JPS584723B2 - α-olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel highly active α-olefin polymerization catalyst.

A low-pressure production method for polyethylene using a catalyst consisting of an organomagnesium compound and a transition metal compound is described by AK. It is already known in Ziegler's patent (Japanese Patent Publication No. 32-1
No. 546).

However, organomagnesium compounds themselves are not effectively used because they are insoluble in the inert hydrocarbon medium used for catalyst synthesis and polymerization reactions, and have not been effective in obtaining high activity.

As catalysts whose activity is enhanced by using organomagnesium compounds in specific forms, systems using organomagnesium halides, so-called Grignard test complexes with ethers, or organomagnesium alkoxides are known. No. 47-40959, Japanese Unexamined Patent Publication No. 46-19274).

Although these catalysts have fairly high activity per transition metal atom, they are still insufficient in terms of residual halogens as catalysts capable of completely omitting the catalyst removal step in the polyethylene manufacturing process.

As a result of research on catalyst systems using organomagnesium, the present inventors discovered that a specific solid obtained by reacting an organomagnesium compound soluble in an inert hydrocarbon medium with a titanium or vanadium compound and an organometallic compound. Due to the reaction,
The present inventors have discovered that an extremely excellent and highly active catalyst for α-olefin polymerization can be obtained, leading to the present invention.

That is, the present invention provides (1) general formula MgR1pH2qX,
・D, (AR1, R2 may be the same or different, a hydrocarbon group with a carbon atom number of 6 or more, X is a negative group containing 0AN or S atom, D is Al.Be,B
, Zn, Sit or Li, p,
q is O~2, r is 0~1 with the relationship p+q+r=2, and S is a number of 0.005≦S<0.1). A(■
) A solid catalyst obtained by reacting with a titanium or vanadium compound containing at least one halogen atom, or this solid catalyst is further combined with (V) an organic or inorganic aluminum, silicon, antimony compound and/or (V) A solid catalyst obtained by reacting with a titanium or vanadium compound containing at least one halogen atom;
-Olefin polymerization catalyst, and an α-olefin polymerization catalyst comprising the polymerization catalyst and a halogenated hydrocarbon.

The first feature of the present invention is that the catalyst efficiency is extremely high.

Therefore, there are few catalyst residues such as transition metals and halogens remaining in the polymer, making it suitable as a catalyst for use in processes that omit the catalyst removal step.

The second feature of the present invention is that the particle size of the polymer is uniform,
It does not contain coarse particles that would interfere with continuous polymerization, and has extremely excellent particle properties such as high bulk density.

The third feature of the present invention is that it is possible to produce a polymer with high molecular weight, high rigidity, narrow molecular weight distribution, and high impact strength.

Furthermore, by using, as the solid catalyst, a reaction product between the solid catalyst and an organic or inorganic aluminum, silicon, tin, antimony compound, and/or a titanium or vanadium compound containing at least one halogen atom. , a polymer with a relatively wide molecular weight distribution and suitable for film and sheet molding can be obtained.

Furthermore, by combining halogenated hydrocarbons, it may be possible to produce polymers that have a wide molecular weight distribution and are suitable for blow molding using an extruder and for film and sheet molding.

The various components used in the catalyst of the present invention will be explained in detail below.

Organomagnesium compounds used in the synthesis of solid catalysts [
Component (I)] is represented by the general formula M2RbR or Xr-Ds (wherein R', R2, X, D, p, q, r, and s have the above-mentioned meanings).

In the above formula, Rl and R2 are hydrocarbon groups having 6 or more carbon atoms, and specifically, n C6H13, (
C2H5)2CHCH2-, n-C7H15, F-℃7
H15, n-CgH17, t-C3H17, (C6H1
3) E(C2H5)”He%, n-CgH1g, i-C
gH1g, (C7H15)・(CH2)・HC−, (C
4H,)2HC-, n-C10H21, n C11H2
3, nC12H25, n-C16H33-, C6H5C
H2-, C6H5CH2CH2-, C6H11CH2-
, etc. are used.

Examples of the negative group containing an 01N or S atom represented by X include alkoxy, siloxy, aritoxy, amino, amido, and groups in which R5 is a hydrocarbon group.

Preferably, alkoxy or siloxy groups are used.

The organometallic compound of Al, Be, B, Zn, Si or Li represented by D includes trialkylaluminum,
Alkylaluminum alkoxide, trialkoxyaluminum, dialkylberyllium, trialkylboron, dialkylzinc, tetraalkylsilane, trialkylhydrosilane, alkyllithium, and the like are used.

Preferably, it is an organoaluminum compound of the general formula AlR6n(OR")3-n (wherein R6, R7 is a C1-1o hydrocarbon group n is 0-3), and includes trialkylaluminum, alkylaluminum alkoxide, trialkoxy Aluminum etc. are used.

p, q is a number between 0 and 2, r is a number between O and 1, and p+q
+r=2.

r is an important component in narrowing the molecular weight distribution, and ranges from 0.2 to
The effect of high activity and narrow molecular weight distribution is achieved between 0.6 and 0.6.

S is a number in the range 0.005≦S<0.1, and in order to take advantage of the characteristics of the organomagnesium compound and to lower the viscosity of the solution and make it easier to handle, it should be between 0.02 and 0.09. That's wishful thinking.

Next, titanium or vanadium compounds containing at least one halogen atom [component (■)] include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium Trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride, vanadium tetrachloride, vanadyl trichloride, monobutoxyvanadyl dichloride,
A single or a mixture of titanium and vanadium halides, oxyhalides A alkoxyhalides, such as dibutoxyvanadyl dichloride, are used.

Preferred compounds are those containing three or more halogens, and titanium tetrachloride is particularly preferred.

The reaction of organomagnesium compounds with titanium or vanadium compounds is carried out using an inert reaction medium, e.g. hexane,
Aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane,
In alicyclic hydrocarbons such as methylcyclohexane, 15
It is carried out at temperatures down to 0°C, preferably at low temperatures below 50°C.

The reaction ratio of the two types of catalyst components is 0.1 mol of the organomagnesium compound to 1 mol of the titanium or vanadium compound.
A range of 1 to 10 mol, preferably 0.3 to 3 mol, is recommended to obtain high activity.

The composition and structure of the solid catalyst obtained by the above reaction vary widely depending on the type of starting materials and reaction conditions, but are approximately within the following ranges.

The Mg/(Ti+V) molar ratio in the solid catalyst is in the range of 0.1-5.

In addition, this solid surface has an extremely large specific surface area, and B. E. When measured by the T method, 50m2lg or more40
The organic or inorganic aluminum, silicon, tin, and antimony compounds used in the reaction with the solid catalyst exhibiting a high value of up to 0 m2/9 [component (V)] include halogen atoms, hydrogen atoms, and hydrocarbon groups. , alkoxy, or alkoxy groups can be used.

These compounds include, for example, alkoxy aluminum dihalides, alkyl aluminum dihalides, monoalkoxy silicon halides, monoalkyl silicon halides,
These include silicon tetrahalide, monoalkoxytin halide, monoalkyltin halide, tin tetrahalide, antimony pentachloride, and monoalkylantimony halide.

Among these compounds, alkyl aluminum dichloride, silicon tetrachloride, and tin tetrachloride are particularly preferred.

1. As the titanium or vanadium compound [component (V)] containing at least one halogen atom, a compound that is the same as or different from the compound [component (■)] used in the synthesis reaction of the solid catalyst may be used. can.

In the reaction with a solid catalyst, component (V) and component (5) are added in an amount of 1 to 50 mmol, preferably 2 to 2 mmol, per 1 g of solid.
The reaction is carried out in an inert hydrocarbon medium or in the absence of an inert hydrocarbon medium at a temperature ranging from room temperature to 150° C. for a period of 1 to 50 hours.

After completion of the reaction, it is desirable to isolate the solid catalyst and wash it with an inert hydrocarbon.

The reaction between the solid catalyst and this compound can be carried out in two or three multistage steps using the same or different compounds.

Although the solid catalyst or solid catalyst of the present invention is useful as a catalyst for olefin polymerization as it is, it becomes an even more excellent catalyst when combined with an organometallic compound.

As the organometallic compound, compounds of groups I to II of the periodic table are preferred, and complexes containing organoaluminum compounds and organomagnesium are particularly preferred.

This organoaluminum compound has the general formula AIR8
lY3-1 (in the formula, R8 is a hydrocarbon group having 1 to 20 carbon atoms, Y is a group selected from a hydrogen atom, a halogen atom, an alkoxy, antoxy, and a siloxy group, and m is a number of 2 to 3) ) is used alone or as a mixture.

The hydrocarbon group having 1 to 20 carbon atoms represented by R8 in the above formula includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.

Specific examples of these compounds include triethylaluminum, trinormalpylaluminum,
Triisoprobylaluminium, trin-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, trihexadecylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum Recommended are ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylhydrosiloxyaluminum diethyl, etc., and mixtures thereof.

As a complex containing an organomagnesium, general formula M
, dMeR'fR4'g [wherein M is aluminum, boron, beryllium, zinc, AR9, R1° is a hydrocarbon group having 1 to 15 carbon atoms, d, e, f, g are numbers of n or more , d/e-1 to 8, 2d+αe-f-g (α is the valence of M)] is used.

Highly active catalysts can be obtained by combining these organometallic compounds with the above-mentioned solid catalysts or solid catalysts (hereinafter simply referred to as solid catalysts), but especially trialkyl aluminum and dialkyl aluminum hydride achieve the highest activity. It is preferable because

When a negative group Y is introduced into trialkyl aluminum or dialkyl aluminum hydride, the activity tends to decrease, but each exhibits characteristic polymerization behavior and it is possible to produce useful polymers with high activity. .

For example, the molecular weight can be easily controlled by introducing an alkoxy group.

As the negative group, an alkoxy group or a siloxy group is preferable from the viewpoint of reducing halogen in the polymerization process and in the polymer.

The solid catalyst component and the organometallic compound may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization.

Further, the ratio of the two components to be combined is preferably in the range of 1 to 3000 mmol of the organometallic compound per 1 g of the solid catalyst.

Further, the catalyst for olefin polymerization of the present invention can produce a highly active polymer with a wide molecular weight distribution by combining the above-mentioned solid catalyst and organometallic compound with a halogenated hydrocarbon.

The halogenated hydrocarbon is a saturated or unsaturated hydrocarbon having 1 to 15 carbon atoms, preferably a halogenated hydrocarbon in which the number of halogen atoms is at most twice the number of carbon atoms.

These compounds include, for example, dichloromethane, 1
,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2,3
-}Lichloropropane, n-butyl chloride, inbutyl chloride, 1,4-dichlorobutane, 2,3-dichlorobutane, n-hexyl chloride, 1,6-dichlorohexane, 1,2-dichlorooctane, dibromomethane, 1,2 -Di1romuethane, n-butyl bromide, chlorobenzene, phenathyl chloride, allyl chloride, brombenzene, ethyl iodide, etc. are used.

These halogenated hydrocarbons can be reacted with the aforementioned solid catalyst and organometallic compound as the polymerization progresses, or may be carried out in advance prior to the polymerization.

Alternatively, after once reacting a solid catalyst and a halogenated hydrocarbon and isolating the solid, the solid catalyst and an organometallic compound are combined and polymerization is performed with or without adding the same or different halogenated hydrocarbon. You can also do it.

The reaction ratio of the catalyst components is 1 to 3000 mmol of the organometallic compound and 1 to 3000 mmol of the halogenated hydrocarbon per 1 g of the solid catalyst, and the molar ratio of the organometallic compound to the halogenated hydrocarbon is 0.01 to 3000 mmol. 100,
Preferably, it is within the range of 0.1 to 20.

Olefins that can be polymerized using the catalysts of the invention are alpha olefins, especially ethylene.

Further, the catalyst of the present invention can be polymerized in the coexistence of monoolefins such as propylene, butene-1, and hexene-1, and dienes such as butadiene and isobrene, and can also be used to efficiently polymerize propylene. .

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 combined with a polymerization solvent such as an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene, or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane. Introduce ethylene into the reactor and add 2 ethylene under an inert atmosphere.
The polymerization can be carried out at a temperature of room temperature to 300° C. by pressurizing the polymer at a temperature of 00 Kp/Cm3.

On the other hand, in gas phase polymerization, ethylene is mixed at a pressure of 1 to 50 KP/cm3 and at a temperature of room temperature to 120°C using a fluidized bed, a moving bed, or a stirrer to ensure good contact between ethylene and the catalyst. It is possible to carry out polymerization using the following methods.

The polymerization may be carried out in a single-stage polymerization using one reaction zone, or it may be carried out in a so-called multi-stage polymerization using a plurality of reaction zones.

By polymerizing two or more molecules under different reaction conditions, it is possible to produce polymers with a wider molecular weight distribution.
It is extremely well suited for products formed by blow molding or film molding.

In order to adjust the molecular weight distribution of the polymer, it is also possible to add hydrogen or an organometallic compound that is likely to undergo chain transfer.

Furthermore, it is also possible to carry out the polymerization by combining methods such as adding a titanate ester to adjust the density.

Examples of the present invention are shown below, but the present invention is not limited to these Examples.

In addition, the polymerization average molecular weight Mw in the examples is [η]=6.8
X10-4MwO.67 [see Journal of Polymer Science, 36, 91 (1957)], where Mw/Mn is an index of molecular weight distribution; P.
It was measured by c method (gel permeation chromatography method).

The term catalytic efficiency refers to the amount of polymer produced per 1 g of solid catalyst per hour per ethylene pressure Kp/cm3.

Example 1 (1) Synthesis of organomagnesium compound Magnesium powder 7 was placed in a 500 rl flask purged with nitrogen.
．． 29g (300mmol) and Al(OC2H5)30
．． 6 g (10 mmol) was introduced.

To this, add 41.2 ml of n-C6H13Cl (300 mm
1/10 of a 300M mixture of butane was added to ol) and n-, and the mixture was stirred at 90°C, and the reaction started about 10 minutes later.

The remaining n-C6H13C was stirred while keeping the internal temperature at 90C.
1 solution was added over 2 hours, and the reaction was further carried out at 90° C. for 1 hour.

After the reaction was completed, the reaction solution was allowed to stand and the supernatant was removed to obtain a solution of the organomagnesium compound.

As a result of analyzing Mg, Al, and Cl in this solution, Mg0
．． 35mol/l, Al0.026mol/l, Cl0
．． It was less than 0.01 mol/l.

(I) Synthesis of solid catalyst Oxygen and moisture inside a flask with a capacity of 500 mα equipped with two dropping funnels were removed by replacing with dry nitrogen.
60 mi of n-hebutane was added and cooled to -5°C.

Next, the above (n-CaH1a)2Mg/[Al(OC2
H5)3] 80 rr of n-hebutane solution containing 30 mmol of 0.07 and 80 rr of n-hebutane solution containing 50 mmol of titanium tetrachloride were weighed into each dropping funnel and stirred at -5°C. Both components were added to the bottom at the same time over a period of 2 hours, and a thermal reaction was further carried out at this temperature for 2 hours.

The produced hydrocarbon-insoluble solid catalyst was isolated, washed with n-hebutane, and dried to obtain a solid catalyst.

(I) Polymerization reaction 5 mg of the solid catalyst synthesized in (I) and 0.4 mmol of triisobutylaluminum were mixed with 0.8 liter of n-heptane, which had been dehydrated and deaerated, and the interior was vacuum degassed and replaced with nitrogen.
It was introduced into a 5 l autoclave.

Keep the internal temperature of the autoclave at 85℃ and heat the hydrogen to 1.5K.
The pressure was increased to a gauge pressure of p/Cm2, and then ethylene was added to bring the total pressure to a gauge pressure of 4.0 Ky/cm3.

By replenishing ethylene, the total pressure is reduced to 4. OKp/cm
Polymerization was carried out for 1 hour while maintaining the pressure at a gauge pressure of 3, and 113 g of polymer was obtained.

Mw was 1.12×105, MW/Mn was 6.3, and catalyst efficiency was 9400.

The bulk density of this polymer when cut was 0.35.

Example 2 Magnesium powder 250 mmol, n-C10H21C
1250 mmol, B(C2H5)3 10 mmol were reacted according to the method of Example 1, and (n-C1oH21
)2Mg/(B(C2H5>3)0.08 solution was obtained.

20 mmol of the organomagnesium compound and TxCl3.
Using 0.516 mmol of 5(Oi-C3H7), both components were added at -10°C over 8 hours, and further added at 20°C for 4 hours.
A solid catalyst was obtained by carrying out the reaction under the same conditions as in Example 1 except for performing the time aging.

5 mg of this solid catalyst, 0.
Polymerization was carried out in accordance with Example 1 using 2 mmol and 0.4 mmol of methylene chloride to obtain 77 g of polymer.

Mw was 1.72×105, Mw/Mn was 15.3, and catalyst efficiency was 6400.

Moreover, the bulk density of this polymer was 0.41.

Example 3 Al(C2H5)36 instead of Al(OC2H5)3
An organomagnesium compound was synthesized under the same conditions as in Example 1 except that mmol was used.

(n-C6H13)2Mg-CA synthesized in this way
g(C2H5)3]o. To 150 rl of n-heptane solution containing 50 mmol of os, 10
mmol was added, and the reaction was carried out at 30°C for 4 hours.

A part of this solution was taken and analyzed for Mg and octoxy groups, and the molar ratio was found to be n-C8H170-/Mg=0.2
Met.

20 mmol of this organomagnesium compound and TiCl4
Using 20 mmol, the reaction was carried out under the same conditions as in Example 1, except that both components were added over 2 hours at -5°C and further aged at 5°C for 1 hour, to obtain a solid catalyst.

5 ng of this solid catalyst, 0.0 ng of triisobutylaluminum.
Polymerization was carried out in accordance with Example 1 using 2 mmol and 0.8 mmol of 1j2-dichloroethane to obtain 80 g of polymer.

Mw was 1.94×105, Mw/M was 19.8, and catalyst activity was 6700.

The bulk density of this shredded polymer was 0.38.

Examples 4 to 8 The organomagnesium compounds shown in Table 1 [component (I)] and the titanium or vanadium compound containing at least one halogen atom [component (I)] are reacted according to the conditions of Example 1. A solid catalyst was obtained.

5 mg of this solid catalyst and the organometallic compound [component (I) in Table 1]
I] and halogenated hydrocarbon [component (VD),
Ethylene polymerization was carried out under the conditions of Example 1, and the results shown in the table were obtained.

Examples 9 to 19 2 g of solid catalyst synthesized under the conditions of Example 3 and organic or inorganic aluminum, silicon, tin,
antimony compound [component (IV)) or at least 1
Using the solid catalyst obtained by the reaction with a titanium or vanadium compound [component (V)] containing 2 halogen atoms and the components (I) and (VD) shown in Table 1, ethylene was reacted under the conditions of Example 1. Polymerization was carried out and the results shown in the table were obtained.

Example 20 2 g of the solid catalyst obtained in Example 3 was mixed with 1 part of dichloromethylsilane.
The mixture was placed in a 200 ml flask purged with nitrogen along with 2 mmol of n-hebutane (70 LA), and reacted at 60° C. for 1 hour.

The supernatant liquid was removed by decantation, and the mixture was washed twice by decantation using 50 ml of n-heptane, and then 20 mmol of titanium tetrachloride and 60 rl of n-heptane were added, and the reaction was carried out at 90° C. for 4 hours.

The solid catalyst was then isolated, washed with n-butane, and then dried.

Using the solid catalyst, polymerization was carried out according to Example 1 to obtain 104 g of polymer, Mw was 1.73×105, Mw
/Mn was 16.9, bulk density was 0.47 g/cc, and catalyst efficiency was 8,700.

Comparative Example 1 (1) Synthesis of solid catalyst Oxygen and moisture inside a 500 mA flask equipped with two dropping funnels were removed by dry nitrogen replacement.
0rl of n-hebutane was added and the mixture was cooled to -50°C.

Next, 220 ml of the n-hebutane solution containing 30 mmol of (n-C6H13)2Mg and 50 ml of titanium tetrachloride were added.
20 rl of n-hebutane solution containing mmol was weighed into each dropping funnel, and both components were added simultaneously over 2 hours while stirring at -50°C, and the aging reaction was further carried out at this temperature for 2 hours. .

The produced hydrocarbon-insoluble solid catalyst was isolated, washed with n-hebutane, and dried to obtain a solid catalyst.

(I) 5 mg of the solid catalyst synthesized in polymerization reaction (1) and 0.4 mmol of triinbutylaluminum were dehydrated and deaerated together with 0.81 n-heptane, and the inside was vacuum degassed and replaced with nitrogen.
It was introduced into a 5 l autoclave.

Keep the internal temperature of the autoclave at 85℃ and heat the hydrogen to 1.6K.
Pressurize to g/cm3 gauge pressure, then add ethylene to bring the total pressure to 4. The gauge pressure was OKg/cm3.

By replenishing ethylene, the total pressure is increased to 4.0Kg/cm.
Polymerization was carried out for 1 hour while maintaining the pressure at a gauge pressure of 3, and 24 g of polymer was obtained. Mw was 0.65×105, Mw/Mn was 7.1, and catalyst efficiency was 2000.

Moreover, the bulk density of this polymer was 0.17.

Comparative Example 2 (1) Synthesis of solid catalyst Oxygen and hydrogen inside a flask with a capacity of 500 Ij equipped with two dropping funnels were removed by dry nitrogen substitution, and 1
60 rI of n-hebutane was added and the mixture was cooled to -5°C.

Next, the above (n-C6H13)2Mg/(Al(C2H
5) Weigh out 80 ml of n-heptane solution containing 30 mmol of 3) 0.25 and 80 ml of n-heptane solution containing 50 mmol of titanium tetrachloride into each dropping funnel, -
Both components were added simultaneously over 2 hours while stirring at 5°C, and the mixture was further aged at this temperature for 2 hours.

The produced hydrocarbon-insoluble solid catalyst was isolated, washed with n-hebutane, and dried to obtain a solid catalyst.

(I) 5 mg of the solid catalyst synthesized in polymerization reaction (1) and 0.4 mmol of triynebutylaluminum were dehydrated and deaerated to 0.81 n-hebutane, and the inside was vacuum degassed and replaced with nitrogen.
It was introduced into a 5 liter autogrape.

Keep the internal temperature of the autoclave at 85℃ and heat the hydrogen to 1.6K.
The pressure was increased to a gauge pressure of p/cm3, and then ethylene was added to bring the total pressure to a gauge pressure of 4.0 Kp/cm3.

By replenishing ethylene, the total pressure is increased to 4.0Kg/cm.
Polymerization was carried out for 1 hour while maintaining the pressure at a pressure of 3, and 144 g of polymer was obtained. Mw was 1.08 x 105, Mw/Mn.
was 5.9, and catalyst efficiency was 12,000.

Moreover, the bulk density of this polymer was 0.27.

Claims (1)

[Claims] 1 (I) General formula MgR1bR2qXr-D3 (however,
Rl and R2 are hydrocarbon groups having 6 or more carbon atoms which may be the same or different; X is a negative group containing 0, N or S atoms; D is Al, Be, B, Zn, Si or represents an organometallic compound of Li, p, q are O~2, r
has the relationship p+q+r=2 with O~1, and S is 0.00
(I) at least 1
A solid catalyst obtained by reacting with a titanium or vanadium compound containing halogen atoms and A(I
) An α-olefin polymerization catalyst comprising an organometallic compound. 2 X is alkoxy, siloxy, antoxy, aR3,
R4 and R5 represent hydrocarbon groups), are β-keto acid residues, and the value of r is O≦r≦0.6, Claim 1
Nobi-olefin polymerization catalyst described in Section 1. 3 D has the general formula AIR6n(OR7)3-n(R6,R
7 is a hydrocarbon group having 1 to 20 carbon atoms, and n is a number of 0 to 3. 4. The α-olefin polymerization catalyst according to claims 1 to 3, wherein the titanium or vanadium compound (■) is a compound containing three or more halogen atoms. 5. The α-olefin polymerization catalyst according to claims 1 to 4, wherein the titanium or vanadium compound (■) is titanium tetrachloride. 6 The molar ratio of the organomagnesium compound (I) and the titanium or vanadium compound (■) is Mg/(Ti+V)
=0.1-10, preferably 0.3-3. 7 (The organometallic compound of ID has the general formula AlR8mY3T
n (in the formula, R8 is a hydrocarbon group having 1 to 20 carbon atoms, Y is a group selected from a hydrogen atom, a halogen atom, an alkoxy, antoxy, or a siloxy group, and m is a number from 2 to 3. ) The α-olefin polymerization catalyst according to claims 1 to 6, which is an organoaluminum compound represented by the following. 8. The α-olefin polymerization catalyst according to claims 1 to 7, wherein the organometallic compound (m) is trialkylaluminum or dialkylaluminum hydride. 9 (l) General formula MgR1pR'qXr-D8 (however,
Rl and R2 are hydrocarbon groups having 6 or more carbon atoms, which may be the same or different, X is 0, N is a negative group containing an S atom, and D represents an organometallic compound of Al + BetBtZn + Si or Li. , p, q are O~2, r is O
~1 and has the relationship p+q+r=2, and S is 0.005≦
A solid obtained by reacting an organomagnesium compound soluble in a hydrocarbon medium represented by S<0.1 with a titanium 1 or vanadium compound containing at least one halogen atom. Add the catalyst further (
10) Organic or inorganic aluminum, silicon, tin,
An α-olefin polymerization catalyst consisting of an antimony compound and/or (V) a solid catalyst obtained by reacting with a titanium or vanadium compound containing at least one halogen compound, and (II) an organometallic compound. 10 ( Claim 9, characterized in that the organic or inorganic aluminum, silicon, tin, antimony compound of I) contains at least one halogen atom and is soluble in a carbon-hydrogen medium. 11. The α-olefin polymerization catalyst according to claims 9 to 10, wherein the titanium or vanadium compound (V) is a compound containing three or more halogen atoms. 12 Solid state A (v) and/or (V) per 1 g of solid catalyst obtained by the reaction of (1) and (')
The α-olefin polymerization catalyst according to claims 9 to 11, which is obtained by reacting 1 to 50 mmol of the compound at 0 to 150°C. 13 (1) The general formula M, R″pR is also qXr-Ds (However, Rl, R2 may be the same or different and have 6 carbon atoms.
The above hydrocarbon group, X is a negative group containing 0, N or S, D represents an organometallic compound of Al, Be, B, Zn, Si or Li, p and q are O~2 , r has the relationship p1q+r=2 with θ~1, and S is 0.005
A solid catalyst obtained by reacting an organomagnesium compound soluble in a hydrocarbon medium represented by ≦S 01 with a titanium 1 or vanadium compound containing at least one halogen atom. ,or,
A solid catalyst obtained by further reacting this solid catalyst with (V: an organic or inorganic aluminum, silicon, tin, antimony compound and/or (V) a titanium or vanadium compound containing at least one halogen atom) and (I) an organometallic compound and (V) a halogenated hydrocarbon. 14 The halogenated hydrocarbon in (V) has 1 to 1 carbon atoms.
15, and the halogen atom number is not more than twice the carbon atom number. 15 The molar ratio of the organometallic compound (II) to the halogenated hydrocarbon (VD) (VD/(II) is 100 or less, preferably 0.1 to 20.
The α-olefin polymerization catalyst described in 1.