JPS584724B2 - Catalyst for polymerization of α-olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel highly active catalyst for polymerizing α-olefins.

A low-pressure method for producing polyethylene using a catalyst comprising an organomagnesium compound and a transition metal compound is described by K. 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 in catalyst synthesis and polymerization reactions, and it has not been possible to achieve high activity.

As catalysts whose activity is enhanced by using organomagnesium compounds in a specific form, systems using organomagnesium halides, so-called complexes of Grignard reagents and 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 inventors have discovered that an extremely excellent and highly active catalyst for polymerizing α-olefins can be obtained, leading to the present invention.

That is, the present invention provides general formula MgR1aR2bXo. Dp
(However, R1 has 2 to 3 carbon atoms, and R2 has 4 carbon atoms.
In the above hydrocarbon groups, the difference in the number of carbon atoms between R1 and R2 is 2
above, X is a negative group containing 0, N or S atom, and D is AI, B, Be, Zn, Si or Li
represents an organometallic compound, where a and b are numbers greater than O and less than or equal to 1, C is a number greater than or equal to 0 and less than or equal to 1, and have the relationship of a + b + c = 2, and p is a number less than 0.1) A hydrocarbon medium soluble organomagnesium compound (1) represented by: titanium containing at least one halogen atom and/or
or solid catalyst (a) obtained by reacting with a vanadium compound, or a titanium or vanadium compound further containing organic or inorganic aluminum, silicon, tin, antimony compounds and/or at least one halogen atom. This relates to a catalyst for polymerizing α-olefins comprising a solid catalyst (c) obtained by reacting with a solid catalyst (c) and an organometallic compound, and a catalyst for polymerizing α-olefins comprising a halogenated hydrocarbon as the polymerization catalyst. be.

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 has a high molecular weight, high rigidity, and a narrow molecular weight distribution. The production of polymers with high impact strength is achieved.

In addition, by using a reaction product of the solid catalyst with an organic or inorganic aluminum, silicon, tin, antimony compound and/or a titanium or vanadium compound containing at least one halogen atom, it is possible to A polymer with a wide molecular weight distribution suitable for film and sheet molding can be obtained.

Furthermore, by combining halogenated hydrocarbons, it is 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 (
1) has the general formula MgR1aR2bXo. It is represented by Dp (in the formula, R', R2, X, D, a, b, c, and p have the above-mentioned meanings).

In the above formula, Rl is a hydrocarbon group having 2 to 3 carbon atoms, and specifically, it is an ethyl, n-propyl, or iso-propyl group, and preferably an ethyl group is used.

R2 is a hydrocarbon group having 4 or more carbon atoms, specifically, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl group, etc., and preferably butyl, pentyl, and hexyl group are used. .

It is important that the difference in the number of carbon atoms between R1 and R2 is 2 or more in order to dissolve in a hydrocarbon medium at a high concentration.

The negative group containing 0, N or S atom represented by X includes alkoxy, siloxy, allyloxy, amine,
(R5 is a hydrocarbon group) and a β-keto acid residue.

Preferably, alkoxy or siloxy groups are used.

The organometallic compound of AI, Be, B, Zn, Si or Li represented by D includes trialkylaluminum,
Examples include alkyl aluminum alkoxide, trialkoxy aluminum, dialkyl beryllium, trialkyl boron, dialkyl zinc, tetraalkyl silane, trialkylhydrosilane, and alkyl lithium.

Preferably, trialkyl aluminum, alkyl aluminum alkoxide, and trialkoxyaluminum are used.

a and b are greater than O and less than or equal to 1, and C is a number greater than or equal to 0 and less than or equal to 1, and has a relationship of a+b+c=2.

C 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.

p is a number of 0.1 or less, and is preferably 0.09 to 0.02 in order to reduce the viscosity of the solution and make it easier to handle.

Next, the titanium and/or vanadium compound (2) containing at least one halogen atom will be explained.

Specifically, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium, trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride, vanadium tetrachloride, Titanium and vanadium halides, oxyhalides, and alkoxyhalides, such as vanadyl chloride, monobutoxyvanadyl dichloride, and dibutoxyvanadyl dichloride, are used alone or in mixtures.

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

The reaction of organomagnesium compounds with titanium and/or vanadium compounds can be carried out using an inert reaction medium, such as aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane. It is carried out in cycloaliphatic hydrocarbons at temperatures up to 150°C, preferably at low temperatures below 50°C.

The reaction ratio of the two catalyst components is high, with the organomagnesium compound being 0.05 to 50 mol, preferably 0.2 to 10 mol, particularly preferably 0.5 to 5 mole per mol of the titanium and/or vanadium compound. Recommended for gaining 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 ranges from 0.1 to 5.

In addition, this solid surface has an extremely large specific surface area, and B. B. When measured by the T method, it is 50n2/g or more40
It shows high values up to 0rl/1.

As the organic or inorganic aluminum, silicon, tin, or antimony compound 3) used in the reaction with the solid catalyst, those containing a halogen atom, hydrogen atom, hydrocarbon group, alkoxy, or alkoxy group can be used. Preferably, it contains at least one halogen atom and is soluble in the hydrocarbon medium.

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.

Further, as the titanium or vanadium compound (4) containing at least one halogen atom, the same or different compound as the compound (2) used in the synthesis reaction of the solid catalyst can be used.

In the reaction with the solid catalyst, component (3) and component (4) are added in an amount of 1 to 100 mmol, preferably 2 to 100 mmol, per 1 g of the solid.
The reaction is carried out in an amount of 50 mmol at a temperature from room temperature to 150° C. in an inert hydrocarbon medium or in the absence of an inert hydrocarbon medium for a period of 1 to 50 hours.

After the reaction is completed, the solid catalyst is preferably isolated and washed 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.

The organometallic compound is preferably a compound of groups I to II of the periodic table, and in particular a complex containing an organoaluminium compound and an organomagnesium compound.

As an organoaluminum compound, general formula AIR8mY
31m (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 group, an alioxy group, and a siloxy group;

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, trinormalpropylaluminum,
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, ethyldimethylsiloxyaluminum diethyl, etc., and mixtures thereof.

As a complex containing organomagnesium, the general formula MgaM
eR9fR10gC In the formula, M is aluminum, boron,
Beryllium, zinc, B9, RIO has 1 carbon atom
~15 hydrocarbon groups, d, e, f, g are numbers of 0 or more,
A compound represented by the relationship 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 trialkyl aluminum and dialkyl aluminum hydride in particular 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-toJ chloroethane, 1,1,2.2-tetrachlorethane, ■,2-dichloropropane, ■,3-dichloropropane A1,2.3
-Trichloropropane, normal butyl chloride, inbutyl chloride, 1,4-dichlorobutane, 2,3-dichlorobutane, normal hexyl chloride, 1,6-dichlorohexane, 1,2-dichlorooctane, dibromomethane, (2), 2-dibromoethane, n-butyl bromide, chlorobenzene, phenathyl chloride, allyl chloride, bromobenzene, 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.

In addition, after once reacting a solid catalyst and a halogenated hydrocarbon and isolating the solid, this 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 that.

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.

Furthermore, 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 isoprene, 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 1 ethylene under an inert atmosphere.
Pressurize to ~200kg/cm2 and store at room temperature to 300℃
Polymerization can proceed at a temperature of

On the other hand, in gas phase polymerization, ethylene is mixed at a pressure of 1 to 50k9/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 performing polymerization under two or more different reaction conditions, it is possible to produce polymers with a wider molecular weight distribution,
It is extremely well suited for products shaped by blow molding or film molding.

Furthermore, in order to adjust the molecular weight of the polymer, it is also possible to add hydrogen or an organometallic compound that tends to cause 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 any way.

In addition, the weight average molecular weight Mw in the examples is (m) -6.8
X10-'Mw0.67 (see Journal of Polymer Science, 36, 91 (1957))], Mw/Mn is an index of molecular weight distribution, and G.P.
Measurement was performed using C method (gel permeation chromatography method).

Further, the catalyst efficiency represents the amount of polymer produced per 1 g of solid catalyst, 1 hour, and ethylene pressure k9/cm2.

Example 1 (1) Synthesis of organomagnesium compound 6.1 kg of magnesium powder was placed in a 1 liter flask purged with nitrogen.
g (250 mmol) was introduced.

To this, 1/10 of 300 ml of n-hebutane solution containing 250 mmol of C2H5Br was added and stirred at 90°C, and the reaction started after about 10 minutes.

While maintaining the internal temperature at 90°C, the remaining n-hebutane solution was added over 2 hours with stirring, and the reaction was further carried out at 90°C for 1 hour.

Next, a hebutane solution of n-butyllithium (concentration 1 mo
1/1) was added, and the reaction was carried out under heating and reflux for 6 hours.

After the reaction was completed, the reaction solution was allowed to stand and the supernatant liquid was drawn out.

Analysis of Mg and Br in this liquid revealed that it was 0.37 mol of Mg.
/l, BrO. It was less than 0.01 mol/l.

Furthermore, when this reaction solution was reacted with 2 equivalents of iodine to Mg and the alkyl iodide produced was analyzed by gas chromatography, the molar ratio of n-C4H,I to C2H5 was 1.
It was 05.

(I) Synthesis of solid catalyst Oxygen and moisture inside a 500 rl flask equipped with two dropping funnels were removed by dry nitrogen substitution, and 1
60 rl of n-hebutane was added and the mixture was cooled to -5°C.

Next, the above Mg(C2H5)(n-C4Ho)Cn-C
80 Ll of n-hebutane solution containing 40 mmol of 4HgLi)ooi and 80 ml of n-hebutane containing 60 mmol of titanium tetrachloride were weighed into each dropping funnel, and both components were mixed simultaneously at -5°C with stirring for 2 hours. The mixture was added over a period of time, and the aging reaction was further carried out at 5° C. for 1 hour.

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

(1) 5 mg of the solid catalyst synthesized in polymerization reaction (I) and 0.4 mmol of triisobutylaluminum were dehydrated and degassed in n-hebutane 0.
．． The inside was vacuum degassed and replaced with nitrogen along with 8 liters.
1 autoclave.

Keep the internal temperature of the autoclave at 85℃ and add 1.6k of hydrogen.
The pressure was increased to a gauge pressure of g/cm2, and then ethylene was added to bring the total pressure to a gauge pressure of 4.0 kg/cm2.

By replenishing ethylene, the total pressure is increased to 4.0 kg/cm.
Polymerization was carried out for 1 hour while maintaining the pressure at a gauge pressure of 2, and 134 g of polymer was obtained.

Mw was 125,000, Mw/Mn was 10.3, catalyst efficiency was 11,200, and bulk density was 0.39 g/cc.

Examples 2 to 9 Using components (1) and (2) shown in Table ■, a solid catalyst was synthesized according to the method of Example 1 under the conditions shown in the table, and polymerization was carried out using this under the conditions of Example 1. went.

The results are shown in Table I.

Examples 10 to 18 Polymerization was carried out under the same conditions as in Example 1, except that components (8) and (d) shown in Table H were used, and the results shown in Table H were obtained.

Examples 19 to 28 2 g of the solid catalyst synthesized in Example 2 and the components shown in Table N (
3) or (4) was reacted under the conditions shown in the table to synthesize a solid catalyst.

5 mg of this solid catalyst and component (b) shown in Table 1 and (
Polymerization was carried out using d) under the same conditions as in Example 1, and the results shown in the table were obtained.

Example 29 2 g of the solid catalyst synthesized in Example 8 and 128 mmol of AI(C2H5) were mixed with 10 g of n-heptane.
The reaction was carried out in 0ml at 80°C for 2 hours.

After the reaction, the supernatant was removed by decantation, washed twice with 50 ml of n-hebutane, and then washed with TiCl41
Introduce 0 mmol and H-w butane 50 mA, and heat at 80°C.
After carrying out the reaction for 1 hour, the solid catalyst was isolated.

Polymerization was carried out under the same conditions as in Example 1, yielding 87 g of polymer.

Catalyst efficiency 7250, Mwl93000, Mw/Mnl6
．． 3. The bulk density was 0.47 f/cc.

Comparative Example 1 (1) Synthesis of solid catalyst Oxygen and moisture inside a 500 ml flask equipped with two dropping funnels were removed by dry nitrogen substitution, and 1
60ml of hebutane was added and cooled to -5°C.

Next, Mg(C2H5)o. s(n-C+H9)o,s(
On-C4Hg)o. 4(AI(C2H5)3)0.2
80 Ll of n-hebutane solution containing 40 mmol and 8 Ll of n-hebutane solution containing 40 mmol of titanium tetrachloride.
0 Ll was weighed into each dropping funnel, and both components were added simultaneously over 2 hours while stirring at -5°C, and further, an aging reaction was performed at 5°C for 1 hour.

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

(I) 0.8 n-heptane obtained by dehydrating and degassing 5 mg of the solid catalyst synthesized in polymerization reaction (1) and 0.4 mmol of triethylaluminum.
The inside of the autoclave was vacuum degassed and the autoclave was replaced with nitrogen.

Keep the internal temperature of the autoclave at 85℃ and add 1.6k of hydrogen.
The pressure was increased to a gauge pressure of g/cm3, and then ethylene was added to bring the total pressure to a gauge pressure of 4.0 kg/cm2.

By replenishing ethylene, the total pressure is increased to 4.0 kg/cm.
Polymerization was carried out for 1 hour while maintaining the pressure at a gauge pressure of 2, and 200 g of polymer was obtained.

Mw is soooo, Mw/Mn is 5.9, catalyst efficiency is 1
6700, and the bulk density was 0.35.

Comparative Example 2 (1) Synthesis of solid catalyst Oxygen and moisture inside a 500 ml flask equipped with a dropping funnel were replaced with dry nitrogen, and 240 ml of n-hebutane and (n-C4H,)2Mg solid were added. Prepare 40mmof-
Cooled to 5°C.

Next, 80 ml of n-heptane containing 40 mmol of titanium tetrachloride was weighed into a dropping funnel, added over 2 hours with stirring at -5°C, and further aged at 5°C for 1 hour.

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

(n) 5 mg of the solid catalyst synthesized in polymerization reaction (1) and 0.4 mmol of triethylaluminum were introduced into a 1.5 liter autoclave with 0.8 liter of degassed n-hebutane, the inside of which was vacuum degassed and replaced with nitrogen. did.

Keep the internal temperature of the autoclave at 85℃ and add 1.6k of hydrogen.
The pressure was increased to a gauge pressure of g/cm2, and then ethylene was added to bring the total pressure to a gauge pressure of 4.0 kg/cm2.

Polymerization was carried out for 1 hour while maintaining the gauge pressure at 4.0 kg/cm2 by replenishing ethylene to obtain 15 g of polymer.

Mw is 7500, Mw/Mn is 9.7, catalyst efficiency is 12
50, and the bulk density was 0.21.

Claims (1)

[Claims] 1 General formula MgR1aR2bXc. DD (However, Rl is a hydrocarbon group having 2 to 3 carbon atoms, R2 is a hydrocarbon group having 4 or more carbon atoms, the difference in the number of carbon atoms between R1 and R2 is 2 or more, and
is a negative group containing 0, N or S atom, D represents an organometallic compound of AI, B, Be, Zn, Si or Li, a, b are greater than 0 and less than or equal to 1, C is O or more ,
Numbers less than or equal to 1 have the relationship a + b + c = 2, and p is 0.1
A solid catalyst obtained by reacting an organomagnesium compound (1) soluble in a hydrocarbon medium represented by a smaller number) with a titanium and/or vanadium compound (2) containing at least one halogen atom. A catalyst for the polymerization of α-olefins, which comprises an organic metal compound (B) and an organometallic compound (B). 2. The catalyst for polymerizing α-olefins according to claim 1, wherein R1 is an ethyl group and R2 is a butyl, pentyl, or hexyl group. 3 X is alkoxy, siloxy, antoxy, AB3,
R4 and R5 represent hydrocarbon groups), are β-keto acid residues, and the value of C is O≦C≦0.6, the α-olefins according to claims 1 to 2 Polymerization catalyst. 4 D has the general formula AIR6n(OR7)s-n(R6,R
7 is a hydrocarbon group having 1 to 20 carbon atoms, and n is a number of 0 to 3. Catalyst for use. 5. The α-olefin polymerization catalyst according to claims 1 to 4, wherein p is a number in the range of 0.02≦p≦0.09. 6. The catalyst for polymerizing α-olefins according to claims 1 to 5, wherein the titanium and/or vanadium compound (2) is a compound containing three or more halogen atoms. 7. The catalyst for polymerizing bi-olefins according to claims 1 to 5, wherein the titanium and/or vanadium compound (2) is titanium tetrachloride. 8 The molar ratio of (1) and (2) is Mg/(Ti+V)=0
．． The catalyst for polymerizing α-olefins according to claims 1 to 6, wherein the reaction is carried out at a temperature of 05 to 50%. 9 The organometallic compound of (B) has the general formula AIR8mY3-
m (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, alkoxy, siloxy, alkoxy or siloxy group, and m is 2
The catalyst for polymerizing α-olefins according to claims 1 to 7, which is an organoaluminum compound represented by the following formula (a number of 1 to 3). 10 General formula MgR1aR2bXc. Dp (where Rl is a hydrocarbon group having 2 to 3 carbon atoms, R2 is a hydrocarbon group having 4 or more carbon atoms, and the difference in the number of carbon atoms between R1 and R2 is 2 or more,
X is a negative group containing 0, N or S atoms, D
represents an organometallic compound of AI, B, Be, Zn, Si or Li, a and b are larger than O and 1 or less, C is a number of 0 or more and 1 or less and has the relationship a-b + C-2, p is 0.
is obtained by reacting a hydrocarbon medium soluble organomagnesium compound (1) represented by (a number smaller than 1) with a titanium and/or vanadium compound (2) containing at least one halogen atom. A solid catalyst obtained by further reacting the solid catalyst with an organic or inorganic aluminum, silicon, tin, antimony compound (3) and/or a titanium or vanadium compound containing at least one halogen atom (4) 5
) and an organometallic compound. Claim 10, characterized in that the organic or inorganic aluminum, silicon, tin, antimony compound of 11(3) contains at least one halogen atom and is soluble in a hydrocarbon medium. Nobi - A catalyst for the polymerization of olefins. 12. The catalyst for polymerizing bi-olefins according to claims 10 to 11, wherein the titanium or vanadium compound (4) is a compound containing three or more halogen atoms. 13 Solid catalyst obtained by the reaction of (1) and (2) (
a) A solid catalyst (
Claim 10 characterized in that c) is synthesized.
The catalyst for polymerizing α-olefins according to items 1 to 11. 14 General formula MgR1aR2bXc. Dp (where R1 is a hydrocarbon group having 2 to 3 carbon atoms, R2 is a hydrocarbon group having 4 or more carbon atoms, and the difference in the number of carbon atoms between R1 and R2 is 2 or more,
X is a negative group containing 0, N or S atoms, D
indicates an organometallic compound of AI, B, Be, Zn, Si or Li, a and b are greater than 0 and less than or equal to 1, C is a number greater than or equal to θ and less than or equal to 1, and has the relationship a-b 10 = 2. and p is 0.
by reacting an organomagnesium compound starch (1) soluble in a hydrocarbon medium with a titanium and/or vanadium halide (2) containing at least one halogen atom, the number being less than 1. The obtained solid catalyst (a) or component (a) is further combined with an organic or inorganic aluminum, silicon, tin, or antimony compound (3) and/or a titanium or vanadium compound starch containing at least one halogen atom (4). 1. A catalyst for polymerizing α-olefins comprising a solid catalyst (c) obtained by reacting with ), an organometallic compound (b), and a halogenated hydrocarbon (t). 15 The number of carbon atoms of the halogenated hydrocarbon in (d) is 1 to
15, and the number of halogen atoms is not more than twice the number of carbon atoms, the catalyst for polymerizing bi-olefins according to claim 14. 16 The molar ratio (b)/(d) of (b) and (d) is 0.0
Claims 14 to 15 range from 1 to 100.
Catalyst for polymerization of α-olefins as described in 2.