JPS64969B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst for producing ethylene polymers or ethylene copolymers by polymerizing ethylene or a component containing ethylene as a main component. Polyolefin, general formula

No. 3,752,795 discloses a method of polymerizing chromyl bis(triorganotitanate) represented by the formula [Formula] (wherein R represents an alkyl alkaryl, aryl, or cycloalkyl group) by contacting it with an organoaluminum compound. stated in the statement, and
JP-A-51-116192 discloses a method in which a solid inorganic support material having a surface hydroxyl group, a catalyst consisting of a reaction product of chromium trioxide, a phosphorus compound, and an aluminum compound are combined with a reducing agent (boron compound). is disclosed. The present inventors used chromium trioxide, titanium,
A reaction product obtained by reacting a polyhydrocarbyloxy compound of vanadium, zirconium, or hafnium is reacted with a silica or silica/alumina support having a specific water content. A solid obtained by reacting with a polyhydrocarbyloxy compound of vanadium, zirconium, or hafnium is heated under certain conditions with oxygen. It was discovered that by combining a solid catalyst obtained by calcination in the presence of a specific organometallic component, a catalyst that provides an ethylene polymer with high activity and excellent melt flowability could be obtained, and the present invention was achieved based on this discovery. did. That is, the present invention provides: 1 [A] (1) A silica or silica-alumina support having a moisture content of 0.01 to 1% by weight, (2) a component selected from hydrocarbyloxy compounds of titanium, vanadium, hafnium, and zirconium, and trioxide. A solid catalyst component obtained by supporting a chromium reactant and calcining it in the presence of oxygen [B] (1) General formula M〓Mg〓R ¹ _p R ² _q X _r Y _s (in the formula,
M is an element selected from Al, B, Be, Zn, Li, α is 0 or a number larger than 0,
p, q, r, s are 0 or a number larger than 0, p, q are not 0 at the same time, and 0≦
(r+s)/(α+β)≦1.5 and p+q+
The relationship is r+s=mα+2β, m is the valence of M, R ¹ and R ² are the same or different groups, and OR ³ , OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ ,
SR ⁹ represents a halogen group, R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen groups or hydrocarbon groups having 1 to 20 carbon atoms, and R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms.
represents a hydrocarbon group. ) and (2) 0.1 to 1 mole of carbinol having 1 to 10 carbon atoms, or silanol or siloxane per mole of the trialkylaluminum compound.
A catalyst for producing polyethylene or ethylene-olefin copolymer, which is a component consisting of an organoaluminum component reacted with 0.1 to 1 mole, and is composed of [A] and [B]. 2. The first solid catalyst has a chromium content of 0.01 to 10% by weight in terms of chromium atoms.
Catalyst 3 for producing polyethylene or a copolymer of ethylene and olefin described in Section 3. The organomagnesium component is α>0, β/α
Catalyst 4 for producing a copolymer of polyethylene or ethylene and olefin according to the above item 1 or 2, where α>0.2, β/α
≧0.5 Catalyst 5 for producing polyethylene or a copolymer of ethylene and olefin according to Items 1 to 3 above In the organomagnesium component, X and Y are
Catalyst 6 for producing a copolymer of polyethylene or ethylene and olefin according to the above items 1 to 4, which is OR ³ or OSiR ⁴ R ⁵ R ⁶ In the organomagnesium component, 0≦(r+
Catalyst 7 for producing polyethylene or a copolymer of ethylene and olefin according to any of the above items 1 to 5, wherein 0≦(r+
s)/(α+β)≦0.8 Catalyst 8 for producing polyethylene or a copolymer of ethylene and olefin according to the above items 1 to 6 General formula M〓Mg〓R ¹ _p R ² _q X _r Y _s In the hydrocarbon-soluble organomagnesium component represented by
The polyethylene or ethylene and olefin according to the above items 1 to 7, which is a group OSiR ⁴ R ⁵ R ⁶ (R ⁴ , R ⁵ , R ⁶ are hydrogen groups or hydrocarbon groups having 1 to 20 carbon atoms) ^Catalyst _{9 for} ^producing a _{copolymer of}
Items 1 to 8 above, which is a group OSiR ⁴ R ⁵ R ⁶ , wherein R ⁴ is a hydrogen group, or R ⁴ , R ⁵ , and R ⁶ are a hydrocarbon group having 1 to 7 carbon atoms. Catalyst 10 _for ^{producing polyethylene} or _a copolymer _of ethylene and _olefin described in
A group OSiR ⁴ R ⁵ R ⁶ , where R ⁴ is a hydrogen group, and R ⁵ and R ⁶ are methyl, ethyl, propyl,
The organoaluminum component of the catalyst 11 [B] for producing a copolymer of polyethylene or ethylene and olefin according to items 1 to 9 above is a hydrocarbon group selected from butyl, amyl, hexyl, phenyl, and tolyl. , Catalyst 12 for producing a copolymer of polyethylene or ethylene and olefin according to Items 1 to 10 above, which is a component obtained by reacting trialkylaluminium and silanol or siloxane. [B] Silicon group contained in component Catalyst 13 for producing polyethylene or a copolymer of ethylene and olefin according to Items 1 to 1 above, which is a compound having an Si-H bond, wherein the silicon group contained in the [B] component is
Catalyst 14 for producing a copolymer of polyethylene or ethylene and olefin as described in Items 1 to 12 above, which is 0.1 to 2 mol per gram atom of metal in the organometallic compound as a component. Provided is a catalyst for producing polyethylene or a copolymer of ethylene and olefin according to any one of the above items 1 to 13, which is used as the component [A] after being brought into contact with a small amount of component [B] in advance. The first feature of the present invention is that the catalyst has a high efficiency in terms of polymer yield per gram of catalyst. (The step of removing the catalyst residue can be omitted.) The second feature is that the produced polymer has excellent melt fluidity as indicated by swell. The carrier used in the present invention is silica, silica-
Alumina is used, but silica is preferred, and among silica, the specific surface area measured by the BET method is 200
Particularly preferred are those having a specific pore volume of ~600 m ² /g, a specific pore volume of 1 to 2 ml/g, and an average pore diameter of 50 to 300 Å. The amount of water attached to the carrier (hereinafter referred to as water content) is 0.01 to 1.
The weight percentage is important and preferably ranges from 0.1 to 0.8 weight percent. Commercially available chromium trioxide can be used as the chromium trioxide in the present invention. Purified ones are preferred. The hydrocarbyloxy compounds of titanium, vanadium, hafnium, and zirconium used in the present invention will be explained. Titanium has the general formula Ti (OR ¹⁰ ) _l X _4-l [in the formula,
^{R 10} is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and l represents a number of 1≦l≦4. Specifically, the group is methyl,
ethyl, propyl, butyl, amyl, hexyl,
Examples include heptyl, octyl, nonyl, decyl, dodecyl, phenyl, tolyl, cyclohexyl and the like, preferably 2≦l≦4, particularly preferably 3≦l≦4. Further, when l<4, X is preferably chlorine. Zirconium has the general formula Zr (OR ¹⁰ ) _l X _4-l
[In the formula, R ¹⁰ , X, and l are the same as described above. ], preferably 2≦l≦4, particularly preferably 3≦l≦4. When l<4, X is preferably chlorine. Examples of preferred compounds are:
Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , Zr (OC ₅ H ₁₁ ) ₄ , Zr
(OC ₆ H ₅ ) ₄ , Zr(OC ₄ H ₉ ) ₃ Cl. Hafnium has the general formula Hf (OR ¹⁰ ) _l X _4-l
[In the formula, R ¹⁰ , X, and l are the same as described above. ] is used. Vanadium has the general formula VO (OR ¹⁰ ) _l X _3-l
(In the formula, R and X are the same as above, and l is 1≦l≦3
[representing a number]] can be mentioned. The reaction between chromium trioxide and titanium, vanadium, zirconium or hafnium compounds can be carried out in an inert organic solvent. The reaction includes
The presence of oxygen and moisture is undesirable and should be prevented from entering, and exposure to light is also undesirable. After the reaction is completed, it is preferable to remove unreacted chromium trioxide. Among the above reaction products,

It is presumed that something with the structure of [Formula] exists, but it is not certain. Regarding the method of supporting the above reaction product on silica or a silica carrier, there are methods such as adding the carrier to the reaction product solution and distilling off the solvent, and separating methods, but methods of removing the solvent and supporting it. is preferred. The supporting temperature is -10 to 70°C,
Preferably it is 0 to 55°C. The amount of chromium compound supported on the carrier is 0.01 to 10% by weight in terms of chromium atoms.
and preferably 0.05 to 5% by weight. Activation is performed by firing the supported solid thus obtained. This activation by calcination is generally performed in the presence of oxygen. In particular, it is important that the moisture content in the atmosphere is low, and the moisture content is 20 ppm or less, preferably 10 ppm or less, and particularly preferably 1 ppm or less. Although it is possible to perform the firing under reduced pressure, it is preferable to perform the firing under an oxidizing atmosphere such as air. The activation temperature is 300°C to 900°C, preferably 500 to 800°C. Activation time is 0.5
~10 hours, but can be determined depending on the activation temperature. The [B] component used in combination with the solid catalyst component will be explained. The organic magnesium component has the general formula M〓Mg〓R ¹ _p R ² _q
X _r Y _s (where M is an element selected from Al, B, Be, Zn, Li, α is 0 or a number greater than 0, p,
q, r, s are 0 or a number greater than 0,
p and q are not 0 at the same time, but p+q+r+s=mα+
2β relationship, m is the valence of M, R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X,
Y is the same or different groups, and OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ SR ⁹ represents a group selected from halogen, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen groups or have 1 to 20 carbon atoms. R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms. ) is a hydrocarbon-soluble organic magnesium component. In the above formula, the hydrocarbon group represented by R ¹ to R ⁹ is an alkyl group, a cycloalkyl group, or an aryl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc. are mentioned, especially R ¹
is preferably an alkyl group. Further, R ³ to R ⁸ may be a hydrogen group, and R ³ is preferably a hydrogen group. When α>0, aluminum, boron, zinc, beryllium, and lithium are preferable as M because they facilitate the formation of a hydrocarbon-soluble organomagnesium complex.
Ratio of magnesium to metal atom M (β/α)
is not particularly limited, but is preferably a hydrocarbon-soluble organomagnesium complex in the range of 0.2 or more, particularly 0.5 or more. Relational expression p+q+ of symbols α, β, p, q, r, s
r+s=mα+2β indicates stoichiometry in the organomagnesium component, and 0≦(r+s)/(α+β)≦
It is 1.5. The preferred range is 0≦(r+s)/
(α+β)≦1.0 means that X and Y
indicates that the sum is 0 or more and less than 1.0, and a more preferable range is 0 to 0.8. These organomagnesium complex compounds have the general formula
Organomagnesium compounds represented by R ^{1 MgX} , ^{R 1} _{2 Mg} ⁽ R ¹ is _the above-mentioned meaning, meaning)
It is synthesized by reacting an organometallic compound represented by the formula in an inert hydrocarbon solvent such as hexane, heptane, cyclohexane, benzene, toluene, etc. at room temperature to 150°C. Furthermore, MgX ₂ and MR ² _n , MR ² _n-1 H
or R ¹ MgX, MgR ¹ ₂ and R ² _o MX _no (where M,
R ¹ and R ² have the above-mentioned meanings, and n is a number from 0 to m). Next, when α=0 and r=0, that is, the general formula
The hydrocarbon-soluble organomagnesium compound represented by MgR ¹ _p R ² _q will be explained. (a) When at least one of R ¹ and R ² is a secondary to tertiary alkyl group having 4 to 6 carbon atoms. (b) When R ¹ and R ² are alkyl groups with different numbers of carbon atoms. (c) When at least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms. Preferably, R ¹ and R ² are in any of the following three cases. (a) When R ¹ and R ² both have 4 to 6 carbon atoms, and at least one of them is a secondary or tertiary alkyl group. (b)′ R ¹ is an alkyl group having 2 to 3 carbon atoms, and R ²
is an alkyl group having 4 or more carbon atoms. (c) When R ¹ and R ² are both alkyl groups having 6 or more carbon atoms. These groups will be specifically shown below. (b) and (b)′
Examples of secondary to tertiary alkyl groups having 4 to 6 carbon atoms include sec-C ₄ H ₉ , tert-C ₄ H ₉ , -
CH( _C2H5 ) ₂ , -C _{( C2H5} )( _CH3 ) ₂ , _-CH ( _CH3 )
( _C4H9 ) _, -CH( _C2H5 ) _{( C3H7} ), -C _{( CH3} ) ₂
( _C3H7 ), -C( _CH3 )( _C2H5 ) ₂ , etc. are used, preferably _a secondary alkyl group, and sec _{- C4H9} is particularly _preferred . In (b) and (b)', examples of the alkyl group having 2 to 3 carbon atoms include ethyl and propyl, with ethyl being particularly preferred. Examples of the alkyl group having 4 or more carbon atoms include butyl, amyl, hexyl, octyl and the like, with butyl and hexyl being particularly preferred. In (c) and (c)', the hydrocarbon group having 6 or more carbon atoms is preferably an alkyl group such as hexyl, octyl, decyl or phenyl group, with hexyl group being particularly preferred. Examples of such organomagnesium compounds include (sec- _C4H9 ) _{2Mg ,} (tert- _C4H9 ) _{2Mg ,} n-
C ₄ H ₉ −Mg−C ₂ H ₅ , n−C ₄ H ₉ −Mg・secC ₄ H ₉ ,
n- _C4H9 - _Mg -tert- _C4H9 , n _{- C6H13 -} Mg
−C _{2 H 5 ,} (n−C ₄ H ₉ ) _1.5 (n−C ₈ H ₁₇ ) _0.5 Mg, n−
C ₈ H ₁₇ −MgC ₂ H ₅ , (n−C ₆ H ₁₃ ) ₂ Mg, (n−
_Examples include _C8H17 ) _2Mg , (n- _C10H21 ) _{2Mg ,} and the like. As X, OR ³ , OSiR ⁴ R ⁵ R ⁶ are preferable,
Particularly preferred is OSiR ⁴ R ⁵ R ⁶ . OR ³ or
The amount of OSiR ⁴ R ⁵ R ⁶ relative to the metal magnesium atom, that is, R, is preferably 0.1 to 2, particularly preferably,
It is between 0.2 and 1.5. As the organic aluminum component, a component obtained by reacting and/or mixing a trialkylaluminum compound and an urbinol and/or silanol or hydroxyloxy compound is used. Examples of trialkylaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-i-
propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, triamylaluminum, trihexylaluminum,
Examples include trioctylaluminum, tridecylaluminum, tridodecylaluminum, isoprenylaluminum, and the like. Mixtures of these can also be used. Carbinol having 1 to 10 carbon atoms includes methyl alcohol, ethyl alcohol, n- and i-propyl alcohol, n-, i- and t-butyl alcohol, n-, i, sec, t-amyl alcohol,
Examples include phenol and cresol. The reaction ratio of trialkylaluminium and carbinol is 0.1 to 1 mol, preferably 0.15 mol of carbinol to 1 mol of trialkylaluminium.
~0.9 mol, particularly preferably 0.2-0.8 mol. Silanol or siloxane will be explained. Silanol includes trimethylsilanol,
Hydrolysates of triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, chlorosilane, etc. can also be used, and polysilanol can also be used. As the siloxane, methylhydropolysiloxane (

[Formula] n≧1) Ethylhydro Polysiloxane (

[Formula] n≧1), professional pill hydrosiloxane (

[Formula] n≧1), butylhydrosiloxane (

[Formula] n≧1), phenylhydrosylo Kisan (

[Formula]n≧1), etc. The reaction ratio of trialkylaluminium and silanol or siloxane is 1 mole of trialkylaluminium, silanol or siloxane.
The amount is 0.1 to 2 mol, preferably 0.1 to 1.5 mol, particularly preferably 0.2 to 1.2 mol. The ratio of organomagnesium component to organoaluminum component is 1 mole of organomagnesium component,
The organoaluminum component is preferably 0.05 to 50 mol,
Particularly preferred is 0.1 to 10 mol. The organomagnesium component and the organoaluminum component may be added to the polymerization system separately from the solid catalyst component, or the organomagnesium component and the organoaluminum component may be mixed in advance and added. It is preferable to bring the solid catalyst component into contact with a small amount of component [B] in advance. The ratio of [A] component and [B] component to be combined is metal in [B] component/Cr in [A] component from 0.01.
3000, preferably a range of 0.1 to 100 is recommended. Polymerization of ethylene and copolymerization of ethylene containing ethylene as the main component are carried out using the above catalyst.
~12 monoolefins or diolefins. Specifically, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1,
4-methylpentene-1,3-ethylbutene-
1, heptene-1, octene-1, decene-1,
butadiene, isoprene, 1,4 hexadiene,
Examples include 1,5 hexadiene, 1,7 octadiene, dicyclopentadiene, ethylidene, and rubornene. One or two types can be selected from these and used. The ethylene polymer or ethylene copolymer obtained according to the present invention has a molecular weight of about 0.91 to 0.97
Produced in density range of g/ml. The polymerization reaction is carried out at room temperature to about 300° C., but conditions vary depending on the polymerization pressure, monomer partial pressure, and the type and concentration of catalyst components. Generally, it is in a slurry state at room temperature to 100℃, and
It becomes a solution at ~200℃. In the catalyst of the present invention, the temperature is preferably 60 to 200°C, and polymerization in a slurry state is particularly preferred. The polymerization can also be carried out in the gas phase in the substantial absence of an inert organic solvent. When the polymerization reaction is carried out in the presence of an inert organic solvent, hydrocarbon solvents are preferred. Specific organic solvents that can be used include butane, isobutane, pentane, hexane, heptane, octane, isooctane, decane, aliphatic saturated hydrocarbons such as refined kerosene, cyclopentane, cyclohexane, dimethylcyclopentane, methylcyclohexane, etc. Examples include alicyclic saturated hydrocarbons such as saturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and isobutane, pentane, hexane, heptane, cyclohexane, and the like are preferred. As a molecular weight modifier, the polymerization reaction can be carried out in the presence of hydrogen or hydrogen halide, and hydrogen is particularly preferred. The amount of the molecular weight regulator can be arbitrarily adjusted as necessary. The polymerization may be carried out in a conventional one-stage polymerization using one reaction zone, or may be carried out in a so-called multi-stage polymerization using a plurality of reaction zones. The polymer polymerized using the catalyst of the present invention has a wide molecular weight distribution even in normal one-stage polymerization, and has a relatively high molecular weight.
Extremely suitable for blow molding and film molding. 2
Multi-stage polymerization, in which polymerization is carried out under more than one different reaction conditions, makes it possible to produce polymers with a wider molecular weight distribution. Examples of the present invention will be shown below, but the present invention is not limited thereby. In the examples, catalyst efficiency refers to the amount of polymer produced per gram of solid catalyst and per hour. MI is based on ASTM D-1238, temperature 190
FR means the melt index measured at a temperature of 190℃ and a load of 21.6Kg.
It means the quotient of MI divided by MI measured at a temperature of 190°C and a load of 2.16 kg, and represents the molecular weight distribution. Example 1 (i) Reaction of titanium hydrocarbyloxy compound and chromium trioxide. 15 ml of titanium tetra-n-butoxide, 120 ml of carbon tetrachloride, and 2 g of anhydrous chromium trioxide were collected in a flask, heated to reflux under stirring under a nitrogen atmosphere, and reacted for 24 hours. The solid was separated from the dark green solution to obtain a reactant solution. (ii) Synthesis of solid catalysts. 100g of commercially available silica (product name: Davison952),
n-hexane 1, the above titanium reactant solution (Cr
The reaction mixture was stirred at 60° C. for 4 hours, the solvent was distilled off, and the mixture was further dried under reduced pressure for 2 hours. This solid was calcined at 800° C. for 4 hours in dry air to obtain a solid catalyst. (iii) Synthesis of hydrocarbon-soluble organomagnesium components. 13.6 g of di-n-butylmagnesium and 1.83 g of triethylaluminum were placed in a flask purged with nitrogen along with 100 ml of n-heptane, and reacted at 80° C. for 2 hours to obtain an organomagnesium complex solution. As a result of analyzing this complex, the composition was found to be AlMg _6.0 (C ₂ H ₅ )
_3.0 (n-C ₄ H ₉ ) _11.9 , and the organometallic concentration is
It was 1.18 mol/. (iv) Synthesis of organoaluminium components. Triethyl aluminum 22.9g, n-pentane
430 ml and 12.05 g of hydromethylsiloxane tetramer were placed in a pressure-resistant container and reacted at 120°C for 5 hours. The resulting reaction product was collected and the aluminum concentration and ethane concentration resulting from decomposition were measured, and the composition of the reaction product was found to be Al(C ₂ H ₅ ) ₂ (OSiH・CH ₃・C ₂ H ₅ ). . (v) Polymerization of ethylene. 50 mg of the solid catalyst synthesized in (i), 0.05 mmol of the organomagnesium component synthesized in (iii), and 1.6 mmol of hexane obtained by dehydrating 0.15 mmol of the organoaluminum compound synthesized in (iv), and the interior was thoroughly vacuum-dried and replaced with nitrogen. The mixture was placed in an autoclave with an internal temperature of 80°C, ethylene was added at 10 kg/cm ² , hydrogen was added, and polymerization was carried out for 2 hours while maintaining the total pressure at 14 kg/cm ² .
270g of polyethylene was obtained. Catalyst efficiency is 2700
g-PE/g-solid catalyst/time, the MI of the polymer is
0.1g/10min, FR was 255. As a result of measuring the swell ratio, which is one of the melt flow properties of the obtained polymer, it showed a small value compared to that obtained with a Phillips type catalyst. Example 2 An experiment was conducted in the same manner as in Example 1 except that an organoaluminum compound synthesized as follows was used instead of the organoaluminum component synthesized in Example 1, and the following results were obtained. Ta. 125 mmol of triethylaluminum, 200 ml of n-pentane, methylhydropolysiloxane with a viscosity of 50 centistokes at 30°C on a Si basis.
125 mmol was added and reacted at 80°C for 2 hours. A portion of the reactant was analyzed to confirm the composition of Al(C ₂ H ₅ ) ₂ (OSiHCH ₃ C ₂ H ₅ ). Polyethylene yield: 254g Catalyst efficiency: 2540g-PE/g-solid catalyst time MI: 0.09g/10min FR: 220 Example 3 Commercially available silica (trade name: Davison952) 100g,
500 ml of n-hexane, titanium reactant solution synthesized in (i) of Example 1 (equivalent to 1 g of Cr metal atoms)
was added and reacted at 60° C. for 4 hours with stirring, and the solid was filtered and dried in a nitrogen stream. The above solid was calcined at 800° C. for 4 hours in dry air to form a solid catalyst. Using the above solid catalyst, ethylene was polymerized in the same manner as in Example 1, and the following results were obtained. Polyethylene yield: 240 g Catalytic efficiency: 2400 g-PE/g-solid catalyst time MI: 0.46 g/10 min FR: 147 Example 4 100 mg of the solid catalyst synthesized in Example 1 was added with organomagnesium component AlMg _6.0 (n-C ₄ H ₉ ) ₁₂ (C ₂ H ₅ ) _3.0
0.01 mmol and organic aluminum component Al
(C ₂ H ₅ ) ₂ [OSiH・CH ₃・C ₂ H ₅ ]0.01 mmol (both in hexane solution: 1 mol/) was added and reacted at room temperature for one day. Other than being used as a catalyst component,
The experiment was conducted in the same manner as in Example 1, and the following results were obtained. Polyethylene yield: 308 g Catalyst efficiency: 3080 g-PE/g solid catalyst time MI: 0.06 g/10 min FR: 290 Examples 5 to 14 The organomagnesium component and organoaluminum component in Example 1 were used as shown in Table 1. Ethylene polymerization was carried out in the same manner as in Example 1 except that the results shown in Table 1 were obtained.

【table】

[Table] Examples 15 to 21 In the synthesis of solid catalysts, everything was carried out in the same manner as in Example 1 except for using the compounds shown in Table 2. Table 2
I got the result. Example 22 Using an ethylene-butene-1 mixed gas containing 2 mol% of butene-1 instead of ethylene, using isobutane instead of hexane, the partial pressure of ethylene was 10 Kg/cm ² at 80°C, and the partial pressure of hydrogen was 1Kg/ ^cm2 ,
An experiment was conducted in the same manner as in Example 1 except that the total pressure was 23 Kg/cm ² , and the following results were obtained. Polyethylene yield: 312g Catalyst efficiency: 3120g-PE/g-solid catalyst time MI: 0.18g/10min FR; 234

【table】 [Brief explanation of the drawing]

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

Claims (1)

[Scope of Claims] 1 [A] (1) A silica or silica-alumina support having a moisture content of 0.01 to 1% by weight, (2) a component selected from hydrocarbyloxy compounds of titanium, vanadium, hafnium, and zirconium and trioxide. A solid catalyst component obtained by supporting a chromium reactant and calcining it in the presence of oxygen. [B] (1) General formula M〓Mg〓R ¹ _p R ² _q X _r Y _s (in the formula, M
is an element selected from Al, B, Be, Zn, Li, α is 0 or a number larger than 0, p, q,
r and s are 0 or a number larger than 0,
p and q are not 0 at the same time, 0≦(r+s)/
(α+β)≦1.5 and p+q+r+s=mα+2β
m is the valence of M, R ¹ and R ² are the same or different groups, and OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a halogen group, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are hydrogen groups or hydrocarbons having 1 to 20 carbon atoms. Group, R ⁹
represents a hydrocarbon group having 1 to 20 carbon atoms. ) and (2) 0.1 to 1 mole of carbinol having 1 to 10 carbon atoms, or silanol or siloxane per mole of the trialkylaluminum compound.
A catalyst for producing polyethylene or a copolymer of ethylene and olefin, which is a component consisting of an organoaluminum component reacted with 0.1 to 2 moles of [A] and [B].