JPS64971B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides ethylene or ethylene and other α
- It relates to a catalyst used in the polymerization of olefins. More specifically, a solid component (A) in which a reaction product of a specific chromium component, zirconium component, and aluminum component is supported on an inorganic oxide and fired;
The present invention relates to a novel and highly active catalyst for ethylene polymerization or ethylene-α-olefin copolymerization that is combined with a component (B) containing a specific organomagnesium. An ethylene polymerization catalyst obtained by supporting a chromium compound such as chromium oxide on an inorganic oxide support such as silica or silica-alumina and firing it is
It is widely known as a so-called Phillips type catalyst. However, when using this catalyst, the activity of the catalyst and the average molecular weight of the polymer greatly depend on the polymerization temperature, and commercially suitable polymers with molecular weights of tens of thousands to hundreds of thousands can be produced with sufficient catalytic activity. In order to achieve this, it was generally necessary to set the polymerization temperature to 100 to 200°C.
When polymerization is carried out in such a temperature range, the resulting polymer is dissolved in the reaction solvent, so
The viscosity of the reaction system increases significantly, resulting in
It was difficult to increase the concentration of the produced polymer above 20%. Therefore, there has been a strong demand for the development of a catalyst that exhibits high catalytic activity at a polymerization temperature of 100° C. or lower, at which polymerization becomes so-called slurry polymerization.
In addition, in order to reduce production costs,
It is important to be able to omit the catalyst removal step in the post-polymerization process, and for this purpose there is a need to develop catalysts that exhibit even higher activity. In the past, in order to improve the polymerization activity of this Phillips-type chromium-based catalyst, many catalyst systems combining organoaluminum compounds, organozinc compounds, etc. have been proposed (for example, Japanese Patent Publication No. 36-22144, Japanese Patent Publication No. 43-27415). No., Special Publication No. 1972-23668, Special Publication No. 1977-
34759 etc.). Further, a system has been proposed in which a reaction product of a chromium-1,3 diketo compound and an organometallic compound is supported as a solid component (for example, JP-A-53-1277). However, there is still a strong demand for improved catalyst activity, and there has been a strong desire to further improve the activity. As a result of various studies from the above point of view, the present inventors have developed a solid in which a reaction product of a specific chromium component, zirconium component, and aluminum component is supported on a carrier such as silica and activated by firing, and a specific organic magnesium component. The catalyst combined with the compound is 100
We have discovered that it is possible to easily produce a polymer that exhibits extremely high catalytic activity not only at temperatures above 100°C but also at low temperatures below 100°C, has a molecular weight that is easily molded, and has a wide molecular weight distribution, and has thus arrived at the present invention. That is, the present invention provides (A) (1-) general formula Cr(OCR′CR″CRO) ₃ (wherein R′ and R are the same or different alkyl groups having 1 to 10 carbon atoms; R″ is a chromium-1,3-diketo compound represented by (representing a hydrogen atom or an alkyl group having 1 to 10 carbon atoms);
-) a zirconium tetraalkoxide represented by the general formula Zr(OR) ₄ (in the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms) and (1-) an organoaluminum compound containing no halogen atom. reaction products in an inert hydrocarbon medium,
(2) A solid component supported on an inorganic oxide carrier and fired, and (B) an inert hydrocarbon-soluble organomagnesium complex represented by the general formula M〓Mg〓R ¹ _p R ² _q R ³ _r X _s Y _t Compound (where α, β are numbers greater than 0, p, q, r,
s, t are 0 or greater than 0, and 0<(s+
t)/(α+β)≦1.5 and p+q+r+s+t
= mα + 2β, where M is Al, Zn, B,
Atom selected from the group consisting of Be, Li, m is M
R ¹ , R ² , R ³ are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X and Y are the same or different OR ⁴ , OSiR ⁵ R ⁶ R ⁷ , NR ⁸ R ⁹ and represents a group selected from SR ¹⁰ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ are hydrogen atoms or hydrocarbon groups,
R ⁴ and R ¹⁰ each represent a hydrocarbon group). The catalyst of the present invention, which is a combination of a solid obtained by supporting a reaction product of a specific chromium component, a zirconium component, and an aluminum component on a carrier such as silica and activated by firing, and a specific organomagnesium compound, can be used in the following Examples and As is clear from the comparative example,
The catalytic activity is several times higher than that of a catalyst containing no zirconium component or a catalyst in combination with organic aluminum or the like that has been proposed in the past, and the activity is significantly improved. This is a surprising effect. Furthermore, compared to a catalyst combination with a dialkylmagnesium complex compound containing no alkoxy group or siloxy group, the catalyst combination with a specific organomagnesium complex compound containing an alkoxy group or siloxy group of the present invention is This produces a polymer with a high average molecular weight that is easy to mold and process. In particular, it is preferable to contain a siloxy group. This polymer has a sufficiently broad molecular weight distribution for hollow molding. Also, the so-called
Compared to the Grignard type compound ether solution, the alkoxy or siloxy organomagnesium complex hydrocarbon solution used in the present invention exhibits much higher activity. In the catalyst system of the invention containing a zirconium component, the effect is particularly remarkable. Further, the solid component of the catalyst of the present invention belongs to a so-called non-aqueous chromium catalyst that supports a chromium compound and a zirconium compound using a hydrocarbon solvent without using water. Normal chromium catalyst solid components use water to support chromium compounds, but when water is distilled off,
In order to save drying time and reduce the influence of residual moisture during firing, it is desirable to use a non-aqueous type. In this sense as well, it can be said that it is very suitable that the solid component of the catalyst of the present invention is supported in a non-aqueous system. The present invention will be explained in detail below. As the inorganic oxide carrier used in the present invention, silica, alumina, silica-alumina, thoria, zirconia, etc. can be used, but silica and silica-alumina are preferable, and silica is particularly preferable. Examples of the chromium-1,3-diketo compound used in the present invention (1-) include chromium () acetylacetonate, chromium ()hexane-2,4-dionate, chromium ()octane-3,5-dionate, etc. However, chromium () acetylacetonate is particularly preferably used. As the zirconium tetraalkoxide used in the present invention (1-), various alkoxides can be used, preferably zirconium tetra n-propoxide or zirconium tetra n-butoxide, with the latter being particularly preferably used. Examples of the organic aluminum compound containing no halogen atom used in the present invention (1-) include various trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum alkoxides, dialkylaluminum siloxides, etc., such as triethylaluminum, triisobutylaluminum, trinium -Hexylaluminum, tridecylaluminum, diethylaluminum hydride, diethylaluminum ethoxide, methylethylhydrosiloxyaluminum diethyl, aluminum isoprenyl, and the like. Preferred are trialkyl aluminum and dialkyl aluminum hydride, with the former being particularly preferred. Next, we will explain how to react (1-), (1-), and (1-) to create a hydrocarbon solution containing chromium and zirconium, and then support chromium and zirconium on an inorganic oxide support. . (1-) chromium-1,3-diketo compound (generally insoluble in hydrocarbons), (1-) zirconium tetraalkoxide, and (1-) halogen-free organic aluminum compound are mixed and reacted. , the solubility of (1-) in hydrocarbons increases and a homogeneous solution is produced. Although there is no restriction on the order of the reaction, it is preferable that (1-) a chromium compound [preferably chromium () acetylacetonate] and (1-) a halogen-free organic aluminum compound (preferably a trialkylaluminum, e.g. triisobutylaluminum)
are first mixed and stirred, and then (1-) zirconium tetraalkoxide (preferably zirconium tetra n-butoxide) is added to create a homogeneous solution. There are no particular restrictions on the temperature and time of the mixing reaction; for example, it is sufficient to carry out the reaction at room temperature or higher for several tens of minutes or longer. Hydrocarbon media used in the reaction include hexane, heptane,
Aliphatic hydrocarbons such as isooctane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane,
Examples include aromatic hydrocarbons such as benzene and toluene, but aliphatic hydrocarbons or alicyclic hydrocarbons are preferably used. There is no particular restriction on the molar ratio of the reaction, but preferably the molar ratio of Zr/Cr is 0.2 to 10, particularly preferably 0.4 to 3,
[(1-)Al]/(Cr+Zr) molar ratio is 0.1~
10, particularly preferably in the range of 0.25 to 2.5. The hydrocarbon solution containing chromium and zirconium prepared in this manner is mixed with an inorganic oxide support such as silica or silica-alumina to be supported.
At this time, it is preferable to support the particles while stirring. There are no particular restrictions on the temperature, time, etc. for supporting, and the solvent is removed by filtration or distillation. If most of the chromium and zirconium compounds are deposited directly from the solution onto the support, most of the color of the solution will be transferred to the support. If direct adhesion is not possible, the solvent can be removed by distillation to allow chromium and zirconium to be adhered and supported. Regarding the amount of chromium and zirconium to be supported, the chromium content in the solid after being supported is 0.02 to 2.5% by weight, especially
It is preferably in the range of 0.05 to 1.5% by weight.
Note that it is preferable that silica, silica-alumina, etc. used as a carrier be heated and dried in advance, for example, under a nitrogen stream. Next, firing activation of the supported solid will be explained. Firing activation is generally performed in the presence of oxygen, but it can also be performed in the presence of an inert gas or under reduced pressure. Preferably, air substantially free of moisture is used. Firing temperature is over 300℃,
It is preferably carried out at a temperature range of 400 to 900°C for several minutes to several tens of hours, preferably 30 minutes to 10 hours. During firing, it is recommended to blow in sufficient dry air and activate firing under a fluidized state. Of course, it is also possible to use a known method of adjusting activity, molecular weight, etc. by adding titanates, fluorine-containing salts, etc. during the supporting or firing process. Next, the general formula M〓Mg〓R ¹ _p R ² _q used in the present invention
The inert hydrocarbon soluble organomagnesium complex compound represented by R ³ _{r X s} Y _t will be explained. In the above formula, M is an atom selected from the group consisting of Al, Zn, B, Be, and Li, preferably Al, Zn
Or B, particularly preferably Al.
In the above formula, the hydrocarbon group represented by R ¹ , R ² , and R ³ is an alkyl group, a cycloalkyl group, or an aryl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, Examples include dodecyl, dichlorohexyl, phenyl groups, and alkyl groups are preferably used. The ratio β/α of Mg to M is particularly important;
It is preferably 0.5 or more, particularly 1 or more. The polar group represented by X and Y is an alkoxy group, a siloxy group, an amino group or a sulfide group,
Preferred is an alkoxy group or siloxy group, particularly preferred is a siloxy group. Ratio of polar groups to metal atoms (s+t)/(α
+β) is also important and is preferably 1 or less, particularly preferably 0.8 or less. The above-mentioned inert hydrocarbon soluble organomagnesium complex compound is synthesized in accordance with the published publications and publications of the present applicants [for example, JP-A-50-150786, JP-A-50 -154388, JP-A-50-157490, JP-A-51-97687, JP-A-Sho
No. 51-107384, JP-A-52-71421, JP-A-53-
40696 etc.]. Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Cyclic hydrocarbons are preferred. Next, a method of combining a solid catalyst component (ie, a chromium- and zirconium-containing solid supported on a carrier and activated by calcination) and an organomagnesium component will be described. The solid catalyst component and the organomagnesium component may be added into the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. It is also possible to use a method in which the solid catalyst component is previously treated with the organomagnesium component and then further combined with the organomagnesium component and fed into the polymerization system. The ratio of both components to be combined is (organometallic)/
A range of Cr from 0.01 to 3000, preferably from 0.1 to 100 is recommended. Next, a method for polymerizing olefin using the catalyst of the present invention will be explained. Olefins which can be polymerized using the catalysts of the invention are alpha-olefins, especially ethylene. Furthermore, the catalyst of the present invention can also be used for copolymerization of ethylene with monoolefins such as propylene, butene-1, hexene-1, etc., or for polymerization in the coexistence of dienes such as butadiene, isoprene, etc. By carrying out copolymerization using the catalyst of the present invention, it is possible to produce a polymer having a density in the range of 0.91 to 0.97 g/cm ³ . As the polymerization method, usual suspension polymerization, solution polymerization, and gas phase polymerization are possible. In the case of suspension polymerization or solution polymerization, the catalyst is a polymerization solvent such as propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into the reactor under an inert atmosphere. By pressurizing ethylene at 1 to 200 kg/cm ² to the bottom, polymerization can be carried out at a temperature of room temperature to 320°C. On the other hand, in gas phase polymerization, ethylene is heated at room temperature or at a pressure of 1 to 50 kg/ ^cm2 .
Polymerization can be carried out at a temperature of 120° C. by using means such as a fluidized bed, moving bed, or stirring to achieve good contact between ethylene and the catalyst. The catalyst of the present invention has high performance, 80℃, 10Kg/cm ²
It shows sufficiently high activity even under relatively low temperature and low pressure polymerization conditions. In this case, since the produced polymer exists in the polymerization system in a slurry state, the increase in viscosity of the polymerization system is extremely small. Therefore,
The polymer concentration in the polymerization system can be increased to 30% or more, which has great advantages such as improved production efficiency. Furthermore, due to its high activity, the step of removing catalyst residue from the produced polymer can be omitted. The polymerization may be carried out in a conventional one-stage polymerization using one reaction zone, or using multiple reaction zones.
It may also be carried out by so-called multi-stage polymerization. The polymer polymerized using the catalyst of the present invention has a wide molecular weight distribution even in ordinary one-stage polymerization, has a relatively high molecular weight, and is extremely suitable for blow molding and film molding applications. Multi-stage polymerization in which polymerization is carried out under two or more different reaction conditions makes it possible to produce polymers with a wider molecular weight distribution. In order to adjust the molecular weight of the polymer, it is of course possible to use known techniques such as adjusting the polymerization temperature, adding hydrogen to the polymerization system, or adding an organometallic compound that tends to cause chain transfer. Furthermore, it is also possible to perform polymerization by combining methods such as adding a titanate ester to control density and molecular weight. Examples of the present invention will be shown below, but the present invention is not limited to these Examples in any way. In addition, the catalytic activity in the examples refers to the monomer pressure.
At 10 kg/cm ² , it represents the amount of polymer produced (g) per 1 g of catalyst solid component/1 hour. Also, MI
stands for melt index, ASTM D-
1238, measured at a temperature of 190°C and a load of 2.16 kg. FR has a temperature of 190℃ and a load of 21.6Kg.
It is the quotient obtained by dividing the value measured by MI by MI, and is known to those skilled in the art as an index representing the breadth of molecular weight distribution. Example 1 (1) Synthesis of solid component (A) 1 The inside of a flask equipped with a stirrer, reflux condenser and dropping funnel was replaced with dry nitrogen, and 500 ml of dehydrated and degassed hexane and chromium () were placed in the flask.
604 mg (1.73 mmol) of acetylacetonate was charged. This suspension was heated to 60°C, and triisobutylaluminum was added through the dropping funnel while stirring.
Drop 0.1mol/34.6ml (3.46mmol) of solution,
Stir for 30 minutes. Next, from the dropping funnel, 0.1 mol of zirconium tetra-n-butoxide/19.8 ml of solution was added.
(1.98 mmol) was added dropwise and stirred for 1 hour.
Heating was stopped and the flask was allowed to return to room temperature. A green solution containing chromium and zirconium was thus obtained. The inside of another flask was replaced with dry nitrogen,
Silica gel (Fuji Davison grade) pre-dried for 5 hours under dry nitrogen flow at 500℃
952) and 400 ml of dehydrated and degassed hexane were charged, and the entire amount of the above chromium-zirconium solution was added dropwise at room temperature while stirring, and the mixture was stirred for 1 hour. A phenomenon was observed in which the color of the liquid phase was transferred to the carrier (the color of the liquid phase became lighter and the carrier became green).
Next, the hexane solvent was removed by distillation, followed by vacuum drying at 60° C. for 5 hours to obtain a chromium-zirconium supported solid. Next, this supported solid is placed in a quartz firing tube,
The mixture was calcined at 800° C. for 5 hours under dry air circulation to obtain a catalyst solid component (A). The obtained solid component (A) contained 0.3% by weight of chromium and 0.6% by weight of zirconium (Zr/Cr=1.14 in molar ratio), and was stored at room temperature under a nitrogen atmosphere. (2) Synthesis of organomagnesium component (B) 13.80 g of di-n-butylmagnesium, composition Al
(C ₂ H ₅ ) _1.5 (OSi・H・CH ₃・C ₂ H ₅ ) _1.5 and 6.81 g of an organoaluminum compound were placed in a 500 ml flask with 200 ml of n-heptane and reacted at 80°C for 2 hours. , composition AlMg _3.0 (C ₂ H ₅ ) _1.5
A siloxy-containing organomagnesium complex _{solution of} (n _{- C4H9} ) _6.0 ( _{OSi.H.CH3.C2H5} ) _1.5 was synthesized. (3) Polymerization 20mg of the solid component (A) synthesized in (1) and 0.1ml of the siloxy-containing organomagnesium complex solution synthesized in (2)
mol [0.1 mmol as organometallic (Mg + Al)] was placed in a 1.5 autoclave whose interior was vacuum degassed and replaced with nitrogen, along with 0.8 mole of dehydrated and deoxygenated hexane. The internal temperature of the autoclave was maintained at 80°C, ethylene was added at 10 kg/cm ³ , and hydrogen was added to bring the total pressure to 14 kg/cm ² . Polymerization was carried out for 2 hours while maintaining the total pressure at 14 kg/cm ² by replenishing ethylene to obtain 210 g of polymer. Catalytic activity is
5250g polymer/gSolid・hr, polymer MI is
0.25, FR was 125. Comparative Example A The same procedure as in Example 1 was carried out except that the use of zirconium tetra-n-butoxide in Example 1 was omitted. Polymerization results show a polymer yield of 104g.
Catalyst activity 2600g/gSolid・hr, MI0.30, FR120
It was hot. Comparative example B 0.1 m of organomagnesium complex in Example 1
The same procedure as in Example 1 was repeated except that 0.1 mmol of triethylaluminum was used instead of mol. Polymerization results show polymer yield of 40g and catalyst activity of 1000.
g/gSolid・hr, MI0.32, and FR132. Comparative Example C n-butylmagnesium chloride (di-n-butyl ether solution) was used instead of 0.1 mmol of the organomagnesium complex (heptane solution) in Example 1.
Everything was carried out in the same manner as in Example 1, except that 0.1 mmol was used. The polymerization results were a polymer yield of 30 g, a catalyst activity of 750 g/g Solid·hr, and an MI of less than 0.01. Examples 2 to 11 The zirconium component, aluminum component, and organomagnesium complex component in Example 1 were changed to the conditions shown in Table 1, and the other conditions were the same as in Example 1. The results are shown in Table 1.

【table】

[Table] Example 12 13.80 g of di-n-butylmagnesium and 2.85 g of triethylaluminum were placed in a 500 ml flask with 200 ml of n-heptane and reacted at 80°C for 2 hours, resulting in a composition of AlMg ₄ (C ₂ H ₅ ) ₃ (n
−C ₄ H ₉ ) ₈ organomagnesium complex solution 125 mmol
[125 mmol as organic metal (Mg+Al)] was synthesized. Next, methylhydropolysiloxane with a viscosity of 50 centistokes at 30°C was added to this solution.
By adding 125 mmol as standard and reacting at 80℃ for 2 hours, the composition AlMg ₄ (C ₂ H ₅ ) _1.64 (n-C ₄ H ₉ ) was obtained.
_4.36 (OSi・H・CH ₃・C ₂ H ₅ ) _1.36 (OSi・H・
A siloxy-containing organomagnesium complex solution _{of CH3.n} - _C4H9 ) _3.64 was synthesized. Polymerization was carried out in the same manner as in Example 1 except that this siloxy-containing organomagnesium complex solution was used as the organomagnesium component. Polymerization result is polymer yield
200g, catalyst activity 5000g/gSolid・hr, MI0.22,
It was FR128. Example 13 Using a mixed gas of ethylene and butene-1 containing 15 mol% of butene-1 instead of ethylene,
Using isobutane as a polymerization solvent instead of hexane, mixed gas partial pressure 10Kg/cm ² and hydrogen partial pressure 1 at 80℃.
Polymerization was carried out in the same manner as in Example ¹ except that the total pressure including the solvent vapor pressure was 23 Kg/cm ² and the catalyst of Example 1 was used in other respects. Polymerization results show polymer yield of 202g,
Catalytic activity was 5050 g/g Solid·hr, MI 0.47, and polymer density 0.923.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing a catalyst in the present invention.

Claims (1)

[Claims] 1 (A) (1-) General formula Cr (OCR′CR″CRO)
Chromium-1,3 represented by ₃ (wherein R' and R are the same or different alkyl groups having 1 to 10 carbon atoms, and R'' represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) -diketo compound, (1
-) Zirconium tetraalkoxide represented by the general formula Zr(OR) ₄ (in the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms) and (1-) an organoaluminum compound containing no halogen atom. The reaction product in an inert hydrocarbon medium, (2)
A solid component supported on ^an inorganic oxide carrier ^and calcined _, and _{( B} ) an inert hydrocarbon ^- soluble organomagnesium _complex compound ₍ formula medium, α, β are numbers greater than 0, p, q, r,
s, t are 0 or greater than 0, and 0<(s+
t)/(α+β)≦1.5 and p+q+r+s+t
= mα + 2β, where M is Al, Zn, B,
Atom selected from the group consisting of Be, Li, m is M
valence, R ¹ , R ² , R ³ are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X, Y are the same or different OR ⁴ , OSiR ⁵ R ⁶ R ⁷ , NR ⁸ R ⁹ and represents a group selected from SR ¹⁰ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ are hydrogen atoms or hydrocarbon groups,
R ⁴ and R ¹⁰ represent hydrocarbon groups) A catalyst for ethylene polymerization or ethylene-α-olefin copolymerization. 2. The catalyst according to claim 1, wherein the inorganic oxide support is selected from the group consisting of silica, silica-alumina, and alumina. 3 In the chromium-1,3-diketo compound,
The catalyst according to claim 1 or 2, wherein R'' is a hydrogen atom. 4. The catalyst according to claims 1 to 3, wherein the chromium-1,3-diketo compound is chromium () acetylacetonate. The catalyst according to any one of Items 5. In the zirconium tetraalkoxide,
5. The catalyst according to claim 1, wherein R has 3 or 4 carbon atoms. 6. The catalyst according to any one of claims 1 to 5, wherein the zirconium tetraalkoxide is zirconium tetra n-butoxide. 7. The catalyst according to any one of claims 1 to 6, wherein the halogen-free organoaluminum compound is trialkylaluminum or dialkylaluminum hydride. 8. The catalyst according to any one of claims 1 to 7, wherein the Zr/Cr molar ratio is 0.2 to 10. 9. The catalyst according to any one of claims 1 to 7, wherein the Zr/Cr molar ratio is 0.4 to 3. 10. The catalyst according to any one of claims 1 to 9, wherein the molar ratio of [(1-) Al]/(Cr+Zr) is 0.1 to 10. 11. The catalyst according to any one of claims 1 to 9, wherein the molar ratio of [(1-) Al]/(Cr+Zr) is 0.25 to 2.5. 12 In the organomagnesium complex compound of (B),
12. The catalyst according to claim 1, wherein M is selected from the group consisting of Al, Zn, and B. In the organomagnesium complex compound of 13 (B),
Claims 1 to 1 in which M is Al
Catalyst according to any one of Item 1. In the organomagnesium complex compound of 14 (B),
The catalyst according to any one of claims 1 to 13, wherein β/α≧0.5. In the organomagnesium complex compound of 15 (B),
The catalyst according to any one of claims 1 to 13, wherein β/α≧1. In the organomagnesium complex compound of 16 (B),
The catalyst according to any one of claims 1 to 15, wherein X and Y are OR ⁴ or OSiR ⁵ R ⁶ R ⁷ . In the organomagnesium complex compound of 17 (B),
The catalyst according to any one of claims 1 to 16, wherein S>0 and X is OSiR ⁵ R ⁶ R ⁷ . In the organomagnesium complex compound of 18 (B),
The catalyst according to any one of claims 1 to 17, wherein 0<(s+t)/(α+β)≦1. In the organomagnesium complex compound of 19 (B),
The catalyst according to any one of claims 1 to 17, wherein 0<(s+t)/(α+β)≦0.8.