JPS5840962B2 - 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, venti-1
．． suitable for the stereoregular polymerization of 4-methylpente-7-1,3-methylbutene-1 and similar olefins;
It is also suitable for copolymerizing the cleaved olefin with ethylene or other olefins.

Transition metal compounds of Groups ■ to ■A of the periodic table and Periodic table ■
It is well known that a stereoregular polymer can be obtained by bringing an olefin into contact with a Ziegler-Natsuta catalyst system consisting of an organometallic compound of groups .

In particular, a combination of titanium oxide and an organoaluminum compound such as triethylaluminum or diethylaluminum chloride is widely used industrially as a stereoregular polyolefin polymerization catalyst.

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 residues 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 for the polymerization of propylene, the proportion of boiling hebutane solubles, that is, non-grade polymers, is very high in the total polymer produced, and the steric polymerization of olefins such as propylene is industrially difficult. It is difficult to use it as a specific polymerization catalyst (for example, JP-A No. 47-9342,
Special Publication No. 43-13050).

As a solution to these problems,
No. 31, Japanese Patent Publication No. 52-36153, and Japanese Patent Publication No. 1973-
A method described in No. 16988 has been proposed.

These methods use 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 aluminum trialkyl and an electron donor. It is a catalyst system consisting of

However, even with these methods, the proportion of boiling butane insoluble matter in the resulting polymer is still not high enough to satisfy
In particular, the polymer yield per solid catalyst component is insufficient, leading to corrosion of manufacturing process equipment and molding machines.The content of rogens in the polymer is high, and the product properties are not fully satisfactory.

In order to improve these points, the present inventors have investigated and researched various types of organomagnesium compounds and various reaction reagents. The complex solution is reacted with a rogen compound such as silicon, germanium, tin, antimony, etc. as a reaction reagent to produce a rogen-containing magnesium compound basic solid, and this is combined with a titanium compound and a carboxylic acid or a 7m conductor. It has been discovered that a specific solid obtained by reacting and/or pulverizing with has long-lasting and excellent performance as a catalyst for olefin polymerization,
We have arrived at the present invention.

That is, the present invention provides CA) (IX i) general formula M
aMgβR' pR2qXrYs (where α is a number greater than 0 or O, ps qs ry 8 is a number greater than 0 or O, and p + q + r + s =
The relationship is mα+2β, where M is a metal element belonging to Groups 1 to 2 of the periodic table, R1, R2 are hydrocarbon groups having the same or different numbers of carbon atoms, and X and Y are the same or Different groups OR3,08iR'R5R', NR7R3
, SR9, R39R' I R5S R
) 'R'7゜R8 is a hydrogen atom or a hydrocarbon group,
R9 represents a hydrocarbon group) is an organomagnesium compound represented by (il) general formula LJjROa-j (in the formula,
L is an atom selected from germanium and mercury, J is...Rogge/atom, RO is a hydrocarbon group, a is the valence of L, and j is Q (a number where j ≦a). A solid obtained by reacting with a halogen compound containing (2) a titanium compound (3) containing at least one - halogen atom (3) a carboxylic acid or its derivative (however, sulfur-containing, oxygen-containing to nitrogen-containing, (excluding ring carboxylic acid ester) The solid obtained by reacting and/or pulverizing the above (1), (2), and (3); It is an olefin polymerization catalyst consisting of oxygen- or nitrogen-containing heterocyclic carboxylic acid esters (excluding oxygen or nitrogen-containing esters) and other components that have not been added in the past.

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,
Another advantage is that polymer powder with high bulk density can be produced.

Furthermore, the fourth feature is that when molded using the polymer produced by this catalyst, the color of the molded product is extremely good.

The essential factors behind the surprising performance of the catalyst of the present invention as described above are not yet clear, but as shown in the examples below, according to Mizutoshi, it has a high surface area and contains an alkyl group with reducing power. It is thought that a basic solid of activated magnesium chloride is synthesized.

General formula MaMgβ used in the synthesis of the solid catalyst of the present invention
R' p R'' q Xr Y s (in the formula, α, β-
p, q.

The organomagnesium compound (rs 8n MI R' n R2s Xs Y is as defined above) will be described.

Although this compound is shown as a complex compound of organomagnesium, it includes all R2Mg1- and complexes of these with other metal compounds.

The hydrocarbon group represented by R1 to R9 in the above formula is
an alkyl group, a cycloalkyl group or an allyl group,
Examples include methyl, ethyl, propyl, methyl, amyl, hexyl, tecyl, cyclohexyl, phenol, etc. R1 is particularly preferably an alkyl group.

There is no preclude that R3 to R8 are hydrogen atoms.

As the metal atom M, metal elements belonging to Groups I to II of the periodic table can be used, such as sodium, potassium, calcium, beryllium, zinc, barium, boron, aluminum, etc., but in particular aluminum, Zinc, boron, and aluminum are particularly preferred because they are easy to prepare as hydrocarbon-soluble organomagnesium complexes.

Although the ratio β/α of magnesium to the metal atom M can be set arbitrarily, a hydrocarbon-soluble organomagnesium complex having a range of preferably 0 to 10 J, particularly 1 to 10 is particularly preferred.

Symbols α, βs p* qs r, relational expression of 8 p+q+r
+ s = mα + 2β indicates the stoichiometry between the valence of the metal atom and the substituent, and the preferable range is O≦(r+
s)/(α+β) (1,0 is X for the sum of metal atoms
Indicates that the sum of and Y is greater than or equal to 0 and less than 1.0.

A particularly preferable range is 0 to 0.8.

These organomagnesium compounds or organomagnesium complexes are an organomagnesium compound represented by the general formula RIMgQ, present Mg (R' has the above-mentioned meaning, and Q is -.logen), and a general formula MR2m or MR2m.
An organometallic compound represented by iH (Mg R2x rn is the above-mentioned meaning) is reacted between room temperature and 150°C in an inert hydrocarbon medium such as hexa/, heptane, cyclohexane, benzene, toluene, etc. , if necessary, by further reacting it with an alcohol, water, chloroxane, amine, im/, mercaptan or dithio compound.

Furthermore, if the organomagnesium compound ← is the organomagnesium complex, Mg
-IH,t or RIMgX.

MgR7 and R2nMXm-n, t or R'MgX, M
gR2 and YnMXm-n (in the formula, M, R'', R2,
, Y are as described above, including the case where X and Y are . . . rogen, n is the number of Om).

In general, organomagnesium compounds are insoluble in inert hydrocarbon media, whereas organomagnesium complexes where α>0 are soluble.

Certain organomagnesium compounds, such as sec -Bu2Mg, are soluble in hydrocarbon media even when α=0, and such compounds have also been used in the present invention with good results. The compound will be explained.

General formula MgβR1pR2qXrYs
, R2 shall be any one of the following three RDs, (n), (III).

(I) At least one of R' and R2 is a secondary or tertiary alkyl group having 4 to 6 carbon atoms.

Preferably, both R1 and R2 have 4 to 6 carbon atoms, and at least one of them is a secondary or tertiary alkyl group.

(If) R' and R2 are alkyl groups having different numbers of carbon atoms.

Preferably, R1 is an alkyl group having 2 or 3 carbon atoms, and R2 is an alkyl group having 4 or more carbon atoms.

(III) At least one of R1 and R2 has 6 carbon atoms
or more hydrocarbon group.

Preferably, both R1 and R2 are alkyl groups having 6 or more carbon atoms.

These groups will be specifically shown below.

In (I), a secondary or tertiary alkyl group having 4 to 6 carbon atoms is used, preferably a secondary alkyl group, and formulas -C and R9 are particularly preferred.

Next, in (■), examples of the alkyl group having 2 or 3 carbon atoms include ethyl group and propyl group, with ethyl group being particularly preferable, and examples of the alkyl group having 4 or more carbon atoms include butyl group and amyl group. , hexyl group, octyl group, etc., butyl group and hexyl group are particularly preferred.

In (III), examples of the hydrocarbon group having 6 or more carbon atoms include hexyl group, octyl group, decyl group, phenyl group, etc., and alkyl groups are preferred, with hexyl group being particularly preferred.

It is important that the organomagnesium compound used in the present invention is soluble in a hydrocarbon medium.

Increasing the number of carbon atoms in an alkyl group makes it easier to dissolve in a hydrocarbon medium, but the viscosity of the solution tends to increase, and it is not preferable to use an alkyl group with an unnecessarily long chain in terms of handling.

The above-mentioned organomagnesium compound is used as a hydrocarbon solution, but it can be used without any problem even if a trace amount of a complexing agent such as ether, ester, or amine is contained or remains in the solution.

Next, the general formula LJ jROa −j (where L, j,
Ro.

The halogen compound represented by j and a have the above-mentioned meanings will be explained.

The element represented by L in the above formula is germanium, mercury,
The halogen of J is chlorine,
Examples include bromine and iodine, but chlorine is particularly preferred.

The hydrocarbon group of RO is an alkyl group, a cycloalkyl group, or an aryl group, such as methyl, ethyl,
Examples include propyl, butyl, amyl, hexyl, tesyl, cyclohexyl, phenyl, etc., preferred are alkyl groups 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 Q < j 4 a, but it is preferable that j is larger, and it is particularly preferable to include RO which is j2a! Examples include halogen compounds that do not contain

There are many halogen compounds as explained above, but among them, those that are easy to use in the present invention are those that are soluble in hydrocarbon media or ether media, and give favorable results.

Preferred specific halogen compounds include germanium tetrachloride, dichlorodimethylgermane, mercuric chloride, etc. Particularly preferred compounds include germanium tetrachloride, mercuric chloride, etc. .

These compounds may be used alone or as a mixture.

The reaction of the organomagnesium compound or organomagnesium complex with the above-mentioned -.logen compound is carried out using an inert reaction medium,
For example, aliphatic hydrocarbons such as hexane, heptane,
Aromatic hydrocarbons such as benzene, toluene, xylene,
The reaction can be carried out in an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, an ether medium such as ether or tetrahydrofuran, or a mixed medium thereof.

Due to its catalytic performance, an aliphatic hydrocarbon medium is recommended.

There is no particular restriction on the reaction temperature, but it is carried out at a temperature of 1 or 40° C. or higher in order to allow the reaction to proceed.

There is no particular restriction on the reaction ratio of the two components, but preferably 0.01 mol to 100 mol, particularly preferably 0.1 mol to 10 mol of the halogen compound component per 1 mol of the organomagnesium component. Range is recommended.

Regarding the reaction method, there is a simultaneous addition method (method ■) in which two components are simultaneously introduced into the reaction zone and reacted, or -.
A method in which the halogenated component is charged in advance into the reaction zone and then the organomagnesium complex component is introduced into the reaction zone and subjected to S reaction (method @), or a method in which the organomagnesium complex component is charged in advance and the halogenated component is added. (Method O), but Methods @ and O are preferable, and Method O in particular gives preferable results.

When the organomagnesium component is insoluble, it is also possible to use a rogen compound as a reaction reagent in a heterogeneous treatment reaction in the reaction zone.

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 substance obtained by the above reaction is:
Although it may vary depending on the type of starting materials and reaction conditions, from the compositional analysis value, it is approximately 0.1 to 5.5 per basic solid 11.
It is presumed to be a halogenated magnesium compound containing an alkyl group with millimole of Mg-C bonds.

This basic solid has an extremely large specific surface area, and B
, E, T, method measurement: 70-250 m"/f
According to the present invention, it is possible to easily produce a high surface area active magnesium halide basic solid, which has conventionally been difficult to produce.

Next, a titanium compound containing at least one --Rogge/atom will be explained.

As for the titanium compound, a titanium compound containing at least three halogen atoms is preferable, and tetravalent and trivalent ones are preferable.

A combination of tetravalent and trivalent compounds may be used.

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

Particularly preferred is titanium tetrachloride.

Next, the trivalent titanium halide will be explained.

Examples of trivalent titanium halides include titanium trichloride,
Examples include titanium tribromide and titanium Misawa, but a solid solution containing these as a component may also be used.

As a solid solution, a solid solution of titanium trichloride and aluminum trichloride, a solid solution of titanium tribromide and aluminum tribromide,
Examples include solid solutions of titanium trichloride and vanadium trichloride, solid solutions of titanium trichloride and trichloride, and solid solutions of titanium trichloride and zirconium trichloride.

Among these, titanium trichloride, a solid solution of titanium trichloride and aluminum trichloride (TiC13.1/
3AIC12).

Next, carboxylic acid or its derivative will be explained.

Carboxylic acids or derivatives thereof include aliphatic, cycloaliphatic and aromatic saturated and unsaturated mono- and polycarboxylic acids, acid anhydrides, and esters.

Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid,
These include maleic acid, acrylic acid, benzoic acid, toluic acid, and terephthalic acid, and among these, benzoic acid and toluic acid are more preferred.

Examples of carboxylic anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, fluoric anhydride, and talic acid. Among these, benzoic anhydride is friendly.

Examples of carboxylic acid esters include ethyl formate,
Methyl acetate, ethyl acetate, n-propyne acetate, quaternary ethyl propylate, ethyl n-butyrate, ethyl valerate, ethyl caproate, ethyl n-hebutanoate, di-n-butyl oxalate, 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,
Benzoic acid n*1s 5ec-1' and te
rt-butyl, methyl p-toluate, ethyl p-toluate, p-) i-7”lopyl toluate, n- and i-amyl toluate 1.-ethyl toluate, m-ethyl toluate, p- Methyl ethylbenzoate, ethyl p-ethylbenzoate, methyl anisate, ethyl anisate,
i-propyl anisate, methyl p-ethoxybenzoate,
There are ethyl p-ethoxybenzoate, methyl terephthalate, etc., and among these, aromatic carboxylic acid esters are preferable, especially methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-toluate, anisic acid. Methyl and ethyl anisate are preferred.

Next, we will explain how to obtain a catalytic solid by reacting and/or pulverizing the basic solid obtained by the reaction between the organomagnesium component and the above-mentioned -rogen compound with a titanium compound and a carboxylic acid or its derivative. .

The reaction between a basic solid and a titanium compound or a carboxylic acid or its derivative can be carried out using a method [1] of reacting a titanium compound or a carboxylic acid derivative in a liquid phase or a gas phase, or a reaction in a liquid phase or a gas phase. Any method can be adopted, such as the method [2] in which the reaction and the pulverization reaction are combined.

First, the reaction of the basic solid with the titanium compound, carboxylic acid, or its derivative and/or the order of pulverization will be explained.

Regarding method [1], a method in which a basic solid, a titanium compound, and a carboxylic acid or a derivative thereof are reacted simultaneously (synthesis method ■), or a method in which a basic solid and a titanium compound are first reacted, and then a carboxylic acid or a derivative thereof is reacted. There is a method of reacting (synthesis method ①), or a method of first reacting a basic solid with a carboxylic acid derivative and then reacting with a titanium compound (synthesis method ①).

Both methods are possible, but the latter two methods are preferable.
In particular, synthesis method (2) is preferred.

Regarding method [2], when the titanium compound is (I) tetravalent, (I[) trivalent, (I[[) tetravalent and trivalent)
We will discuss the case when using both valence and valence.

(In the case of D, a method of simultaneously reacting a basic solid, a titanium compound, a carboxylic acid or a derivative thereof and pulverizing the solid obtained (synthesis method J), or reacting the above solid substance and a titanium compound without stirring, and then reacting a carboxylic acid Or a method of pulverizing a solid obtained by reacting a derivative thereof (synthesis method ■), or a method of first reacting the above solid substance with a carboxylic acid or its derivative, and then pulverizing a solid obtained by reacting a titanium compound. There is a method (synthesis method ■).

Although either method is possible, the latter two methods are more preferable, and particularly synthesis method (1) gives preferable results.

In the case of (n), various methods are possible for synthesizing the solid component from the three components: basic solid, trivalent titanium chloride, and carboxylic acid or carboxylic acid derivative, but the following three methods are particularly preferred. give.

That is, a method of co-pulverizing the three components (synthesis method ■), a method of bringing the solid component into contact with a carboxylic acid or a carboxylic acid derivative in advance, and then adding a trivalent titanium/logenide and mechanically crushing the solid component ( Synthesis method (2), or a method (synthesis method (2)) in which the solid component and the trivalent titanium chloride are brought into mechanical crushing contact and then treated with a carboxylic acid or a carboxylic acid derivative.

In the case of (II[), the basic solid (1), the tetravalent titanium compound (2-1), the trivalent titanium compound (2-2), and the carboxylic acid tobacco derivative (3) are simultaneously ground. Method (synthesis method ■), method of treating the solid obtained by reacting (1) and (2-1) with (3) and pulverizing it together with (2-2) (synthesis method 0), (1) and A method of reacting (3), treating the resulting solid with (2-1), and pulverizing it together with (2-2) (synthesis method ■), a method of reacting (1) with (2-1), Examples include a method of adding and pulverizing the solid, h(2-2) and (3) (synthesis method ①), but synthesis method ① is preferred.

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

First, the solid catalyst synthesized by method [1] is further
The method of treatment with the tetravalent titanium compound is a method in which a basic solid, a titanium compound, a carboxylic acid, or a derivative thereof are simultaneously reacted, and then further treated with a tetravalent titanium compound. (Synthesis method ■), A method in which the basic solid and a titanium compound are reacted, followed by a reaction with a carboxylic acid or its derivative, and then further treated with a tetravalent titanium halide (Synthesis method ■), A basic solid and a carboxylic acid There is a method (synthesis method ①) in which after reacting with acid or a derivative thereof, and then reacting with a titanium compound, the product is further treated with a rogenation compound of tetravalent titanium.

Next, regarding the method of further treating the solid catalyst synthesized by method [2] with a tetravalent titanium halide, α), (II)i- and GII) will be explained.

In the case of α), synthesis method [2] → ■) −■, (2) −(
I)-■Alternatively, it is possible to treat the solid catalyst prepared by [2]-(I)-○ with a tetravalent titanium chloride, but the latter two methods are more effective. It's nice.

In the case of (I[), the synthesis method (2) - (II) →: 1),
(2,1-(I[)-■, [2)-(II)-■
It is possible to further treat the solid catalyst synthesized by , [2]-ke)--2 with a tetravalent titanium halide.

In the case of (II[), the basic solid 0), the tetravalent titanium (
2-1), trivalent titanium compound (2-2), %-4 and carbo-4 or its derivative (3), after grinding at the same time, 4
Method of treating titanium with halogenated titanium (synthesis method ■)
,0) and (2-1) to form a solid obtained by reacting (3)
(2-2), followed by treatment with a tetravalent titanium halide (synthesis method ■), (2- A method of treating with 1), pulverizing with (2-2), and then further treating with a tetravalent titanium halide (synthesis method ①).

The solid obtained by reacting (1) and (2-1) and (2-
2)> Method of adding 3) and pulverizing (synthesis method ■),
The solid obtained by reacting (1) and (2-1) with (3)
f treatment, pulverization with (2-2), and then treatment with a tetravalent titanium halide (synthesis method ①), but method ■■■■ is preferable.

Next, the reaction of the basic solid with the titanium compound, carboxylic acid or its derivative and/or the pulverization operation will be explained.

(1) The reaction between a solid substance obtained by reacting an organomagnesium component and a halogen compound, a reaction product of a solid substance of tobacco residue and a carboxylic acid or its derivative, and a titanium oxide will be explained.

The reaction is carried out using an inert reaction medium or without an inert reaction medium, using the undiluted titanium compound itself as the reaction medium.

Examples of the inert reaction medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Group hydrocarbons are preferred.

There are no particular restrictions on the temperature during the reaction and the temperature of the titanium compound, but preferably a temperature of 80° C. or higher and a titanium compound temperature of 2 mol/liter or higher.

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.

(11) The reaction between a solid substance obtained by reacting an organomagnesium component and a rogen compound, a reaction product of a tobacco 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 residual alicyclic hydrocarbons may be used.

The temperature during the reaction is not particularly limited, and is preferably in the range from room temperature to 100°C.

When a solid substance is reacted with a carboxylic acid or its derivative, the reaction ratio of the two components is not particularly limited, but it is preferable to react the carboxylic acid or its derivative with respect to 1 mol of the alkyl group contained in the organomagnesium component. The recommended amount of the derivative is 0.001 mol to 50 mol, particularly preferably 0.005 mol to 10 mol.

When a reaction product of a solid substance and a titanium compound is reacted with a carboxylic acid or its derivative, the reaction ratio of the two components is as follows: 1 mole of titanium atom in the organomagnesium solid component: 0.01 mole to 1
A range of 0.00 mol, particularly preferably 0.1 mol to 10 mol, is recommended.

(m) A method for pulverizing the solid produced by the reactions (1) to (11) 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 100 hours, preferably 1 to 30 hours, and the grinding temperature is 0 to 200°C, preferably 10 to 150°C.
It is ℃.

(IV) The case of treatment with the solid component tetravalent titanium halide obtained in (1) to (iii) will be explained.

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. It's nice.

Regarding the concentration of titanization, the concentration is preferably 2 mol/or more.

There is no particular restriction on the temperature of the reaction, but a reaction temperature of 80° C. or higher gives favorable results.

The composition and structure of the solid catalyst component obtained by the reaction (i) 1 to 1) above will vary depending on the type of starting materials and reaction conditions, but from the composition analysis value, it is approximately 50-2 containing 1-10 wt. titanium
50? ? It turned out to be a solid catalyst named Z2/f.

(2) As the organometallic compound used as the acid component, compounds of groups (1) to (2) of the periodic table are preferred, and organoaluminum compounds are particularly preferred.

As the organic aluminized proboscis, the general formula A1R1σt
Z3-t (wherein RIO is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, a group selected from rogene, alkoxy, allyloxy, and siloxy groups, and t is a number of 2 to 3) The species shown in (a) use the proboscis as a single proboscis or a mixed proboscis.

In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by RIO includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.

Specific examples of these compounds include triethylaluminum, trinormalpropylaluminum,
Triisopropyl aluminum, trin-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tridodecyl aluminum, trihexadecyl aluminum, diethylaluminium hydride, diisobutyl aluminum hydride, diethylaluminum ethoxide, diisobutyl Aluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isoprenyl, etc., and mixtures thereof is recommended.

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

The carboxylic acid or derivative thereof added to the organometallic compound may be the same or different from the carboxylic acid or derivative thereof used in forming the solid catalyst component.

Regarding the addition method, the two components may be moistened in advance prior to polymerization, or they may be added separately into the polymerization system.

The ratio of the two components to be combined is 0 mol to 10 mol of the carboxylic acid or its derivative per 1 mol of the organometallic compound;
A particularly favorable range is IL < 1 mol - 1 mol.

The catalyst consisting of the solid catalyst component of the present invention and a component in which a carboxylic acid group or a carboxylic acid derivative is added to an organometallic compound or not may be added to the polymerization system under polymerization conditions, or may be added to the polymerization system in advance. They may be combined in advance.

Particularly preferably, the organometallic compound and the carboxylic acid or its derivative are reacted in advance, and the organometallic compound is separately added to the polymerization system.

The ratio of each component to be combined is such that carboxylic acid or carboxylic acid derivative is added to the organometallic compound to 11 parts of the solid catalyst component, and 1 part is added to the solid catalyst component based on the organometallic compound.
Preferably, the amount is in the range of mmol to 3000 mmol.

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

In particular, the present invention provides propylene, phthene-1, pentene-1
, 4-methylpentene-1,3-methylbutene-1 and similar olefins alone in a regular orderly manner.

It is also suitable for copolymerizing the olefin with ethylene or other olefins, and for efficiently polymerizing ethylene.

In addition, in order to adjust the molecular weight of the polymer, hydrogen,...a
It is also possible to add a genated hydrocarbon or an organometallic compound that tends 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 reacts with polymerization solvents such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. into a container and add olefins such as propylene under an inert atmosphere.
Polymerization can be carried out at a temperature of room temperature to 150° C. by injecting 20#/crd.

In the bulk polymerization, olefins can be polymerized using a liquid olefin as a heavy a solvent under conditions where the catalyst olefin such as propylene is a liquid.

For example, in the case of propylene, polymerization can be carried out in liquid propylene at a temperature of room temperature to 90° C. and under a pressure of 10 to 45 Ay/cut.

On the other hand, gas phase polymerization is performed under conditions in which the olefin such as propylene is a gas, in the absence of a solvent, at a pressure of 1 to 50 kgy6A, and at a temperature of room temperature to 120°C, allowing good contact between the olefin such as propylene and the catalyst. Polymerization can be carried out using means such as a fluidized bed, moving bed, or mixing using a stirrer so that the polymerization can be carried out.

The present invention will be explained below with reference to Examples.

In addition, the boiling n-heptane extraction residue used in the examples means the residue obtained by extracting a polymer with boiling n-heptane for 6 hours.

Example 1 (i) Synthesis of hydrocarbon-soluble organomagnesium complex 13.55S' of di-n-butylmagnesium and 1.84f of triethylaluminum were placed in a 200ml nitrogen-substituted flask with 100ml of heptane, and reacted at 80°C for 2 hours. By doing so, an organomagnesium complex solution was obtained.

As a result of the analysis, the composition of the complex with AIMgo, o(C2H
5) 3.0 (n-C, Ho) 12.0, and the organic metal concentration was 20 m01/l.

(ii) Capacity 5oom equipped with basic solid synthesis addition funnel and water-cooled reflux condenser
Oxygen and moisture inside the flask of g were removed by dry nitrogen substitution, and 1 mo of germanium tetrachloride was added in a nitrogen atmosphere.
Prepare 200 mmol of l/7 hebutane solution and heat to 70°C.
The temperature rose to .

Next, under a nitrogen atmosphere, the above organomagnesium complex solution 1
00 mmol was weighed into the dropping funnel.

The mixture was added dropwise over 1 hour while stirring at 70°C, 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, solid lI? Hit, MS'9.
11mmol zCl 18.2mmol pS
i 1.05 mmol b alkyl group 0.68 mm
The specific surface area measured by the B, E, T method was 186 d/S'.

(rrz) Synthesis of catalyst solid The above white solid 3.01 was taken into a flask that had been sufficiently purged with nitrogen, and 60 ml of n-hexane and 0.1 ml of ethyl benzoate were added.
Add 3.0 mmol of ol/l hexane solution and add 80
The reaction was carried out with stirring at ℃ for 1 hour, the solid was separated from the oven, and
- Thoroughly washed with hexane and dried.

2.51 of this solid and 50 ml of titanium tetrachloride were placed in a pressure-resistant container purged with nitrogen, and the mixture was heated at 100°C with stirring.
The reaction was allowed to proceed for a period of time, and the solid 1 was separated, washed with n-hexane, and dried to obtain a pale yellow solid catalyst.

As a result of analyzing this solid catalyst, the Ti content was 2.85% by polymerization.

(V) Slurry polymerization of propylene + solid catalyst 501nfI synthesized by (iii), triethylaluminum 3.0 mmol p p -) ethyl ruylate 1. Ommol and 0.8 t of dehydrated and deaerated hexane were placed in a 1.5 t autoclave whose interior was replaced with nitrogen and vacuum degassed.

Keep the internal temperature of the autoclave at 60℃, and add 5% propylene.
．． Pressure is increased to 0 kg/cd, and the total pressure is 4.8 kq/
Polymerization was carried out for 2 hours while maintaining the gauge pressure of CRD, resulting in polymerized hexane-insoluble polymer 721? , polymerized hexane soluble material 2
．． I got 41.

Catalyst efficiency is 720 ypp/S' solid catalyst time, 50
The titanium component, time, and propylene pressure were 50 fpp/'F, and the residue obtained by extracting the polymerized hexane-insoluble polymer with boiling n-hebutane was 95.8%.

Particle characteristics also have a bulk density of 0.341 S'/cyd, 3
5-150 mesh (7) Powder ratio is 88.5%
It was good.

Example 2 Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 501 nIi of the solid catalyst synthesized in Example 1 and 3.0 mmol of triethylaluminum, and polymerized hexane-insoluble polymer 931 and polymerized hexane-soluble polymer 9. 81
I got it.

The catalyst efficiency is 6230 fpp/f titanium fraction/time/propylene pressure, and the polymerized hexane-insoluble polymer is boiled n
-The residue extracted with hebutane was 84.6%.

Example 3 Catalyst synthesis and polymerization were carried out in the same manner as in Example 1.

The Ti content of the catalyst solid was 3.12% by weight.

As a result of the polymerization, 69 grams of polymerized hexane-insoluble polymer and 2.31 grams of polymerized hexane-soluble material were obtained.

Catalyst efficiency is 4420 fp pl? Titanium component/time/
The pressure was propylene, and the residue of the polymerized hexane-insoluble polymer extracted with boiling n-hebutane was 94.9%.

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 the reaction of the organomagnesium complex compound and germanium tetrachloride in Example 1.

Anhydrous MgCl23. Of and ethyl benzoate 3.0mm
2.5 fI of the obtained solid and 50 ml of titanium tetrachloride were reacted at 100° C. for 2 hours.

The titanium in the solid catalyst was 0.46% by weight.

This solid catalyst 4007711! , triethylaluminum 3.0 mmol, pF ethyl ruylate 1.
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using Ommol.

Polymerized hexane-insoluble polymer 421, hexane-soluble material 9.
I got 51.

The boiling n-hebutane extraction residue of the polymerized hexane-insoluble polymer is 81.8, and the catalyst efficiency is 53 I? pp/f solid catalyst/time, 2280 ypp/y titanium component/time/propylene pressure.

Example 4 (i) Synthesis of organomagnesium compounds Capacity 500772/! with dropping funnel and water-cooled reflux condenser installed! The flask was replaced with dry nitrogen, and 19.81 m of 100-200 mesh metal magnesium powder and 300 m of n-hebutane were added.
1 was charged, and the temperature of the flask was raised to 90°C.

0.81 mol of n-butyl chloride was weighed into a dropping funnel, and added dropwise over 1 hour while stirring at 90°C.

After the reaction started, stirring was continued at 90-95°C for another 2 hours to form a gray slurry (the solid portion in the slurry was n
-BuMgCl, and the liquid portion of the slurry contained no organic magnesium).

Next, 0.81 mol of Atsushi-butyllithium (cyclohexane solution) weighed into the I lower funnel was gradually dropped into this slurry at room temperature.

After the dropwise addition was completed, the mixture was stirred at 50° C. for 2 hours, and the solid portion was removed under a nitrogen atmosphere to obtain an organic magnesium solution.

As a result of analyzing the obtained organic magnesium solution, see
-BuMgn-Bu, and its C-Mg
The concentration of binding was 1.08 mol/l.

The concentration of C-Mg bond was L08 ml/l.

(1:) 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 germanium tetrachloride, and this solid was reacted with ethyl benzoate and titanium tetrachloride. A solid catalyst was obtained.

As a result of analyzing this solid catalyst, the Ti content was 2.98% by weight.

This solid catalyst 50μ, triethylaluminum 3.0m
mol, ethyl p-ethylbenzoate 1. Omm ol
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using the following.

Polymerized hexane-insoluble polymer 691, hexane-soluble material 2.
I got 81.

The boiling n-heptane extraction residue of the polymerized hexane-insoluble polymer is 95.3%, and the catalyst efficiency is 690 rpp/f solid catalyst time, 4630 fpp/? These were titanium component, time, and propylene pressure.

Examples 5 to 13 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 p-anisate and titanium tetrachloride to form a solid catalyst. I got it.

Solid catalyst 50η, triethylaluminum 3.0 mm
ol % ethyl benzoate 1. Propylene was polymerized in a hexane solvent in the same manner as in Example 1 using Ommol.

Table 1 shows catalyst synthesis conditions and polymerization results.

Example 14 AlMg6. (1(C2H5)2.g (n-C4H
g) 12.1 Germanium tetrachloride, ethyl benzoate and titanium tetrachloride were reacted to give a pale yellow solid.

This solid 4, Of is made into a steel ball 2 with a diameter of 9 mm under a nitrogen atmosphere.
1000v in a steel mill with an internal volume of 100cm containing 5 pieces.
It was ground for 5 hours in a vibrating ball mill at ib/min or higher.

The Ti content of the obtained solid catalyst was 2.89 deuterons.

This solid catalyst 50μ and triethylaluminum 3.0
mmol z p -)ethyl ruylate 1. Ommo
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 1.

The results are shown in Table 2. Example 15 (sec-Bu)1.5Mg (On-Bu)0-
5 was reacted with germanium tetrachloride, ethyl p-anisate, and titanium tetrachloride to obtain a pale yellow solid.

This solid 3.9Of and titanium trichloride (AA grade TiCl3.1/3 AIC13 manufactured by Toyo Stoffer) 0.
15f in a nitrogen atmosphere in the same manner as in Example 11.
Time crushed.

The Ti content of the obtained solid catalyst was 3.68 wt.

This solid catalyst 50μ and triethylaluminum 3.0
mmol, p-toluic acid ethyl yv: l,
Slurry polymerization of propylene was performed in the same manner as in Example 1 using Ommol.

It is shown in Table 2. Example 16 50 kg of the solid catalyst synthesized in Example 15 and 3. Slurry polymerization of propylene was performed in the same manner as in Example 1 using Ommol.

The results are shown in Table 2.

Example 17 A basic solid was synthesized by reacting with germanium tetrachloride in the same manner as in Example 1, and further reacting with ethyl benzoate.

This solid 4. Example 11 O2 and titanium trichloride (AA grade manufactured by Toyo Stoffer Co., Ltd.) 0.35f under nitrogen atmosphere
It was ground for 5 hours in the same manner as above.

The Ti content of the obtained solid catalyst was 2.02 wt.

This solid catalyst 5011II! , triethyl 1. Omm
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using OL.

The results are shown in Table 2. Example 18 Example 1 was prepared using 501 ng of the solid catalyst synthesized in Example 17 and 3.0 mmol of triethylaluminum.
Slurry polymerization of propylene was carried out in the same manner.

The results are shown in Table 2.

Example 19 In the same manner as in Example 17, the basic solid was reacted with ethyl benzoate, and then the obtained solid and titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were pulverized.

This solid 4. Of and 60 ml of titanium tetrachloride were mixed under stirring.
After reacting at 30° C. for 2 hours, the solid portion was isolated by p-filtration, thoroughly washed with hexane, and dried to obtain a solid catalyst.

Analysis of this solid revealed that it contained 3.68% by weight of titanium.

50 mg of this solid catalyst and 3.0 mg of triethylaluminum.
0 mmol s p-ethyl toluate 1. Omm
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using OL.

The results are shown in Table 2. Example 20 In the same manner as in Example 14, the basic solid was reacted with ethyl benzoate, and then the obtained solid was reacted with titanium tetrachloride.

This solid was ground in a vibrating ball mill under nitrogen atmosphere for 5 hours.

Furthermore, this solid 4. After reacting Of with 760 ml of titanium tetrachloride at 130°C for 2 hours with stirring, the solid portion was
It was filtered, isolated, thoroughly washed with hexane, and dried to obtain a solid catalyst.

Analysis of this solid revealed that it contained 3.20% titanium by weight.

This solid catalyst 50η and triethylaluminum 3.0
mmol s p-ethyl toluate 1. Omm
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using OL.

The results are shown in Table 2.

Example 21 350f of liquefied propylene was placed in a 1.5 t autoclave whose interior was purged with nitrogen and vacuum dried, and the internal temperature was brought to 60
℃, add 10η of the solid catalyst synthesized in Example 20, 5 mmol of triethylaluminum I and 0.5 mmol of ethyl p-)ruylate to the autoclave.
Polymerization was carried out at 60°C for 2 hours to produce 110 tons of polypropylene.
I got it.

Catalyst efficiency is 5500 S'pp/f solid catalyst/hour, 17
2000 fpp/? The titanium component/time was 93.3%, and the n-hebutane extraction residue of the produced polypropylene was 93.3%.

Example 22 Hexane solution of triethylaluminum (1 mol/l
) 2. Ommol and ethyl p-toluate in hexa/solution (1 mol/l)1. A pre-mixed solution of Ommol and the solid catalyst 30111 synthesized in Example 20
9 and triethylaluminum 1. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using Ommol to obtain 1281 polymerized hexa/insoluble polymers and 6.11 polymerized hexane solubles.

The n-hebutane extraction residue of the polymerized hexane-insoluble polymer is 9
The catalyst efficiency was 13,300 fpp/P titanium component/time/propylene pressure.

Examples 23 to 28 50 μl of a solid catalyst synthesized in the same manner as in Example 1, 3.0 mmol of triethylaluminum, and the compound 1. shown in Table 3. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using Ommol, and the results shown in Table 3 were obtained.

Examples 29-30 In the same manner as in Example 1, 50 cm of solid catalyst synthesized in the same manner as in Example 1, 1.0 mmol of ethyl benzoate, and Ommol of organometallic compound 3 shown in Table 4 were added. Slurry polymerization of propylene was carried out, and the results shown in Table 4 were obtained.

Example 31 Propylene containing 2 moles of ethylene was prepared in the same manner as in Example 1 using 50η of a solid catalyst synthesized in the same manner as in Example 1 and 3.0 mmol of triethylaluminum and 1.0 mmol of sp-ethyl tolutoate. Slurry polymerization was carried out using -ethylene mixed gas to obtain 73 grams of white polymer.

Example 32 500 kg of solid catalyst synthesized in the same manner as in Example 1,
Polymerization of butene-1 in hexane using 6.0 mmol of triethylaluminum was carried out in the same manner as in Example 1 to obtain 88 g of a white polymer.

Example 33 500 kg of solid catalyst synthesized in the same manner as in Example 1,
Example 1 Polymerization of 4-methylpentene-1 in hexane using 6.0 mmol of triethylaluminum
A white polymer 601 was obtained in the same manner as above.

Example 34 50 mg of the solid catalyst synthesized in Example 1, triisobutylaluminum 1. Ommol and 0.1 mmol of methyl p-toluate were placed together with dehydrated and degassed n-hexane O, St in a 1.5 t autoclave whose interior was vacuum dried and replaced with nitrogen, and the internal temperature was raised to 80°C. The blade pressure was maintained at 1.6 kg/era with hydrogen, and then ethylene was added. Total pressure 4.0. kq/cr? +

By replenishing ethylene and 5, the total pressure is increased to 4.0ky/
cr? Polymerization was carried out for 1 hour while maintaining the gauge pressure of 37
A white polymer of No. 1 was obtained.

Claims (1)

[Claims] 1 [A] (υ (1)-) function MaMgβR1p R
2qX, rY s (where α is a number greater than 0 or O, p.qyr,8 is a number greater than 0 or O, p + q
+ r + s = mα + 2β, where M is a metal element belonging to Groups 1 to 2 of the periodic table, m is the valence of M, and R1 and R2 are hydrocarbons with the same or different numbers of carbon atoms. Base, X. Y is the same or different groups, OR3. 08iR'R"t NR7R8p SR', R3j R'#R6jR7J R8 is a hydrogen atom or a hydrocarbon group, and R9 is a hydrocarbon group) is an organomagnesium compound represented by (1i) general formula LJ
jROa-j (wherein L represents germanium, an atom selected from the following, J represents a halogen atom, RO represents a hydrocarbon group,
a is the valence of L, j is indicated by 0 (j≦a)/・Rogeni5. Solid obtained by reacting with bJ4 proboscis (2 Titanium compounds containing at least one rogen atom (3 carboxylic acids or derivatives thereof (excluding 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 [B] an organometallic compound containing a carboxylic acid or a derivative thereof (
(excluding sulfur-containing, oxygen-containing or nitrogen-containing ring carboxylic acid esters) and a residue that is not added. 2. The catalyst for olefin polymerization according to claim 1, wherein the organomagnesium compound in CA) (i) is a hydrocarbon-soluble organomagnesium compound in which α is a larger number than O. In the organomagnesium compound of 31Al(1), α
The catalyst for olefin polymerization according to claim 1 or 2, wherein M is a larger number than O, and M is an aluminum, zinc, boron, or beryllium atom. 4. The catalyst for olefin polymerization according to claim 1, 2 or 3, wherein α>O and 1≦β/α410. 5, (r+s), / (α+β) ratio is 04
The catalyst for olefin polymerization according to claim 1, 2, 3, and 4, wherein (r + s, )/(α+β)≦0.8. 6 [A] In the (+) organomagnesium compound, α is O and at least one of R1 and R2 is a secondary residue or a tertiary alkyl group having 4 to 6 carbon atoms, or A patent for a hydrocarbon-soluble organomagnesium compound in which R1 and R2 are alkyl groups having different numbers of carbon atoms, or at least one of R1 and R2 is a hydrocarbon group having 6 or more carbon atoms. Claim 1
The catalyst for olefin polymerization described in Section 1. 7CA) In the organomagnesium compound of (1),
R1 is an alkyl group having 2 or 3 carbon atoms, R2 is an alkyl group having 4 carbon atoms
The catalyst for olefin polymerization according to claim 6, which is an alkyl group as described above. 8. The catalyst for olefin polymerization according to claim 6, wherein in the organomagnesium compound of (i), R1 and R2 are both alkyl groups having 6 or more carbon atoms. s cAl<t+>...In the rogen compound, L
is an atom selected from germanium and mercury, and this compound is soluble in a hydrocarbon medium or an ether type medium, Claims 1, 2, 3, 4, 5
, 6.7 or 8. 10 CA) (j+)...J in rogene compounds
Claims 1, 2, 3, 4, and 5 in which is a chlorine atom
Olefin polymerization catalyst according to item 6.7, 84 or 9. 11cA1 (11)... In the rogogen compound proboscis, j =
Scope of claims No. 1, 2. 3, 4, 5, 6゜7
．． 8.9 or the catalyst for olefin polymerization according to item 10. 12CA) (2) is a tetravalent titanium compound containing at least one rogen atom,
), (21 and (3)) or reacting and pulverizing to synthesize a solid catalyst component.
The catalyst for olefin polymerization described in Section 1. 13 [A] The titanium compound in (2) is a trivalent titanium halide, and (1), (2) and (3) are co-pulverized, or (1) and (3) are co-pulverized. By pulverizing the solid obtained by the reaction and (2), or by treating it with the solid material 3) obtained by co-pulverizing (1) and (2),
Claims 1.2, 3, which synthesize solid catalyst components;
The catalyst for olefin polymerization according to item 4, 5° 6.7, 8, 9, 10 or 11. 14 (At G2) is (a) a titanium compound containing at least one halogen atom, and
←) A 7-rogenide of trivalent titanium, (1),
Claim 1.2: A solid catalyst component is synthesized by pulverizing and reacting (2) and (3).
．． 3.4.5.6.7.8.9.10 The catalyst for olefin polymerization according to item 11. 15CA) The titanium compound in (2) is titanium tetrachloride and/or titanium trichloride, Claim 1.2.
3,4,5,6,7,8,9,10,11゜12.13
4. Catalyst for olefin polymerization according to item 14. 16CA) (3) and the carboxylic acid residue or derivative thereof is a carboxylic acid, an acid anhydride, or a carboxylic acid ester.
7,8,9,10,11,12,13゜14o or 15
The catalyst for olefin polymerization described in Section 1. 17 [The amount of G, carboxylic acid residue, or carboxylic acid derivative used depends on the alkyl group contained in the solid obtained by reacting the organomagnesium compound of (1) with the rogen compound of germanium, mercury, etc. Claim 1.2.3.4.5. The number of moles is 0.001 to 50 times the number of moles.
6.7.8.9.10゜11.12,13,14,15
The catalyst for olefin polymerization according to item 4 or 16. The organometallic compound of 18 [B] has the general formula AlR10Z3-
0 (wherein R10 is a CIMO hydrocarbon group, Z is hydrogen,
A group selected from halogen, alkoxy, allyloxy, hexagram, and siloxy group, and t is a number of 2≦tl-3)
Claims 1.2, 3, 4, 5, 6° 7.8, 9, 10, 11 which are organoaluminum compounds represented by
, 12, 13, 14, 15. The catalyst for olefin polymerization according to item 16 or 17. Claims 1, 2, 3, 4, 5, 6° 7.8, 9, wherein the organometallic compound of 19(B) is trialkylaluminum or dialkylaluminium/) hydride.
10. IL 12, 13, 14, 15° 16 or 11
The catalyst for olefin polymerization described in Section 1. 2[ICAl](υ(f-shaped MaMgβR'pR2qX
rYs (where αbat or a number greater than O, p, q
-rm8 is a number greater than 0 or O, and has the relationship p+q+r+s=mα+2β, M is a metal element belonging to Groups Ⅰ to Ⅲ of the periodic table, m is an atomic drawing of M, and R1 and R2 are the same or Hydrocarbon radicals, X, of different numbers of carbon atoms. Y is the same or different group, 0R30SiR4:
Represents a group R5R6, NR7R85R9, R3, R
4, R5, R6, R7, R8 represent a hydrogen atom or a hydrocarbon group, R9 represents a hydrocarbon group), <+;) general formula LJ jROa -j
(In the formula, L is an atom selected from germanium, mercury, J is...a rogen atom, RO is a hydrocarbon group, and a
A solid obtained by reacting with a rogen compound. A titanium compound containing at least one rogen atom. (3) Carboxylic acids or derivatives thereof (excluding sulfur-containing, oxygen-containing or nitrogen-containing heterocyclic carboxylic acid esters) (1), (2L) After reacting and/or pulverizing (3), at least one additional 7.4 containing a rogen atom
CB) a solid catalyst component obtained by treatment with a titanium compound (4) of 20% or less; Ingredients added or not added. An olefin polymerization catalyst consisting of.