
．． It was 3%. Reference Example 1 A solid catalyst was synthesized in the same manner as in Example 1, except that commercially available anhydrous magnesium chloride was used in place of the magnesium-containing solid in (ii).

As a result of analyzing this solid catalyst, the Ti content was 0.8% by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 100:9, 2.4 mol of triethylaluminum, and 0.8 mmol of ethyl thiophene-2-carboxylate, and 7.6 mol of the polymerized hexane-insoluble polymer was obtained. Polymerized hexane soluble material 2.1 was obtained. The n-hebutane extraction residue of the polymerized hexane-free polymer was 77.9%, and the catalyst efficiency was 916 terpp/unit - Ti component/time/propylene pressure. Reference Example 2 In the synthesis of the magnesium-containing solid material in Example 1-(ii), magnesium As a result of synthesizing the solid material contained, 2.06 pieces of white solid were obtained.

Compared to Example 1-(ii), the yield of solid material was about 1/20. Examples 5 to 9 Propylene slurry was prepared in the same manner as in Example 1 using 9 of 30 of the solid catalyst (S-3) synthesized in Example 3, 2.4 mmol of triethylaluminum, and 0.8 mmol of the compound shown in Table 1. Polymerization was carried out and the results shown in Table 1 were obtained.

Table 1 Example 10 5.0 mmol of the magnesium-containing solid synthesized in the same manner as in (ii) of Example 1 and 40 mmol of ethyl benzoate were reacted in the same manner as in (iii) of Example 1.

4.5 hours of the obtained solid and 0.38 hours of titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were ground in a vibrating ball mill under a nitrogen atmosphere for 5 hours. This solid (C-10)
4.3 days and 60' of titanium tetrachloride, 13,000 under Azusa
After reacting for 2 hours, the solid part was filtered, washed with
It was dried to obtain a solid catalyst (S-10). As a result of analyzing this solid, the Ti content was 2.2% by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 9 of 50 of the solid catalyst (S-10), 2.4 mmol of triethylaluminum, and 0.8 mol of ethyl thiophene-2-carboxylate. Got the results.

Example 11 Slurry polymerization of propylene was carried out in exactly the same manner as in Example 1 using the solid (C-10) 80 female synthesized in Example 10 as a solid catalyst (Ti content: 1% by weight). Got the results.

**Example 12 In the same manner as in Example 1, a magnesium-containing solid was first reacted with ethyl benzoate, and then reacted with titanium tetrachloride. AA grade) 0.16 millimeter was ground in a vibrating ball mill for 5 hours.

After reacting this solid (C-12) with 60 pieces of titanium tetrachloride for 2 hours at Nawa Azusa 13000, the solid portion was filtered, washed, and dried to form a solid catalyst (S-12). I got it. As a result of analyzing this solid catalyst, the Ti content was 4. % by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using the above solid catalyst (S-12) 30-9, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl thiophene-2-carboxylate.
The results shown in Table 2 were obtained.

Example 13 0 Using 9 of 50 of the solid (C-12) synthesized in Example 12 as a solid catalyst (Ti content: 3.0% by weight), slurry polymerization of propylene was carried out in exactly the same manner as in Example 1. 2
I got the result.

Table 2 Example 14 Together with 15% of the solid (A-1) synthesized in Example 1 and 250% of titanium tetrachloride, the mixture was placed in a pressure-resistant container purged with nitrogen.
After reacting for 2 hours at a temperature of 130 oo, the solid portion was filtered, washed with foil, and dried to obtain a solid (8-14).

Four days of this solid (B-14) was mixed with 200 units of n-hexane and 3.0 mmol of benzoic acid, and the atmosphere was replaced with nitrogen.
The mixture was placed in the same container and allowed to react at 80 qo for 1 hour while stirring to obtain a solid catalyst (S-14). As a result of analyzing this solid catalyst, the Ti content was 2.5% by weight. Using the above solid catalyst (S-14) 80-9: 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl thiophene-2-carboxylate, slurry polymerization of propylene was carried out in the same machine as in Example 1, and the results shown in Table 3 were obtained. .

Example 15 In the synthesis of the solid catalyst of Example 14, everything was the same as that of Example 14 except that benzoic acid was changed to benzoic anhydride.
A solid catalyst (S-15) was synthesized in the same manner as above.

As a result of analyzing this solid catalyst, the Ti content was 2. % by weight. The above solid catalyst (S-15) 80-9; 2.4 mmol of triethylaluminum and thiophene-
Example 1 using 0.8 mmol of ethyl 2-carboxylate
Slurry polymerization of propylene was carried out in the same manner as above, and the results shown in Table 3 were obtained.

**Example 16 A solid catalyst (S-16) was synthesized in the same manner as in Example 14 except that benzoic acid was changed to penzoyl chloride.

As a result of analyzing this solid catalyst, the Ti content was 2.9% by weight.
Met. The above solid catalyst (S-16) 80-9, triethylaluminum 2.4 mmol and thiophene-2
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 0.8 mmol of ethyl carboxylate, and the results shown in Table 3 were obtained.

Table 3 Examples 17 to 22 In the synthesis of the solid catalyst of Example 1, the compounds shown in Table 3 were used as the hydrocarbon 2-soluble organomagnesium component and the chlorosilane compound, and the solid catalysts (B-17 to 22) were synthesized in the same manner as in Example 1. B-22) was synthesized, 3.0 mmol of each solid and 2.4 mmol of titanium tetrachloride were added, and pulverized for 5 hours in the steel mill used in Example 2, and further treated with titanium tetrachloride to form a solid. The catalyst was synthesized.

This solid catalyst 30:9, triethylaluminum 2.4
mmol and ethyl thiophene-2-carboxylate 0.
Slurry monopolymerization of propylene was carried out in the same manner as in Example 1 using 8 mmol, and the results shown in Table 4 were obtained.

Table 4 Examples 23 to 24 Examples were carried out using the solid catalyst (S-3) 30-9 synthesized in Example 3, 0.8 mol of ethyl thiophene-2-carboxylate, and the organometallic components shown in Table 5. Slurry monopolymerization of propylene was carried out in the same manner as in 1, and the results shown in Table 5 were obtained.

Table 5 Examples 25 to 27 The same procedure as in Example 1 was carried out using 30 females of the solid catalyst (S-3) synthesized in Example 3, 2.4 mol of triethylaluminum, and 0.8 mmol of the compound shown in Table 6. Slurry polymerization of propylene was carried out, and the results shown in Table 6 were obtained.

Table 6 Example 28 Using 2.4 mol of 9,4 triethylaluminum of the collective catalyst (S-3) 30 synthesized in Example 3 and 0.8 mol of ethyl thiophene-2-carboxylate, propylene was added to 2 mol of ethylene. Polymerization was carried out in the same manner as in Example 1, except that a propylene-ethylene mixed gas having a content of

Example 29 Polymerization of butene-1 was carried out in Example 1 using 9 of 200 of the solid catalyst (S-3) synthesized in Example 3, 4.6 mmol of triethylaluminum, and 1.2 mol of ethyl thiophene-2-carboxylate. Accordingly, a white polymer 51 was obtained.

Example 30 4-
Polymerization of methylbentene-1 was carried out according to Example 1 to obtain white polymer 45.

Example 31 9 of the solid catalyst 60 synthesized in Example 3, 1.0 mmol of triisobutyzyl aluminum and 0.1 mol of ethyl thiophene-2-carboxylate were dehydrated.
Degassed n-hexane (0.8 m) was placed in an autoclave whose interior was vacuum dried and replaced with nitrogen, the internal temperature was maintained at 8030, and hydrogen was pressurized to 1.6 k9/h.
Ethylene was then added to bring the total pressure to 4.0k9/c.

Claims (1)

[Claims] 1 [A] (1) (i) General formula MαMgβR^1_
pR^2_q (where M is an aluminum, zinc, boron or beryllium atom, R^1 and R^2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms, α≧0, β>0,
p, q>0, m is the valence of M, β/α≧0.1, p+q
= mα + 2β)), a hydrocarbon-soluble organomagnesium component represented by (ii) the general formula HaSiCl_
bR_4_-_(_a_+_b_) (where a, b are 0
a larger number, a+b≦4, R represents a hydrocarbon group having 1 to 20 carbon atoms. Containing titanium compound, (3)
Carboxylic acids or derivatives thereof (excluding sulfur-containing heterocyclic carboxylic acid esters), (1), (2),
(3) a solid catalyst component obtained by reacting and/or pulverizing [B] an organometallic compound and a component consisting of a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester;
] and [B] A catalyst for producing polyolefin. 2. The catalyst for producing polyolefin according to claim 1, wherein the ratio β/α is 1 to 10. 3 [A] In the hydrocarbon-soluble organomagnesium compound of (i), α=0, R^1, R^2 are any of the following three cases, as described in claim 1 catalyst for the production of polyolefins. (a) Both R^1 and R^2 have 4 to 6 carbon atoms,
At least one of them is a secondary or tertiary alkyl group. (b) R^1 is an alkyl group having 2 to 3 carbon atoms, and R^2 is an alkyl group having 4 or more carbon atoms. (c) R^1, R
Both ^2 are alkyl groups having 6 or more carbon atoms. 4. The catalyst for producing polyolefin according to any one of claims 1 to 3, wherein the value of a is 0<a<2. 5 [A] Claims 1 to 4, wherein the titanium compound in (2) is a compound containing three or more halogens.
2. Catalyst for producing polyolefin according to any one of the above. 6. The catalyst for producing polyolefin according to any one of claims 1 to 4, wherein the titanium compound in [A] (2) is titanium tetrachloride and/or titanium trichloride. 7. The catalyst for producing polyolefin according to any one of claims 1 to 6, wherein the carboxylic acid or its derivative in [A](3) is a carboxylic acid, a carboxylic anhydride, or a carboxylic acid ester. 8 [A] The carboxylic acid or its derivative of (3), [
A] 0.00 per mole of alkyl group in the solid of (1)
The catalyst for producing polyolefin according to any one of claims 1 to 7, which is reacted at a ratio of 1 to 50 moles. 9 [A] The carboxylic acid or derivative thereof of (3), [
A] 0.1 to 10 per gram of titanium atom in the solid
The catalyst for producing polyolefin according to any one of claims 1 to 7, which is subjected to a molar reaction. 10 The organometallic compound [B] has the general formula AlR^1^0_nZ_3_-_n (in the formula, R^1_0
is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, halogen,
The polyolefin according to any one of claims 1 to 9, which is an organoaluminum compound represented by a group selected from alkoxy, allyloxy, and siloxy groups, and n is a number from 2 to 3. Catalyst for production. 11. The catalyst for producing a polyolefin according to any one of claims 1 to 10, wherein the organoaluminum compound [B] is trialkylaluminum or dialkylaluminum hydride. 12 [A] (1) (i) General formula MαMgβR^1
_pR^2_p (where M is aluminum, zinc, boron or beryllium atom, R^1 and R^2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms, α≧0, β>0,
p, q>0, m is the valence of M, β/α≧0.1, p+q
= mα + 2β)), a hydrocarbon-soluble organomagnesium component represented by (ii) the general formula H_aSiCl
Reaction with a Si-H bond-containing chlorosilane compound represented by _bR_4_-_(_a_+_b_) (wherein a and b are numbers larger than 0, a+b≦4, and R represents a hydrocarbon group having 1 to 20 carbon atoms) (2) a titanium compound containing at least one halogen atom, (3
) Carboxylic acids or derivatives thereof (excluding sulfur-containing heterocyclic carboxylic acid esters), above (1), (2)
, (3) and a solid catalyst component obtained by further treating the solid obtained by reacting and/or pulverizing with (4) a tetravalent titanium compound containing at least one halogen atom, and [B] an organic A component consisting of a metal compound and a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester, [A]
A catalyst for producing polyolefin consisting of and [B]. 13 Claim 12 in which the ratio β/α is 1 to 10
Catalyst for producing polyolefin as described in . 14 [A] In the hydrocarbon-soluble organomagnesium compound (i), α=0 and R^1 and R^2 are in any of the following three cases, as described in claim 12 catalyst for the production of polyolefins. (a) Both R^1 and R^2 have 4 to 6 carbon atoms,
At least one of them is a secondary or tertiary alkyl group. (b) R^1 is an alkyl group having 2 to 3 carbon atoms, and R^2 is an alkyl group having 4 or more carbon atoms. (c) R^1, R
Both ^2 are alkyl groups having 6 or more carbon atoms. 15 Claim 12 in which the value of a is 0<a<2
The catalyst for producing polyolefin according to any one of items 1 to 14. 16. The catalyst for producing polyolefin according to any one of claims 12 to 15, wherein the titanium compound in [A] (2) is a compound containing three or more halogens. 17. The catalyst for producing polyolefin according to any one of claims 12 to 16, wherein the titanium compound in [A](2) is titanium tetrachloride and/or titanium trichloride. 18. The catalyst for producing polyolefin according to any one of claims 12 to 17, wherein the tetravalent titanium compound containing at least one halogen atom in [A](4) is titanium tetrachloride. 19. The catalyst for producing polyolefin according to any one of claims 12 to 18, wherein the carboxylic acid or derivative thereof in [A](3) is a carboxylic acid, a carboxylic anhydride, or a carboxylic acid ester. 20 [A] (3) Carboxylic acid or its derivative,
[A] The catalyst for producing polyolefin according to any one of claims 12 to 19, which is reacted at a ratio of 0.001 to 50 moles per mole of alkyl groups contained in the solid of (1). . 21 [A] (3) The carboxylic acid or its derivative,
0.1 per gram atom of titanium in the solid [A]
The catalyst for producing polyolefin according to any one of claims 12 to 19, which is reacted with ~10 moles. 22 The organometallic compound [B] has the general formula AlR^1^0
_nZ_3_-_n (in the formula, R^1^0 is the number of carbon atoms 1 to 2
0 hydrocarbon group, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, siloxy group, n is 2 to
The catalyst for producing polyolefin according to any one of claims 12 to 21, which is an organoaluminum compound represented by the number 3). 23. The catalyst for producing a polyolefin according to any one of claims 12 to 22, wherein the organoaluminum [B] is trialkylaluminum or dialkylaluminum hydride. 24 Claims 12 to 23, wherein the sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester is a thiophene carboxylic acid ester or a furan carboxylic acid ester
The catalyst for producing polyolefin according to any one of the above.