JPS625926B2 - - 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
Suitable for the stereoregular polymerization of propylene, butene-1, pentene-1, 4-methylpentene-1, 3-methylbutene-1 and similar olefins, and for copolymerizing said olefins with ethylene or other olefins. It is also suitable for Ziegler consisting of a transition metal compound of Groups A to A of the periodic table and an organometallic compound of Groups A to A of the periodic table. It is well known that stereoregular polymers can be obtained by contacting olefins with Natsuta catalyst systems. In particular, combinations of titanium halides and organoaluminum compounds such as triethylaluminum or diethylaluminum chloride are widely used industrially as stereoregular polyolefin polymerization catalysts. When olefins such as propylene are polymerized using this catalyst, a boiling heptane-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 to remove catalyst residue is required. 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 boiling heptane solubles, relative to the total polymer produced,
That is, the proportion of amorphous polymer is very large, and it is difficult to use it as it is as a stereospecific polymerization catalyst for olefins such as propylene in industry (for example, JP-A-47-9342, JP-B-Sho 43-13050). As a solution to these problems,
No. 39431, Special Publication No. 36153 and Publication No. 1973-
The method described in No. 16988 has been proposed. These methods use a catalyst consisting of a solid component obtained by co-pulverizing a complex compound of a titanium halide compound and an electron donor and anhydrous magnesium halide, and an addition reaction product of aluminum trialkylaluminium and an electron donor. It is a system. However, even with these methods, the proportion of boiling heptane insolubles in the produced polymer is still not high enough to satisfy the requirements, especially the yield of polymer per solid catalyst component is insufficient, and the production process equipment and The content of halogen in the polymer, which causes corrosion of the molding machine, is high, and the physical properties of the product are not fully satisfactory. Generally, alkylmagnesium compounds are insoluble in hydrocarbon media, but these compounds with specific R′ and R″ are soluble in hydrocarbon media, and are therefore extremely advantageous industrially. For example, the above-mentioned patent application No. 115400 and the patent application No. 115400
The alkylmagnesium component preferably used in No. 145695 is hydrocarbon soluble, but
In order to make the component soluble in hydrocarbons, it is necessary to add other organic metals such as aluminum alkyl and zinc alkyl to form a complex (e.g. AlMg ₆ R ¹ ₃ R ² ₁₂ ). I needed it. On the other hand, in the present invention, by limiting R′ and R″ to specific values, the alkylmagnesium compound itself is soluble in hydrocarbons, so it can be handled as a solution without using extra aluminum alkyl, etc. It is extremely advantageous in terms of synthesis, handling, and cost.As a result of intensive study on these points, the present inventors have found that a chlorosilane compound containing a Si--H bond can be added to a solution of an organomagnesium compound soluble in an inert hydrocarbon medium. is used as a reaction reagent to produce a halogen-containing magnesium compound solid, and this is reacted and/or pulverized with a titanium compound and a carboxylic acid or its derivative.The specific solid obtained has extremely excellent performance as an olefin polymerization catalyst. The present invention has been accomplished by discovering that [A] (1) an organomagnesium compound soluble in a hydrocarbon medium having the general formula MgR′uR″vXw (wherein R′ , R'' represents a hydrocarbon group, 0<u≦2, 0<v≦2, and 0<w≦1, and R′ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms. or 0<u≦2, 0<v≦2, and 0<w≦1, and R′ and R″ are alkyl groups having different numbers of carbon atoms, or 0 <u≦2, 0≦v≦
2, and 0<w≦1, R' is a hydrocarbon group having 6 or more carbon atoms, X is a negative group containing O, N, or S atoms, and u, v, w has the relationship u+v+w=2) (ii) general formula H _a
SiCl _b R _4-(a+b) (wherein a and b are numbers larger than 0, a+b≦4, and R represents a hydrocarbon group) by reacting with a Si—H bond-containing chlorosilane compound. Solid (2) Titanium compound containing at least one halogen atom (3) Carboxylic acid or its derivative A solid obtained by reacting and/or pulverizing the above (1), (2), and (3), and B This is an olefin polymerization catalyst consisting of an organometallic compound and a carboxylic acid or its derivative. 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 Example 15 below, in the case of propylene polymerization in liquid propylene, the catalyst efficiency was 3.0 x 10 ⁵ g polymer/1 g titanium for 1 hour;
More than 8550g polymer/1g catalyst solid component/hour is easily obtained. From the activity of the catalyst of the present invention, the Ti content and Cl content in the polypropylene produced during polymerization are:
They are about 1.6ppm and 39ppm, respectively. This shows that polypropylene polymerized using the catalyst of the present invention does not require removal of catalyst residues, that is, it is an extremely high-performance catalyst that enables a non-deashing process. The second feature of the present invention is that in addition to the above-mentioned high activity, high stereoregularity can be obtained. By the way, the boiling n-heptane extraction residue is
It reaches 94.0%. The third feature of the present invention is that the particle size of the polymer is good and that a polymer powder with high bulk density can be produced. Furthermore, the fourth feature is that when molded using the polymer produced by this catalyst, the color of the molded product is extremely good. Although the essential factors behind the surprising performance of the catalyst of the present invention as described above are still unclear, as shown in the examples described later, according to the present invention, alkyls having an extremely high surface area and a reducing power It is believed that an active magnesium halide basic solid containing groups has been synthesized. General formula used in the synthesis of the solid catalyst of the present invention
MgR′uR″vXw (where R′, R″, X, u, v, w
The organomagnesium compound soluble in the hydrocarbon catalyst represented by (has the above-mentioned meaning) will be explained. In the above formula, R′, R″ are the following three groups (),
() or (). () 0<u≦2, 0≦v≦2, and 0<w≦
1, and R' is a secondary or tertiary alkyl group having 4 to 6 carbon atoms. () 0<u≦2, 0<v≦2, and 0<w≦
1, and R′ and R″ are alkyl groups having different numbers of carbon atoms. () 0<u≦2, 0≦v≦2, and 0<w≦
1, and R' is a hydrocarbon group having 6 or more carbon atoms. Preferably, R′ and R″ are the following three groups (′),
(') or ('). (') Both R' and R'' have 4 to 6 carbon atoms, and at least one is a secondary or tertiary alkyl group. (') R' is an alkyl group having 2 or 3 carbon atoms. Yes, and R'' is an alkyl group with 4 or more carbon atoms. (') Both R' and R'' are alkyl groups having 6 or more carbon atoms. These groups are specifically shown below. In () and ('), As a class or tertiary alkyl group, sec-
C ₄ H ₉ , tert-C ₄ H ₉ ,

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] etc. are used, preferably a secondary alkyl group, and sec-C ₄ H ₉ is particularly preferred. In ('), examples of the alkyl group having 2 or 3 carbon atoms include ethyl group and propyl group, with ethyl group being particularly preferred, and examples of the alkyl group having 4 or more carbon atoms include butyl group, amyl group, hexyl group, octyl group. Among these groups, butyl group and hexyl group are particularly preferred. Examples of the hydrocarbon group having 6 or more carbon atoms in () and (') include a hexyl group, an octyl group, a decyl group, a phenyl group, and the like, with an alkyl group being preferred and a 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 this tends to increase the viscosity of the solution, and it is not preferable to use an alkyl group with an unnecessarily long chain from the viewpoint of handling. Next, as the negative group containing O, N, or S atom represented by X, alkoxy, siloxy, allyloxy, amino, amido

[Formula] -SR〓, β-keto acid residue (R, R〓, R〓 are hydrocarbon groups), and preferably an alkoxy group or a siloxy group is used. Specifically, −OC ₂ H ₅ , −
_{OC4H9 ,}

[Formula] etc. u, v, w are 0≦u≦2, 0≦v≦2, 0<w
A number in the range ≦1, and u+v+w=2
From the viewpoint of catalyst performance, it is recommended that the range of the value of w be preferably 0<w≦0.8. 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 H _a SiCl _b R _4-(a+b) (in the formula a, b,
The Si--H bond-containing chlorosilane compound represented by (R has the above-mentioned meaning) will be explained. The hydrocarbon group represented by R in the above formula is an alkyl group,
A cycloalkyl group or an allyl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc., preferably having 1 to 10 carbon atoms.
is an alkyl group, and lower alkyl groups such as methyl and ethyl are particularly preferred. There is no particular restriction on the range of values of a and b as long as a>0, b>0 and a+b≦4, but preferably 0<a<2. These compounds include HSiCl ₃ ,
HSiCl ₂ CH ₃ , HSiCl ₂ (C ₂ H ₅ ), HSiCl ₂ (n-
_C3H7 ) _{, HSiCl2} (i- _C4H9 ) _{, HSiCl2} ( _C6H5 ) _,
HSiCl ₂ (CH=CH ₂ )HSiCl ₂ CH ₂ (C ₆ H ₅ ), HSiCl
( _CH3 ) ₂ , HSiCl _{( C2H5} ) ₂ , HSiCl( _CH3 )
(C ₆ H ₅ ), H ₂ SiClCH ₃ , H ₂ SiCl (C ₂ H ₅ ), etc., a single compound, a mixture, or a mixture partially containing these compounds is used, preferably with 0<a<2. Chlorosilane compounds in which R is a lower alkyl group, such as trichlorosilane HSiCl ₃ ,
Monomethyldichlorosilane _HSiCl2CH3 , diethylchlorosilane HSiCl( _C2H5 ) _{2 ,} etc. _are used. As can be seen from Example 1 and Comparative Examples 1 and 2, Si
- When using silicon compounds that do not contain H bonds, favorable results are not obtained. The reaction of an organomagnesium compound or an organomagnesium compound with 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, cyclohexane, methylcyclohexane, etc. The reaction can be carried out in an alicyclic hydrocarbon, an ether medium such as ether or 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° C. or higher in view of the progress of the reaction. There is no particular restriction on the reaction ratio of the two components, but preferably 0.001 to 100 mol of the chlorosilane component, particularly preferably 0.1 mol to 1 mol of the organomagnesium component.
In the range of 10 moles. Regarding the reaction method, the two components are simultaneously introduced into the reaction zone and reacted simultaneously (method ○a), or the chlorosilane component is charged into the reaction zone in advance, and then the organomagnesium component is introduced into the reaction zone. There is a method of continuous reaction (Method ○B), or a method of preparing the organomagnesium component in advance and adding the chlorosilane component (Method ○C).
Methods ○B and ○C are preferred, and method ○B particularly gives preferable results. The composition and structure of the solid substance (1) obtained by the above reaction may vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, approximately
It is estimated to be a halogenated magnesium compound containing an alkyl group having 0.1 to 2.5 mmol of Mg--C bonds. This solid material has an extremely large specific surface area, and as measured by the BET method, it has a surface area of 100
It shows a high value of ~300 m ² /g. Compared to conventional magnesium halide solids, the solid material of the present invention is characterized in that it is an active magnesium halide compound that has a very high surface area and contains an alkyl group with reducing power. Next, a titanium compound containing at least one halogen atom will be explained. Preferred titanium compounds are those containing at least three halogen atoms. Tetravalent or trivalent compounds are preferred, and tetravalent and trivalent compounds may be used in combination. Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride, etc. halides,
Alkoxy halides may be used alone or in mixtures. Titanium tetrachloride is preferred. Next, the trivalent titanium halide will be explained. As a trivalent titanium halide,
Examples include titanium trichloride, titanium tribromide, and titanium triiodide, but a solid solution containing these as one component may also be used. Examples of solid solutions include solid solutions of titanium trichloride and aluminum trichloride, solid solutions of titanium tribromide and aluminum tribromide, solid solutions of titanium trichloride and vanadium trichloride, solid solutions of titanium trichloride and iron trichloride, and solid solutions of titanium trichloride and aluminum trichloride. Examples include solid solutions of zirconium trichloride. Among these, preferred are titanium trichloride and a solid solution of titanium trichloride and aluminum trichloride (TiCl ₃ .1/2AlCl ₃ ). 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,
Examples include propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, acrylic acid, benzoic acid, toluic acid, terephthalic acid, and among these, benzoic acid and toluic acid are more preferred.
Examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, n-butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, and phthalic anhydride, among which benzoic anhydride is preferred. Examples of carboxylic acid esters include ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl caproate, ethyl heptanoate, and di-n-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, Benzoic acid n-, i-, Sec-, and
tert-butyl, methyl p-toluate, ethyl p-toluate, i-propyl p-toluate, n- and i-amyl toluate, ethyl o-toluate, ethyl m-toluate, p-ethylbenzoic acid Methyl, ethyl p-ethylbenzoate, methyl anisate, ethyl anisate, i-propyl anisate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, methyl terephthalate, etc.
Among these, aromatic carboxylic acid esters are preferred, especially methyl benzoate, ethyl benzoate, p
-Methyl toluate, ethyl p-toluate, methyl anisate, and ethyl enisate are preferred. Next, it will be explained how to obtain a catalytic solid by reacting and/or pulverizing the basic solid obtained by the reaction of an organomagnesium organism with a chlorosilane compound with a titanium compound and a carboxylic acid or a derivative thereof. The reaction between a basic solid and a titanium compound, a carboxylic acid, or a derivative thereof can be carried out by a method of reacting a titanium compound, a carboxylic acid, or a derivative thereof in a liquid phase or a gas phase, or a reaction in a liquid phase or a gas phase and a pulverization reaction. Any method such as combination method [2] can be adopted. First, the order in which the basic solid is reacted with a titanium compound, a carboxylic acid, or a derivative thereof and/or pulverized will be explained. Method [1] is a method in which a basic solid, a titanium compound, a carboxylic acid or a derivative thereof are reacted simultaneously (synthetic method), or a method in which the basic solid and a titanium compound are first reacted and then a carboxylic acid or a derivative thereof is reacted (synthetic method). ), or a method (synthesis method) in which a basic solid is first reacted with a carboxylic acid or its derivative, and then a titanium compound is reacted. Although either method is possible, the latter two methods are preferred, and the synthetic method is particularly preferred. For method [2], titanium compound (),
If it is tetravalent, (), if it is trivalent, (),
The case where tetravalent and trivalent are used together will be described. In the case of (), a method of simultaneously reacting a basic solid, a titanium compound, a carboxylic acid or its derivative and pulverizing the solid obtained (synthesis method), or a method of first reacting the above solid substance with a titanium compound and then further reacting a carboxylic acid or its derivative. A method of pulverizing the solid obtained by reacting a derivative (synthetic method), or a method of first reacting the above solid substance with a carboxylic acid or its derivative, and then pulverizing the solid obtained by reacting with a titanium compound (synthetic method) ). Although either method is possible, the latter two methods are more preferable.
In particular, synthetic methods give favorable results. In the case of (), various methods are possible for synthesizing the solid component from the three components of the basic solid, trivalent titanium halide, and carboxylic acid or carboxylic acid derivative, but the following three methods give particularly favorable results. . That is, a method in which the three components are co-pulverized (synthetic method), and a method in which the solid component is brought into contact with carboxylic acid or a carboxylic acid derivative in advance, and then a trivalent titanium halide is added and mechanically pulverized (synthetic method). , or after mechanically crushing and contacting the solid component and the trivalent titanium halide,
This is a method (synthesis method) of treatment with a carboxylic acid or a carboxylic acid derivative. In the case of (), the basic solid (1), a tetravalent titanium compound, (2-1), a trivalent titanium compound (2-2),
and carboxylic acid or its derivative (3) (synthesis method), the solid obtained by reacting (1) and (2-1) is treated with (3) and then crushed together with (2-2). (synthesis method), the solid obtained by reacting (1) and (3) is treated with (2-1), and (2
-2) and the solid obtained by reacting (1) and (2-1), and (2-
Method of adding and pulverizing 2) and (3) (synthesis method)
etc., but synthetic methods are preferred. Furthermore, the catalyst efficiency can be improved by further treating the solid catalyst synthesized by the above method [1] and method [2] with a tetravalent titanium compound (4) containing at least one halogen atom. An increase is brought about. First, the method of further treating the solid catalyst synthesized by method [1] with the above-mentioned tetravalent titanium halide involves simultaneously reacting the basic solid, the titanium compound, the carboxylic acid or its derivative, and then further treating the solid catalyst with the tetravalent titanium halide. A method of treating with a tetravalent titanium halide (synthesis method), reacting a basic solid with a titanium compound,
Subsequently, a method of reacting with a carboxylic acid or a derivative thereof and then further treating with a tetravalent titanium halide (synthesis method), a method of reacting a basic solid with a carboxylic acid or a derivative thereof, and then reacting with a titanium compound After that, there is a method (synthesis method) of further treating with a tetravalent titanium halide. Next, regarding the method of further treating the solid catalyst synthesized by method [2] with a tetravalent titanium halide, (), (), and () will be explained. In the case of (), synthesis method [2]-()-,
It is possible to treat the solid catalyst synthesized by [2]-()- or [2]-()- with a tetravalent titanium halide, but the latter two methods are more preferable. . In the case of (), synthesis method [2]-()-,
[2]-()-, [2]-()-, [2]
The solid catalyst synthesized by -()- was further added to 4
A method of treatment with a titanium halide of high valence is possible. In the case of (), after simultaneously crushing the basic solid (1), the tetravalent titanium compound (2-1), the trivalent titanium compound (2-2), and the carboxylic acid or its derivative (3), A method of treating with a titanium halide (synthesis method), the solid obtained by reacting (1) and (2-1) is treated with (3), and after pulverizing with (2-2), the tetravalent A method of treating with a titanium halide (synthesis method), the solid obtained by reacting (1) and (3) is treated with (2-1), pulverized with (2-2), and then further , A method of treating with a tetravalent titanium halide (synthesis method) A method of adding the solid obtained by reacting (1) and (2-1) with (2-2) and (3) and pulverizing ( Synthesis method), the solid obtained by reacting (1)-(2-1) is treated with (3), and after pulverizing with (2-2), 4
For example, a method of treating titanium with a titanium halide (synthesis method) is preferred. 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 chlorosilane compound, or a reaction product of this solid substance and a carboxylic acid or its derivative, 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. Hydrocarbons are preferred. There are no particular restrictions on the temperature during the reaction and the concentration of the titanium compound, but preferably the temperature is 100°C or higher and the titanium compound concentration is 4 mol/liter or more, and more preferably the undiluted titanium compound itself is used as the reaction medium. Perform a reaction. Regarding the reaction molar ratio, for the magnesium component in the solid substance,
Preferable results are obtained by carrying out the reaction in the presence of a sufficient excess amount of the titanium compound. (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. Inert reaction media include the aliphatic, aromatic,
or 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, there is no particular restriction on the reaction ratio of the two components;
Preferably, the carboxylic acid or its derivative is used in an amount of 0.001 mol to 50 mol, particularly preferably 0.005 mol to 10 mol, per 1 mol of the alkyl group contained in the organomagnesium component. 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 0.01 of the carboxylic acid or its derivative per 1 mole of titanium atom in the organomagnesium solid component. A range of mol to 100 mol, particularly preferably 0.1 mol to 10 mol is recommended. (iii) A method for pulverizing the solid produced by the reactions (i) to (ii) above will be explained. As the pulverization method, well-known mechanical pulverization means such as a rotary ball mill, a vibrating ball mill, and 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. (iv) The case where the solid components obtained in (i) to (iii) are treated with a tetravalent titanium halide 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. is preferred. The concentration of the titanium compound is preferably 4 mol/l or more, and it is particularly preferable to react using the titanium compound itself as a reaction medium. Although there are no particular restrictions on the reaction temperature, it is preferable to carry out the reaction at a temperature of 80°C or higher. The composition and structure of the solid catalyst component obtained by the reactions (i) to (iv) above will vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, approximately 1% It was found that 50-300 m ² /g of solid catalyst contained ~10% by weight of titanium. The organometallic compound used as the component [B] is a compound of groups 1 to 10 of the periodic table, and a complex containing an organoaluminum compound and an organomagnesium is particularly preferable. The organoaluminum compound has the general formula AlR ¹⁰ _t Z _3-t (wherein R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms, and Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group). and t is a number from 2 to 3) is used alone or as a mixture. In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by ^R10 includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include, for example,
triethylaluminum, trinormalpropylaluminum, triisopropylaluminum,
tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tridodecyl aluminum, trihexadecyl aluminum, diethylaluminium hydride, diisobutyl aluminum hydride,
Diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum budoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isoprenyl etc., and mixtures thereof are recommended. A highly active catalyst can be obtained by combining these alkylaluminum compounds with the solid catalyst described above, and trialkylaluminum and dialkyl aluminum hydride are particularly preferred because they achieve the highest activity. The 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 the synthesis of the solid catalyst component. Regarding the addition method, the two components may be mixed in advance prior to polymerization, or they may be added separately into the polymerization system. Particularly preferably, an organometallic compound and a carboxylic acid or a derivative thereof are reacted in advance;
It is better to add the organometallic compound separately to the polymerization system. The ratio of both components to be combined is 1 organometallic compound
There is no particular restriction on the mole, but the carboxylic acid or derivative thereof is 10 moles or less, particularly preferably 1 mole.
It can be used in a molar or less range. The catalyst consisting of the solid catalyst component of the present invention and a component obtained by adding a carboxylic acid or a carboxylic acid derivative to an organometallic compound may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. good. The ratio of each component to be combined is the solid catalyst component.
The amount of the organometallic compound plus carboxylic acid or carboxylic acid derivative per 1 g is preferably in the range of 1 mmol to 3000 mmol based on the organometallic compound. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins. In particular, the invention is suitable for the stereoregular polymerization of propylene, 1-butene, 1,4-methylpentene-1,3-methylbutene, and similar olefins alone. It is also suitable for copolymerizing the olefin with ethylene or other olefins, and for efficiently polymerizing ethylene. Furthermore, in order to adjust the molecular weight of the polymer, it is also possible to add hydrogen, halogenated hydrocarbons, or organometallic compounds that tend to undergo chain transfer. As the polymerization method, usual suspension polymerization, bulk polymerization in a liquid monomer, and gas phase polymerization are possible. Suspension polymerization involves using a catalyst in a polymerization solvent such as an aliphatic hydrocarbon such as hexane, heptane, benzene,
Aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into a reactor, and an olefin such as propylene is injected at 1 to 20 kg/cm ² under an inert atmosphere. , the polymerization can be carried out at temperatures from room temperature to 150°C. In the bulk polymerization, olefin 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 olefin. For example, in the case of propylene, polymerization can be carried out in liquid propylene at temperatures from room temperature to 90° C. and under pressures of 10 to 45 Kg/cm ² . On the other hand, gas phase polymerization involves contact between an olefin such as propylene and a catalyst in the absence of a solvent at a pressure of 1 to 50 kg/cm ² and at a temperature of room temperature to 120°C, under conditions where the olefin such as propylene is a gas. For better results, polymerization can be carried out using a fluidized bed, a moving bed, or mixing using a stirrer. The present invention will be explained below using examples. In addition,
The boiling n-heptane extraction residue used in the Examples refers to the residue obtained by extracting a polymer with boiling n-heptane for 6 hours. Example 1 (i) Synthesis of organomagnesium compound 24 g (250 mmol) of anhydrous magnesium chloride and 50 ml of n-heptane were introduced into a 500 ml flask purged with nitrogen, and 1.3N sec-C ₄ H ₉ Li of cyclohexane was added at room temperature with stirring. Add 100ml of solution. After stirring for 30 minutes, the reaction residue was filtered and the magnesium concentration was determined.
A solution of 0.55 mol/l was obtained. [Journal of
According to the method of Organ Chemistry, 34, 1116 (1969). ] Synthesized in this way (sec-
C ₄ H ₉ ) ₂ Heptane solution containing 100 mmol of Mg
50 mmol of n-butanol was added to 180 ml at 10° C. over 30 minutes. Take a portion of this solution,
As a result of analyzing Mg and butoxy groups, the molar ratio was n
_{-C4H9O- /} Mg=0.5. (ii) Synthesis of basic solid Capacity with dropping funnel and water-cooled reflux condenser
Oxygen and moisture inside the 250 ml flask were removed by dry nitrogen substitution, and 1 mol of trichlorosilane (H Si Cl ₃ )/heptane solution was added in a nitrogen atmosphere.
50mol/ was charged and the temperature was raised to 50°C. Next, under a nitrogen atmosphere, 50 m of the above organomagnesium solution was added.
mol was weighed into the dropping funnel. 1 under stirring at 50℃
The mixture was added dropwise over time and further aged at this temperature for 1 hour, resulting in a total reaction of 2 hours. The resulting hydrocarbon-insoluble white precipitate was isolated, washed with hexane and dried to yield a white basic solid. As a result of analyzing this solid, per 1g of solid Mg9.8m mol, Cl.14.6m mol,
Si0.9m mol, alkyl group 0.7m mol, butoxy group
The specific surface area measured by BET method was 205 m ² /g. (iii) Synthesis of catalyst solid 3.0 g of the above white solid was placed in a flask that had been sufficiently purged with nitrogen, and 60 ml of n-hexane and ethyl benzoate were added.
Add 3.0mmol of 0.1mol/hexane solution and add 80
The reaction was allowed to proceed at 1 hour with stirring at 0.degree. C., and the solids were filtered off, thoroughly washed with n-hexane, and dried. 2.5 g of this solid and 50 ml of titanium tetrachloride were placed in a pressure vessel purged with nitrogen, and reacted for 2 hours with stirring at 100°C. The solid was separated by filtration and washed with n-hexane.
After drying, a pale yellow solid catalyst was obtained. Analysis of this solid catalyst revealed that the Ti content was 2.65% by weight. (iv) Slurry polymerization of propylene 50 mg of the solid catalyst synthesized in (iii), 3.0 m mol of triethylaluminum, and 1.0 m of ethyl p-anisate.
mol was placed in a 1.5 mol autoclave with 0.8 mol of dehydrated and deaerated hexane, the interior of which was replaced with nitrogen and vacuum degassed. The internal temperature of the autoclave is 60℃
The propylene was pressurized to a pressure of 5.0 Kg/cm ² and polymerization was carried out for 2 hours while maintaining the total pressure at a gauge pressure of 4.8 Kg/cm ² to form a polymerized hexane-insoluble polymer.
123g and 3.9g of polymerized hexane soluble material were obtained. The catalyst rate is
The pressure was 1230 gpp/g solid catalyst/time, 9280 gpp/g titanium component/time/propylene pressure, and the residue obtained by extracting the polymerized hexane-insoluble polymer with boiling n-heptane was 96.4%. Particle properties also include bulk density
The ratio of powder of 0.362 g/cm ³ and 35 to 150 meshes was 9.2%, which was good. Comparative Example 1 A solid catalyst was synthesized in the same manner as in Example 1 except that methyltrichlorosilicon (SiCl ₃ .CH ₃ ) was used instead of trichlorosilane as a reaction reagent. The yield of the basic solid was about 1/20 compared to (ii) of Example 1. Results of analyzing solid catalyst
It contained 4.6% titanium by weight. Comparative Example 2 A solid catalyst was synthesized in the same manner as in Example 1, using magnesium chloride instead of the solid substance obtained by reacting the organomagnesium compound and chlorosilane in Example 1. 3.0 g of anhydrous MgCl ₂ and 3.0 mmol of ethyl benzoate were reacted, and 2.5 g of the obtained solid was reacted with 50 ml of titanium tetrachloride at 100° C. for 2 hours. Titanium in the solid catalyst was 0.46% by weight. 400mg of this solid catalyst, 3.0m of triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 1.0 mmol of p-ethyl anisate. 42.0 g of polymerized hexane-insoluble polymer and 9.5 g of hexane-soluble material were obtained. The boiling n-heptane extraction residue of the polymerized hexane-insoluble polymer was 81.8%, and the catalyst efficiency was 53 gpp/g solid catalyst/hour and 2280 gpp/g titanium component/time/propylene pressure. Examples 2 to 9 In the same manner as in Example 1, using the organomagnesium compounds _{shown in Table 1 in place of (sec-Bu) 1.5 Mg} (On-Bu) _0.5 in Example ₁ , A solid catalyst was obtained by reacting the organomagnesium compound with trichlorosilane (H Si Cl ₃ ) or monomethyldichlorosilane (HSiCl ₂ .CH ₃ ), ethyl benzoate, and titanium tetrachloride. Solid catalyst 50mg, triethylaluminum 3.0m mol, p-ethyl toluate 1.0m
Polymerization of propylene was carried out in hexane solvent in the same manner as in Example 1 using mol. Table 1 shows catalyst synthesis conditions and polymerization results. Example 10 (sec-Bu _{) 1.5 Mg} (O
_o - B _u ) _0.5 was reacted with trichlorosilane, p-ethyl anisate and _titanium tetrachloride to obtain a pale yellow solid. 4.0g of this solid under nitrogen atmosphere,
9mmφ

【table】

[Table] In a steel mill with an internal volume of 100 ^cm3 containing 25 steel balls.
The material was pulverized for 5 hours using a vibrating ball mill with a speed of 1000 vib/min or more. The Ti content of the obtained solid catalyst was 2.48
Weight% hot. 50mg of this solid catalyst and triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 3.0 mmol of ethyl p-toluate and 1.0 mmol of ethyl p-toluate. The results are shown in Table 2. Example 11 (sec-Bu _{) 1.5 Mg} (O
_o - B _u ) _0.5 was reacted with trichlorosilane, p-ethyl anisate and _titanium tetrachloride to obtain a pale yellow solid. 3.90 g of this solid and titanium trichloride (AA grade TiCl _3.1 /3 manufactured by Toyo Stoffer Co., Ltd.)
0.15 g of AlCl ₃ ) was pulverized for 5 hours in the same manner as in Example 10 under a nitrogen atmosphere. of the obtained solid catalyst
The Ti content was 3.41% by weight. 50mg of this solid catalyst and triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 3.0 mmol of ethyl p-toluate and 1.0 mmol of ethyl p-toluate. The results are shown in Table 2. Example 12 In the same manner as _{in Example 1, (sec-Bu) 0.8 (} n-
_Bu ) _0.8 Mg ₍ On-Bu) _0.4 was reacted with trichlorosilane (HSiCl ₃ ) to synthesize a basic solid, _which was further reacted with ethyl benzoate. 4.0 g of this solid and 0.35 g of titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were pulverized for 5 hours in the same manner as in Example 10 under a nitrogen atmosphere. The Ti content of the obtained solid catalyst was 2.00% by weight. This solid catalyst 50mg triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 3.0 mmol of ethyl p-toluate and 1.0 mmol of ethyl p-toluate. The results are shown in Table 2. Example 13 In the same manner as in Example 12, the basic solid and ethyl benzoate were reacted, and then the obtained solid and titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were pulverized. After reacting 4.0 g of this solid with 60 ml of titanium tetrachloride at 130° C. for 2 hours with stirring, the solid portion was filtered and isolated, thoroughly washed with hexane and dried to obtain a solid catalyst. As a result of analyzing this solid,
It contained 3.55% titanium by weight. 50mg of this solid catalyst and triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 3.0 mmol of ethyl p-toluate and 1.0 mmol of ethyl p-toluate. The results are shown in Table 2. Example 14 In the same manner as in Example 10, the basic solid was reacted with p-ethyl anisate, 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. Further, 4.0 g of this solid and 60 ml of titanium tetrachloride were reacted for 2 hours at 130° C. with stirring, and the solid portion was filtered and isolated, thoroughly washed with hexane and dried to obtain a solid catalyst. Analysis of this solid revealed that it contained 2.81% titanium by weight. 50mg of this solid catalyst and triethylaluminum
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 3.0 mmol of ethyl p-toluate and 1.0 mmol of ethyl p-toluate. The results are shown in Table 2.

[Table] Example 15 350 g of liquefied propylene was placed in a 1.5 autoclave whose interior was purged with nitrogen and vacuum dried, and the internal temperature was maintained at 60°C.
1.5 mmol of triethylaluminum, and 0.5 mmol of ethyl p-toluate were added to an autoclave, and polymerization was carried out at 60° C. for 2 hours to obtain 171 g of polypropylene. The catalyst efficiency was 8,550 gpp/g solid catalyst/hour, 304,000 gpp/g titanium component/hour, and the n-heptane extraction residue of the produced polypropylene was 94.0%. Example 16 A solution prepared by mixing 2.0 mmol of a hexane solution of triethylaluminum (1 mol/) and 1.0 mmol of a hexane solution of p-ethyl toluate (1 mol/) and the solid catalyst 30 synthesized in Example 14
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 1.0 mmol of triethylaluminum and 205 g of polymerized hexane-insoluble polymer and 5.4 g of polymerized hexane-soluble material. The n-heptane extraction residue of the polymerized hexane-insoluble polymer was 95.1%, and the catalyst efficiency was 24,300 gpp/g titanium component, time, and propylene pressure. Examples 17-22 50 mg of solid catalyst synthesized in the same manner as Example 1
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 3.0 mmol of triethylaluminum and 1.0 mmol of the compound shown in Table 3, and the results shown in Table 3 were obtained. Examples 23-24 50 mg of solid catalyst synthesized by the same method as Example 1
Thriller polymerization of propylene was carried out in the same manner as in Example 1 using 1.0 mmol of ethyl benzoate and 3.0 mmol of the organometallic compound shown in Table 4. The results shown in Table 4 were obtained.

【table】

[Table] Example 25 50 mg of solid catalyst synthesized by the same method as Example 1
Propylene containing 2 mol% of ethylene was prepared in the same manner as in Example 1 using 3.0 m mol of triethylaluminum and 1.0 m mol of p-ethyl toluate.
Slurry polymerization was performed using ethylene mixed gas to obtain 138 g of a white polymer.

Claims (1)

[Scope of Claims] 1 [A] (1) (i) An organomagnesium compound soluble in a hydrocarbon medium represented by the general formula Mg R′u R″v Xw (wherein R′ and R″ are hydrocarbon represents a group, 0<u≦2, 0≦v≦2 and 0
<w≦1 and R′ has 4 to 4 carbon atoms
6, or 0<u≦2, 0<v≦2, and 0<w≦1, and R′ and R″ are mutually exclusive in number of carbon atoms. are different alkyl groups, or 0<u≦2, 0<v≦2, and 0<w≦1, and R′ has 6 carbon atoms.
The above hydrocarbon group, X is a negative group containing O, N, or S atom,
u, v, and w have a relationship of u+v+w=2. ), (ii) general formula H _a SiCl _b R _4-(a+b) (where a, b
is a number greater than 0, a+b≦4, and R represents a hydrocarbon group. ) denoted by Si-H
A solid obtained by reacting with a bond-containing chlorosilane compound. (2) Titanium compounds containing at least one halogen atom. (3) Carboxylic acids or their derivatives. A catalyst for olefin polymerization comprising a solid catalyst component obtained by reacting and/or pulverizing (1), (2), and (3), and [B] a component obtained by adding a carboxylic acid or a derivative thereof to an organometallic compound. 2 [A] A patent claim in which in the organic magnesium compound soluble in a hydrocarbon medium (i), at least one of R' and R'' both having 4 to 6 carbon atoms is a secondary or tertiary alkyl group. Catalyst for olefin polymerization according to item 1. 3 [A] In the organomagnesium compound soluble in the hydrocarbon medium of (i), R' has 2 or 3 carbon atoms.
The catalyst for olefin polymerization according to claim 1, wherein the alkyl group R'' is an alkyl group having 4 or more carbon atoms. 4 [A] In the organomagnesium compound soluble in a hydrocarbon medium of (i), The catalyst for olefin polymerization according to claim 1, wherein R' and R'' are both alkyl groups having 6 or more carbon atoms. 5 [A] In the organic magnesium compound soluble in a hydrocarbon medium (i), X is alkoxy, siloxy, allyloxy, amino, amide,
[Formula]-SR〓where R, R〓, R〓 are hydrocarbon groups), β-keto acid residues, and the value of w is 0<w≦0.8 Claims 1 to 4 2. The catalyst for olefin polymerization according to any one of the above. 6. The catalyst for olefin polymerization according to claim 5, wherein X is an alkoxy or siloxy group. 7. The catalyst for olefin polymerization according to any one of claims 1 to 6, wherein in the Si-H bond-containing chlorosilane compound [A], the value of a is 0<a<2. 8 [A] The titanium compound in (2) is a tetravalent titanium compound containing at least one halogen atom, and (1), (2) and (3) are reacted or reacted and pulverized. The catalyst for olefin polymerization according to any one of claims 1 to 7, which synthesizes a solid catalyst component by. 9 [A] The titanium compound in (2) is a trivalent titanium halide, and (1), (2) and (3) are co-milled, or (1) and (3) are reacted. The solid catalyst component is synthesized by pulverizing the solid obtained by grinding (2) or by treating the solid obtained by co-pulverizing (1) and (2) with (3). The catalyst for olefin polymerization according to any one of items 1 to 7. 10 [A] The titanium compound of (2) is (a) at least 1
a titanium compound containing halogen atoms, and (b) a trivalent titanium halide,
The catalyst for olefin polymerization according to any one of claims 1 to 7, wherein a solid catalyst component is synthesized by pulverizing or pulverizing and reacting (1), (2), and (3). 11. The catalyst for olefin polymerization according to any one of claims 1 to 10, wherein the titanium compound in [A](2) is titanium tetrachloride and/or titanium trichloride. 12. The olefin according to any one of claims 1 to 11, wherein the carboxylic acid or derivative thereof in [A](3) and [B] is a carboxylic acid, an acid anhydride, or a carboxylic acid ester. Polymerization catalyst. 13 [A] The amount of carboxylic acid or carboxylic acid derivative used in (3) is the same as that of the organomagnesium compound in (1).
The number of moles of alkyl groups contained in the solid obtained by reacting Si--H bond-containing chlorosilane compounds.
The catalyst for olefin polymerization according to any one of claims 1 to 12, wherein the number of moles is 0.001 to 50 times the amount. 14 The organometallic compound [B] has the general formula
AlR ¹⁰ tZ _3-t (wherein, R ¹⁰ is a C _1-20 hydrocarbon group, Z
is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy, and t is 2≦
Claims 1 to 13 are organoaluminum compounds represented by t≦3.
2. The catalyst for olefin polymerization according to any one of the above. 15. The catalyst for olefin polymerization according to claim 14, wherein the organoaluminum compound is trialkylaluminum or dialkylaluminum hydride. 16 [A] (1) (i) General formula Mg R′u R″v Xw
An organomagnesium compound soluble in a hydrocarbon medium represented by
and 0<w≦1, and R' is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, or 0<u≦2, 0<v≦
2, and 0<w≦1, and R′ and R″ are alkyl groups having different numbers of carbon atoms, or 0<u≦2, 0<v≦2,
and 0<w≦1, R′ is a hydrocarbon group having 6 or more carbon atoms, and X is O,
It is a negative group containing N or S atom, and u, v, and w have the relationship of u+v+w=2. ), (ii) general formula H _a SiCl _b R _4-(a+b) (where a, b
is a number greater than 0, a+b≦4, and R represents a hydrocarbon group. ) denoted by Si—H
A solid obtained by reacting with a bond-containing chlorosilane compound. (2) Titanium compounds containing at least one halogen atom. (3) Carboxylic acids or their derivatives. A solid catalyst component obtained by reacting and/or pulverizing (1), (2), and (3) and then further treating with a tetravalent titanium compound (4) containing at least one halogen atom. and [B] a component obtained by adding a carboxylic acid or a derivative thereof to an organometallic compound, an olefin polymerization catalyst comprising: 17 [A] A patent in which R' and R'' both have 4 to 6 carbon atoms and at least one is a secondary or tertiary alkyl group in the organomagnesium compound soluble in a hydrocarbon medium (i) The catalyst for olefin polymerization according to claim 16. 18 [A] In the hydrocarbon medium-soluble organomagnesium compound of (i), R' is an alkyl group having 2 or 3 carbon atoms, and R'' is an alkyl group having a carbon number of 17. The catalyst for olefin polymerization according to claim 16, which has 4 or more Aruryl groups. 19 [A] The catalyst for olefin polymerization according to claim 16, wherein in the organomagnesium compound soluble in a hydrocarbon medium (i), R' and R'' are both alkyl groups having 6 or more carbon atoms. 20 [A] In the organic magnesium compound soluble in a hydrocarbon medium (i), X is alkoxy, siloxy, allyloxy, amino, amide,
[Formula] -SR〓 (where R, R〓, R〓 are hydrocarbon groups), β-keto acid residue, w
Claim 16 in which the value of is 0<w≦0.8
The catalyst for olefin polymerization according to any one of items 1 to 19. 21. The catalyst for olefin polymerization according to claim 20, wherein X is an alkoxy or siloxy group. 22. The catalyst for olefin polymerization according to any one of claims 16 to 21, wherein in the Si--H bond-containing chlorosilane compound [A], the value of a is 0<a≦2. 23 [A] The titanium compound in (2) is a tetravalent titanium compound containing at least one halogen atom, and the titanium compound in (2) is a tetravalent titanium compound containing at least one halogen atom, and by reacting or reacting and pulverizing (1), (2) and (3), The catalyst for olefin polymerization according to any one of claims 16 to 22, which synthesizes a solid catalyst component. 24 [A] The titanium compound in (2) is a trivalent titanium halide, and (1), (2) and (3) are co-pulverized, or (1) and (3) are reacted. The solid catalyst component is synthesized by pulverizing the solid obtained by grinding (2) or by treating the solid obtained by co-pulverizing (1) and (2) with (3). The catalyst for olefin polymerization according to any one of Items 16 to 22. 25 [A] The titanium compound of (2) is (1) at least 1
a titanium compound containing halogen atoms, and (b) a trivalent titanium halide,
The catalyst for olefin polymerization according to any one of claims 16 to 22, wherein a solid catalyst component is synthesized by pulverizing or pulverizing and reacting (1), (2), and (3). 26. The catalyst for olefin polymerization according to any one of claims 16 to 25, wherein the tetravalent titanium compound containing at least one halogen atom in [A](4) is titanium tetrachloride. 27. The catalyst for olefin polymerization according to any one of claims 16 to 26, wherein the titanium compound in [A](2) is titanium tetrachloride and/or titanium trichloride. 28. For olefin polymerization according to any one of claims 16 to 27, wherein the carboxylic acid or derivative thereof in [A](3) and [B] is a carboxylic acid, an acid anhydride, or a carboxylic acid ester. catalyst. 29 [A] The amount of the carboxylic acid or carboxylic acid derivative in (3) is the same as that of the organomagnesium compound in (1).
The number of moles of alkyl groups contained in the solid obtained by reacting Si--H bond-containing chlorosilane compounds.
The catalyst for olefin polymerization according to any one of claims 16 to 28, wherein the number of moles is 0.001 to 50 times the amount. 30 The organometallic compound [B] has the general formula
AlR ¹⁰ tZ _3-t (wherein, R ¹⁰ is a C _1-20 hydrocarbon group, Z
is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy, and t is 2≦
Claims 16 to 2 are organoaluminum compounds represented by t≦3.
The catalyst for olefin polymerization according to any one of Item 9. 31. The catalyst for olefin polymerization according to claim 30, wherein the organoaluminum compound is trialkylaluminum or dialkylaluminum hydride.