JPS61127703A - Production of polyethylene - Google Patents

Abstract

PURPOSE:To obtain polyethylene in high yield, by polymerizing ethylene or ethylene and an alpha-olefin in the presence of a novel and highly active Ziegler catalyst and hydrogen at a temperature < the melting point of the polymer. CONSTITUTION:A Ziegler catalyst consisting of (A) a solid catalyst component obtained by reacting (i) a reaction product prepared by reacting one or more Mg-containing reagent selected from a reagent comprising metallic Mg and an organic hydroxide compound, and O-containing organic compound of Mg, a Mg halide, and an organomagnesium compound with a transition metal- containing reagent having at least one titanium compound selected from an O-containing organic compound of transition metal and a halogen-containing compound of transition metal in such a way that at least one of them is selected to have C-O-M (M is Mg or transition metal element) with (ii) at least one aluminum halide compound, (B) one or more organometallic compound of Ia, IIa, IIb, IIIb and IVb groups of periodic table, and (C) a one or more halogenated hydrocarbons is used for polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a process for producing ethylene polymers in which the polymerization is carried out in the presence of a novel catalyst system at a reaction temperature below the melting point of the polymer. More specifically, the present invention relates to a method for producing an ethylene polymer having a weight average molecular weight of 10,000 or more at a high yield per ethylene consumed.

[Conventional technology]

It is already known that a catalyst system consisting of a transition metal compound and an organometallic compound is used in the low-pressure polymerization of ethylene, but recently a reaction product of an inorganic or organomagnesium compound and a transition metal compound has been used as a highly active catalyst. Catalyst systems containing as components are often used. Furthermore, in order to control the molecular weight distribution over a wide range in the presence of these catalyst systems, a so-called multistage polymerization method is also known, in which ethylene is polymerized in a plurality of polymerization steps with different reaction conditions. Such polymerization methods are further divided into methods in which the reaction temperature is higher than the melting point of the K1 coalescence, and methods in which the reaction temperature is lower than the melting point.

In the former method, since the polymerization is carried out at a reaction temperature of, for example, 120 to 250°C, there is no problem in using hydrogen as a molecular weight regulator, but a large amount of energy is required for heating and the like. Furthermore, since the solution viscosity is limited in order to obtain a homogeneous polymer, it has an industrial disadvantage of low productivity.

On the other hand, the latter method performs polymerization at a temperature below the melting point, so it does not have the above-mentioned disadvantages, but it usually uses hydrogen as a molecular weight regulator, and a large amount of hydrogen is required, especially when lowering the molecular weight. . In this case, in the conventional Ziegler type catalyst system which has high activity, a reaction in which a part of ethylene is hydrogenated by hydrogen and ethane, which is industrially disadvantageous, is produced as a by-product occurs at a non-negligible rate, which is inconvenient. be.

On the other hand, in the field of ethylene wax, JP-A-55-1
No. 64206 uses a catalyst consisting of a specific highly active titanium component, an organic aluminum component, and a halogen compound component, and the viscosity average molecular weight is 4 at a reaction temperature of about 140°C or higher.
000 or less, but as in the present invention, l
In the production process of polymers having an average molecular weight of 10,000 or more, no technology has been established to suppress the by-product of ethane.

[Problem to be solved]

The method of conducting polymerization at a reaction temperature below the melting point of the polymer produces a large amount of ethane, which is industrially disadvantageous, as a by-product during normal polymerization, especially multi-stage polymerization, resulting in a decrease in the polymer yield per ethylene raw material and a decrease in productivity. In addition to this, there is a disadvantage that ethane is deteriorated, and unnecessary ethane produced as a by-product accumulates in the polymerization system, so this is discharged outside the system, resulting in the loss of raw materials such as ethylene. The present inventors therefore maintained the characteristics of conventional catalysts and processes, which provide polymers with high catalytic activity (and excellent quality and diversity in molecular weight distribution), while suppressing the by-product of ethane. We have continued to conduct intensive studies with the aim of providing a method for polymerizing ethylene with a weight average molecular weight of 10.
We have discovered a method for producing over 1,000 ethylene polymers.

[Means of solution]

That is, the present invention provides a method for producing polyethylene in which ethylene or ethylene and α-olefin is polymerized in the presence of a Ziegler type catalyst and hydrogen at a reaction temperature below the melting point of the polymer so as to have high activity. , (A) (+) A reactant consisting of metallic magnesium and a hydroxide organic compound, an oxygen-containing organic compound of magnesium,
At least one magnesium-containing reactant selected from the group of halogenated magnesium compounds and organomagnesium compounds, and at least one titanium compound selected from the group of transition metal oxygen-containing organic compounds and transition metal)/logen-containing compounds. a transition metal-containing reactant containing a compound,
At least one of the reactants is selected to have a c-0-M (in the formula, M represents magnesium or a transition metal element) bond in its chemical structural formula, and a product obtained by reaction is obtained. and (1) a solid catalyst component (A) obtained by reacting at least one type of aluminum halide compound.
) and (B) Periodic Table 1a, Ila, Ib, Ib and v
At least one catalyst component (B) selected from the group of organometallic compounds of group B metals; and (C) at least one catalyst component (C) selected from halogenated hydrocarbon compounds. This is a method for producing polyethylene.

[Effect]

The solid catalyst component used in the present invention (a magnesium-containing reactant for producing N includes, for example, a reactant consisting of metallic magnesium and a hydroxide organic compound, an oxygen-containing organic compound of magnesium, a magnesium halide, or an organic magnesium Examples include compounds.

First, when using magnesium metal and an organic hydroxide compound, the magnesium metal can be in various shapes, such as one particle of powder, foil or ribbon, and the organic compound hydroxide can be used in any shape. Alcohols, organic silanols, and phenols are suitable.

As alcohols, linear or branched aliphatic alcohols, cycloaliphatic alcohols or aromatic alcohols having 1 to 18 carbon atoms can be used. Examples include methanol, ethanol, n-propanol, 1-propanol, n-butanol, n-hexanol, 2-ethylhexanol, n-octatool, cyclohexanol, ethylene glycol, and the like. In addition, the organic silanol includes an alkyl group, a cycloalkyl group, an aryl group having at least one human o $ group, and the organic group has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. selected from alkyl groups, aryl groups, alkylaryl groups and aromatic groups. For example, we can give the following example.

Trimethylsilanol, triethylsilanol.

Triphenylsilanol, t-butyldimethylsilanol. Furthermore, phenols include phenol, cresol, xylenol, and hydro-? /7 etc.

These hydroxylated organic compounds may be used alone or in analogous mixtures. Of course, they can be used alone, but when used as a mixture of two or more, they may produce a unique effect on the powder characteristics of the polymer.

In addition, when using metallic magnesium to obtain the solid catalyst component (A) described in the present invention, for the purpose of promoting the reaction, substances that react with metallic magnesium or produce addition compounds, For example, iodine, mercuric chloride,
It is preferable to add one or more polar substances such as alkyl halides, organic acid esters, and organic acids.

Next, examples of compounds belonging to oxygen-containing organic compounds of magnesium include magnesium alkoxides, such as methylate, ethylate, isopropylate, descartes,
Methoxyethylate and cyclohexaltate, magnesium alkyl alkoxides such as ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, magnesium phenoxides such as phenolate, 7-thenate, 7-enanthrenate and cresolate, magnesium Carboxy 1/-)E,
For flJ, acetate and stearate.

Benzoate, phenylacetate, adipate.

Sepacate, 7-talates, acrylates and oleates, magnesium oximates such as butyl oximate, dimethyl glyoximate and cyclohexyl oximate, magnesium hydroxamates, magnesium hydroxylamine salts such as N-nitrone-dopheni Examples include hydroxylamine derivatives, magnesium erates, such as acetylacetonate, and magnesium syralates.

Examples of magnesium halides include magnesium cybarides, such as magnesium chloride.

Examples include magnesium bromide, magnesium iodide, magnesium hydroxyhalides such as magnesium hydroxychloride, magnesium alkyl halides such as ethylmagnesium chloride, and magnesium alkoxyquinohalides such as ethoxymagnesium chloride and butoxymagnesium chloride.

Examples of organomagnesium compounds include ethylbutylmagnesium and diptylmagnesium.

These magnesium compounds may be used alone or as a mixture of two or more. The solid catalyst component (A)
Examples of the transition metal-containing reactant containing a titanium compound for producing the titanium compound include the titanium compound itself, an oxygen-containing organic compound of titanium, a halogenated titanium compound, and the like. Examples of oxygen-containing organic compounds of titanium include titanium/tetrapropoxide, titanium tetrabutoxide, and hexabroboxydititanate, and examples of halogenated titanium compounds include titanium tetrachloride and titanium tetrabromide. Further, titanium jetoxy dichloride, titanium triethoxy chloride, etc. can also be used.

Further, this component (A>) may contain a silicon compound to provide a polymer with good particle properties.

Furthermore, it may contain transition metal components other than titanium.

As the silicon compound for improving the particle properties of the solid catalyst component, polysiloxanes and silanes can be used. Examples of polysiloxane include dimethylborisiloxane, methylhydropolysiloxane, diphenylboriaoxane, and examples of silanes include hexamethyldisilane.

Examples include tetraethoxysilane and diphenyldiethoxysilane.

As the transition metal-containing reactant other than the titanium compound,
Zirconium compounds, such as zirconium tetrachloride, ethoxytrichlorozirconium, dyptoxy7dichlorozirconium, tributoxychlorozirconium, tetrabutoxyzirconium.

Vanadium compounds such as vanadium trichloride, vanadium trichloride, and tributoxyvanadium can be used in combination.

However, when specifically selecting and using these reactants, at least one of the magnesium-containing reactants, titanium compounds, or transition metal-containing reactants other than titanium compounds should be c-0-M (in the formula, M It is necessary to use a compound containing a group with a bond (representing magnesium or a transition metal element). Examples of groups forming a C-0-M bond include alkoxy//, alkylalkoxy, arylalkoxy, etc. represented by the general formula OR'(R'': hydrocarbon group), specifically methoxy, Ethoxy.

Examples include butoxy, ethylhexyloxy, and phenoxy groups.

As the above (outside) aluminum halide compounds,
A compound of the general formula R2AIX, -2 is used.

However, in the general formula, R represents a hydrocarbon group having 20 carbon atoms, preferably 1 to 8 carbon atoms, or represents a halogen atom, and 2 represents the number of 0≦z (3, preferably represents a number of 0≦2≦2.

-Also, R is preferably a straight or branched alkyl group selected from a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. - Specific examples of such aluminum halide compounds include aluminum trichloride, diethylaluminum chloride, ethylaluminum dichloride, 1-butylaluminum dichloride, and the like.

The above aluminum halide compound may be used alone or in combination.
It can be used as a mixture of more than one species. A mixture of triethylaluminum and aluminum trichloride can also be used.

The solid catalyst component (A) used in the present invention can be prepared by reacting the above aluminum halide compound with a reaction product obtained by reacting the above magnephram-containing reactant and the transition metal-containing reactant. I can do it.

These reactions are preferably carried out in a liquid medium. It should therefore be carried out in the presence of an inert solvent, especially if these reactants themselves are not liquid under the operating conditions or if the amount of liquid reactants is insufficient. As the inert organic solvent, any solvent commonly used in the art can be used, including aliphatic, alicyclic or aromatic hydrocarbons, or mixtures thereof, such as isobutane, hexane, heptane, Cyclohexane, benzene, toluene, xylene and the like are preferably used.

The conditions for each of the above reactions are not particularly limited, but -50 to 5
00C1, preferably at a temperature in the range of 0 to 200C, for 15 to 50 hours, preferably 1 to 6 hours, in an inert gas atmosphere under normal pressure or increased pressure.

Suitable examples of production methods that provide such a solid catalyst fraction (A) are disclosed in Japanese Patent Publication No. 52-15110 and Japanese Patent Publication No. 52-59.
No. 714, JP-A-56-155205, JP-A-56-
151704, Japanese Patent Application No. 59-102661, Japanese Patent Application No. 59-118120, and the like.

In the present invention, the catalyst component (B), which is the first
a, lla, nb, mb, organogold of group IVb metals 1, [
Examples of the compound include organometallic compounds consisting of a metal such as lithium, magnesium, lead, tin, or aluminum and an organic group. As the above-mentioned organic group, an alkyl group can be cited as a representative example. As this alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is used. Examples of organometallic compounds having such an organic group include n-butyllithium, diethylmacnesium, diethylzinc, trimethylaluminum, triethylaluminum, 1J-1-phthylaluminum, tIJ-n-butylaluminum, trin - Decylaluminum, tetraethyltin, tetrabutyltin, etc. Above all, it is preferable to use trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms.

As component (B), it is also possible to use an alkyl metal hydride having an alkyl group having 1 to 20 carbon atoms. Specifically, such compounds include G-1
-Butylaluminum hydride.

Can you name trimethyltin hydride? Also, alkyl metal halides having an alkyl group having 1 to 20 carbon atoms, such as ethylaluminum sesquichloride,
Diethylaluminum chloride, di-butylaluminum chloride or alkyl metal alkoxides such as diethylaluminum ethgicide can also be used.

Note that X4'', which is trialkylaluminum having an alkyl group having 1 to 20 carbon atoms, is an organoaluminum compound obtained by the reaction of a dialkylaluminum hydride and a diolefin having 4 to 20 carbon atoms, such as a compound such as imprenyl aluminum. You can also use

It is also possible to use aluminoxane compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms, such as tetramethylaluminoxane and polymethylaluminoxane.

The halogenated hydrocarbon compound of the catalyst component (c) used in the present invention is not particularly limited, but is generally a halogen derivative of a hydrocarbon having 1 to 12 carbon atoms, and is usually in a liquid form. . Specific examples of such compounds include:
Propyl chloride, -n-butyl chloride, -5ec-butyl chloride, -tθrt-butyl chloride, amyl chloride, -n chloride
-octyl, n-butyl bromide, chlorobenzene, m-benzyl, methylene dichloride, 1,2-dichloroethane,
1,5-dichloropropane, 1,4-dichlorobutane,
Examples include trichloroethane, tetrachloroethane, tetrachloroethylene, carbon tetrachloride, and chloroform.

In carrying out the present invention, the use of catalyst component (A) is limited to 1 titanium atom per 16 solvent or per reactor 1.
It is preferable to use it in an amount corresponding to 0.001 to 2.5 millimoles (mmol), and higher concentrations can be used depending on the conditions.

The organometallic compound of component (B) is used in a concentration of (L 02 to 50 mmol, preferably [12 to 5 mmol) per 16 of the solvent or per reactor 1.

The halogenated hydrocarbon of component (C) is 14% of the solvent,
or per reactor 16, 1lLooooot~500
mmol, preferably Q, (IOol~foommo
Use at a concentration of 1.

In the present invention, the mode of feeding the five components into the polymerization vessel is not particularly limited, and for example, the components (((conversion)).

A method in which component (C) is separately fed into a polymerization vessel, or a method in which component (A) and component (0) are brought into contact with each other and then brought into contact with component (E) for polymerization. Component (B) ) and component (0) and then contact with component (Shu) to polymerize, or adopt a method in which component (A), component (B), and component (C) are brought into contact in advance and polymerized, etc. I can do it.

The polymerization of ethane/ is carried out in the liquid phase or in the gas phase at a reaction temperature below the melting point of the polymer.

When carrying out the polymerization in a liquid phase, it is preferable to use an inert solvent. This inert solvent can be any one commonly used in the art, but
Particularly suitable are alkanes and cycloalkanes having 4 to 20 carbon atoms, such as isobutane, pentane, hexanes, cyclohegysanes and the like.

The polymerization according to the present invention includes not only homopolymerization of ethylene, but also
Also includes copolymerization of ethylene and α-olefin. As the α-olefin used for copolymerization, probyley, 1-
7'tene, 1-pentene, 1-hexene, 4-methyl-
Examples include 1-pentene or a mixture thereof.

Although the polymerization of ethane according to the present invention can be carried out by a conventional method, it is especially effective when a multistage polymerization method is employed. The multi-stage polymerization method used herein refers to a method in which a polymer is produced through a plurality of polymerization steps, including a step for obtaining a relatively low-molecular-weight component and a step for obtaining a relatively high-molecular-weight component.

A suitable example of such multistage polymerization is disclosed in JP-A-56-161.
The details are shown in Japanese Patent No. 405. For example,
The first stage polymerization is performed in parallel in at least two polymerization steps: a polymerization step for producing a high molecular weight polymer and a polymerization step for producing a low molecular weight polymer. Next, in the second step, the reaction mixture containing the polymer produced in each of the previous polymerization steps is mixed to form a new single reaction mixture, and in the presence of the reaction mixture, the polymer produced in each of the above polymerization steps is mixed. Ta -
It is carried out in a polymerization process that produces a polymer with a molecular weight located in the center of the molecular weight of the polymer. Further, for example, it is possible to generate a low molecular weight component in the first step and then generate a high molecular weight component in the second step, or conversely, to generate a high molecular weight component and then generate a low molecular weight component.

The reaction conditions in the present invention are not particularly limited as long as the reaction temperature is lower than the melting point of the polymer, but usually the reaction temperature is 2.
In the present invention, polyethylene having a weight average molecular weight of 10,000 or more is produced. Polyethylene generally needs to have both solid and melt properties to an appropriate degree.
If the weight average molecular weight is less than 10,000, the fluidity will be too high and the solid physical properties will be too low, making it impossible to manufacture molded products by injection molding, extrusion molding, blow molding, etc.

The hydrogen a degree for adjusting the weight average molecular weight is the ratio of hydrogen partial pressure/ethylene partial pressure to the ethylene concentration, and is usually 1
001-2a, especially in multi-stage polymerization, 1L01-20 in the process of low molecular weight components, and 0-20 in the process of Ig molecular weight components.
[Selected by Ll. Here, the molecular weights of both the low molecular weight component and the high molecular weight component are selected with the aim that their average molecular weight matches that of the target polymer, and that the difference in molecular weight between them matches the width of the molecular weight distribution of the target polymer. It is necessary.

The reactor used in each polymerization step can be appropriately used as long as it is commonly used in the technical field. For example, the polymerization operation is carried out in a continuous manner using a stirred tank wall reaction 5 or a circulation reactor.

It can be carried out either by a semi-batch method or a batch method.

〔Effect of the invention〕

According to the present invention, by using a catalyst that is further improved from the conventional catalyst that provides high catalytic activity and excellent quality polymer, it is possible to significantly reduce the amount of ethane produced as a by-product during ethylene polymerization. can. That is, according to the present invention, even when polyethylene having a wide molecular weight distribution is produced, the by-product of ethane, which is industrially disadvantageous, can be suppressed and the production can be carried out without impairing productivity.

The second effect of the present invention is that the amount of ethane produced as a by-product can be suppressed to a significantly low level, which greatly reduces the occurrence of unnecessary ethane being FFfft in the polymerization system. Internal gas emissions can also be proportionally reduced significantly. Therefore, the loss of raw materials such as ethylene and hydrogen to the outside of the 5 system due to this discharge is minimized, and productivity is improved. Combining the prevention of ethylene loss through this and the prevention of ethane by-product mentioned above, by appropriately selecting the type and amount of halogenated hydrocarbon in the catalyst component (0), the loss of raw ethylene can be halved compared to conventional methods. It can be reduced to 1/10 or less.

The third effect of the present invention is that ethylene can be polymerized without impairing the characteristics of conventional catalysts or processes, which are to provide polymers with high catalytic activity, excellent quality, and a diversity of molecular weight distribution. It is possible. In other words, the catalytic activity is high and the yield of polymer obtained per catalyst component is extremely large, so there is no need to use special means to remove catalyst residue from the polymer, and there is no need to worry about polymer deterioration or coloring during molding. Problems can be avoided. In addition, it is possible to easily produce a uniform polymer with a wide molecular weight distribution, good moldability, and little gel or phish eyes.

〔Example〕

The present invention will be illustrated below by examples, but the present invention is not limited in any way by these examples. In addition,
In the Examples and Comparative Examples, the ELM/M process has a high load melt index (HLM process, ASTM D-12
58 Condition F) melt index (xr, AST
MD-1238 Condition E), the density was determined according to ASTM D-1505, and the weight average molecular weight was determined by measuring a solution of 〇-dichlorobenzene by gel permeation chromatography. Further, the amount of by-produced ethane was determined by gas chromatography and determined as the rate of occurrence [by-produced ethane t/amount of polymer produced x 1oO8)].

Example 1 a) Preparation of solid catalyst component (A) In a 4911 t flask equipped with a stirrer, 57 g (115 m01) of metallic magnesium powder and titanium tetrabutoxide 10291029 (Ql) were added,
The temperature was raised to 80°C, and 2 Fg of n-butanol (α52 mol) in which α18 iodine was dissolved was added dropwise over 1 hour, and then the mixture was heated to 120°C to react. After adding 250 d of hexane to the reaction product thus obtained at room temperature, 115 g of ethylaluminum dichloride ((1
9 mol) was added dropwise at 45°C over 2 hours to obtain a solid catalyst component (A). The titanium content of this solid component is 14
It was wt%.

13) Using two stainless steel electromagnetic stirrer reactors with a polymerization internal W% of 51, 36 hexafluorides were charged into one reactor, and after adjusting the internal temperature to 85°C, the catalyst components (tried as a uniform 1
-butylaluminum 1.72 (a5 mmol), -n-butyl chloride 1250In9 as the catalyst component (C), and the solid catalyst component (A) zsoq obtained in the above IL) were added. The reactor internal pressure was increased to 1ky/cr/1a by nitrogen gas.
After adjusting Vc, hydrogen partial pressure is 190'? /c! /l and further the total pressure is 25 Ie9. Ethylene was continuously added so that AGK was obtained, and polymerization was carried out for 65 minutes to produce a low molecular weight polymer. A small sample of each of the gas phase and liquid phase of this reactor was sampled, and the molecular weight of the polymer and the amount of by-produced ethane were measured.

The other reactor was charged with 3 tons of hexane, and
Butyl aluminum 1.7 g (& 8 + nmol
) and 125η of the solid catalyst component (A) obtained in a) above were added. The reactor internal pressure was increased to 1 kty/by nitrogen gas.
After adjusting the crdaK, 9/d was added to the hydrogen partial pressure of 11, and ethylene was added continuously so that the total pressure became 40 kg/cdta, and polymerization was carried out for 65 minutes to produce a high molecular weight polymer.

Next, each reaction mixture containing these polymers was pumped through a connecting tube to a stirred reactor having a content of fi10t. After replacing the gas phase of this reactor with nitrogen, the internal temperature was adjusted to 80-C.
The internal pressure is 1.0 God/crd G, and the hydrogen partial pressure is t 21a
7/Qn and the total pressure is 5.2 kg/crd.
Polymerization was carried out for 45 minutes by continuously supplying ethylene to G, and the reaction mixture was filtered and dried. The obtained polymer was 22109. In addition, as a result of grasping the raw rtt of each stage by the ethylene flow rate, the production ratio was 40 wt% for the low molecular weight polymer in the first stage, 40 wt% for the high molecular weight polymer in the same way, and 20 wt% for the latter stage.
It was wt Chi.

Low molecules! The weight average molecular weight of the polymer was 39,000. In addition, the by-product rate of ethane was very low (1048%).Furthermore, the obtained polymer powder was
M5 extruder was used to pelletize the pellets. The density is α
It was 956. In addition, when this pellet was formed into a film using a balance film forming machine, there were few fish eyes, and the number of fish eyes with a diameter Q of 2 or more was about 2,700/- on a film with a thickness of 60 μm, and it was good. It became a great film.

Examples 2-5. Comparative Example 1 In the method of Example 1, component (C) -n-chloride
Experiments were conducted by varying only the amount of butyl added as shown in Table 1. That is, the solid catalyst component (A) prepared in Example 1, tri-1-butylaluminum, was used in the same manner as in Example 1, and in Examples 2 to 5, the amount of n-butyl chloride added was changed, and in Comparative Example 1. In this case, polymerization was carried out without addition. The results are shown in Table 1.

Examples 4 to 10 Example 10 Experiments were conducted in the same manner as in Example 1, except that various halogenated hydrocarbons shown in Table 2 were used instead of -n-butyl chloride as component (C) in the polymerization. I did it. The results are shown in Table 2.

Example 11 a) Preparation of solid catalyst component (A) In a 1 L flask equipped with a stirrer, 57 g (115 m01) of metallic magnesium powder and 102 g (cL3 mal) of titanium tetrabutoxide were added under a nitrogen atmosphere.
The temperature was raised to 80°C, and 257 g (152 mo1) of n-butanol dissolved in α18 iodine was added dropwise over 1 hour, and then the mixture was heated to 120°C to react. Add hexane 2 to the reaction product obtained at room temperature.
After adding 50TRt, 1~butylaluminum dichloride 1989 (1989) diluted to 50 wt% with hexane
1,28no1) was added dropwise at 45° C. over 2 hours to obtain a solid catalyst component (A). The titanium content of this solid component was 15irt.

Prior to polymerization pressure, 1,
160 g of 2-dichloroethane was added.

b) Polymerization An experiment was conducted in the same manner as in Example 10 Polymerization.

That is, in one reactor, a mixture of component (A) and component (C) obtained above [200 In9. At the same time, a mixture of component (A) and component (C) [component ( 100q as A), component (C
) as 9311! F), 155 g of tri-1-butylaluminum was used to polymerize a high molecular weight component, and the reaction mixture was then pumped into a third reactor, whereupon the subsequent polymerization was performed. The polymerization conditions at each stage were the same as in Example 1. The resulting polyethylene weighed 2380 g, and the ethane by-product rate was C1069%. In addition, the pellet M process was (LO45, ELM process/M process was 210).

Comparative Example 2 The method of Example 11 was carried out without using the component (c), 1,2-dichloroethane. The polyethylene obtained as a result is 25109, and the by-product rate of ethane is cL
It was 235%. Also, the MX of the pellet is αQ 60.
HLMX/MX was 190.

Example 12 a) Preparation of solid catalyst component (A) In a 1.6 t autoclave equipped with a pumping device, n-
Add 70g of butanol ((L94mO1), add iodine CL559.11g of metal magnesium powder (α45
mol ) and titanium tetrabutoxide 61 w(1
After adding 18 mO1) and further adding 770° of hexane, the temperature was raised to 80°C, and the mixture was stirred for 1 hour under a nitrogen blanket while excluding generated hydrogen gas. Continuing to 120℃
The temperature was raised to 150°C, and the reaction was carried out for 1 hour to obtain a solution containing magnesium and titanium.

In a flask with an internal volume of 500 mg, 048 mol of magnesium equivalent of a solution containing magnesium and titanium was added, the temperature was raised to 45°C and 17°C, and a hexane solution of tri-1-butylaluminum (0,048 mol) was added over 1 hour. After everything was added, it was stirred at 60"C for 1 hour.

Then methylhydropolysiloxane (viscosity approximately 50 centistokes at 25°C) 2.8 m (silicon IIL0
4B gram atom) was added and reacted under reflux for 1 hour.

After cooling to 45 °C, 1-butylaluminum dichloride 5159 (α
22 mob) was added over 2 hours. After adding everything, stirring was performed at 70°C for 1 hour to obtain a solid catalyst component (g). The titanium content of this solid component (A) is 9.
It was Owt%.

b) Polymerization An experiment was conducted in the same manner as in Example 10 Polymerization.

That is, component (A) 20 obtained above in one reactor
oIF9, tri-1-butylaluminum 155g ('
Lammo 1), n-butyl chloride 4001+1i7 was used to polymerize the low molecular weight component, while component (A)f OQag, t+)-1-butylaluminum (L55F) was used to polymerize the high molecular weight component. Polymerization was carried out, and the reaction mixture was then pumped into a third reactor, followed by subsequent polymerization.The polymerization conditions at each stage were the same as in Example 1.The resulting polyethylene is 2
4509, and the ethane by-product rate was cL067. Also, Berrett's MI is (LO55, FILM Engineering/M
The engineering was 180.

Example 13 a) Preparation of solid catalyst component (A) In a t6t autoclave equipped with a stirring device, n-butanol 52-2F (αa 21FIOI) was charged, and iodine (L459.metallic magnesium powder a) was added to it.
, 86 F (120 mob) and titanium tetrabutoxide 27.29 (IILOB mol) were added, and after adding 200 ml of hechusan, the temperature was raised to 80 °C, and the temperature was raised to 80 °C, and the mixture was heated under a nitrogen blanket while excluding the generated hydrogen gas. Stirred for 1 hour. Continue to raise the temperature to 12G'C and
A time reaction was performed. Dimethylpolysiloxane (viscosity about 50 centistokes at 25°C) 155F (12 gram atoms of silicon) was then pumped in with nitrogen at 120'C and reacted for 1 hour at 12G'C. After the reaction, add 500% of hexane, cool to 45°C, and add 50% of hexane.
1-Butylaluminum dichloride 186 F (1.2 mol) diluted to t% was added over 3 hours. After everything was added, the mixture was stirred at 60°C for 1 hour to obtain a solid catalyst component (A).

The titanium content of this solid component (A) was 9.4 wt%.

b) Polymerization An experiment was conducted in the same manner as in Example 10 Polymerization.

That is, 250% of component (A) obtained above in one reactor
M9. ) di-1-butylaluminum [L55f (2
-8 mmol), -n-butyl chloride 500In9 to polymerize a low molecular weight component, and at the same time, in the other reactor, polymerize a high molecular weight component using component (A) 120111P, ) +7-1-butylaluminum 1L559, and then After these reaction mixtures were sent to the third reactor &lE, the latter stage polymerization was carried out. The polymerization conditions at each stage were the same as in Example 1. The resulting polyethylene is 2
45G? The by-product rate of ethane was 1008 cm. Also, the pellet MI is α06゜HLM machining/M machining is 15
It was 0.

Example 14 a) Preparation of solid catalyst component (A) In a 1-ton flask equipped with a stirrer, 49 g (1120 m01) of metallic magnesium powder, 17p ([L05mox), and tetrachloride in titanium tetrabutylene were added. Zirconium 11.65P ((105m01) was added, the temperature was raised to 80℃, and n-butanol 64.19 (c8Qmol) in which iodine of (L20) was dissolved was added dropwise over 1 hour, and then heated to 120℃. The reaction product thus obtained was diluted with hexane 2 at room temperature.
After adding 00m, add ethylaluminum dichloride 5009 (1,2m
ol) was added dropwise at 45°C over 2 hours to dissolve the solid catalyst component (
I got ~. The titanium content of this solid component is 5.5 vt
%Met.

b) The inside of a stainless steel electromagnetic stirring type reactor with a polymerization content of 2 tons was sufficiently purged with nitrogen, 1.2 tons of hexane was charged, and the internal temperature was adjusted to 70°C. Thereafter, 25 g (1 L) of tri-1-butylaluminum was added as catalyst component (B).
, 2 mmol), 1,2-dichloroethane 42IR9 as component (0), and the above component (A) 2 G m
y were added sequentially. 1kg inside the reactor with nitrogen gas
After adjusting /dGK, 1s5ky/Cr/I of hydrogen was added to bring the total pressure to 207I9/C4GK. Polymerization was carried out for 1.5 hours while continuously adding ethylene. After the polymerization was completed, the gas phase and liquid phase were sampled at sunset and the ethane produced as a by-product was measured. Further, polyethylene was taken out from the autoclave and separated from the solvent by filtration. As a result, 1
659 polyethylene was obtained, and the by-product rate of eta/ was (1
It was 009chi. Also, MI was 145 (LO7, HIIM/M).

Comparative Example 3 An experiment similar to Example 14 was conducted except that 1,2-dichloroethane, component (C) in the method of Example 14, was not used and 25 m9 of the above component (N) was used.

The amount of polyethane obtained was 205 g, and the amount of ethane was 71%. Also, M engineer [L08, HLMI]
/M Elm family 140.

Example 15 a) Preparation of solid catalyst component 4.99 (120 mob) of metallic magnesium powder and -
f-7 Tetrabutoxide 27.29 ((LO8mol
) was added, the temperature was raised to 80"C, and 31.1 g of n-butanol ((142 m
ob) was added dropwise over 1 hour, and then heated to 120°C to react. After adding hexa/340- to the reaction product thus obtained at room temperature, 50
Ethylaluminum dichloride diluted to wt% 1
249 (Q, 8 mol) was added dropwise at 45° C. over 2 hours to obtain a solid catalyst component (conversion). During this time, the titanium content of the solid catalyst component was 9.5 wt4.

b) The inside of a stainless steel 11E magnetic stirrer type reactor having an internal volume of 10 tons was sufficiently purged with nitrogen, hexane and chlorine were charged, and the internal temperature was adjusted to 85°C. After that, the catalyst component (B
) as tri-1-butylaluminum 1.199 (&
0 mm0:L), 200 In9 of 1,2-dichloroethane as component (C), and 100 da of the above component (A) were successively added. 1 kg inside the reactor by nitrogen gas
/crd G, hydrogen was added to 1⁻okq/d, and while ethylene was continuously added so that the total pressure became 20 kp/dG, polymerization was carried out for 60 minutes to produce a low molecular weight polymer. A small amount of each of the gas phase and liquid phase of this reactor was sampled, and the molecular weight of the polymer and the amount of by-produced ethane were measured.

Next, 1. The gas phase of this reactor was replaced with nitrogen, and the internal temperature was adjusted to 75°.
The internal pressure of C2 is 1.0 kq/ail G, and the hydrogen partial pressure is 1.
．． 0 kg/d is added, and the total pressure is to tel /
Polymerization was carried out for 45 minutes by continuously supplying ethylene to reach cr/l a of 5, and the reaction mixture was filtered and dried. The weight of the obtained polymer was 2500 g. Further, the amount produced in each stage was determined by the ethylene flow rate, and the production ratio was 50 wtJ for the low molecular weight polymer in the first stage and 50 wtJ for the high molecular weight polymer in the latter stage.

The weight average molecular weight of the low molecular weight i1-polymer was 22,000. Furthermore, the rate of by-product of ethane during polymerization was very low, with a range of 1015. Furthermore, pelletization was performed in the same manner as in Example 1, but the M process of this pellet was (L(158, H
LMI/MI was 190° and density was α957. In addition, when a film was formed using this pellet-ke balance film forming machine, there were few fish eyes and the thickness was 30 μm.
With this film, approximately 2 fisheyes with a diameter of 12m or more
500 pieces/-, and the film was good.

Example 16 In the method of Example 15, the tree 1-
Experiments were conducted using triethylaluminum instead of butylaluminum. That is, the solid catalyst component (A) prepared in Example 15, 1,2-dichloroethane, was washed and used in the same manner as in Example 15, and triethylaluminum A (168
Polymerization was carried out under the same conditions using (1 (& [1 mmol)).

As a result, the molecular weight of the low molecular weight polymer was 21000, and the production ratio was 50 wt% for the low molecular weight polymer in the first stage and 50 vrt% for the high molecular weight polymer in the latter stage. Furthermore, the rate of by-product of ethane during polymerization was very low at 1005% of the ethylene supplied. Furthermore, the polymer powder obtained in the same manner as in Example 1 was pelletized, and the M process of the pellets was α
065. I (LM work/y work) was 180. Also, when this pellet was formed into a film using an I Ku/S film film forming machine, there was little occurrence of fish eyes, and a film with a thickness of 30μ had a diameter of α2 or more. The fish eye is about 26
00 pieces/-, and the film was good.

Example 17 In the method of Example 15, a small amount of 1-
An experiment was conducted in the same manner as in Example 15 except that butene was added. That is, the solid catalyst component (A) prepared in Example 15, tri-1-butylaluminum, 1.2-
Dichloroethane was used in the same manner as in Example 15 to produce a low-molecular-weight polymer in the first stage, and then 1-butene was supplied at 30 ml during the high-molecular-weight polymerization in the latter stage. the result,
The weight average molecular weight of the low molecular weight polymer was 20,000.

In addition, the by-product rate of ethane at this time is 1 of the ethylene supplied.
There were very few in 004chi. Furthermore, the obtained polymer powder was made into pellets, and the M process of this pellet was α06
8. The 180° density of HLM work/M work was 0.948. In addition, when this pellet was formed into a film using a balance film molding machine, there was little occurrence of fisheyes, and the number of fisheyes with a diameter of 12m5 or more was approximately 2,400/- with a film thickness of 30μ, and it was a good film. Ta.

Comparative Example 4 An experiment similar to Example 14 was conducted except that 1,2-dichloroethane, component (C) in the method of Example 14, was not used. The obtained polyethylene was 2059,
Eta7(1') by-product rate was (1248%-?ni).

Also, M engineering is Q, 07, HI, MI / M engineering is 1
It was 75.

Example 18 Using the solid catalyst component (A) prepared in Example 15, polymerization was carried out in a gas phase. Contents: In a stainless steel, electromagnetic stirred reactor of 21 mm, 50 g of polyethylene powder of KM 12 was charged and dried at 70°C for 2 hours, and then the internal temperature was adjusted to 60°C. After that, the catalyst component (B)
1146 g of tri-1-butylaluminum (2,
4 mmol 1 ), 20 Ing of 1,2-dichloroethane as component (C), and component (A > 20 μ) were added sequentially.The interior of the reactor was heated with nitrogen gas to 9/CrdGVC.
After adjusting, add 2 kg/cm of hydrogen until the total pressure is 5
Polymerization was carried out for 1.5 hours while continuously adding ethylene to give kg/cttla. After polymerization,
A small amount of the gas phase was sampled and the amount of ethane produced as a by-product was measured. In addition, when polyethylene was taken out from the autoclave, 106 g of polyethylene was obtained, and the by-product rate of ethane was [
It was 1021 chi. Also, M engineering is 10, I (LM engineering/
M engineer was 32.

Comparative Example 5 The same experiment as in Example 18 was conducted except that 1,2-dichloroethane, component (C) in the method of Example 18, was not used. The obtained polyethylene was 103
The by-product rate of ethane was 0.267%. Also, M engineer is 1
1, and HLM work/M work was 32.

Claims (1)

[Claims] (1) A method for producing polyethylene in which ethylene or ethylene and α-olefin are polymerized in the presence of a highly active Ziegler-type catalyst and hydrogen at a reaction temperature below the melting point of the polymer, wherein the catalyst is (A) ( i) At least one magnesium-containing reactant selected from the group of a reactant consisting of metallic magnesium and an organic hydroxide compound, an oxygen-containing organic compound of magnesium, a halogenated magnesium compound, and an organomagnesium compound, and a transition metal oxygen and a transition metal-containing reactant containing at least one titanium compound selected from the group of organic compounds containing transition metals and halogen-containing compounds, at least one of which has a C-O-M ( (in which M represents magnesium or a transition metal element), and by reacting the resulting product with (ii) at least one aluminum halide compound. The obtained solid catalyst component (A) and (B) Ia, IIa, IIb, IIIb and I of the periodic table.
Vb is replaced by at least one catalyst component (B) selected from the group of organometallic compounds of group metals, and (C) at least one catalyst component selected from the group of halogenated hydrocarbon compounds (
C) A method for producing polyethylene, characterized by comprising: