JPS595205B2 - Catalyst used in polyethylene production - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ethylene polymerization catalyst capable of producing polyethylene having novel properties.

The properties required for polyethylene vary depending on the molding method and application, and the properties of the polymer are designed to suit each.

In other words, polymers with a relatively low molecular weight and narrow molecular weight distribution are suitable for products molded by injection molding, and polymers with a relatively low molecular weight and narrow molecular weight distribution are suitable for products molded by blow molding, inflation molding, etc. Polymers with high molecular weight and wide molecular weight distribution are used. As required characteristics derived from the uses of these molded products, polymers with higher functionality have recently been required from the viewpoint of resource saving and energy saving.
Polyethylene has different properties such as physical properties and moldability depending on the production method such as the polymerization catalyst and the polymerization method.

Manufacturers of polyethylene molded products use many different polyethylene grades to manufacture products that meet the diverse demands of the market. However, since these grades are manufactured under different conditions, they each have characteristic moldability. When the moldability of the polymer varies, the molding conditions can be adjusted to some extent, but this becomes a serious problem, especially when the die swell changes significantly during blow molding. When the molten polymer is extruded through the die of the molding machine, swelling occurs due to the ballast effect. This is called a dice well. When blow molding is used, a bottle is formed from a certain length of cylindrical molten polymer (parison). Therefore, when the die well changes, the wall thickness of the bottle changes, making it difficult to obtain a product of constant quality. Such a phenomenon tends to be particularly noticeable in the case of functional resins. The present inventors investigated a method for producing polyethylene that has good moldability and excellent physical properties, and found that a melting medium containing a solid component synthesized under specific conditions has extremely unique moldability. Moreover, they have discovered that they can provide a polymer with excellent physical properties, leading to the present invention. That is, the present invention is directed to the general formula ^(l) (wherein R is a secondary or tertiary hydrocarbon group having 3 or more carbon atoms, which may be the same or different, and n is 2
A solid component produced by reacting a solid product obtained by reacting a polytitanate ester represented by the above integer with titanium tetrahalide and thermally decomposing it with (11) an organomagnesium solution; B) A catalyst for producing polyethylene consisting of an organometallic compound.

The first feature of the present invention is that by using the catalyst according to the present invention, a polymer having extremely characteristic moldability can be obtained. As is clear from the examples below, polyethylene produced using the catalyst according to the present invention exhibits extremely large die swell, and the moldability of polymers with low die swell can be easily improved. The second feature of the present invention is that such useful polymers can be produced with high activity and smooth polymerization performance.

The bulk specific gravity of the resulting polymer powder is extremely high, and the content of fine particles is extremely low. The third feature of the present invention is that the resulting polymer has excellent physical properties. That is, this polymer itself is useful as a highly functional polymer because it has a wide molecular weight distribution, high rigidity, and excellent environmental stress cracking resistance. The surface of the bottle molded by blow molding is smooth, and the film molded by inflation molding is gel-free and homogeneous, and the film formation stability is extremely good. The polytitanate ester of the general formula used in the synthesis of the solid component of the present invention will be explained.

In the formula, R is a secondary or tertiary hydrocarbon group having 3 or more carbon atoms, which may be the same or different, and may include aliphatic,
Selected from aromatic and alicyclic hydrocarbon groups. Preferably, it is a secondary to tertiary aliphatic hydrocarbon group having 3 to 6 carbon atoms. Examples of these groups include isopropyl, secondary or tertiary butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, cyclohexyl, phenyl, and the like. n is an integer of 2 or more, preferably in the range of 2 to 20. Such a polytitanate ester may be a commercially available product, or one synthesized by a known method of quantitatively hydrolyzing titanate Ti(0R)4 to form an oligomer. Furthermore, it is of course possible to use a mixture of two or more different polytitanate esters. next,
Titanium tetrahalide will be explained.

Examples of the titanium tetrahalide include titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc., and titanium tetrachloride is preferably used. Next, the polytitanate ester and titanium tetrahalide are reacted and a force a
Obtaining a solid product by thermal decomposition will be explained.

This thermal decomposition reaction is carried out at temperatures above 50° C. in the presence or absence of an aliphatic, cycloaliphatic, or aromatic hydrocarbon medium. In order to allow the decomposition reaction to proceed smoothly and to obtain an active solid component, the molar ratio, concentration, and temperature are important. Regarding the molar ratio, [Ti in titanium tetrahalide]/[Ti in polytitanate]≧
It is preferable that it is 3. Regarding concentration: 1m01/l
The reaction temperature is preferably 4 m01/l or more, and the reaction temperature is 5'C or more, preferably 80°C or more, particularly preferably 100°C or more and 220°C or less. Thermal decomposition reactions are carried out on so-called solid supports such as metal oxides such as silica, alumina, silica/alumina, zirconia, magnesia, metal chlorides such as magnesium chloride, manganese chloride, and even metal hydroxides such as titanium hydroxide. It is also possible to carry out in the presence. The solid reaction product is preferably separated from the liquid phase and washed with an inert hydrocarbon medium until no halogen is detected. The solid product has titanium atoms and halogen atoms in a [halogen]/Ti molar ratio of 1.0 to
It contains in the range of 1.8 and 0 present in the starting material.
R groups are virtually undetectable. Next, the organic magnesium solution will be explained.

As the organomagnesium solution, any solution containing a compound having a magnesium carbon bond or a complex compound can be used in the present invention, but preferred is an organomagnesium compound soluble in an inert hydrocarbon or an inorganic compound of a complex compound. It is an activated hydrocarbon solution. Organic magnesium soluble in inert hydrocarbons has the general formula RlMg (0R
2), R3Mg(0SiR4R5R6) (wherein, Rl
, R2, R3 are hydrocarbon groups, preferably alkyl groups, R4, R5, R6 are hydrocarbon groups or up to two of them are hydrogen), an alkoxy, allyloxymagnesium, or siloxymagnesium compound; Furthermore, dialkylmagnesium compounds having a secondary or tertiary alkyl group, asymmetric dialkylmagnesium compounds, and dialkylmagnesium compounds having a long-chain alkyl group can be used. These compounds include;
For example, n-C4H9Mg (0C3H7), n-C4H
, Mg(0C4H,), n-C4H9Mg(0C5H1
1), n-C4H9Mg (0C6H13), n-C4H
9Mg (0C8H17), C5HllMg (0C4H,
), C6H,3Mg (0C3H7), n-C4H9Mg
(0SiH-CH3・C4H9), n-C4H9Mg(
0SiH-C6H5・C4H9), (SeC-C4H9
)2Mg, (Tert-C4H,)2Mg, C2H5M
Examples include gn-C4H2, SeC-C4H9Mgn-C4H9, and the like. The organomagnesium complex compound has the general formula R7aMgX2-3JD (wherein R7 is a hydrocarbon group, X is a halogen, a is a number from 1 to 2, D is an electron-donating organic compound, and j is a number of 1 to 2), or a compound represented by the general formula MaMgβR8,R9qXr
Y8 (wherein M is an atom selected from aluminum, zinc, boron, lithium, or perylium, R8 and R9 are the same or different hydrocarbon groups having 1 to 10 carbon atoms,
X, Y are the same or different 0R10, 0SiR11R
12R13, NR14R15, SR16 groups, RlO and Rl6 are hydrocarbon groups having 1 to 10 carbon atoms,
Rll, Rl2Rl3, Rl4, Rl5 represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, α, β are larger than O, P, q, r, s are O or larger than O, β/α
≧0.5, p+q+r+s=mα+2β, O≦r+s/
It is a complex compound represented by the relationship α+β≦1,0, where m represents the valence of M. R7aM,X2-2・J
The organomagnesium component of the complex D is preferably a compound in which R7 is an alkyl group and X is chlorine.

These compounds include, for example, (CH3)2Mg
, (C2H5)2Mg, (C3H7)2Mg (C4H
9) 2Mgy(C5Hll)2Mgtsu(C6Hl3)2
Mg, dialkylmagnesium such as (C3Hl7)2Mg, CH3MgCl, C3H7MgCl, C4H9Mg
Cl, C6H, 3MgCl, C8Hl7MgCl, C4
Alkylmagnesium halides such as H9MgBr, C4H9MGI or mixtures thereof are used. As the electron-donating organic compound represented by D, ether, siloxane, amine, nitrile, ketone, aldehyde, organic acid ester, etc. can be used. These compounds include, for example, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether,
Tetrahydrofuran, methylpropyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene oxide, hexamethyldisiloxane, symmetrical dihydrotetramethyldisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, methylhydropolysiloxane, triethylamine tributylamine , pyridine, ethylenediamine, acetonitrile, propionitrile, acrylonitrile, benzylnitrile, benzonitrile,
These include acetone, methyl ethyl ketone, diphenyl ketone, acetylacetone, acetaldehyde, ethyl acetate, butyl benbrozoate, and the like. The value of j is preferably 1-2. Next, a complex with the general formulas MaM, βR8pR9, and XrY8 will be explained.

In the above formula, the hydrocarbon group represented by R8 and R9 is an alkyl group, a cycloalkyl group, or an allyl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc. In particular, R8 is preferably an alkyl group. The ratio β/α of magnesium to metal atom M is preferably 0.5 to 20, particularly preferably 0.5 to 10. an organomagnesium compound soluble in the above inert hydrocarbon medium,
The complex compound is synthesized according to the publications, publications, literature, etc. filed by the present applicant. [For example, JP-A-48-18235, 50150786, 50-1543
88,50-157489,50-157490,51
-97687, Annalen der Hiemi Volume 605, 93
(1957), Journal of Chemical Society 2483-85 (1964), Chemical Communication, page 559 (1966), Journal of Organic Chemistry, Volume 34, page 1116 (1969). ] Solutions containing these organomagnesium compounds and complex compounds are all effective in obtaining the effects of the present invention, but solutions containing inert hydrocarbons of these compounds are preferred in order to achieve the effects of the present invention. A particularly preferable solution is Macho βR8pR9, as is clear from the examples below.
This is an inert hydrocarbon solution of a complex compound represented by XrY8. Examples of the inert hydrocarbon 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.
Aliphatic or cycloaliphatic hydrocarbons are preferably used. Next, a description will be given of how the solid product (1) is reacted with the organomagnesium solution (11) to obtain the catalyst solid component.

The reaction is carried out in an inert reaction medium, e.g., aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, from -80°C to 150°C. temperature, preferably between -300C and 10
It is carried out at temperatures up to 00C. The reaction ratio is between 0.05 and 50% magnesium compound based on magnesium atoms per gram atom of titanium in the solid reactant.
Gram atoms, preferably 0.1 to 5 gram atoms, are used. After the reaction has ended, the solid components are preferably isolated and washed with an inert hydrocarbon. Next, the organometallic compound (B) used as the solid component will be explained.

The organometallic compound is preferably a compound of Groups 1 to 1 of the periodic table, and particularly an organoaluminum compound or a complex containing organomagnesium. The organoaluminum compound has the general formula AlRl7lZ3-t (wherein, R
l7 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group, and t is a number of 2 to 3) alone or Use as a mixture.

In the above formula, the number of hydrocarbon atoms represented by Rl7 is 1 to 20
The hydrocarbon group includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum,
Tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum,
Trioctyl aluminum, tridecyl aluminum,
Tridodecyl aluminum, trihexadecyl aluminum, diethylaluminium hydride, diisobutyl aluminum hydride, diethylaluminium ethoxide, diisobutylaluminium ethoxide, dioctyl aluminum butoxide, diisobutyl aluminum octyl oxide, diethylaluminum chloride, diisobutyl aluminum chloride, dimethylhydrosiloxy aluminum Dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isoprenyl, etc., and mixtures thereof are recommended. A highly active catalyst can be obtained by combining these alkyl aluminum compounds with the solid catalyst described above, and trialkyl aluminum and dialkyl aluminum hydride are particularly preferred because they achieve the highest activity. As the complex containing organomagnesium, the general formula MaMg7R8,
A complex represented by R9qXrY8 is used.

Particularly preferred are complexes in which M is aluminum. The solid catalyst component (A) and the organometallic compound UB) 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 to the solid catalyst 19. Olefins that can be polymerized using the catalysts of the invention are alpha olefins, especially ethylene.

Furthermore, the present invention converts ethylene into monoolefins such as propylene, butene-1, hexene-1, and butadiene,
It can be used for polymerization in the coexistence of a diene such as isoprene, and furthermore, it can be used for polymerization of a diene. 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 added to the polymerization solution, 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. ＼Ethylene is introduced into the reactor under pressure in an inert atmosphere at a concentration of 1 to 20 k9/Cl, and the temperature is between room temperature and 1.
Polymerization can proceed at a temperature of 50°C. On the other hand, gas phase polymerization uses ethylene at a pressure of 1 to 50 kT at room temperature to 12
Polymerization can be carried out at a temperature of 0.degree. C. by using a fluidized bed, a moving bed, or a stirrer for mixing to ensure good contact between ethylene and the catalyst. The polymerization may be carried out in a single-stage polymerization using one reaction zone, or in a so-called multi-stage polymerization using a plurality of reaction zones. This catalyst can also be used in normal one-stage polymerization.
Although it is possible to produce a polymer with a sufficiently wide molecular weight distribution, it is possible to produce a polymer with an even wider molecular weight distribution by carrying out multi-stage polymerization in which polymerization is carried out under two or more different reaction conditions. 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. 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 the examples, MI stands for melt index, AST
Temperature 190℃, load 2.1 according to M-D-1238
This was measured under the condition of 6 kg. FR is temperature 19
The value measured under the conditions of 0°C and a load of 21.6 kg is MI.
The higher the value, the wider the molecular weight distribution. The die well has an outer diameter of 16 mm and an inner diameter of 10 mm.
Parison 20? was extruded using a die at a temperature of 170°C? It is expressed as per weight (3). Example 1 (1) Synthesis of solid components
A 0ml flask was purged with nitrogen, 700 mmol of titanium tetrachloride was charged into the flask, and 1Pr0-f-+ of isopropyl titanate decamer (manufactured by Nippon Soda) was added to the flask.
100 mmol of l-0+1Pr was weighed out based on Ti.

The flask was heated to 110°C, and titanate was added dropwise over 1 hour while stirring under a nitrogen stream.
The reaction was carried out for a total of 3 hours. During the course of the reaction, a pale ocher solid was formed with gas evolution. The solid product was isolated, washed with n-hexane and dried. Yield is 2
6.99, the T1 and Cl contents of this solid product are 36.3% and 38.0%, respectively, and 0iC3
The H7 group was 0.1% or less.

A 100 wL1 flask equipped with a dropping load and a stirrer was purged with nitrogen, and 50 ml of n-hexane and 10 mmol (based on Ti) of the above solid product were put into the flask to form a slurry, which was cooled to -1'C.

While stirring this slurry, at -1'C, composition A
lM86. O(C2H5)2.9(n-C4H9)12
．． An n-hexane solution 20a containing 10 mmol (based on Mg) of the organomagnesium complex No. 1 was added dropwise over 30 minutes, and after the dropwise addition, the mixture was stirred at 25° C. for 1 hour. The resulting black solid component was isolated, washed and dried. (2) Polymerization Hexane 151 obtained by dehydrating and deoxidizing the above solid component 800719 and 7.5 mmol of triisobutylaluminum.
Then, the inside was vacuum degassed and placed in a 301 autoclave which was purged with nitrogen.

Keep the internal temperature of the autoclave at 85℃ and add hydrogen to 5.0k.
gZ? Then, ethylene was added to a pressure of 10 g. By replenishing ethylene, the total pressure can be reduced to 1
Polymerization was carried out for 4 hours while maintaining the gauge pressure of 0k9/Cll to obtain a polymer of 6.51<9.

MI was 0.39, FR was 85, true specific gravity was 0.965, and bulk density was 0.42. (3) Moldability The produced polymer was formed into pellets using an extruder with a screw diameter of 40 mu, and the die swell was measured.

The effect on die swell is clear from Table 1. That is, the polymer of the present invention itself has an extremely large die swell, and the improvement effect on polymers with a small die swell is also remarkable. The bottle molded using the polymer of this example had a good surface condition and extremely excellent environmental stress resistance. Example 2 (
1) Synthesis of solid component A solid product was synthesized in the same manner as in Example 1, except that titanium tetrachloride was used as a 4 mol/l octane solution and 1100 mmol of this was used.

Tl and Cl in the solid were 37.8% (Fb and 42.0%). 10 mmol of this solid (based on Ti) and composition A
IM, 3. O(C2H5)3.1(n-C4H9)5.
A solid component was synthesized by reacting a hexane solution containing 5 mmol (based on M8) of organomagnesium complex No. 9 at -20°C for 6 hours (additional 5 hours after dropping for 1 hour) in the same manner as in Example 1. . (2) Polymerization 800T of the above solid components
Polymerization was carried out using n9 and 30 mmol of tri-n-butylaluminum under the same conditions as in Example 1, and 6.01<
A polymer of No. 9 was obtained.

MI was 0.35, FR was 87, true specific gravity was 0,962, and bulk density was 0.45. (3) Moldability The produced polymer was made into pellets using an extruder with a screw diameter of 40 m7IL, and the die swell was measured.

The results are shown in Table 2. The bottle molded using the polymer of this example had a good surface condition and excellent environmental stress crack resistance. Example 3 (1) Synthesis of solid components Titanium tetrachloride was used as a 4 mol/l octane solution, and 500 mmol of this was used, and a pentamer of isopropyl titanate was used as a polytitanate ester at 4 mol/l.
A solid product was synthesized in the same manner as in Example 1 except that an octane solution (based on Ti) was used.

The Ti content in the solid was 34.20I) and the Cl content was 34.1%. 10 mmol of this solid (based on Ti) and the composition Zn
Mg2. A hexane solution containing 20 mmol (based on Mg) of an organomagnesium complex of O(C2H5)2.0(C6Hl3)4.1 was heated at 40°C for 1.5 hours (an additional 1 hour after dropping for 30 minutes) Example 1 React in the same way as
A solid component was synthesized. (2) Polymerization of the above solid component 800T
Polymerization was carried out under the same conditions as in Example 1 using f9 and 3.75 mmol of triethylaluminum to obtain 5.5 kg of polymer.

MI was 0.15, FR was 93, true specific gravity was 0.960, and bulk density was 0.44. (3) Moldability The die swell was measured in the same manner as in Example 1.

The results are shown in Table 3. The film molded from the polymer of this example contained less gel, had good molding stability, and had excellent strength. Example 4 (1) Synthesis of solid components Titanium tetrachloride was used as a 4 mol/l octane solution, isoamyl titanate pentamer was used as the polytitanate ester, and the reaction conditions were 130°C for 5 hours (1 hour after dropwise addition). for an additional 4 hours), otherwise the solid product was synthesized in the same manner as in Example 1.

Tl and Cl in the solid were 37.5% and 40.8 (fl), respectively. 10 mmol of this solid (based on Ti) and composition M8(C2H5)2.5(n-C4H9)1.5(0n
-C4H9). ．． A solid component was synthesized by reacting a hexane solution containing 10 mmol (based on M8) of an organomagnesium complex of , under the same conditions as in Example 1. (2) Polymerization The above solid components 80η and triisobutylaluminum 0
．． 4 mmol of dehydrated and deoxygenated hexane 0.81 and ＼
Both were placed in a 1.511 autoclave whose interior was vacuum degassed and replaced with nitrogen.

The internal temperature of the autoclave was maintained at 85° C., hydrogen was pressurized to 5°C, and then ethylene was added to bring the total pressure to 10°C.

Polymerization was carried out for >2 hours while maintaining the total pressure at 10 mm gauge by replenishing ethylene, yielding 240 g of polymer.

MI was 0.58 and FR was 75. Example 5 (1) Synthesis of solid components Titanium tetrachloride was used as a 4 mol/l octane solution, tert-butyl titanate dimer was used as the polytitanate ester, the reaction conditions were 13'C5 hours, and the other conditions were as in Example A solid product was synthesized in the same manner as in 1.

Ti and Cl in the solid were 35.8% and 39.1%, respectively. 10 mmol of this solid (based on Ti) and composition AIM, 2
．． O(C2H5)2.0(n-C4H9)4.0{0S
iH・(CH3)・(C2H5)}, . A solid component was synthesized by reacting a hexane solution containing 10 mmol (M, standard) of organomagnesium complex of 0 under the same conditions as in Example 1.

(2) Polymerization Polymerization was carried out in the same manner as in Example 4 using 80 mg of the above solid component and 0.4 mmol of diethylaluminium hydride to obtain polymer 2709.

MI was 0.70 and FR was 78. Example 6 (1) Synthesis of solid component A cyclohexyl titanate dimer was used as the polytitanate ester, the reaction conditions were 150°C for 3 hours (1 hour of dropwise addition, and 2 hours more after dropping), and the other conditions were the same as in Example 1. A solid product was synthesized.

Ti in solid product is 36.2 (f), Cl is 38.7
It was (f/). 10 mmol of this solid (based on Ti)
and composition EMg3. O(C2H5)2.1(n-C4H
9)5. , 10 mmol of organomagnesium complex (M,
A solid component was synthesized by reacting a hexane solution containing (standard) under the same conditions as in Example 1. (2) Polymerization 80T of the above solid components! V! Polymerization was carried out in the same manner as in Example 4 using 1.6 mmol of trihexylaluminum and 2459 polymer.

MI was 0.25 and FR was 90. Example 7 (1
) Synthesis of solid component A solid product was synthesized in the same manner as in Example 1 except that Sec-butyl titanate pentamer was used as the polytitanate ester and the reaction conditions were 100° C. for 3 hours.

Tl in the solid product is 37.70I), Cl is 38.3
It was %. A solid component was synthesized by reacting 10 mmol of this solid (based on Ti) with a methylcyclohexane solution containing 10 mmol of didecylmagnesium under the same conditions as in Example 1. (2) Polymerization of the above solid component 80η and aluminum isoprenyl 1.
Polymerization was carried out in the same manner as in Example 4, using 6 mmol, to obtain a polymer of 2001.

MI was 0.10 and FR was 105. Example 8 (
1) Synthesis of solid components 300 mmol of titanium tetrachloride was used as a 4 mol/l octane solution, the reaction conditions were 80°C for 5 hours (1 hour of dropwise addition, and a further 4 hours after dropping), and all other conditions were the same as in Example 1. A solid product was synthesized.

The solid product contained 37.1% Ti and 35.5% Cl. 10 mmol of this solid (based on Ti) and composition (n
A solid component was synthesized by reacting a hexane solution containing 10 mmol (based on Mg) of an organomagnesium complex of -C4H9)2M8.1.2C4H40 under the same conditions as in Example 1.

(2) Polymerization The above solid component 80η and composition Al (1s0-C4H,)
Polymerization was carried out in the same manner as in Example 4 using 0.8 mmol of organic aluminum represented by 2.5CI0.5 to obtain a polymer 1309.

MI was 0.91 and FR was 64. Example 9 (1) Synthesis of solid component Anhydrous magnesium chloride powder 109 was suspended in 700 ml of a 1 mol/l titanium tetrachloride octane solution and charged into a No. 11 flask.

100 mmol of isopropyl titanate decamer (Tl standard) was weighed out into the dropping load, and a solid product was synthesized under the same conditions as in Example 1. 10 mmol of this solid (
Ti standard) and composition n-C4H, M8Cl・1.1 (n-
5 mmol (M
, reference) under the same conditions as in Example 1 to synthesize a solid component.

(2) Polymerization The above solid component 801n9 and composition Al(C2H5)2.
5 (0C2H5).

．． Polymerization was carried out in the same manner as in Example 4 using 0.8 mmol of organic aluminum represented by No. 5, and 265f!
of polymer was obtained. MI was 0.57 and FR was 78. Example 10 (1) Synthesis of solid component A solid product was synthesized under the same conditions as in Example 9, except that silica (grade 952 manufactured by Fuji Davison) 109 was used in place of anhydrous magnesium chloride 109 in Example 9. did.

10 mmol of this solid product (based on Ti) and composition (Se
c-C4H9)Mg(0S1H-CH3・n-C4H9
) with a heptane solution containing 5 mmol (M8 standard) of organomagnesium complex under the same conditions as in Example 1 to synthesize a solid component. (2) Polymerization The above solid component 80rf19 and composition AIM, 2. O(C
Polymerization was carried out in the same manner as in Example 4 using 1.6 mmol (M, standard) of the organomagnesium complex shown in 2H5)2.1(n-C4H9)3.9 to obtain a polymer of 1609. Obtained.

MI was 0.43 and FR was 80. Example 11 (1) Synthesis of solid component A solid product was synthesized under the same conditions as in Example 9, except that titanium hydroxide 109 was used in place of anhydrous magnesium chloride 109 in Example 9.

10 mmol of this solid product (based on Ti) and composition (Se
A solid component was synthesized by reacting c-C4H, )M, (n-C4H9) with a heptane solution containing 3.3 mmol (M, standard) of organomagnesium under the same conditions as in Example 1. (2) Polymerization The above solid components 80η and triisobutylaluminum 0
．． Polymerization was carried out in the same manner as in Example 4 using 4 mmol to obtain 1259 polymer.

MI was 0.35 and FR was 85. Example 12 (
1) Synthesis of solid components Magnesium oxide 10f was substituted for anhydrous magnesium chloride 109 in Example 9! A solid product was synthesized under the same conditions as in Example 9 except that .

10 mmol of this solid product (based on Ti) and (C2H
5) A heptane solution containing 10 mmol of organomagnesium Mpan-C4H9) was reacted under the same conditions as in Example 1 to synthesize a solid component. (2) Polymerization The above solid components 80η and triisobutylaluminum 0
．． Polymerization was carried out in the same manner as in Example 4 using 4 mmol to obtain a polymer of 2009.

M was 0.14 and FR was 94. Example 13 (1
) Synthesis of solid components 10 mmol (based on Ti) of the solid product synthesized in Example 1 and composition AlM86. O(C2H5)2. .

(n-C4H9)9. A hexane solution containing 3.3 mmol (M8 standard) of an organic 7gnesium complex of 3.5 S(0-n-C4H9) was reacted under the same conditions as in Example 1 to synthesize a solid component.

(2) Polymerization Polymerization was carried out in the same manner as in Example 4 using 80 mg of the above solid component and 0.4 mmol of diisobutylaluminum hydride to obtain polymer 3209.

MI was 0.52 and FR was 79. Comparative Example 1 Polymerization was carried out in the same manner as in Example 4 using 80 m9 of the solid product synthesized in Example 1 (before reaction with the organomagnesium component) and 0.4 mmol of triisobutylaluminum.

The obtained polymer was only 759 and the MI was 0.01.
It was below. Comparative Example 2 Polymerization was carried out in the same manner as in Example 4 using 80η of the solid product synthesized in Example 2 (before reaction with the organomagnesium component) and 0.4 mmol of triisobutylaluminum.

The obtained polymer was only 709 and the MI was 0.01.
It was below. Example 14 Same as Example 4 except that 80η of the solid component synthesized in Example 1 and 0.4 mmol of triisobutylaluminum were used, and an ethylene-propylene mixed gas containing 4f6 of propylene was used instead of ethylene. Polymerization was carried out using the following methods to obtain a polymer of 2659.

MI was 1.47, FR was 71, and true specific gravity was 0.957. Example 15 Polymerization was carried out using the same catalyst and under the same polymerization conditions as in Example 14, except that an ethylene-buden-1 mixed gas containing 2(f) puden-1 was used instead of the ethylene-propylene mixed gas, and 2459 of polymer was obtained.

Claims (1)

[Claims] 1 (A) (i) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a secondary or tertiary hydrocarbon group having 3 or more carbon atoms, May be the same or different, n is 2
A solid product obtained by reacting a polytitanate ester represented by (the above integer) with titanium tetrahalide and thermally decomposing it; and (ii) a solid component produced by reacting with an organomagnesium solution; (B)
A catalyst for polyethylene production consisting of an organometallic compound. 2 In the polytitanate ester, R has 3 or more carbon atoms
The catalyst for producing polyethylene according to claim 1, which is a secondary to tertiary aliphatic hydrocarbon group of No. 6. 3 The molar ratio when reacting polytitanate with titanium tetrahalide is [Ti in titanium tetrahalide]
The catalyst for producing polyethylene according to claim 1 or 2, wherein: /[Ti in polytitanate ester]≧3. 4. The catalyst for producing polyethylene according to claims 1 to 3, wherein the Ti concentration is 4 mol/l or more and the reaction temperature is 80° C. or more when reacting the polytitanate ester with titanium tetrahalide. . 5. The catalyst for polyethylene production according to claims 1 to 4, wherein the titanium tetrahalide is titanium tetrachloride. 6. The catalyst for producing polyethylene according to claims 1 to 5, wherein the organomagnesium solution is an inert hydrocarbon solution of an organomagnesium compound or a complex compound soluble in an inert hydrocarbon. 7 Organomagnesium solution has the general formula M_αM_g_βR^8_pR^9_qX_rY_s(
In the formula, M is an atom selected from aluminum, zinc, boron, lithium, and perylium, R^8 and R^9 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, and X and Y are the same or different. TsutaOR^1^0, OSiR^1^1R
^1^2R^1^3, NR^1^4R^1^5, SR^
1^6 group, R^1^0, R^1^6 has 1 carbon atom
~10 hydrocarbon groups, R^1^1, R^1^2, R^1
^3, R^1^4, R^1^5 represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, α and β are greater than 0, and p, q, r, and s are 0 or 0. larger than β/α≧0.5
, p+q+r+s=mα+2β, 0≦r+s/α+β≦
1.0, and m represents the valence of M). Catalyst for polyethylene production. 8. The catalyst for polyethylene production according to claims 1 to 7, wherein the organometallic compound (B) is an organoaluminum compound or an organomagnesium complex compound soluble in an inert hydrocarbon.