JPS61145205A - Production of polyethylene - Google Patents

Abstract

PURPOSE:To obtain PE of a narrow MW distribution in high yields and excel lent polymerization activity, by polymerizing C2H4 by using a catalyst formed by combining a specified transition metal compound-carrying final solid product with an organo-aluminum compound. CONSTITUTION:A solid product is obtained by mixing a trivalent metal halide such as A1C13 with 0.01-20% bivalent metal (hydr)oxide, carbonate, etc., [e.g., Mg(OH)2], grinding the mixture and reacting the ground mixture by heating. This solid product is mixed with a halogen-containing transition metal compound (e.g., TiC14) in the presence of an electron-donating compound such as an alkoxy group-containing silicon compound in an atmosphere of an inert gas, and the mixture is allowed to react at 40-300 deg.C for 10min-20hr. To this reaction mixture a halogen-free transition metal compound (e.g., tetra-n-butyl orotho tianate) is added with stirring in the presence of an electron-donating compound such as an ether, and the resulting mixture is allowed to react at 40-300 deg.C for 10min-20hr to obtain a transition metal compound-carrying final solid product. C2H4 is polymerized by using a catalyst formed by combining this product with an organoaluminum compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Technology] The present invention relates to a method for producing polyethylene in which ethylene is polymerized using a novel catalyst having extremely high polymerization activity.

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

[Purpose of the invention]

In recent years, technology to produce polyethylene using Ziegler-type supported catalysts has become widespread, mainly because it improves catalyst utilization efficiency, eliminates the catalyst removal process, and simplifies the manufacturing process. It is based on 'Nl. However, by further increasing catalyst utilization efficiency,
The search continues to enable more economical methods of producing polyethylene.

As supports for Ziegler-type supported catalysts, anhydrous magnesium chloride or its modified products, organomagnesium halides such as Grignard reagents, organomagnesium compounds such as magnesium ethoxide, or compounds other than magnesium such as alumina and silica alumina have already been used. It is publicly known that this has been done.

In contrast, the present inventors have developed a compound with a complex composition produced by a chemical reaction between a trivalent metal halide such as aluminum chloride and a divalent metal compound such as magnesium hydroxide, which is woody different from those supports. We have developed a method that increases the catalyst efficiency and makes it possible to omit the catalyst removal step by using the catalyst as a carrier. For example, in JP-A No. 57-42705 (hereinafter referred to as the invention of light), in the presence of polysiloxane, a transition metal compound of Group 48 or Group 5a containing a halogen (Group A) and (Group B) At least two selected from each group of transition metal compounds that do not contain halogen.
Although this method is characterized by the use of a solid product prepared by simultaneously reacting various transition metal compounds, it is desired that the polymer yield be further improved. On the other hand, JP-A-55-5
No. 931 and JP-A-55-12165 disclose that a solid product prepared by reacting a $4a group or a group 58 transition metal compound with the above-mentioned carrier in the presence of a polysiloxane is further subsequently treated with a halogen. Group 48 or Group 58 containing
It is characterized by the use of a solid product prepared by reacting a Group 4a or Group 58 transition metal compound with a halogen-free Group 4a or Group 58 transition metal compound, the polymer having a very broad molecular weight distribution. It is something.

As a result of various studies on improvements to the previous invention, the present inventors have determined the type of compound to be present when reacting the solid product (I) with the transition metal compound, and the solid product CI.
) has been discovered that the polymer yield can be significantly improved by devising a method for reacting a transition metal compound with a transition metal compound, leading to the present invention.

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

[Structure of the invention]

The present invention is a solid product CI obtained by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or an aquarium of a divalent metal compound.
) is reacted with an electron-donating compound and a transition metal compound of group 4a or group 5a of the periodic table to polymerize ethylene using a catalyst that combines a transition metal compound-supported final solid product and an organoaluminium compound. In the method for producing polyethylene, a halogen-containing Group 48 or Group 5a transition metal compound (hereinafter referred to as a halogen-containing transition metal compound) is added to the solid product (I) in the presence of an electron-donating compound (Step A). (hereinafter referred to as step A); and (step B) in the presence of an electron-donating compound, a halogen-free Group 48 or Group 58 transition metal compound (hereinafter referred to as halogen-free transition metal compound) is reacted. This is a method for producing polyethylene, characterized in that a solid product (n) obtained through two steps (hereinafter referred to as step B) in which a metal compound is reacted (hereinafter referred to as step B) is used as a final solid product supporting a transition metal compound.

As a trivalent metal halide, aluminum trichloride (
(anhydrous), iron trichloride (anhydrous) are shown.

Examples of divalent metal compounds include Mg(OH)2°Ca(OH)2. Zn(OH)2. Hydroxides such as Mll(OH)2, MgO, CaO, ZnO, MnO(7
), MgA h 04 , MgtSiO4
, a double oxide containing a divalent metal such as y6MnOs, M
Carbonates such as gCO3, MnCO3, CacO3,
MgCh *6 R20,5nG12* 21 (20,
MnCl2* 4H20, KMgG13 ”6 R20
, halide water supplies such as NiCl2.6H20,
3Mg0・MgC12・4H20 and other double salt aquariums containing halides and 3Mg0・2Si02
- Hydrates of double salts containing oxides of divalent metals such as 2ToO, hydrates of double salts of carbonates and hydroxides such as 3MgC(h.Mg(OH)2.3H20, and M! .Al1 (OH)ib C(h 114 R20
Examples include hydroxide carbonate aquariums containing divalent metals such as.

The solid product (I) is obtained by reacting a trivalent metal halide and a divalent metal compound. In order to cause this reaction, it is preferable to mix and crush the two in advance for 5 to +000 min in a ball mill or for 1 to 10 hours in a vibration mill, and then heat the reaction after thoroughly mixing them. It is also possible to carry out the reaction by heating. 3
The ratio of the valent metal halide to the divalent metal compound, expressed as the atomic ratio of the divalent metal to the trivalent metal, is usually 0.
A range of 0.01 to 20 is sufficient, preferably a range of 0.05 to 10. The reaction temperature is usually 20 to 500°C, preferably 50 to 300°C. The reaction time is suitable for 30 minutes to 50 hours, and if the reaction temperature is low, the reaction is carried out for a long time so that no unreacted trivalent metal halide remains, and the obtained solid product is converted into a solid product. (I).

Hereinafter, a method will be described in which the solid product (1), which is one embodiment of the present invention, is subjected to the reaction of (Step A) and then subjected to the reaction of (Step B).

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

The electronic goo compound has the general formula R'y 5i(OR2)a -vn (wherein R1 is C+
- a hydrocarbon group up to C20, a hydrogen atom or a halogen atom, R2 is a hydrocarbon group up to C+''C20, and O≦m×4); Oxygen-containing organic compounds selected from ethers, esters, aldehydes, ketones, and carboxylic acids are used.

Commonly used alkoxy group-containing organosilicon compounds include tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane,
Ethyltriethoxysilane, diethyljethoxysilane, methyltriethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, tetraoctoxysilane, pentyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane,
Examples include trimethoxysilane, triethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, trimethoxychlorosilane, dimethoxydichlorosilane, and triethoxychlorosilane.

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

In addition to being used alone, these electron-donating compounds can also be used with 2 inserts-1.
- can also be used in combination.

Examples of halogen-containing transition metal compounds include compounds such as titanium and vanadium halides, oxyhalides, alkoxyhalides, and acetoxyhalides; for example,
Titanium tetrachloride, titanium tetrabromide, titanium trichlormonopropoxy, titanium dichlordiisopropoxy, titanium monochlortriisopropoxy, titanium dichlormonobutoxy, titanium dichlordibutoxy, titanium trichlormonoethoxy, vanadium tetrachloride, titanium oxytrichloride Examples include vanadium chloride, but titanium tetrachloride is most preferred.

(1) The solid product (I), the electron-donating compound, and the halogen-containing transition metal compound may be mixed in any order under an inert gas atmosphere, such as nitrogen, but the mixture of the electron-donating compound and the transition metal compound may be mixed in any order. Preferably, the solid product (I) is added to. The mixing is from -50°C to +50°C, preferably from -209°C to +30°C. At that time, there is no restriction on the presence or absence of a solvent. The reaction time is 10 to 20 minutes.
time, preferably 10 minutes to 10 hours.

The mixing ratio of solid product (1), electron donating compound, and halogen-containing transition metal compound is solid product (I) + 00g
In contrast, the electron-donating compound is 10 to 10,000 g, preferably 20 to 1,000 g, and the halogen-containing transition metal compound is 10 to 10,000 g, preferably 20 to 1.0 g.
00g, and the halogen-containing transition metal compound is 10 to 1,000g per 100g of the electron donating compound,
Preferably it is 20-500g. The reaction conditions are 40°C to 300°C, preferably 50°C to 200°C with stirring.
The reaction is carried out for 10 minutes to 20 hours, preferably 10 minutes to 10 hours.

For mixing the solid product (1), an electron donating compound, and a halogen-containing transition metal compound, and for their reaction,
Although it is not always necessary to use a solvent, it is preferable to react uniformly, so any or all of the above components may be dissolved or dispersed in a solvent in advance. It is sufficient that the total amount of solvent used is about 10 times (by weight) or less the total amount of the above three components.

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

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

The solid product (II) is obtained from the above (Step A), ie.

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

As the electron donating compound, the above electron donating compound is used, but it does not need to be the same as that used in the reaction of (Step A). In addition, when proceeding to the next reaction (B process) with the slurry state as it is after the reaction in (A process), there is an unreacted electron donating compound, so a new electron donating compound is added. Although not particularly necessary, a new electron-donating compound may be added if desired.

Examples of halogen-free transition metal compounds include alkoxides of titanium and vanadium, such as tetraethyl orthotitanate (tetraethoxytitanium), tetra-2propyl orthotitanate (tetraisopropoxytitanium), and tetra-n-butyl orthotitanate (tetra-n). Other polytitanate esters include tetraalkyl orthotitanates (tetraalkoxytitanium) such as n-butoxytitanium), vanadyl trialcholates such as vanadyl triisopropylate, vanadyl triisopropylate, vanadyl triisopropylate, and n-butyrad. can be used. This product can be represented by the general formula RO(T+(OR)2-0]mR, where m is an integer of 2 or more, preferably 2 to 10.R represents an alkyl group, an aryl group, or an aralkyl group, It is not necessary that all R groups are of the same type, and they may be mixed.The number of carbon atoms in H is preferably 1 to 10, but is not particularly limited.Specifically, examples include polymethyl titanate,
These include polyethyl titanate, isopropyl polytitanate, n-butyl polytitanate, n-hexyl polytitanate, and the like. In the general formula, some of the alkoxy groups may be hydroxyl groups.

A solid product that is a reactant in the previous step, an electron donating compound,
The amount of the halogen-free transition metal compound to be used is from 10 to 10,000 g of the electron donating compound, preferably from 10 to 1.00 g, per 100 g of the original solid product (I).
0g, halogen-free transition metal compound is 10-5,0
00 g, preferably 15 to 1,000 g, and the halogen-free transition metal compound is 10 to 1,000 g, preferably 20 to 1,000 g per 100 g of the electron donating compound.
It is 500g.

The reaction conditions are 40°C to 300°C, preferably 50°C to 200°C, with stirring for 10 minutes to 20 hours, preferably 1
React for 0 minutes to 10 hours.

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

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

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

After the above reaction, the unreacted transition metal compound and the electron-donating compound are separated using a conventional method and a solvent such as aliphatic hydrocarbon or aromatic hydrocarbon is used at room temperature, preferably 50°C or higher. The washing is repeated until it is no longer detected and dried to obtain a solid product (TI).

The reaction sequence of the above-mentioned halogen-containing or non-halogen-containing transition metal compound to the solid product (I) may be carried out in any order. That is, as described above, after (Step A) (Step B)
(Step A) may be carried out after (Step B).

The catalyst of the production method according to the present invention is a solid product of L (II
) and an organoaluminum compound. Examples of organoaluminum compounds include trialkyl aluminum such as triethylaluminum, triimbutylaluminum, and trihexylaluminum, dialkylaluminum monohalides such as diethylaluminum monochloride, and ethylaluminum sesquichloride.
Other examples include alkoxyalkyl aluminums such as monoethoxy diethyl aluminum and jetoxy monoethyl aluminum.

The catalyst thus obtained is used in the production of polyethylene. Examples of α-olefins for copolymerization of ethylene include linear monoolefins such as propylene, butene-1, and hexene-1, branched monoolefins such as 4-methyl-pentene-1, and diolefins such as butadiene. can give.

Polymerization reactions are usually carried out in a hydrocarbon solvent such as hexane, heptane, octane, decane, etc.

Polymerization temperature is 30°C to 150°C, preferably 60°C to 1
The polymerization is carried out at 20 DEG C. and at a pressure of normal pressure to 50 kg/crn', preferably 5 to 40 kg/crn'. During polymerization, an appropriate amount of hydrogen can be added to adjust the molecular weight.

〔Effect of the invention〕

The main advantage of the present invention is that the polymerization activity is extremely high and the polymer yield is extremely high. In the present invention, the polymer yield is defined by the formula (Ep=polymer (g)/(solid product (II) (g)
)X polymerization time (Hr)
”)))) (hereinafter, the polymer yield is expressed as Ep)
It is sometimes abbreviated as. ), but the polymer yield Ep according to the present invention shows a high value of 3600 to 5210 (see Example 1-12).

In contrast, the method of the invention of the light described above (JP-A-57-42705) involves simultaneously reacting the solid product (I) with a halogen-containing transition metal compound and a halogen-free transition metal compound in the presence of polysiloxane. ) the value of Ep is low;
2850C Comparative Example 2), and the Ep value is low even in the method of simultaneously reacting the solid product (I) with a halogen-containing transition metal compound and a halogen-free transition metal compound in the presence of an electron donating compound, and the Ep value is 1800C. ~2780 (Comparative Examples 1.12 to 15).

Moreover, when even one component is missing among the components used in Example 1, the value is as low as 120 to +910 (Comparative Examples 3 to I+).

As described above, the Ep is extremely low when using the method of the previous invention or the method lacking essential components of the present invention, but the Ep is significantly improved according to the method of the present invention.

Another advantage of the present invention is that a polymer with a narrow molecular weight distribution can be obtained. (/and 5 to 8, and '41 is a polymer suitable for injection molding and certain types of extrusion molding.
I. Further, the shape of the obtained polymer is very good, and the bulk specific gravity of the polymer reaches 0.47. Therefore, the production efficiency per hour per volume of polymerization vessel is high,
During polymerization, there is no or very little polymer adhesion to the walls of the polymerization vessel, and stable continuous polymerization can be carried out for a long period of time in the same polymerization vessel.

〔Example〕

In Examples and Comparative Examples, Ml is melt index (AST
MD-1238), N/R is an index of the distribution amount distribution (m is the weight average molecular weight, O is the number average molecular weight), and BD is the bulk specific gravity of the polymer powder.

Example 1 (1) Preparation of solid product (I) 80 g of magnesium hydroxide and 140 g of aluminum trichloride (anhydrous) were mixed in advance in a vibrating mill with a capacity of 2 g.
After mixing and pulverizing at room temperature, the mixture was reacted at 150°C for 5 hours. Thereafter, it was cooled and pulverized to obtain a solid product (I).

(2) Production of solid product (II) While maintaining the temperature at 20°C and stirring, toluene 2001, 70 g of tetraethoxysilane and 130 g of titanium tetrachloride are added to a round bottom flask with a capacity of ti and equipped with a stirrer and mixed. Then, after adding the solid product (I) toog, the temperature was increased to 80°C.
The mixture was reacted for 3 hours. Next, remove the supernatant and add 2 hexane
The solid product was washed with 001.

To the remaining solid product was added 2001 toluene, 30 g of tetraethoxysilane and 44 g of tetra-n-butyl orthotitanate.
After adding 0 g, the reaction was carried out at 80°C for 2 hours. After the reaction is completed, first filtration is performed, and the remaining solid product is washed with hexane until no unreacted titanium compound is detected in the filtrate, and dried under reduced pressure to obtain solid product (II) as the final solid product. Obtained. Solid product (JI) 1g
The content of titanium atoms therein was 58 mg.

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

(3) Production of polyethylene After purging a stainless steel polymerization vessel with an internal volume of 201 m with nitrogen gas, 10 m of hexane and 350 m of triethyl aluminum
g and 25 g of solid product (TI) were put thereinto, and the polymerization vessel was sealed. Next, the temperature was raised to 80°C, and hydrogen was added at a gauge pressure of 4
kg/crn' and the total pressure is 15k in gauge pressure.
After polymerization was carried out at 80°C for 2 hours while continuously introducing ethylene to maintain g/cm', methanol 1
00g was injected under pressure to deactivate the catalyst and stop the polymerization reaction. Subsequently, after the reaction was completed, the polyethylene slurry was filtered and dried without deashing, to obtain 2680 g of a white polymer. The Ml of this polymer is 8.0, and the BD is 0.
．． 47, 7 countries were 7, Ep (polymer yield) was 5210. This is shown in Table 1.

Example 2 100 g of solid product CI) in Example 1 (2),
First, a reaction in step B was carried out using 30 g of tetraethoxysilane and 40 g of or-I tetra-n-butyl titanate.

After the reaction in step B, the reaction in step A was carried out using 70 g of tetraethoxysilane and 130 g of titanium tetrachloride.Other than that, the solid product (TI
) was obtained.

Using this solid product (II), the others were as follows from Example 1 (
Polyethylene was produced in the same manner as in 3). The results are shown in Table 1.

Comparative Example 1 While keeping the temperature at 20°C and stirring, add 200 nl of toluene and Tetra A to a round bottom flask with a stirrer made by Koto Ichibun.
・Add and mix 70 g of xysilane, 130 g of titanium tetrachloride, and 40 g of orthotitanium alcoholic acid un-butyl, and then add 100 g of the solid product (I) obtained in Example 1 (1).
was added, and then reacted at 80°C for 3 hours. After the reaction was completed, filtration was first performed, and the remaining solid product was washed with hexane until no unreacted titanium compound was detected in the filtrate, followed by drying under reduced pressure to obtain the final solid product. The content of titanium atoms in 1 g of the final solid product was 52 II g.

50ff1g of this final solid product was added to the solid product (II
), and polyethylene was produced in the same manner as in Example 1 (3) except for the following. Table 1 shows the polymer yield and the physical properties of the obtained polymer.

Comparative Example 2 Catalyst preparation and polyethylene production were carried out by the method of JP-A No. 57-42705, and comparisons were made.

That is, a final solid product was obtained in the same manner as in Comparative Example 1, except that 100 g of linear dimethylpolysiloxane (viscosity: 100 centistokes) was used instead of tetraethoxysilane.

Using this final solid product, the following procedure was carried out in the same manner as in Comparative Example 1.

Comparative Example 3 Same as (2) of Example 1 except that tetraethoxysilane is not used when reacting the solid product (I) with titanium tetrachloride in Step A in (2) of Example 1. The final solid product was obtained.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 4 In (2) of Example 1, after the reaction of solid product (I), tetraethoxysilane, and titanium tetrachloride, when further reacting with tetra-n-butyl orthotitanate in step B,
A final solid product was obtained in the same manner as in Example 1 (2) except that tetraethoxysilane was not used.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 5 In (2) of Example 1, orthotitanium
The final solid product was prepared in a similar manner except that butyl was not used.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 6 A final solid product was prepared in the same manner as in Example 1 (2) except that titanium tetrachloride was not used.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 7 After carrying out the reaction in Example 1 (2) without using the solid product (I), it was cooled and 7500 nl of hexane was added.
was added to precipitate a solid product, which was filtered and dried to obtain a final solid product.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 8 A final solid product was prepared in the same manner as in Example 1 (2) except that 130 g of polyethyl titanate was used instead of titanium tetrachloride.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 9 A final solid product was prepared in the same manner as in Example 1 (2) except that 130 g of silicon tetrachloride was used instead of titanium tetrachloride.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Comparative Example 10 A final solid product was prepared in the same manner as in Example 1 (2) except that 40 g of titanium tetrachloride was used instead of tetra-n-butyl orthotitanate.

h Using this final solid product, the following is compared to Comparative Example 1.
1 was carried out in the same manner.

Comparative Example 11 Aluminum tri-n-butoxide 40 instead of tetra-n-butyl orthotitanate in (2) of Example 1
The final solid product was prepared in a similar manner, except using g.

The following procedure was carried out in the same manner as in Comparative Example 1 using this final solid product.

Example 3 (1) 40g of magnesium oxide and iron trichloride ($, water)
After mixing and pulverizing 160 g at room temperature for 24 hours in a ball mill with a capacity of 2 mm, the mixture was reacted at 200° C. for 1 hour to obtain a solid product (I).

(2) Keeping the temperature at 20°C and stirring, place 300 m of xylene, 100 g of phenyl]-ethoxysilane, and 130 g of titanium tetrachloride in a 1M capacity round bottom flask with a stirrer.
g, ' a and 100 g of the above solid product (I) were simultaneously added and mixed, and then reacted at 110°C for 2 hours. next"
After adding 45 g of tetraethyl orthotitanate without removing the clear solution (that is, in the presence of unreacted phenyltriethoxysilane), the mixture was reacted at 100°C for 2 hours. After the reaction is completed, first, filtration is performed, and the remaining solid product is washed with hexane until no unreacted titanium compound is detected in the filtrate, and dried under reduced pressure to obtain the final solid product, solid product (II). I got it.

(3) Using this solid product (II), polyethylene was produced in the same manner as in Example 1 (3) except for the following. The results are shown in Table 1.

Example 4 100 g of solid product (I) in Example 3 (2),
First, a reaction in step B was carried out using 100 g of phenyltriethoxysilane and 45 g of tetraethyl orthotitanate. After the reaction in Step B, without removing the supernatant (that is, in the presence of unreacted phenyltriethoxysilane), A was carried out using 130 g of titanium tetrachloride.
A solid product (II) was obtained in the same manner as in Example 3 (2) except that the reactions in the steps were carried out in the same manner as in Example 3 (2). This solid product (II)
Polyethylene was produced in the same manner as in Example 1 (3) except that The results are shown in Table 1.

Comparative Example 12 While keeping the temperature at 20°C and stirring, 3.0 ml of xylene was added to a 1-liter round-bottomed flask with a stirrer. OOmJl, phenyltriethoxysilane 100g, titanium tetrachloride 130g
, 45 g of tetraethyl orthotitanate, and a long solid product (I) obtained in Example 3 (1) were simultaneously added and mixed, and then reacted at 110°C for 2 hours to obtain a final solid product.

Polyethylene was produced in the same manner as in Example 1 (3) except that 50 mg of this final solid product was used in place of solid product (II). The results are shown in Table 1.

Example 5 (1) Solid product (I) was prepared in the same manner as in Example 1 (1) except that 150 g of magnesium chloride (6 water ff1) was used instead of magnesium hydroxide.

(2) - 10 (Ig) of solid product (I) and ethyltriethoxysilane in step A, 4 g in step B.
A solid product (ir) was obtained in the same manner as in Example 1 (2) except that 0 g was used.

(3) Using this solid product (II), polyethylene was produced in the same manner as in (3) of Example 1 except for the solid product (II). The results are shown in Table 1.

Example 6 In (2) of Example 2, a solid product was produced in the same manner except that 40 g of the solid product (I) loOg obtained in Example 5 and ethyltriethoxysilane were used in Step B and 80 g in Step A. Product (II) was obtained. Using this solid product (II), polyethylene was produced in the same manner as in Example 1 (3) except for this.

The results are shown in Table 1.

Comparative Example 13 In Comparative Example 1, the solid product obtained in Example 5 (I
), and 80 g of ethyltriethoxysilane were used. The results are shown in Table 1.

Example 7 (1) Hydromagnesite (3MgC03・Ag(O
Hh ・3H20) 90g and aluminum trichloride
(Anhydrous) 140g was mixed and pulverized in a vibrating mill with a capacity of 2 liters, and heated at 300°C for 1 hour to react.
A solid product (I) was obtained.

(2) While keeping the temperature at -10°C and pumping,
4QOml of toluene in a round-bottomed flask with a pressurizer,
140 g of anisole and 150 g of trichloromonoisopropoxy titanium were added and mixed, and then 100 g of the above solid product (I) was added and reacted at 100° C. for 2 hours. Next, 40 g of n-butyl polytitanate (trimer) was added without removing the supernatant (that is, in the presence of unreacted anisole) and reacted at 100°C for 1 hour to form a solid product ( II) was obtained.

(3) Polyethylene was produced in the same manner as in Example 1 (3) except that 1 g of this solid product (II) 25II and 4QQmg of triisobutylaluminum were used. The results are shown in Table 1.

Example 8 Solid product (I) in Example 7 (2) 100
g.

70 g of anisole, and n-butyl polytitanate (3
First, the reaction in step B was carried out using 40 g of the polymer.

After the reaction in step B, without removing the supernatant (that is, in the presence of unreacted anisole), 1. The reaction in Step A was carried out in the same manner as in Example 7 (2) except that a solid product (I
I) was obtained. Using this solid product (II), polyethylene was produced in the same manner as in Example 1 (3) except for the solid product (II). The results are shown in Table 1.

Comparative Example 14 While keeping the temperature at 20°C and stirring, 400 mJJ of toluene, 140 g of anisole, and 150 g of trichloromonoisopropoxy titanium were added to a 1-liter round-bottomed flask with a shaker.
g and 40 g of n-butyl polytitanate (triacid form) were added and mixed, and then the solid product obtained in Example 7 (I
) was added and reacted at 100°C for 2 hours to obtain a final solid product. 1 Polyethylene was produced in the same manner as in Comparative Example 1 except that 50+ag of this final solid product was used in place of solid product (II). The results are shown in Table 1.

Example 9 (1) Magnesia cement (3KgoΦMgCI 2
・4H20) 70g and aluminum trichloride (anhydrous)
140 g was reacted for 24 hours while heating at 100° C. in a 2-liter ball mill to obtain a solid product (1).

(2) While stirring while keeping the temperature at O'C, add 200ml of toluene to a round bottom flask with a stirrer and a
n-butyl ether 80g, titanium tetrachloride 1'30g,
100 g of solid product (I) and "-" were simultaneously added and mixed, followed by reaction at 80°C for 2 hours. Next, the supernatant liquid was removed, and the solid product was washed with 400 mJJ of hexane. To the remaining solid product, 200 ml of toluene, 25 g of polyethyl titanate (decamer), and 45 g of di-n-butyl ether were added and mixed, and then reacted at 80°C for 2 hours to obtain a solid product (TI). .

(1) Example 1 except using this solid product (If)
Polyethylene was produced in the same manner as in (3). The results are shown in Table 1.

Example 10 Solid product (I) I'0 in Example 9 (2)
First, the reaction in step B was carried out using 0 g of ethyl titanate, 45 g of di-n-butyl ether, and 25 g of ethyl titanate (101). After the reaction in step B, the reaction in step A was carried out using 90 g of di-n-butyl ether and 130 g of titanium tetrachloride, and in the same manner as in Example 9 (2) except that a solid product (II) was obtained. This solid product (II) was evaporated and polyethylene was produced in the same manner as in Example 1 (3). The results are shown in Table 1.

Comparative Example 15 While stirring while keeping the temperature at 0'C, 200w of toluene and J-n-
90 g of butyl ether, 130 g of titanium tetra-1nide, 25 g of polyethyl titanate (IOmer), and 100 g of the solid product (I) obtained in Example 9 were simultaneously added and mixed.
, and then reacted at 80° C. for 2 hours to obtain a final solid product.

50 mg of this final solid product was used in place of solid product (II), and in the same manner as in Comparative Example 1 except for the production of boroethylene. The results are shown in Table 1.

Example 11 Using the solid product (TI) obtained in Example 1, 1. %hand,
Copolymerization of tyrene and propylene was carried out.

In (3) of Example 1, hydrogen was 3Kg at gauge pressure.
Table 2 shows the results of producing an ethylene-propylene co'polymer by side straining in the same manner as in Example 1, except that ethylene containing 8% (volume %) propylene was introduced.

Example 12 The solid product (II) obtained in Example 1 was transferred to River 1. At X,
Ethylene-butene-1 copolymerization was carried out.

In (3) of Example 1, hydrogen was heated to 2.5K at gauge pressure.
Table 2 shows the results of producing an ethylene-butene-1 copolymer in the same manner as in Example 1 except for introducing tyrene containing 5% (volume %) butene-1. Indicated.

Procedural amendment ■, Indication of the case 1982 Patent Application No. 267243 2, Name of the invention Polyethylene manufacturing method 3, Person making the amendment Relationship to the case Patent applicant 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka Prefecture (〒530)
(20?) Chisso Corporation Representative Sadao Nogi 4, Agent 2-8-1 Shinjuku, Shinjuku-ku, Tokyo (160) 5 Date of amendment order Voluntary amendment 6. Number of inventions increased by amendment None 7. Detailed description of the invention in the specification subject to amendment.

8. Contents of amendment Correct the statement as follows.

(1) On page 11, lines 13-14, ['diethylene glycol dimethyl ether] is corrected to "diethylene glycol dimethyl ether."

(2) Next to “propionic acid” on page 12, line 3, write “,
” is inserted.

(3) Delete "The reaction time is 10 minutes to 20 hours, preferably 10 minutes to 10 hours" on page 13, lines 5 to 6.

(4) Correct "Distribution amount distribution J" on page 22, line 3 to "molecular weight distribution".

(5) On page 27, line 16, after “after doing it”, add “
The reaction solution was transferred to a 10-volume round bottom flask. Next, insert the reaction solution.

”− ''I.

lit

Claims (8)

[Claims] (1) A solid product obtained by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound (I)
Polymerization of ethylene using a catalyst consisting of a combination of an organoaluminum compound and a final solid product supporting a transition metal compound obtained by reacting an electron-donating compound and a transition metal compound of group 4a or group 5a of the periodic table. In the method for producing polyethylene, a halogen-containing Group 4a or Group 5a transition metal compound (hereinafter referred to as halogen-containing transition metal) is added to the solid product (I) in the presence of an electron-donating compound (Step A). (hereinafter referred to as step A); and (step B) in the presence of an electron-donating compound, a halogen-free Group 4a or Group 5a transition metal compound (hereinafter referred to as halogen-free transition metal A process for producing polyethylene, characterized in that a solid product (II) obtained through two steps (hereinafter referred to as B step) is used as a final solid product supporting a transition metal compound. (2) As an electron-donating compound, the general formula R^1_mSi
(OR^2)_4_-_m (in the formula, R^1 is C_1 to C_
is a hydrocarbon group, hydrogen atom or halogen atom up to 2_0, R^2 is a hydrocarbon group up to C_1 to C_2_0, and 0≦m<4. ) The method according to claim (1), using an alkoxy group-containing organosilicon compound represented by: (3) As the electron-donating compound, ether, ester,
1 selected from aldehydes, ketones, or carboxylic acids
A method according to claim (1) in which the species or two or more oxygen-containing organic compounds are used. (4) The method according to claim (1), in which a titanium or vanadium halide, oxyhalide, alkoxyhalide, or acetoxyhalide is used as the halogen-containing transition metal compound. (5) The method according to claim (1), in which titanium or vanadium alkoxide is used as the halogen-free transition metal compound. (6) Claim No. 1 in which tetraalkyl orthotitanate, vanadyl trialcholate, or polytitanate is used as the halogen-free transition metal compound.
). (7) As the transition metal compound-supported final solid product, solid product (II) is obtained by subjecting solid product (I) to the reaction of (Step A), followed by the reaction of (Step B). )
A method according to claim (1) using the method. (8) As the transition metal compound-supported final solid product, solid product (II) is obtained by subjecting solid product (I) to the reaction of (B process), followed by the reaction of (A process). )
A method according to claim (1) using the method.