JPS63178109A - Preparation of polyethylene - Google Patents

Abstract

PURPOSE:To prepare PE in a very high polymer yield and in a wide MW distribution, by polymerizing ethylene in the presence of a catalyst consisting of a specified transition metal compound carrier and a specified organoaluminum compound with the addition of a chlorinated hydrocarbon. CONSTITUTION:Ethylene is homopolymerized or copolymerized with other alpha- olefins in the presence of an inert solvent, by the use of a catalyst consisting of a solid transition metal compound carrier A, which is prepared in two steps in which a solid product obtained by reacting a trivalent metal halide with a hydrate of a divalent metal hydroxide, oxide or carbonate, or a double salt containing these or a divalent metal compound is reacted with a group IVa or Va transition metal containing a halogen in the presence of an electron donor compound [e.g. polysiloxane of the formula (where R1 and R2 are each a residue capable of bonding with Si; 3<=n<=10,000)], and the resulting product is then reacted with a group IVa or Va transition metal compound not containing a halogen in the presence of an electron donor compound, a catalyst ingredient consisting of a trialkylaluminum compound B and a catalyst ingredient consisting of a chlorinated hydrocarbon C. As a result, PE of a wide MW distribution is obtained in a high polymer yield.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Technology] The present invention relates to a method for producing polyethylene with a wide molecular weight distribution by polymerizing ethylene with an extremely high polymer yield.

Hereinafter, in the present invention, ethylene polymerization or polymer includes not only ethylene homopolymerization or homopolymer, but also copolymerization or copolymerization with other α-olefins that can be copolymerized with ethylene. Ethylene homopolymers and copolymers containing 50% by weight or more of ethylene units are collectively referred to as polyethylene.

[Conventional technology]

In recent years, technology for producing polyethylene using a Ziegler-type catalyst that combines a transition metal compound-supported catalyst component and an organometallic compound catalyst component has become widespread, but this technology is mainly used to improve catalyst utilization efficiency and reduce the catalyst removal process. This is based on the fact that it allows the manufacturing process to be simplified. However, efforts are being made to further improve the efficiency of catalyst utilization and to enable a more economical method for producing polyethylene.

As the carrier used for this transition metal compound-supported catalyst component, anhydrous magnesium chloride or its modified product,
It is known that organomagnesium halides such as Grignard reagents, organomagnesium compounds such as magnesium ethoxide, or compounds other than magnesium such as alumina and silica alumina are used.

In contrast, we differ woody from those carriers. A catalyst that combines a transition metal compound-supported catalyst component and an organoaluminium compound, which uses as a carrier a compound with a complex composition produced by a chemical reaction between a trivalent metal halide such as aluminum chloride and a divalent metal compound such as magnesium hydroxide. We have developed a method that increases catalyst efficiency and makes it possible to omit the catalyst removal step. For example, JP-A-81-4030111 and JP-A-81-1452.
No. 05 (hereinafter referred to as earlier inventions) discloses a step of reacting a halogen-containing Group 4a or Group 5a transition metal compound with the above-mentioned carrier in the presence of an electron-donating compound; Using a catalyst consisting of a transition metal compound-supported catalyst component and an organoaluminum compound obtained through two steps of reacting a halogen-free Group 4a or Group 5a transition metal compound in the presence of a chemical compound. However, it is desired that the polymer yield is further improved.

In addition, the polyethylene obtained by the method of the previous invention has a narrow molecular weight distribution, so it is very useful for injection molding, but when used for film molding or blow molding, the resin pressure increases during molding, which increases production capacity. It has the disadvantage that the value decreases.

Conventionally, methods to widen the molecular weight distribution have been proposed, such as lowering the polymerization temperature and modifying the transition metal compound catalyst component, but in both cases, as a result of widening the molecular weight distribution, the polymer yield decreases. There was a drawback that

Therefore, a method for producing polyethylene with a wide molecular weight distribution while improving the polymer yield is desired.

[Purpose of the invention]

As a result of intensive studies on new catalyst components and types of organoaluminum compounds for improving the previous invention, the present inventors found that using an appropriate amount of chlorinated hydrocarbon as the third component improves the polymer yield and improves the molecular weight distribution. It has been discovered that polyethylene with a wide range of properties can be obtained, leading to the present invention.

The present invention aims to further increase the polymer yield compared to the above-mentioned invention of light when producing polyethylene with an excellent shape, and to obtain polyethylene with a wide molecular weight distribution.

[Structure of the invention]

The present invention has the following configuration.

(i) A solid product (I) obtained by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a real hydrate of a divalent metal compound (Step A) a step of reacting a halogen-containing Group 4a or Group 5a transition metal compound (hereinafter referred to as a halogen-containing transition metal compound) in the presence of an electron-donating compound (hereinafter referred to as Step A); .

(Step B) Step 2 of the step (hereinafter referred to as Step B) of reacting a halogen-free Group 4a or Group 5a transition metal compound (hereinafter referred to as a halogen-free transition metal compound) in the presence of an electron-donating compound. A solid transition metal compound supported catalyst component obtained through the process (hereinafter referred to as solid product (II)) using a catalyst consisting of (i) a trialkyl aluminum compound catalyst component, and (i) a chlorinated hydrocarbon catalyst component A method for producing polyethylene, which comprises polymerizing ethylene alone or copolymerizing it with other α-olefins in the presence of an inert solvent.

The configuration and effects of the present invention will be explained in detail below.

Solid transition metal compound-supported catalyst component used in uninvented inventions (
The method for producing the solid product (II)) is detailed in the specification of the previous invention and will be shown below.

Examples of the trivalent metal halide used in the present invention include aluminum trichloride (anhydrous) and iron trichloride (anhydrous).

Examples of divalent metal compounds include Mg(OHh).

Ca(OH)2. Zll(OH)2, Mn(OH)2
hydroxides such as, oxides such as MgO, CaO, ZnO, MnO, NgA Iz 04 , Mg*5in
s , a double oxide containing a divalent metal such as Mg6 Mn0-.

Carbonates such as HgC0z, HnCO3, CaCO3, MgCl2・6H20, 5nCl2a 2H20,
MnCl2* 4H20, KMgcl, 661 (20
, former Cl2'' 6 H2O, such as 3Mg(L MgCh*4 H2O(1')
Hydrates of double salts containing oxides and halides, 3M
g0・2Si (h・2A hydrate of a double salt containing an oxide of a divalent metal such as R20, 3MgC (g(OH)2・
hydrates of carbonate and hydroxide double salts such as 3H20;
and genuine hydroxide carbonates containing divalent metals such as Mgs A h (OH)+c CO3.4H20.

The solid product (I) is obtained by reacting a trivalent metal halide and a divalent metal compound. In order to cause this reaction, it is preferable to mix and pulverize the two in advance for 5 to 100 hours using a ball mill or 1 to 10 hours using a vibration mill, and then heat the reaction after sufficiently mixing. It is also possible to carry out the reaction by heating. The ratio of trivalent metal halide to divalent metal compound is usually 0.0 when expressed as the atomic ratio of divalent metal to trivalent metal.
1 to 20 is sufficient, preferably in the range of 0.05 to 10.0 Reaction temperature is usually 20 to 500 °C, preferably 50 to 300 °C.2 Reaction time is suitable, 30 minutes to 50 hours, reaction When the temperature is low, the reaction is carried out for a long time so that no unreacted trivalent metal halide remains, and the obtained solid product is designated as solid product (I).

After the solid product (I) is subjected to the following two steps of reaction (step A) and (step B), the solid product (II) used in the present invention is obtained. At this time (A process) and (B process)
The order of the steps may be either first. Here, a case will be described in which (step B) is performed after (step A).

The obtained solid product (I) is then first reacted with a halogen-containing transition metal compound in the presence of an electron-donating compound (Step A).

As an electron-donating compound, (in the formula, R1 or R2 is a residue of the same or different type capable of bonding to silicon, and 3≦n≦10,000)
Polysiloxane represented by or general formula R'+sS i
(OR2)4-vn In the C formula, n1 is C1 to C20.
'+7) is a hydrocarbon group, hydrogen atom or halogen atom, R2 is a hydrocarbon group from C1 to G20, and 0≦m×4. ), as well as oxygen-containing organic compounds selected from ethers, esters, aldehydes, ketones, and carboxylic acids.

Octamethyltrisiloxane CHa (Sj(CHl)zO)2si(
CH3h, diphenyloctamethyltetrasiloxane (
CHI )3 SiO(Si(CHi)(Cs Hs
)0) Chain lower polymers such as 2si(CHl)3,
Octaethylcyclotetrasiloxane (Si (C3I)
%)20)4, cyclic polymers such as hexafnylcyclotrisiloxane (Si(CsR5)20)3, dimethylpolysiloxane (Si(CHl)z-0)wl
, methylethylpolysiloxane (Si(CHi)(C2
Hs)0)*.

Methylphenylpolysiloxane (S i CCHL) (
Cs Hs )0)9. Chain polymers such as methylhydrogen polysiloxane (5iH(CHi)0)n, chain alkylhydrogensiloxane polymers such as phenylhydrogen polysiloxane (5iH(Cs Is)0)n, chain arylhydrogensiloxane polymers Besides, chloromethylpolysiloxane (5iCl(CHi)0)n, methylethoxypolysiloxane (Si(C)Is) (C3I%0)
0)fi, chlormethoxypolysiloxane (SiC
Examples include chain polysiloxanes such as 1(CHiO)0)* and methylacetoxypolysiloxane (5i(CHi)(CH3CO2)0).The polysiloxane used is preferably liquid, and the viscosity (at 25°C) is 1
0 to 10,000 centistokes are suitable, preferably lO to 1,000 centistokes.

Examples of the alkoxy group-containing organosilicon compounds used in the present invention include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, ethyltriethoxysilane, diethyljethoxysilane, methyltriethoxysilane, tetrapropoxysilane, and tetraethoxysilane. -n-butoxysilane, tetraoctoxysilane, pentyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, trimethoxysilane, triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Examples include trimethoxychlorosilane, dimethoxydichlorosilane, and triethoxychlorosilane.

Furthermore, as the oxygen-containing organic compound, ethers such as di-n-butyl ether, di(isoamyl) ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diphenyl ether, anisole, and tetrahydrofuran, ethyl acetate, butyl acetate,
Esters such as methyl propionate, methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, aldehydes such as butyraldehyde, propionaldehyde, benzaldehyde, methyl ethyl ketone, diethyl ketone, acetylacetone, acetophenone , ketones such as benzophenone, and carboxylic acids such as acetic acid, propionic acid, and benzoic acid.

These electron-donating compounds can be used alone or in combination of two or more.

The halogen-containing transition metal compounds used in the present invention include compounds such as titanium, vanadium halides, oxyhalides, alkoxyhalides, and acetoxyhalides, such as titanium tetrachloride, titanium tetrabromide, trichlormonoisopropoxytitanium, Examples include dichlordiisopropoxytitanium, monochlortriisopropoxytitanium, trichlormonobutoxytitanium, dichlordibutoxytitanium, trichlormonoethoxytitanium, vanadium tetrachloride, vanadium oxytrichloride, and titanium tetrachloride is most preferred.

The solid product (I), the electron-donating compound, and the transition metal compound containing nitrogen may be mixed in any order under an inert gas atmosphere, such as nitrogen, but the mixture of the electron-donating compound and the transition metal compound may be mixed in any order. solid product (I)
It is preferable to add
Preferably it is -20°C to +30°C. At that time, there is no restriction on the presence or absence of a solvent.

The mixing ratio of the solid product (I), the electron donating compound, and the /\logen-containing transition metal compound is 100% of the solid product (I).
g, the electron donating compound is 10 to 10.000 g,
Preferably 20 to 1,000 g, and the halogen-containing transition metal compound is 10 to 10,000 g, preferably 20 to 1.
000g, and the halogen-containing transition metal compound is 10 to 1,000g per 100g of the electron-donating compound.
, preferably 20 to 500 g.The reaction conditions are 40°C to 300°C, preferably 50°C to 200°C with stirring.
The reaction is carried out at 10° C. for 10 minutes to 20 hours, preferably 10 minutes to 10 hours.

Although it is not necessarily necessary to use a solvent in mixing the solid product (I), the electron donating compound, and the /\rogen-containing transition metal compound and in their reaction, it is preferable to react uniformly, so it is preferable to use a solvent in advance. or all of the above components may be dissolved or dispersed in the solvent, and the total amount of the solvent used is sufficient to be about 10 times (by weight) or less the total amount of the above three components.

Solvents used include hexane, heptane, octane,
Aliphatic hydrocarbons such as decane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, carbon tetrachloride, chloroform, dichloroethane, Examples include halogenated hydrocarbons such as trichlorethylene, tetrachlorethylene, and carbon tetrabromide.

After the above reaction (Step A), the supernatant liquid is removed and washed with a solvent such as n-hexane, and then the next reaction (Step B) is carried out. Further, after the reaction in (Step A), the slurry may be used as it is to proceed to the next reaction (Step B).

Solid product (① is the above (Step A), ie.

After the reaction of the solid product (I), the electron donating compound, and the halogen-containing transition metal compound, the reaction product and the halogen-free transition metal compound are further reacted in the presence of the electron donating compound (Step B). Obtained by reaction.

As the electron-donating compound, the above-mentioned electron-donating compound is used, but it does not have to be the same as that used in the reaction of (Step A). When proceeding to the reaction (Step B), there is an unreacted electron-donating compound, so there is no need to add a new electron-donating compound, but if desired, a new electron-donating compound may be added. may be added.

Examples of halogen-free transition metal compounds include alkoxides of titanium and vanadium, such as tetraethyl orthotitanate (tetraethoxytitanium), tetraisopropyl orthotitanate (tetrine propoxytitanium), and tetra-n-butyl orthotitanate (tetra-n- Other polytitanate esters can be used, such as tetraalkyl orthotitanates (tetraalkoxytitanium) such as (butoxytitanium), vanadyl trialcholates such as vanadyl triethylate, vanadyl triisopropylate, and vanadyl tri-n-butylade.

This has the general formula RO(Ti(OR)2-0]++
+R, m is an integer of 2 or more, preferably 2 to 10, R represents an alkyl group, an aryl group, or an aralkyl group, and all R do not need to be the same type of group, but may be mixed. The number of carbon atoms in R is preferably 1 to 10, but is not particularly limited.

Specifically, they include methyl polytitanate, ethyl polytitanate, isopropyl polytitanate, n-butyl polytitanate, n-hexyl polytitanate, and the like. In the above general formula, some of the alkoxy groups may be hydroxyl groups.

A solid product that is a reactant in the previous step, an electron donating compound,
The amount of the halogen-free transition metal compound used is 1 of the electron donating compound per 100 g of the original solid product (I).
O~1G, 000g, preferably lO~1.000g
, 10-5.000g of halogen-free transition metal compound
, preferably 15 to 1,000 g, and the halogen-free transition metal compound is 10 to 1,000 g, preferably 20 to 500 g, per 100 g of the electron donating compound.
It is g. - Reaction conditions are 40°C to 300°C, preferably 50°C to 200°C with stirring for 10 minutes to 20 hours, preferably 1
React for 0 minutes to 10 hours.

Although it is not always necessary to use a solvent during the reaction, it may be used to ensure uniform reaction.

The amount of solvent used is approximately 10 times (by weight) the solid product Cl)
The following is sufficient.

The solvent to be used is the same as the solvent that can be used in the above (Step A), but does not need to be the same as the solvent used in (Step A).

After the above reaction, unreacted transition metal compounds and electron-donating compounds are removed using a solvent such as aliphatic hydrocarbon or aromatic hydrocarbon at room temperature, preferably 50°C or higher. The washing is repeated until no detection is detected and dried to obtain a solid product (II).

The solid product (II) obtained as described above is used as a transition metal compound-supported catalyst component.

Further, specific examples of the trialkylaluminum compound catalyst component used in the present invention include triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octyl aluminum. Examples include aluminum.

Furthermore, the chlorinated hydrocarbons that are catalyst components used in the present invention include methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1.1.
2-trichloroethane, 1,1,1.2-tetrachloroethane, 1,1,2.2-tetrachloroethane, 1.1
-dichloroethylene, l,2-dichloroethylene, trichlorethylene, tetrachloroethane, 1,2,3-trichloropropane, isopropyl chloride, 1,2-dichloropropane, n-butyl chloride, l-chloro-3 -Aliphatic chlorinated hydrocarbons such as methylbutane, 2-Cl-2-methylbutane, dichloropentane, alicyclic chlorinated hydrocarbons such as cyclohexane chloride, or chlorobenzene, Q-dichlorobenzene, 1,2. 44 Lichlorobenzene, Q-
Examples include aromatic chlorinated hydrocarbons such as chlorotoluene, P-chlorotoluene, and benzyl chloride.

The ratio of each catalyst component to be used is such that the chlorinated hydrocarbon catalyst component has an atomic ratio of (i) Cl in the catalyst component/(i) Al in the trialkyl aluminum catalyst component from 0.02 to 10. Use with. If it is less than 0.02, the effect will not be clear, and if it exceeds 10, the molecular weight distribution will be wide, but no improvement in polymer yield can be expected. Further, the trialkyl aluminum compound catalyst component is used in an amount such that the atomic ratio of Al in the (i) catalyst component to Ti in the (D catalyst component) is 1 to 2000. If it is less than 1, the polymerization activity is low. , it is not economical to exceed 2,000.

In addition, it is reasonable to mix the three components in the presence of an inert solvent, and they may be mixed before being supplied to the polymerization vessel, or they may be supplied separately to the polymerization vessel and brought into contact within the polymerization vessel. You can let me.

The thus obtained catalyst according to the method of the present invention is as follows.

Used in the production of polyethylene. α-olefins for ethylene copolymerization include linear chain olefins such as propylene, butene-1, hexene-1, and 4-methyl-
Examples include branched upper olefins such as pentene-1, and diolefins such as butadiene.

The polymerization reaction is usually carried out in an inert hydrocarbon solvent such as hexane, heptane, octane, or decane.The polymerization temperature is 30°C to 150°C, preferably 50 to 120°C, and the polymerization pressure is normal pressure to 50kg. /crn', preferably 3-4
During zero polymerization carried out at 0 kg/cm'', an appropriate amount of hydrogen can be added to the polymerization system to adjust the molecular weight.

〔Effect of the invention〕

The effect of the present invention is that polyethylene with a wide molecular weight distribution can be obtained at an extremely high polymer yield. In the present invention, molecular weight distribution refers to the weight average molecular weight /number average molecular weight), and the larger the value, the wider the molecular weight distribution.

Also, what is 1 polymer yield?

Formula (Ep=polymer (g)/(solid product (■) (g)×
Polymerization time (Hr)Xztyrene pressure (kg/cm1mSi(
OR2))) value of Ep (hereinafter, the polymer yield is expressed as Ep
It is sometimes abbreviated as. ).

According to the method of the present invention, Fc/t is 11~! It shows a large value of 4, has a wide molecular weight distribution, and has a polymer yield Ep of 4.
Shows a high value of 950 to 8420 (see Examples 1 to 6)
.

In comparison, when the catalyst used in the process of the invention lacks a chlorinated hydrocarbon catalyst component, the large/low value is 5.
-8, and the Ep value is also low, about 3B50-5400 (see Comparative Examples 1, 3-6).

Furthermore, even when a halogen-containing organoaluminum compound was used as the organoaluminum compound catalyst component, the EP value was as low as 1100 (comparative example 2), although the /t was as high as 15.
reference).

As described above, according to the method of the previous invention or the method lacking essential components of the present invention, Ep and/or /Mi1 are low values, but according to the method of the present invention, M, , /MN become large, Moreover, the value of Ep is also significantly improved.

The polymer thus obtained is suitable for film molding and blow molding.

Another advantage of the present invention is that the shape of the resulting polymer is very good, and the bulk specific gravity of the polymer reaches 0.47. Therefore, the production efficiency per hour per volume of one polymerization vessel is high, there is no or very little polymer adhesion to the walls of the polymerization vessel during polymerization, and stable continuous polymerization can be carried out for a long time in the same polymerization vessel.

〔Example〕

In Examples and Comparative Examples, Ml is melt index (AST
MD-1238), ni/Mll is an index of molecular weight distribution (he is a weight average molecular weight, country is a number average molecular weight, and was measured by gel permeation chromatography.

), BD indicates the bulk specific gravity of the polymer powder.

Example 1 (1) Production of solid product (I) 80 g of magnesium hydroxide and 140 g of aluminum trichloride (anhydrous) were mixed and ground at room temperature for 5 hours in a vibrating mill with a capacity of 2 ft, and then heated to 150°C. The reaction was allowed to proceed for 5 hours. Thereafter, it was cooled and pulverized to obtain a solid product (I).

(2) Production of solid product (II) While maintaining the temperature at 20°C and stirring, add 200 JL of toluene and 100 g of m-type dimethylpolysiloxane (viscosity 1007 cm) to a 1 fL round bottom flask with a stirrer.
Add and mix 100g of titanium tetrachloride.

After further adding 100 g of solid product (I), the reaction was carried out at 80°C for 3 hours, the supernatant liquid was removed, and 20 g of hexane was added.
The solid product was washed with zero weight. Add 200 grams of toluene and 30 grams of linear dimethylpolysiloxane to the remaining solid product.
(viscosity 100 centistokes) and 30 g of tetra-n-butyl orthotitanate, and then
After 0 hours of reaction, first perform filtration, wash the remaining solid product with hexane until no unreacted titanium compound is detected in the filtrate, dry under reduced pressure, and obtain the final solid product. (II) was obtained.

The content of titanium atoms in 1 g of solid product (tI) is 55
It was mg.

All operations up to the production of the solid product (■) were carried out under a moisture-free nitrogen gas atmosphere. The same applies to the following Examples and Comparative Examples.

(3) Production of polyethylene After purging a stainless steel polymerization vessel with a capacity of 20 tons with nitrogen gas, add 10 fL of hexane and 35 g of triethyl aluminum.
0mg, 1,2-dichloropropane 50■8, and 15mg of solid product (■) were added, the polymerization vessel was sealed, and 8
The temperature was raised to 0°C, hydrogen was introduced to a gauge pressure of 4 kg/cm', and ethylene was continuously introduced to maintain the total pressure at a gauge pressure of 15 kg/cm', while polymerization was carried out at 80°C for 2 hours. After the completion of the reaction, the polyethylene slurry was filtered without deashing and dried to obtain 110 g of a white polymer of 2E. The XI of this polymer is 1O89, BD is 0.47, N/D is 13, and Ep (polymer yield) is 842.
It was 0. This is shown in Table 1.

Example 2 In (3) of Example 1, instead of 1,2-dichloropropane,! Polyethylene was produced in the same manner as in Example 1, except that 300 g of 2-dichloroethane was used. The results are shown in Table 1.

Comparative Example 1 Polyethylene was produced in the same manner as in Example 1 except that 1,2-dichloropropane was not used in (3) of Example 1. The results are shown in Table 1.

Comparative Example 2 Polyethylene was produced in the same manner as in Example 1, except that in (3) of Example 1, 380 g of ethylaluminum dichloride was used instead of triethylaluminum. The results are shown in Table 1.

Example 3 (1) Production of solid product Cl) Solid product (I) was obtained in the same manner as in Example 1 (1).

(2) Production of solid product (■) The solid product (I) obtained in (1) was first subjected to the reaction in step B, and then the reaction in step A.

That is, while maintaining the temperature at 20°C and stirring, 200 layers of toluene, 100 g of linear dimethylpolysiloxane (viscosity 100 centistokes), and 30 g of tetra-n-butyl orthotitanate were placed in a 1-liter round bottom flask with a stirrer.
After adding 100 g of solid product (I) and reacting at 80° C. for 3 hours, the supernatant was removed and the solid product was washed with 200 layers of hexane. To the remaining solid product, add 200 g of toluene, 100 g of linear dimethylpolysiloxane (viscosity 100 centistokes),
After adding 100 g of titanium tetrachloride,
After the reaction was completed for 0 hours, filtration was first performed, and the remaining solid product was washed with hexane until no unreacted titanium compound or unreacted polysiloxane was detected in the filtrate, and dried under reduced pressure. A solid product (II) was obtained as a product.

(3) Polyethylene was produced in the same manner as in Example 1, except that 15 μg of the above solid product (II) and chlorobenzene 99B& were used as the chlorinated hydrocarbon catalyst component. The results are shown in Table 1.

Comparative Example 3 In (3) of Example 3, polyethylene was produced in the same manner as in Example 3 except that chlorobenzene was not used. The results are shown in Table 1.

Example 4 (1) 40 g of magnesium oxide and t of iron trichloride (anhydrous)
Bog was mixed and ground in a 2-liter ball mill for 24 hours at room temperature, and then reacted at 200'0 for 1 hour to obtain a solid product (I).

(2) While keeping the temperature at 20°C and stirring, add 300 mJl of xylene, 100 g of phenyltriethoxysilane, 130 g of titanium tetrachloride to a round bottom flask with a capacity of 11 and a stirrer.
and 100 g of the above solid product (I) were simultaneously added and mixed and then reacted at 110°C for 2 hours. ), 45 g of orthothimono-ugly tetraethyl was added, and the mixture was reacted at 100"C! for 2 hours. After the reaction was completed, filtration was first performed, and the remaining solid product was filtered until no unreacted titanium compound was detected in the filtrate. The solid product (II) was obtained as a final solid product by washing with hexane and drying under reduced pressure.

(3) Polyethylene was produced in the same manner as in Example 1, except that 15 g of the solid product (II) and 94+sg of l-chloro-3-methylbutane were used as the chlorinated hydrocarbon catalyst component. The results are shown in Table 1.

Comparative Example 4 Polyethylene was produced in the same manner as in Example 4 except that 1-chloro-3-methylbutane was not used in (3) of Example 4. The results are shown in Table 1.

Example 5 (1) Hydromagnesite (3MgC(h・Mg(
90 g of OH)2Φ3H20) and 140 g of aluminum trichloride (anhydrous) were mixed in a vibratory mill with a capacity of 2 liters, and while pulverizing the mixture, the mixture was heated at 300° C. for 1 hour to react, thereby obtaining a solid product (I).

(2) While keeping the temperature at -10°C and stirring, the volume is 1 fL.
400+JL of toluene, 140 g of anisole, and 150 g of trichloromonoisopropoxy titanium were added to a round bottom flask with a stirrer and mixed. Then, 100 g of the above solid product (Cl) was added, and the mixture was reacted for 2 hours at 100°C. Next, without removing the supernatant (i.e., in the presence of unreacted anisole), poly(n-butyl titanate) (3
A solid product (II) was obtained by adding 40 g of 100"O polymer and reacting for 1 hour.

(3) Same as Example 1 except that 15 mg of the above solid product (II), 70011 g of triisobutylaluminum as the trialkyl aluminum compound catalyst component, and 94 mg of 2-chloro-2-methylbutane as the chlorinated hydrocarbon catalyst component were used. Polyethylene was produced using The results are shown in Table 1.

Comparative Example 5 In the same manner as in Example 5 except that 2-chloro-2-methylbutane was not used in (3) of Actual M&Example 5,
Manufactured polyethylene. The results are shown in Table 1.

Example 6 Using the same catalyst system as Example 1, ethylene-butene-1
copolymerization was carried out.

In (3) of Example 1, hydrogen at a gauge pressure of 2.5 k
g/crn', and an ethylene-butene-I copolymer was produced in the same manner as in Example 1, except that ethylene containing 5% (volume %) butene-1 was introduced. Table 2 shows the results. .

Comparative Example 6 Ethylene-butene-1 was copolymerized in the same manner as in Example 6, except that 1,2-dichloropropane was not used. The results are shown in Table 2.

[Brief explanation of the drawing]

The figure is a flow sheet illustrating the method of the invention. that's all

Claims (10)

[Claims] (1) (i) A solid product obtained by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. (
(Step A) A step of reacting a halogen-containing Group 4a or Group 5a transition metal compound (hereinafter referred to as a halogen-containing transition metal compound) in the presence of an electron-donating compound (hereinafter referred to as A step). ) and (Step B) a step of reacting a halogen-free Group 4a or Group 5a transition metal compound (hereinafter referred to as halogen-free transition metal compound) in the presence of an electron-donating compound (hereinafter referred to as Step B). ) A solid transition metal compound-supported catalyst component obtained through the two steps (hereinafter referred to as solid product (II)), (ii) a trialkyl aluminum compound catalyst component, and (iii) a chlorinated hydrocarbon catalyst component. A method for producing polyethylene, which comprises polymerizing ethylene alone or copolymerizing it with other α-olefins in the presence of an inert solvent. (2) As an electron-donating compound, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. 10,000).) The manufacturing method according to claim (1), using a polysiloxane represented by: (3) As an electron donating compound, the general formula R^1_mSi
(OR^2)_4_-_m (in the formula, R^1 is C_1 to C_
is a hydrocarbon group, hydrogen atom or halogen atom up to 2_0, R^2 is a hydrocarbon group up to C_1 to C_2_0, and 0≦m<4. ) The manufacturing method according to claim (1), using an alkoxy group-containing organosilicon compound represented by: (4) As the electron-donating compound, ether, ester,
1 selected from aldehydes, ketones, or carboxylic acids
The manufacturing method according to claim (1), which uses one or more oxygen-containing organic compounds. (5) The manufacturing method according to claim (1), in which a titanium or vanadium halide, oxyhalide, alkoxyhalide, or acetoxyhalide is used as the halogen-containing transition metal compound. (6) Claim No. 1 in which tetraalkyl orthotitanate, vanadyl trialcholate, or polytitanate is used as the halogen-free transition metal compound.
) The manufacturing method described in section 2. (7) As a transition metal compound-supported catalyst component, the solid product (I) is subjected to the reaction of (Step A), and then (
The manufacturing method according to claim (1), which uses the solid product (II) obtained through the reaction of step B). (8) As a transition metal compound-supported catalyst component, the solid product (I) is subjected to the reaction of (B step), and then (
The manufacturing method according to claim (1), which uses the solid product (II) obtained through the reaction of step A). (9) The chlorinated hydrocarbon catalyst component is
/Trialkyl aluminum compound The manufacturing method according to claim 1, wherein Al in the catalyst component is used in an amount such that the atomic ratio is 0.02 to 10. (10) Tolualkylaluminum compound catalyst component,
The manufacturing method according to claim (1), wherein the amount of Al in the catalyst component/Ti in the solid product (II) is used in an atomic ratio of 1 to 2000.