JPS591412B2 - Improved method for producing ethylene polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to an improved method for making ethylene-based polymers.

Specifically, the present invention relates to a method for producing an ethylene polymer, which comprises homopolymerizing ethylene or copolymerizing ethylene and other α-olefins using a novel catalyst system with excellent polymerization activity. More specifically, the aryl (aryl) has a complex compound containing special aluminum and a silicon-oxygen bond, and is directly bonded to oxygen.
) group and/or an aralkyl group, and a solid component obtained by contacting a solid reaction product (carrier) obtained by reacting a magnesium alcolade with a tetravalent titanium compound. The catalyst system obtained from organoaluminum compounds has excellent polymerization activity and can produce polymers with high melt flow index and high activity. The present invention relates to an improved method for producing ethylene-based polymers that can produce polymers. BACKGROUND OF THE INVENTION In recent years, treated products obtained as ethylene polymerization catalysts by pre-treating transition metal halides (particularly titanium halides) with a carrier (particularly a magnesium compound) or a compound on the carrier Many proposals have been made to dramatically improve the polymerization activity (catalytic activity) per catalyst by supporting the catalyst on the catalyst, and to substantially omit the step of removing the catalyst residue remaining in the polymerization system after the polymerization is completed.

These carriers include magnesium-containing compounds such as magnesium hydroxychloride, magnesium oxide, magnesium alkoxide, magnesium hydroxide and magnesium dihalide.

Furthermore, it has been proposed that these magnesium-containing compounds are pretreated with compounds such as water, alcohols, aldehydes, ketones, esters, ethers, and carboxylic acids. However, although carrier-supported catalysts using these carriers or carriers pretreated with the above-mentioned compounds greatly improve the polymerization activity, they are not practically satisfactory when polymerizing ethylene or ethylene with other olefins in the following respects. It cannot be called a kimono.

In other words, the problems are: (1) The polymerization activity is not sufficient even if it does not decrease, and although the activity is relatively high in a short time, the deactivation is severe, and therefore the product stability in long-term polymerization is low. productivity (productivity) is low.

(2) The bulk density of the resulting polymer is too low, reducing the productivity of the polymerization apparatus.

(3) When a molecular weight regulator (generally hydrogen) is used to adjust the melt flow index of the resulting polymer, the effect of the molecular weight regulator is relatively small, and therefore a relatively large amount of the molecular weight regulator is However, when a polymer having a high melt index is produced using the above method, it often has the disadvantage that the polymerization activity is significantly reduced.

(4) Poor reactivity of other olefins (as comonomers) in copolymerization, thus requiring high comonomer concentrations.

That is, since the polymerization conversion rate of the comonomer is lower than that of ethylene, the comonomer is wasted. (5) When copolymerizing ethylene with other olefins, the degree of branching distribution of the copolymer is insufficiently homogeneous (branching is fairly distributed in low-molecular-weight polymers, but in high-molecular-weight polymers, Since the branches are hardly distributed in the polymer, it is impossible to exhibit sufficient performance as a copolymer.

etc. can be mentioned.

In the high-density polyethylene industry, copolymers of ethylene and other olefins are widely produced, and in particular, in molding fields such as blow molding, stretch molding, and film molding, most of them use copolymers and have a molecular weight distribution. A wide range of copolymers are often used.

Such copolymers with a wide molecular weight distribution have generally been attempted using a number of catalyst systems. Even if they are copolymerized, the polymerization activity is extremely low, which often has the drawback of significantly reducing productivity.

Furthermore, the molecular weight distribution of the obtained copolymer is often insufficiently wide. Furthermore, among the above-mentioned carriers, many methods using magnesium alcolade have been proposed.

Examples of this method include the following. (1) A method using a reaction product of magnesium alcoholade and a tetravalent titanium compound as a solid catalyst component.

(2) A method in which a transition metal halide is reacted after contacting a magnesium alcoholade with an alkyl aluminum halide.

(3) A method in which magnesium alcoholade is reacted with titanium tetraalkoxide, and the reaction product is reacted with silicon tetrachloride.

(4) A method in which a halogenating agent is allowed to act on magnesium alcoholade, and then a transition metal compound is supported.

When homopolymerizing ethylene or copolymerizing ethylene with other olefins in the presence of a catalyst system obtained from a transition metal compound and an organometallic compound (particularly an organoaluminum compound) supported on a carrier by these methods, Since the above-mentioned problems cannot be completely solved, it cannot be said to be practically satisfactory.

Moreover, it is difficult to maintain a practically satisfactory high activity while producing a polymer having a particularly high MI, and therefore it is difficult to maintain a high activity that is practically satisfactory, and therefore it is difficult to produce a polymer having a high MI and a polymer having a low M. , it is difficult to produce a polymer mixture that is produced on the same catalyst particle by a so-called multi-stage process and has an artificially wide molecular weight distribution while maintaining high productivity.

As described above, in the method of copolymerizing ethylene alone or with a small amount of other olefin in the presence of a molecular weight regulator (generally hydrogen) within a practically possible range,
There are still few proposals regarding catalyst systems capable of producing polymers having a very wide range of M with high polymerization activity. [Objectives, Structures, and Effects of the Present Invention (a) Objectives and Structure of the Present Invention The present inventors have searched various ways to solve the above problems, and as a result, (A) (1) (a) (b) "Complex compound consisting of aluminum oxyhalide and alkoxyaluminum dihalogen compound" (hereinafter referred to as "aluminum-containing complex compound") and "Aryl group and/or aralkyl group directly bonded to the Si-0 bond" A solid reaction product insoluble in a hydrocarbon solvent obtained by reacting (b) magnesium alcolade with a reaction mixture with an organic phylline compound having at least one (hereinafter referred to as a "silicon compound") and (2) a solid component obtained by contacting a [tetravalent titanium compound having at least one halogen atom] (hereinafter referred to as a "titanium-based compound") and (B) a catalyst system obtained from an organoaluminum compound. The present invention has been achieved based on the discovery that an ethylene polymer with high polymerization activity and a wide molecular weight distribution can be obtained by homopolymerizing ethylene or copolymerizing ethylene with another olefin in the presence of.

(b) Effects of the present invention In the present invention, the effects (characteristics) when ethylene is homopolymerized or ethylene and other olefins are copolymerized in the presence of the catalyst system obtained as described above are as follows. .

(1) The catalyst system has high activity.

Therefore, since the content of catalyst residues in the polymer produced after completion of polymerization is extremely small, the step of removing catalyst residues from the polymer can be substantially omitted. (2) Since the bulk density of the obtained polymer is relatively high, the productivity of the polymerization process, drying process of the obtained polymer, and transfer process is excellent.

(3) Due to the low deactivation of the catalyst system used, it is possible to use the catalyst system for a fairly long time. (4) Melt flow index (M) using a molecular weight modifier (e.g. hydrogen)
When producing a polymer with excellent properties, even if a relatively small amount of a molecular weight regulator is used, not only can the effect be fully exhibited, but also high polymerization activity can be maintained.

(5) It is possible to produce polymer mixtures with a wide molecular weight distribution by a multistage process.

(6) Since the soluble content in the polymerization solvent is small, there is relatively little deposit in the equipment during the polymerization process, so the polymer can be produced continuously for a long time without difficulty.

Furthermore, the characteristics of copolymerizing ethylene with other olefins are as follows.

(1) Since the branching degree distribution of the resulting copolymer is relatively homogeneous regardless of the molecular weight of the polymer, the environmental stress cracking resistance of this copolymer is good.

(2) Since it has excellent copolymerizability with other olefins (comonomers), the polymerization conversion rate of comonomers is higher than that of other catalyst systems.

(3) Ethylene polymers with a relatively low density (approximately 0.9209/Cc) are heated at a relatively low temperature (generally 100°C).
Slurry polymerization is possible in the following).

Therefore, the resulting polymer can be easily recovered. Marshal
DETAILED DESCRIPTION OF THE INVENTION (a) Production of hydrocarbon-insoluble reaction product The hydrocarbon-insoluble solid reaction product used in the present invention is obtained by reacting a reaction mixture of an aluminum-containing complex compound and a silicon-based compound with magnesium alcoholade. It can be manufactured by.

(1) Aluminum-containing complex compound The above-mentioned aluminum-containing complex compound mainly consists of aluminum oxyhalide and a proportion of alkoxyaluminum dihalide.

The general formula of the aluminum-containing complex compound is the following formula [() formula]
It is indicated by. (AIOXl)m(RlOA!X?)n
(1) (However, X1 and X2 represent a halogen atom, R1 represents an alkyl group having at most 3 carbon atoms, and m and n represent a mole fraction composition)
In general, the aluminum-containing compound can be produced by decomposing an alkoxyaluminum dihalogen compound, by producing it from a dialkyl ether complex of aluminum halide, or by decomposing a trialkylsiloxyaluminum dihalide.

When decomposing isopropoxyaluminum dichloride among alkoxyaluminum dihalides, the reaction formula is as shown in the following formula [formula (1)].

(1-C3H7O)AlCl2→ →(AIOCI)m(1-C3H7OAlCl2)nThe conditions for the decomposition reaction of this alkoxyaluminum dihalide vary depending on the type, but in the case of isopropoxyaluminum dichloride, the temperature is 25°C. ,
It can be obtained by leaving it for 1 to 2 days.

Moreover, if heated in a temperature range of 65 to 120°C, foaming decomposition occurs instantaneously, and a pale yellow target product can be easily obtained. In addition, a method for producing from a dialkyl ether complex compound of aluminum halide is such that this complex compound is
There is a method of thermal decomposition at 210° C., but the above-mentioned method of thermally decomposing the intermediate alkoxyaluminum dihalide may also be used.

This reaction formula is as shown below [formula (2)].

\ΩVVlkノ11\▲ν υ, Ωiν1kノ1111
V1 list ＼QノThis reaction is Waldemar Menzel (
Wald-Cemar Menzel's method [Waldemer Menzel, Berichteder D.
eutschenChemischenGes-Ell
Schaft, Vol. 75, p. 1055, (1942)], it is possible to synthesize it by a decomposition reaction as shown in formula (2).

Furthermore, the method of Hubert Schmiet-Bauer et al.
He-Rmann), He-Rmann
Hussek) and Fritz Schindra (Fritz
Sehindlar) co-author, Hemitssie Berichte (Ch.
EniseheBerichte), Volume 97, (Rei 1
), p. 255, (1964)] 2 (CH3)
3Si-0-AlX2→(AIOX)2+2CCH3)
3SiX (3) A method using (AIOX) 2 obtained by the reaction shown in formula (3) above, co-authored by Herald Sehafer, Camill Gosel, and Liesel Bayer, Fair UnOrganisieund Allgemeine Hemiichi (Ze-ItschriftFuranOrg
amiseheundallgemeineChemi
e) Vol. 263, p. 87, (1950)] and complexing it with (RlO)AlX2.

Most of the aluminum complex compounds obtained by the above method are hydrocarbons (e.g. benzene, n-hexane).
It is insoluble in

In the above formula (1), the molar fraction of m is 0.60 to 0.
A value of 90 is preferred, and a value of 0.65 to 0.85 is particularly preferred. Furthermore, it is desirable that X1 and X2 are chlorine, bromine or iodine atoms. Further, it is preferable that R1 has at most three carbon atoms. Representative examples of preferable aluminum-containing complex compounds include (AK℃l), n(1-C3H7OAlC!2)n ,
(AIOCI)m(C2H5OAlCl2)n, (AI
OC! )m(CH3OAjCH2)n, (AlOBr)
n1(1-C3H7OAiBr2) and (AlOBr
)m(C2H5OAlBr2)n.

Among these, particularly preferred ones include (AlOCO
m(C2H5OAICl2)n and (AIOCI)n
1(CH3OAlCl2)n. 11) Silicon compound The silicon compound used in the present invention is Si
It is an organosilicon compound having at least one aryl group and/or aralkyl group directly on the -0 bond, and the general formula of the representative one is the following formula [(
H) Formula].

In formula (n), R2 is a hydrogen atom or an alkyl group having at most 10 carbon atoms, an alkoxy group, or a phenyl group, and R3 is a hydrogen atom or a carbon number of at most 3
, and p is a number from O to 3.

Among these silicon-based compounds, silicon-based compounds in which R2 is a hydrogen atom or an alkyl group having at most 7 carbon atoms, an alkoxy group, or a phenyl group are preferred.

Further, as R3, a phenyl group or tolyl (TOll)
yl) group is preferred. Representative examples of the silicon-based compounds include dimethoxydicresylsilane, diethoxydicresylsilane, tetracresylsilane, tricresylmethylsilane, dimethyldicresylsilane. Ran, trimethylcresylsilane, tetraphenoxysilane, triphenoxymethylsilane, diphenoxydimethylsilane, phenoxytrimethylsilane, diphenoxymethylphenylsilane, dicresylmethylphenylsilane 1ran, diphenyl Diphenoxysilane, dicresyl diphenylsilane,
Mention may be made of phenyltricresylsilane, phenyltriphenoxysilane, triphenylcresylsilane and triphenylphenoxysilane, in particular tetracresylsilane, tetraphenoxysilane, diphenoxydimethylsilane and Phenoxytrimethylsilane is preferred.

(1ID Magnesium Alcolade Furthermore, the general formula of a representative one among the magnesium oligonucleotide compounds used in the present invention is shown by the following formula [formula ()].

M9(0R4)2 ()(111)
In the formula, R4 is a hydrocarbon group selected from the group consisting of an alkyl group having at most 8 carbon atoms, a cycloalkyl group, a cycloalkyl group having an alkynyl group, an aryl group, and an aralkyl group.

These magnesium alcoholades are those obtained by reacting magnesium with lower alcohols (for example, methyl alcohol, ethyl alcohol), and those obtained by reacting these magnesium alcoholades with higher alcohols and phenols. Magnesium alcolades are mentioned, and their production methods are well known. Among these magnesium alcoholades, representative ones include magnesium methoxide, magnesium ethoxide, magnesium (n-propoxide), (isopropoxy, de)magnesium butoxide, magnesium hexide, magnesium phenoxide, and magnesium. Examples include cyclohexanoxide, benzyl alcohol alkoxide of magnesium, and magnesium cresolate.

Among these magnesium alcoholades, those in which R4 in the above formula α) is represented by an alkyl group or phenyl group having at most 3 carbon atoms are desirable. These suitable magnesium alcoholades include magnesium ethoxide, magnesium methoxide and magnesium phenoxide.

ψ Reaction ratio In producing the hydrocarbon-insoluble solid reaction product used in the present invention, the reaction ratio of the aluminum-containing complex compound to 1 mol of the magnesium alcoholade is generally 0.5 to 1.0 mol. Yes, especially 0.
5 to 5 mol is preferred.

If the reaction ratio of the aluminum-containing complex compound to 1 mole of magnesium alcoholade is less than 0.5 mole, the polymerization activity of the resulting catalyst system will be low, while if it is more than 10 moles, the bulk specific gravity of the ethylene polymer produced will be low. becomes lower,
Therefore, productivity decreases.

Further, the reaction ratio of the silicon-based compound to 1 mol of the aluminum-containing complex compound is generally 0.2 to 5 mol, and preferably 0.5 to 2 mol.

If the reaction ratio of the silicon-based compound to 1 mol of the aluminum-containing complex compound is less than 0.2 mol or more than 5 mol, the polymerization activity decreases and the bulk specific gravity decreases.

A. Reaction Conditions and Purification (Post-Treatment) To produce the hydrocarbon-insoluble solid reaction product used in the present invention, an aluminum-containing complex compound and a silicon compound are first reacted.

This reaction is carried out under a dry (moisture-free) atmosphere of inert gas (eg, nitrogen, argon).

Furthermore, this reaction is usually carried out in a hydrocarbon solvent that is liquid at room temperature. Representative examples of this hydrocarbon solvent include aliphatic hydrocarbons (e.g., n-hexane, n-
heptane), alicyclic hydrocarbons (eg cyclohexane, methylcyclohexane) and aromatic hydrocarbons (eg benzene, toluene). Also, this? - The reaction is usually carried out at a temperature range of room temperature (25°C) to 150°C with stirring for 10 minutes to 3 hours.

Aluminum-containing complex compounds easily react with silicon-based compounds, and most of them are solubilized in hydrocarbon solvents, forming a slightly viscous yellow to brown solution. Next, the hydrocarbon-insoluble solid reaction product used in the present invention can be produced by reacting this reaction mixture with magnesium alcoholade.

This reaction, like the above reaction, is carried out in a hydrocarbon solvent under an inert gas atmosphere.

The reaction temperature and time in this reaction depend on the mutual reaction ratio of the aluminum-containing complex compound, silicon compound, and magnesium alcoholade used, their types, the hydrocarbon solvent used, and the concentration of the magnesium alcoholade in the hydrocarbon solvent. Generally, the temperature is room temperature to 150°C, and the reaction time is 3 hours or less, although the reaction time varies. In particular, it is preferable that the reaction temperature is 50 to 100°C and the reaction time is in the range of 1 to 2 hours. In the reaction of the aluminum-containing complex compound and the silicon-based compound and the reaction of this reaction mixture with the magnesium alcoholade, the proportion of the hydrocarbon solvent to be used is determined from the viewpoint of the bulk density of the resulting polymer and the final polymerization activity. , generally 5 to 1007!1 per magnesium alcoholade 19
1, and particularly preferably 10 to 50 d.

The supernatant liquid of the reaction product (precipitate) obtained by the above two methods is extracted using the hydrocarbon solvent used during the reaction or another hydrocarbon solvent.

Then a new hydrocarbon solvent (maybe a different type of hydrocarbon)
The hydrocarbon-insoluble solid product can be purified by repeating several times the operation of adding, stirring and washing, and then removing the supernatant liquid. The hydrocarbon-insoluble solid product thus purified was confirmed by analysis to be a complex compound containing magnesium, aluminum and silicon. (b) Production of solid component The solid component used in the present invention is produced by reacting the purified hydrocarbon-insoluble solid product obtained by the above method with the titanium compound described below. can do.

) Titanium compound The titanium compound used to produce the solid component is a tetravalent titanium compound having at least one halogen atom, and its general formula is shown by the following formula [formula ()]. be.

TiX3n(0R5)n1(NR6R7)l(0C0R
8), (IV) In formula (IV), X3 is a chlorine atom, a bromine atom or an iodine atom, and R5, R6, R
7 and R8 are aliphatic, alicyclic or aromatic hydrocarbon groups having at most 12 carbon atoms, and n is a number from 1 to 4. M, ll and p are numbers from O to 3, and n+
m+l+p is 4. Representative examples of titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimethoxytitanium dichloride, trimethoxytitanium chloride, ethoxytitanium trichloride, diethoxytitanium trichloride,
Triethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, dimethylaminotitanium trichloride, bis(dimethylamino)
Mention may be made of titanium dichloride, diethylaminotitanium trichloride, titanium propionate trichloride and titanium benzoate trichloride.

Among them, in formula (), M,' and p are O,
R1 is preferably an alkyl group having at most 6 carbon atoms, and n is 3 or m is O (i.e., n is 4), particularly titanium tetrachloride, methoxytitanium trichloride, ethoxytitanium Trichloride and butoxytitanium trichloride are preferred. (11
) Reaction rate The reaction rate between the solid product containing aluminum, silicon, and magnesium and the titanium compound varies depending on the content of magnesium in the solid product, but in general, the rate of reaction between the solid product containing aluminum, silicon, and magnesium and the titanium compound varies depending on the content of magnesium in the solid product. The minimum amount required is sufficient to ensure that the titanium compound is supported as much as possible on the product, and the reaction ratio of the titanium compound per 1 atom of magnesium in the hydrocarbon-insoluble solid product is usually 0.1 to 200 mol (preferably , 0.2 to 100 mol), but may vary depending on reaction temperature, concentration and time.

Appropriate conditions may be selected such that the amount of titanium atoms supported on the hydrocarbon-insoluble solid product (composite support) containing aluminum, silicon and magnesium is generally 1 to 10% by weight. (111) Reaction conditions and purification (post-treatment) To produce the solid component, the hydrocarbon-insoluble solid product and the titanium-based compound are mixed in the same inert hydrocarbon solvent used to produce the hydrocarbon-insoluble solid product. or by reacting in the absence of a solvent.

The reaction temperature in this reaction depends on the reaction ratio of the titanium compound to magnesium in the hydrocarbon-insoluble solid product, the types of the hydrocarbon-insoluble solid product and the titanium compound, the use or non-use of an inert hydrocarbon solvent, and the Although it depends on the reaction conditions such as the type of inert hydrocarbon solvent used and the ratio of the hydrocarbon-insoluble solid product to the inert hydrocarbon solvent, it is generally
The temperature is 50°C, particularly preferably 50 to 140°C.

If the reaction occurs below room temperature, the reaction will be insufficient. On the other hand, although the desired product can be obtained even if the reaction is carried out at a reaction temperature of 150° C. or higher, it is not necessary. Although the reaction time varies depending on the reaction conditions and reaction temperature, it is usually 10 minutes to 2 hours.

If the reaction time is less than 10 minutes, the reaction is insufficient. Further, even if the reaction is allowed to proceed for 2 hours or more, the reaction may not proceed further and the resulting catalyst may be deactivated. From the above, considering both the reaction temperature and reaction time, it is preferable to carry out the reaction at a temperature of 50 to 140°C for 10 minutes to 2 hours.

The solid component obtained by the above method is generally purified by the following method.

That is, the mixture of solid components and unreacted substances is obtained by decanting the supernatant liquid using the hydrocarbon solvent used during the reaction or another hydrocarbon solvent (preferably one with a relatively low boiling point). The slurry containing the solid component may be extracted by a filtration method and washed using the hydrocarbon solvent until the presence of the titanium-based compound is substantially no longer recognized in the washing liquid. It is also possible to supply a material (substantially free of unreacted titanium compounds) to the polymerization vessel described below.

Alternatively, the hydrocarbon solvent used for washing can be removed under reduced pressure and then supplied to the polymerization vessel as a solid component. (
c) Organoaluminum compound The catalyst system used in the present invention is obtained from the solid component obtained above and an organoaluminum compound.

The organoaluminum compound used in the present invention has a general formula represented by the following formulas [formula (), formula (4), and (4)].

In formula (), (VD formula and (4) formula, R9, Rl
O and Rll, Rl2 and Rl3, Rl, Rl5
, R and Rl6 may be the same or different, and RO, RlO
and Rll is a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having at most 8 carbon atoms, and Rl2 is an alkyl group having at most 8 carbon atoms,
Rl3, RM and Rl5 are alkyl groups having at most 8 carbon atoms, Rl6 is a halogen atom or an alkyl group having at most 8 carbon atoms, and X4 is a halogen atom.

At least one of R9, Rl and Rll is an alkyl group. Representative examples of these include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum, alkylaluminum halides such as diethylaluminum chloride, ethylaluminum sesquichloride and dibutylaluminum chloride, and dialkylaluminums such as diethylaluminum hydride. Mention may be made of hydrides, alkyl aluminum alkoxides such as diethylaluminum ethoxide and dibutyl aluminum methoxide, and alkyl aluminum amides such as diethylaluminum diethylamide. Among these organoaluminum compounds, trialkylaluminums are preferred, and trialkylaluminums in which the alkyl group has at most 6 carbon atoms (eg, triethylaluminum, triisobutylaluminum) are particularly preferred. In obtaining the catalyst system used in the present invention, the aluminum oxyhalides, alkoxyaluminum dihalides, silicon-based compounds and magnesium alcoholades used to produce the solid components, The hydrocarbon-insoluble solid product, the titanium compound, and the organoaluminum compound may each be used alone or in combination of two or more.

(d) Polymerization When carrying out the present invention, the solid component obtained above and the organoaluminum compound may be introduced into the polymerization container separately, but they may also be mixed in advance. It may be used after being diluted in advance with an inert organic solvent such as a hydrocarbon.

(1) Amount of solid component and organoaluminum compound used When using the present invention, there is no restriction on the amount of the solid component and organoaluminum compound obtained as described above, but Inert organic solvent 1
per 1, 171 tV ~ 19 solid components and 0,1 ~
A proportion of 10 mmol of organoaluminum compound is preferred.

In addition, the amount of the organoaluminum compound used is generally 1 to 1 per atomic equivalent of titanium metal contained in the solid component.
000 moles. (4) Comonomer In carrying out the present invention, ethylene alone may be polymerized, or ethylene and a comonomer may be copolymerized.

The comonomer is a hydrocarbon having a double bond at the end, and the number of carbon atoms is at most 12. Typical examples thereof include propylene, butene-1,4-methylbenzene, hexene-1, and octene-1. 1, butadiene and isoprene. The copolymerization ratio of the comonomer (olefin) in the resulting ethylene polymer is generally at most 30 mol%, preferably 20 mol% or less, particularly preferably 10 mol% or less. (
111) Other polymerization conditions Polymerization is carried out by dissolving ethylene or ethylene and olefin in an inert solvent, but if necessary, a molecular weight regulator (generally hydrogen) may be present.

Polymerization temperature is generally -10°C to 200℃, which is practically room temperature or higher. The temperature is 170°C or less.

In addition, the type of polymerization solvent and the ratio of ethylene or ethylene to olefin used are known for the production of ethylene polymers (ethylene homopolymers, ethylene copolymers).

Furthermore, the configuration of the polymerization reactor, the method of controlling the polymerization, the post-treatment method, the proportion of monomer (ethylene or ethylene and comonomer) and the proportion of organoaluminum to the inert organic solvent used in the reaction, the inert organic solvent There are no specific limitations on the type of catalyst and post-treatment method after polymerization, and all known methods can be applied.

[Examples and Comparative Examples] The present invention will be explained in more detail with reference to Examples below.

In addition, in the Examples and Comparative Examples, the melt index (hereinafter referred to as [M..]) was measured according to JISK-6760.

Density was measured according to JISK-6760. The soluble content is the ratio (%) determined by extracting the obtained polymer with boiling cyclohexane for 6 hours. The method for measuring short chain branching using infrared absorption spectroscopy is 4255? determined by infrared absorption spectroscopy. -1 absorption as internal standard, 137
From the absorption of the methyl group of 8 (7L-1), Woolhorn (W
It was measured by the method of IllbOvrn) [Koichi. Etsuchi.
A.H. WillbOvrn, Journal of Polymer Science (JOvrnalQ,
f'POlymerScience) Volume 34, No. 5''
See p. 69 (1959)].

In each Example and Comparative Example, each compound used in the production and polymerization of the catalyst component (inert organic solvent, ethylene, other olefin, titanium compound, organoaluminum compound, aluminum oxyhalide, alkoxyaluminum dihalide, (silicon-based compounds, hydrogen, etc.) were all substantially free of moisture, and the production and polymerization of each catalyst component were conducted in the absence of substantial moisture and in a nitrogen atmosphere.

Examples 1 to 3, Comparative Examples 1 and 2 [(A) (AlOC2).

．． 70 (1-C3H7OAICl2). ．． Synthesis of 30 complex compound] (Example) After sufficiently purging a 500 ml three-necked flask with nitrogen, 16.89 ethylaluminum dichloride (0.133 mol) and 5071 L1 n
- add hexane and immerse the flask in an ice water bath;
Cooled to 0°C.

A mixed solution consisting of 10.19 isopropyl alcohol (0.169 mol) and 30 d of n-hexane was added dropwise through the dropping funnel while stirring for about 30 minutes (the generation of ethane gas was observed at the same time as the dropping). ).

Thereafter, stirring was carried out for one hour at the reflux temperature of n-hexane. Next, the reaction system was cooled to room temperature (25°C), and 5 m
N-hexane and unreacted isopropyl alcohol were distilled off under reduced pressure of m-H9. As a result, white solid isopropoxyaluminum dichloride remained in the flask. As the temperature of the flask was gradually raised, the white solid melted into a liquid when the bath temperature reached 70-80°C. Furthermore, when the temperature was raised to 90 to 10°C, foaming decomposition started all at once while emitting white smoke, and a pale yellow foamy solid in the form of cartan sugar was obtained. Continue stirring for a few more minutes.
It became a powdery, free-flowing solid. Then, drying was carried out for 30 minutes at room temperature under reduced pressure. As a result, 13.57
g of solid product were obtained. Elemental analysis of this complex compound [hereinafter referred to as "complex compound (1)"] revealed that the carbon content was 10.59% by weight and the hydrogen content was 2.07% by weight. . That is, it corresponds to C3H7. Fluorescence X-ray analysis revealed that the aluminum content was 27.1% by weight, and chemical analysis revealed that the salt content was 26.5% by weight. . From the above results, complex compound (1) is (AIO
CI). ．． 70 (1-C3H7OA2C22). ．． 30
It is estimated that the chemical composition is 102 (apparent molecular weight 102 (
The molecular weight was taken as assuming that it was not associated. [(B) Preparation of catalyst component (a)] (Example) 2.58f of powder of complex compound (1) synthesized in (A) above! (25.3 mmol),
6.54 g of tetracresylsilane (16.5 mmol) and 30 ml of benzene were placed in a 200 d flask, and the reaction was carried out at room temperature for 1.5 hours with stirring.

A yellow-red clear liquid was obtained. 0.9419 for this transparent liquid
of magnesium ethylate (8.2 mmol) was reacted for 1.5 hours at a bath temperature of 70° C., resulting in a deep red slurry. After the reaction system was cooled to room temperature, the supernatant liquid was taken out, 50d0) n-hexane was added, stirred, and then taken out. This operation was performed four times. Thereafter, drying was performed at 50° C. under reduced pressure. As a result, 3.169 brown powder (carrier) was obtained. 7TL1 of titanium tetrachloride was added to this powder, and the reaction system was heated to 110°C.
After raising the temperature to , the reaction was carried out for 1 hour.

After cooling the reaction system to room temperature, 50 ml of n-hexane was added and stirred, and unreacted titanium tetrachloride was washed and removed from the supernatant using a decanting method. This operation was performed four times. Thereafter, drying was carried out at 50°C under reduced pressure, and 2.68
A brown solid catalyst component No. 9 (hereinafter referred to as "Catalyst Seishu a)" was obtained. Analysis of this catalyst component (a) revealed that titanium was 3.3% by weight, chlorine was 34% by weight, magnesium was 8.6% by weight, aluminum was 8.3% by weight, and silicon was 3.5% by weight. It was found that it contains %. [(c) Preparation of catalyst Seishu b)] (Comparative example) Instead of the complex compound (1) synthesized in the above prison, 7.0
9 aluminum chloride (52.5 mmol), 20.6
89 tetracresylsilane (52.6 mmol) and 90? Benzene was reacted for 30 minutes with stirring at room temperature, and a pale yellow, transparent, homogeneous solution was obtained.

To this solution was added 3.009 magnesium ethylate (26
．． After adding 2 mmol) and reacting for 2 hours at a bath temperature of 70°C, a light brown slurry was obtained. After the reaction system was cooled to room temperature, the supernatant was extracted and diluted with 90ml (10I)n-
After adding hexane and stirring, the supernatant liquid was removed.
This operation was performed four times. Then, drying was carried out at 50° C. under reduced pressure. As a result, a pale yellow powder (carrier) of 2.8 7 9 was obtained. 21Tflj to this powder
of titanium tetrachloride was added, the temperature of the reaction system was raised to 60°C, and the reaction was carried out for 1.5 hours.

After this reaction system was cooled to room temperature, 100 g of n-hexane was added and stirred, and unreacted titanium tetrachloride was washed from the supernatant by a decanting method. This operation was performed three times. Thereafter, drying was carried out at 50°C under reduced pressure, and 3.0 6
A reddish-brown solid catalyst component [hereinafter referred to as "catalyst Seishu b"] of fl was obtained.
．． 4% by weight, magnesium 20. % by weight, 4% chlorine
1. It was found that it contained 7.5% by weight of aluminum and 4.5% by weight of silicon. [Homopolymerization of ethylene] After sufficiently drying an autoclave (inner volume: 1.21), the autoclave was repeatedly purged with nitrogen, and then cooled to 20°C.

n-heptane solution of triisobutylaluminum (concentration of triisobutylaluminum (0.5 mmol/m
j,) 1.4go(triisobutylaluminum 0.7
mmol) and the amount of catalyst a) (Examples 1 to 3) or catalyst component (b) (Comparative Examples 1 and 2) shown in Table 1.
was added and an additional 346 f7 of isobutane (as an inert solvent) was charged using a rotameter. After the polymerization system was sealed, the temperature was raised to 85°C, and hydrogen was immediately injected to the partial pressure shown in Table 1. Next, ethylene at 10 K'/C! It was pressurized so that the partial pressure of ethylene was shown, and ethylene was homopolymerized for the respective times shown in Table 1 while continuously supplying the polymerization system so as to keep the pressure constant. After the polymerization was completed, unreacted ethylene, hydrogen, and inert solvent were purged from each polymerization system through the discharge tube. Each of the obtained polymer powders was dried at 80° C. under reduced pressure. Table 1 shows the yield of each polymer obtained and the calculated polymerization activity of each catalyst Seishu a) or catalyst Seishu b). Various physical properties of each obtained polymer were measured. The results are shown in Table 1. Hydrogen partial pressure in Table 1 (horizontal axis, unit is K9
/d) versus MI (vertical axis, logarithmic scale, unit is θ/10
Figure 1 shows the relationship between (ethylene partial pressure 10 Kf
7/d).

In FIG. 1 (8 is for Examples 1, 2 and 3,
Moreover, the old one shows Comparative Examples 1 and 2. As is clear from Table 1 and Figure 1, in the catalyst systems used in Comparative Examples 1 and 2, there is a limit to increasing M in terms of hydrogen partial pressure in the homopolymerization of ethylene under a constant total pressure. On the other hand, in the catalyst systems used in Examples 1, 2, and 3, the gradient of M with respect to hydrogen partial pressure is steep, making it easy to control the molecular weight of the polymer. Furthermore, since the polymerization activity per unit amount of titanium contained in the catalyst component is high, it is much more productive to obtain a polymer having the same MI. Examples 4 to 6, Comparative Examples 3 and 4 Z1 [(A) Synthesis of complex compound (2)] (Example) 500T
After thoroughly purging the three-bottle flask of I11 with nitrogen,
．． 749 aluminum trichloride (0.103 mono(c)
I put it in.

While keeping the flask at room temperature, about 40 g of 7.729 diethyl ether (0.104 mol) was added through the addition funnel.
The dropwise addition was carried out with stirring over a period of minutes. The reaction system generated heat due to the heat of complexation, and a gray-green jelly-like complex compound of aluminum chloride and diethyl ether was obtained. The reaction system was heated in an oil bath, and when the temperature reached about 170°C, the complex compound began to undergo a decomposition reaction, and foaming decomposition reached its peak at about 185°C, resulting in a dark yellow cartan sugar-like foam. This foam immediately became powdered by stirring. This powder was dried at room temperature under reduced pressure for 1 hour. As a result, 10.369 solid products were obtained. When this complex compound [hereinafter referred to as "complex compound (2)"] was analyzed, the carbon content was 6.65% by weight, and the hydrogen content was 1.40% by weight. The aluminum content was 28.2% by weight and the chlorine content was 47.0% by weight. From this analytical value, the chemical composition of this complex compound (2) is (AIOCI). ．． 735(C
2H5OAlCl2). ．． Estimated to be 265. [(B
) Preparation of catalyst component (c)] (Example) 1.699 (17.6 mmol) of powder of complex compound (2) synthesized in (A) above, 8.259 of tetracresylsilane (20.8
The reaction was carried out at room temperature in the same manner as in Example 1 (B) except that 30 mmol) and 30 a of benzene were used.
followed by 1.239 magnesium ethylate (10.
76 mmol) was reacted at 75° C. for 1.5 hours, resulting in a pale brown slurry. After cooling the reaction system to room temperature, purification was carried out in the same manner as in Example 1 (B). Subsequently, drying was performed at 50°C. As a result, 1.851
A powder (carrier) was obtained. The reaction between this powder and titanium tetrachloride was carried out in the same manner as in Example 1 (B).

After the reaction was completed, purification and drying were carried out in the same manner as in Example 1 (B). As a result, ZZl. 7l9 of a brown solid catalyst component [hereinafter referred to as "catalyst component (c)"] was obtained.

Analysis of this catalyst component (c) revealed that it contained 4.3% by weight of titanium and 45.1% by weight of chlorine. [(Preparation of O catalyst component (6))] (Comparative Example 3) Same as (B) above except that the tetracresylsilane used in the reaction to produce the support in (B) above was not used. A carrier was produced under the same conditions. This carrier was subjected to a reaction with titanium tetrachloride under the same conditions as in (B) above. After the reaction was completed, purification and drying were performed in the same manner as in (B) of Example 1. As a result, a cream-colored solid catalyst component [hereinafter referred to as "catalyst component (d)"] of 2.919 was obtained. [(D) Preparation of catalyst component (e)] (Comparative Example 4)
In place of the complex compound (2) used in producing the catalyst component (c) in Example 4 (B), 2.519 (
The reaction with tetracresylsilane and magnesium ethylate was carried out under the same conditions as in (B) above, except that C2H5O)AlCl2 (17.6 mmol) was used.

After the reaction was completed, purification and drying were carried out in the same manner as in Example 1 (B). The obtained carrier (powder) was reacted with titanium tetrachloride under the same conditions as in (B) above. After the reaction was completed, purification and drying were carried out in the same manner as in Example 1 (B). As a result, a light brown solid catalyst component (hereinafter referred to as "Catalyst Seishu e)" having a weight of 1.459 was obtained. [(Homopolymerization of ethylene D) Instead of the catalyst component (a) used in Example 1 (D), the catalyst component (c) obtained by the above method,
(D) of Example 1 except that only the amounts of (d) and (e) shown in Table 2 were used, and the polymerization temperature, polymerization time, and hydrogen partial pressure were changed as shown in Table 2. Homopolymerization of ethylene was carried out under the same conditions.

After each polymerization was completed, the obtained polymers were purified and dried in the same manner as in Example 1 (D). The polymerization activity of each catalyst component and the M.I. of the obtained polymer (polyethylene) were determined. I. are shown in Table 2. Comparative example 5 [(
4) Preparation of catalyst component (f)] In the same manner as in Example 1 (B), 1.539 (16
．． 0 mmol) and 2.609 hexamethyldisiloxane (16.0 mmol) and an additional 30 Tf
L1 benzene was added.

The reaction was carried out while stirring these at room temperature (25° C.) for 30 minutes. 0.9149 magnesium ethylate (8.0 mmol) was then added and the
A time reaction was performed. After the reaction was completed, the obtained reaction product was purified and dried in the same manner as in Example 1 (B). As a result, a powder (carrier) with a color of 1.419 was obtained. The reaction with titanium tetrachloride was carried out under the same conditions as in Example 1 (B), except that this powder was used instead of the powder used in Example 1 (B). After the reaction was completed, purification and drying were carried out in the same manner as in Example 1 (B). As a result, a catalyst component [hereinafter referred to as "catalyst component (f)"] of 1.329 greyish-white solid was obtained. [(B) Homopolymerization of ethylene] Completely the same as (E) in Example 3 except that 14.7 m (l) of catalyst component (f) was used instead of catalyst component (a) used in Example 1. Ethylene homopolymerization was carried out for 40 minutes under the same conditions.

After the polymerization was completed, the obtained polymer (polyethylene) was purified and dried in the same manner as in Example 1 (D). As a result, a white powder polymer with a weight of 50.19 was obtained. That is, the polymerization activity is 12,8009/9-Ti/hour/ethylene pressure (atmospheric pressure). M. of the obtained polymer. I. is 1
．． It was 89/10 minutes. Example 7 [(A) (AIOCI).

．． 82 (C2H, OAjCl2). ．． Synthesis of complex compound No. 18] 18.359 (0.
1445 mol) and 80 WLe of n-hexane, and
,701 purified ethyl alcohol and 20wL1! of n-hexane through the dropping funnel.
The dropwise addition was carried out with stirring over a period of 0 minutes.

After the dropwise addition was completed, stirring was continued for an additional 30 minutes at 0°C. The produced ethoxyaluminum dichloride was completely dissolved in n-hexane and was homogeneous. n-hexane and unreacted ethyl alcohol were distilled off under reduced pressure. Furthermore, drying was performed under reduced pressure at room temperature for 30 minutes. As a result, 20.929 ml of white solid ethoxyaluminum dichloride (yield: 101%) was obtained.
When this solid was heated to about 192°C, it became yellowish and started to decompose. When it reaches 198℃, it decomposes while foaming.
Ethyl chloride was observed to fly.

After foaming was completed, drying was carried out under reduced pressure at room temperature. As a result, 12.749 yellow solid powder was obtained. Elemental analysis of this solid powder revealed (AIOCI). ．．
82 (C2H5OAjCl2). ．． It was estimated that it was a complex compound with a composition of 18. [(B) Preparation of catalyst component (g)] Synthesized in (A) above in a flask purged with nitrogen (AIOCI).

．． 82 (C2H5OAlCl2). ．． 1.299 (14.3 mmol) of a complex compound having a composition of 18, 30 m
1 of benzene and 6.769 of tetracresylsilane (17.0 mmol) were added, and the reaction was carried out at room temperature for 1 hour. A brown clear liquid was obtained. 0 in this clear liquid
．． 949 magnesium ethylate (8.2 mmol)
was added, and the reaction was further carried out at 65°C for 1.5 hours. After the reaction was completed, 30a of n-hexane was added and stirred, and then the supernatant liquid was removed. This operation was performed four times. Thereafter, drying was performed at 50° C. under reduced pressure. As a result, 2.259 powder (carrier) was obtained.
Add 7 ml of titanium tetrachloride to this powder to make the reaction system 11
After raising the temperature to 0°C, the reaction was carried out for 1 hour. After cooling the reaction system to room temperature, 30 d of n-hexane was added and stirred, and unreacted titanium tetrachloride was distilled off from the supernatant liquid by a decanting method. This operation was repeated three more times. after that,
Drying was carried out at 50° C. under reduced pressure. As a result, 2
．． 439 as a light brown solid catalyst component [hereinafter referred to as “catalyst component (
g)" was obtained. [(C) Ethylene homopolymerization] 17.3 m9 in a 1.21 stainless steel autoclave
catalyst component (g), triisobutylaluminum n-
Heptane solution (triisobutylaluminum concentration 0
．． 5 mmol/Tnl) 1.4771/(triisobutylaluminum 0.7 mmol) and polymerization temperature (9
The amount of isobutane necessary for the liquid phase volume at 5 mC) to be 700,771/ was charged.

After sealing the polymerization system, the temperature was raised to 95℃, and the hydrogen partial pressure immediately reached 8Kf7/C! l and the partial pressure of ethylene is 1
Hydrogen and ethylene were introduced under pressure so that the pressure was 0 K'/d, and polymerization was carried out for 60 minutes while continuously supplying ethylene at a total pressure of 35 Ky/Cl. After the polymerization was completed, the obtained polymer was purified and dried in the same manner as in Example 1. As a result, 176.79 of a white powder polymer (polyethylene) was obtained. That is, the polymerization activity is 38,
3009/9-Ti・Time・Ethylene pressure (atmospheric pressure). The bulk density of this polymer was 0.249/d. Also, M. I. was 62.79/10 minutes. Example
8 to 11 17 each of the complex compound (2) used in Example 4
．． 6 mmol and silicon-based compounds such as dimethoxydicresylsilane [hereinafter referred to as "compound (A)]", phenoxytrimethylsilane [hereinafter referred to as "compound (B)"], and diphenyldiphenoxysilane [hereinafter referred to as "compound (B)"]. (
The reaction was carried out under the same conditions as in Example 4 (B), except that 17.6 mmol of each of 6) and dimethyldicresylsilane [hereinafter referred to as [compound (D)]] were used. .

Each of the obtained reaction products was reacted with 8.8 mmol of magnesium ethylate under the same conditions as in Example 4 (B). After each reaction was completed, purification and drying were carried out in the same manner as in Example 4 (B). Each of the obtained powders was reacted with titanium tetrachloride under the same conditions as in Example 4 (B), and then purified and dried in the same manner as in Example 4 (B) to determine the content of each catalyst component. Preparation was carried out. [(B
) Homopolymerization of ethylene] Each catalyst component obtained in the above solution was added to
Accurately weigh 20 d of n-heptane solution of triisobutylaluminum (concentration of triisobutylaluminum: 0.5 mmol/ml), add 2.0 d (triisobutylaluminum 1.0 mmol) and polymerization temperature (85°C).
) was charged with the isobutane necessary to have a liquid phase volume of 700 TIII.

After sealing each polymerization system, the temperature was raised to 85℃, and the partial pressure of hydrogen was immediately reduced to 8K2/d and the partial pressure of ethylene to 10K.
Hydrogen and ethylene were pressurized to obtain f7/CTI. Polymerization was then carried out for 60 minutes while continuously supplying ethylene. After the polymerization was completed, the obtained polymers were purified and dried in the same manner as in Example 1. The polymerization activity of each catalyst system and the bulk density and M. I. are shown in Table 3. Example 12 100. Add catalyst component (a) of 0.24989 as a catalyst component and n-heptane solution of triisobutylaluminum (concentration of triisobutylaluminum 2 mmol/?) 30d (triisobutylaluminum 60 mmol) as a catalyst component into a stainless steel autoclave. Ta.

Isobutane (as an inert solvent) was charged into this polymerization system (autoclave) using a level gauge, and the polymerization temperature was set at 85°C.
), the amount was set so as to occupy 601% of the liquid phase. In the first stage polymerization, the temperature of the polymerization system was raised to 85° C., and hydrogen and ethylene were pressurized so that the partial pressure of hydrogen was 0.3 K'/Crit and the partial pressure of ethylene was 5 Kf/d. Immediately, 2019 butene-1 was added, and copolymerization of ethylene and butene-1 was carried out for 39 minutes while supplying ethylene so as to show the above partial pressure. After the copolymerization was completed, the unreacted monomer and solvent (isobutane) were removed from the polymerization system by flashing. 109 was taken as a sample from the obtained copolymer. .M.
I. was 0.2299/10 minutes, the titanium content determined by fluorescent X-ray analysis was 2.44 ppm, and the true density was 0.93359/CTI. As the second stage polymerization, add the same amount of isobutane as above to the polymerization system,
The temperature of the polymerization system was raised to 5°C. Partial pressure of hydrogen is 10.7Kf/
Hydrogen and ethylene were pressurized so that the partial pressure of CTI and ethylene was 8 Kf/d. Homopolymerization of ethylene was carried out for 60 minutes while supplying ethylene at the above partial pressure. After the polymerization was completed, unreacted monomers and solvent were removed from the polymerization system by flashing. The obtained polymer powder was subjected to fluidized drying through a discharge line at 50° C. in a nitrogen stream to obtain a 7.0 Kf polymer mixture. M. of the monopolymer obtained in the second stage polymerization. I. (
estimated) was 309/10 minutes. M. of the polymer mixture.
．． is 0.059/10 minutes, and H. L. M. I. /M
．． I. It was 82.7. Moreover, the true density of this polymer mixture is 0.94939/C! 1 t, and the titanium content was 1.2 ppm. The composition ratio of the copolymer obtained in the first stage polymerization and the monopolymer obtained in the second stage polymerization was 48/52. Example 13 The first stage polymerization (ethylene and butene-1 Copolymerization with

After the polymerization was completed, unreacted monomers and solvent were removed from the polymerization system in the same manner as in Example 12. A sample was taken out from the obtained copolymer in the same manner as in Example 12. H. of the obtained copolymer. L. M. I. is 0.4519/10 minutes,
The titanium content determined by fluorescent X-ray analysis is 3.14p.
pm, and the true density was 0.93479/d. Furthermore, Example 1 except that the polymerization time was changed to 65 minutes.
The second stage polymerization (unipolymerization of ethylene) was carried out under the same conditions as in Example 2.

After the polymerization was completed, unreacted monomers and solvent were removed in the same manner as in Example 12, and then the obtained polymer powder was dried in the same manner as in Example 12. As a result, a polymer mixture of 8.35K' was obtained. M. of the monopolymer obtained in the second stage polymerization. l was estimated to be 309/10 minutes. M. of the polymer mixture. I. is 0.109/10 minutes, and H.
L. M. I. /M. ．． was 91.39/10 minutes.
Moreover, the true density of this polymerization mixture is 0.95279/10
minutes, and the titanium content was 1.32 ppm. The composition ratio of the copolymer obtained in the first stage polymerization and the monopolymer obtained in the second stage polymerization was 42/58.
In general, H. L. M. ．． is 0.2 to 0.59/10 min, and M. I. is about 309/10
The film obtained by press-molding a mixture obtained by mechanically mixing with an ethylene polymer having a is recognized.

On the other hand, the polymer mixtures obtained in Examples 12 and 13 both had approximately the same H. L. M. I
．． An ethylene polymer having M. ．． However, even with a strand of an extruder having a diameter of 20m7n, the surface was very smooth and it was easy to form a blown film. Furthermore, environmental stress cracking resistance (E) in a 10% nonionic aqueous solution
SCR) was a value of F, which was 150 hours for the polymerization mixture obtained in Example 12 and 75 hours for the polymerization mixture obtained in Example 13. Example 1
4-17 [(A) Preparation of each catalyst component] Add the complex compound (2) used in Example 4 in the amount shown in Table 4-1 to a 200 ml three-necked flask, and then add benzene as a solvent. (Benzene was added at a ratio of 30 d to 19 d of magnesium alcoholade used).

While stirring the reaction system, tetratalesylsilane [hereinafter referred to as "Compound (T)"] and phenoxytrimethoxysilane [hereinafter referred to as "Compound D"] are silicon-based compounds.
were added in the amounts shown in Table 4-1, and each was stirred at room temperature for 30 minutes. Although a small amount of precipitate was formed in each reaction system, the majority was a homogeneous brown solution. Magnesium ethoxide [Takumi (0C2H5)2] and magnesium phenoxide [Mg(0C6H5)2] as magnesium alcoholades were added to each solution in amounts shown in Table 4, and the reaction system was heated to 75°C.

Each reaction system was reacted at this temperature with stirring for 1.5 hours, and then cooled to room temperature. The supernatant liquid of each precipitate produced was taken out, and fresh n-hexane (30 a per 19 magnesium alcolade used in the above reaction) was added.
After stirring thoroughly, the supernatant liquid was removed. This washing operation was performed three times. Next, titanium tetrachloride (TiC!4 and n-butoxytitanium trichloride [T.(0C4H9)
Cl3] was added in the amounts shown in Table 4-1, and each reaction system was heated to 90°C. Each reaction was carried out for 90 minutes at this temperature with sufficient stirring. Each reaction system was cooled to room temperature, n-hexane (30 ml per 19 magnesium alcolade used in the above reaction) was added, and after thorough stirring, the supernatant liquid was removed. This washing operation was performed three times. Finally, each reaction product (solid catalyst component) was dried under reduced pressure at 50° C. for 30 minutes. As a result, each catalyst component exhibited a light brown color. Atomic absorption spectroscopy was performed on each catalyst component. The content of titanium atoms in each catalyst component is shown in Table 4-1. [(B) Homopolymerization of ethylene] Instead of the catalyst component (a) used in homopolymerizing ethylene in (D) of Example 1, each catalyst component obtained in the above (B) was used as the fourth catalyst component. −2 Using the amounts shown in the table,
Further, using 0.7 mmol each of triisobutylaluminum [Al(1-C4H9)3] or triethylaluminum as an organoaluminum compound (1.4 a of n-heptane solution containing 0.5 mmol/g of each organoaluminum compound), Furthermore, the hydrogen partial pressure is increased to 8K'/CTl
Ethylene homopolymerization was carried out in the same manner as in Example 1, except that the polymerization time was changed to 60 minutes (ethylene partial pressure was 10 K'/CTIt).

After each polymerization was completed, the obtained polymers were purified and dried in the same manner as in Example 1. M. of each obtained polymer. I.
H. L. M. /M. I. and bulk density are shown in Table 4-2. From the above Examples and Comparative Examples, high M. ．． It is possible to obtain an ethylene polymer having a high polymerization activity.

Furthermore, by carrying out multi-stage polymerization using this catalyst system, it is possible to produce an ethylene polymer mixture with a wide molecular weight distribution, and it is clear that it will have a wide range of applications in the film and blow fields.

[Brief explanation of the drawing]

Examples 1, 2 and 3 (A) and Comparative Examples 1 and 2
In (B), hydrogen partial pressure in homopolymerization of ethylene (
The horizontal axis (unit: Kf/C7l) is the M.I. of each obtained ethylene monopolymer. I. (Vertical axis, logarithmic scale, unit is 9/1
0 minutes) is shown in Figure 1.

Claims (1)

[Claims] 1 (A) (1) (a) (i) A complex compound of aluminum oxyhalide and alkoxyaluminum dihalide; (b) an aryl group having a silicon-oxygen bond and directly bonded to oxygen; A solid reaction product insoluble in a hydrocarbon solvent obtained by reacting (b) magnesium alcoholate with a reaction mixture with an organosilicon compound having at least one aralkyl group and (2) at least one halogen atom. Homopolymerization of ethylene or copolymerization of ethylene with other olefins in the presence of a solid component obtained by contacting with a tetravalent titanium compound having (B) an organoaluminum compound. An improved method for producing an ethylene polymer, characterized by: