JPS58132009A - Production of polyethylene - Google Patents

Abstract

PURPOSE:To obtain polyethylene in good efficiency, by reacting a solid product obtained from a trivalent metal halide, etc., with a polysiloxane and a specified transition metal compound, combining the resulting reaction product with an organoaluminum compound and employing the composition as the catalyst. CONSTITUTION:A solid product obtained by the reaction between a trivalent metal halide and a bivalent metal compound is reacted with a polysiloxane and two kinds of transition metal compounds each selected from the class consisting of a halogen-containing Group IVa or Va transistion metal compound a halogen- free Group IVa or Va transition metal compound. The produced solid product is combined with an organoaluminum compound to form a catalyst. Ethylene is polymerized in the presence of both the catalyst and an inert, solvent, the slurry containing the formed polyethylene is discharged and the vapor portion and the solvent portion are circulated into the polymerization system.

Description

[Detailed description of the invention] The present invention relates to a method for producing polyethylene.

More specifically, the present invention relates to a method for polymerizing ethylene by a solvent circulation method using a novel Ziegler catalyst.

Hereinafter, in the present invention, the polymerization or polymer of ethylene includes, in addition to the homopolymerization or homopolymerization of ethylene, the copolymerization or copolymer of ethylene with other α-olefins that can be copolymerized. Ethylene homopolymers and copolymers are collectively referred to as polyethylene.

In recent years, technology to produce polyethylene using Ziegler-type supported catalysts has become widespread, mainly because it increases the efficiency of using one catalyst, eliminates the catalyst removal process, and simplifies the manufacturing process. Based on. However, still-
1-More economical polyethylene with improved catalyst utilization efficiency/
Research on the manufacturing method continues.

Supports for Ziegler-type supported catalysts include anhydrous magnesium chloride or its modified products, organomagnesium compounds such as Grignard reagents, organomagnesium compounds such as magnesium ethoxide, or compounds other than magnesium such as alumina and silica alumina. is known to be used.

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 essentially different from those carriers. 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, JP-A-54-116078 or JP-A-54-11368
No. 7 c and below are sometimes referred to as earlier inventions. ) is characterized by the use of a solid product prepared by reacting the above-mentioned support with a group 4a or group 5a transition metal compound in the presence of polysiloxa/, but the polymer yield is further improved. It is desirable that the On the other hand, in JP-A-55-5931 and JP-A-55-12165, in addition to the final solid product disclosed in the earlier invention, a halogen-containing group 4a or Fi group 5a transition metal compound is added. It is characterized by using a solid product prepared by reacting a transition metal compound of Group 41 or Group 5a that does not contain a halogen, and the polymer obtained using the catalyst has a molecular weight distribution. It is extremely wide. As a result of various research into improvements to the previous invention, the present inventors discovered that the polymer yield could be significantly improved by devising the selection and combination of transition metal compounds and the reaction thereof, and found that the polymer yield could be significantly improved. No. 119387/1987 (hereinafter referred to as the prior invention).

The object of the prior invention is to increase the polymer yield by -1- compared to conventional methods in producing polyethylene with an excellent shape and narrow molecular weight distribution.

The prior invention is 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. using a catalyst obtained by combining a final solid product supported with a transition metal compound prepared from polysiloxane, a transition metal compound of group 4a or group 5a, and an organoaluminum compound. In a method for producing polyethylene by polymerizing ethylene, the final solid product is a solid product +11 and (group A) a halogen-containing Group 4a or Group 5a transition metal in the presence of polysilicon. Compounds (hereinafter referred to as halogen-containing transition metal compounds) and (group B) halogen-free Group 41 or Group 5a transition metal compounds (hereinafter referred to as halogen-containing transition metal compounds)
A method for producing polyethylene, characterized by using a solid product (sulfuric acid) obtained by reacting at least two transition metal compounds selected from at least one from each group of non-containing transition metal compounds. be.

On the other hand, when ethylene is suspension-polymerized in the presence of an inert solvent (hereinafter simply referred to as solvent) using a Ziegler-type catalyst, polyethylene is separated from the slurry obtained by suspension polymerization, and the separated solvent portion (note A method of circulating the liquid residue into the polymerization system is known from Japanese Patent Publication No. 33-8544. However, in the ethylene suspension polymerization method using solvent circulation, even if a considerable amount of new organoaluminum compound is added in addition to the organoaluminum compound in the circulating solvent, transition metal A drastic decrease in the polyethylene yield per catalyst component (note: the so-called 'polymerization activity') cannot be avoided. On the other hand, if the recycling of solvents in the suspension polymerization of ethylene is avoided and does not lead to other disadvantageous consequences, the consumption and recovery costs of the solvent will be greatly reduced, and the cost of producing polyethylene will be greatly reduced. Not only can this result in a reduction in the amount of water used, but also the solvent recovery and purification equipment can be eliminated or extremely simplified, so the overall benefit is extremely large.

Adopting a gas phase polymerization method for ethylene is one solution. However, the gas phase polymerization method has the disadvantage of requiring the circulation of large amounts of ethylene gas for removal of the heat of polymerization and fluidization.

The present inventors have continued to conduct intensive research into a polymerization method that does not have the above-mentioned drawbacks associated with the adoption of a solvent circulation method, and have developed a method for producing fruit peels. As a result, unexpectedly, when suspension polymerization of ethylene is carried out using a catalyst that combines the solid product (seal) used in the prior invention and an organoaluminum compound, the polymerization activity is significantly improved compared to when no solvent is circulated. The present invention was completed based on the knowledge that not only the physical properties of polyethylene thus obtained are not impaired, but also the melt fluidity of polyethylene is significantly improved.

As is clear from the above description, the purpose of the present invention is to provide a method for expanding or improving the prior invention, and more specifically, the purpose of the present invention is to provide a method for expanding or improving the prior invention. The object of the present invention is to provide a method for producing polyethylene with a significantly higher suspension concentration than in the case of the present invention. Another object is to provide a polyethylene that has high melt flowability and can therefore be efficiently molded.

The present invention has the following configurations (1) to 9).

(1) Solid product obtained by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, a salt containing these, or a hydrate of a divalent metal compound )
and a final solid product supported with a transition metal compound prepared from a polysiloxane and a Group 4a or Group 5a transition metal compound in combination with an organoaluminum compound. in the presence of polysiloxane as the final solid product, the solid product v3j
il+ and (Group A) a transition metal compound of Group 4a or Group 5 that contains a halogen (hereinafter referred to as a halogen-containing transition metal compound) and (Group B) a transition metal compound of Group 4a or Group 5 that does not contain a halogen.
A solid product obtained by reacting at least two transition metal compounds selected from at least one group from each group of transition metal compounds of group a or group 5a (hereinafter referred to as halogen-free transition metal compounds). Suspension polymerization is carried out continuously in the presence of an inert solvent using a sphere.
A part of the obtained slurry containing polyethylene is continuously taken out and separated into a gaseous part, a solvent part and a polyethylene part outside the polymerization system, and the gaseous part and the solvent part are circulated into the polymerization system. A method for producing polyethylene.

(2) The halogen-containing transition metal compound is a titanium or vanadium halide, oxyhalide, alkoxyhalide, or acetoxyhalide according to the above item (1).
The manufacturing method described in section.

(3) The manufacturing method according to item (1) above, wherein the halogen-free transition metal compound is an alkoxide of titanium or vanadium.

(4) The method according to item (1), wherein the halogen-free transition metal compound is tetraalkyl orthotitanate (tetraalfoxytitanium) or vanadyl trialcollade.

(5) 50ffi of polyethylene I11 degree in slurry
The manufacturing method according to item (1) above, characterized in that the weight is maintained at 1% or more by 5% or less.

(6) The production method according to item (1) above, wherein a slurry containing polyethylene is separated into a solvent portion and a wet cake by a centrifugal separation method, and the separated solvent portion is circulated to the polymerization system.

(7) The manufacturing method according to item (6) above, wherein the wet cake is air-dried to separate into solvent vapor and dry powder, and the solvent in the separated solvent vapor is condensed and liquefied and circulated to the i-fold yarn.

(8) The production method according to item (1) above, in which an amount of organoaluminum compound lacking in the organoaluminum compound in the circulating solvent is newly supplied into the polymerization system.

(9) The production method according to item (1) above, in which hydrogen gas is newly supplied into the polymerization system in an amount that is insufficient in the hydrogen gas in the gas portion to be circulated.

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

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

As the divalent metal compound, for example, Mg(OH)z
.

Ca(OH)1, Zn(OH)1, Mn(OH)
)2 such as hydroxides, MgO,, CaO, ZaO, M
Oxides like nO, MgAl2O3, Mg, 5to4
．． Complex oxides containing divalent metals such as Mg@MnO@
Carbonates such as MgC01, MnC01, CaCO3, MgCZs・6Hzo, 8nC/z・2H20.

MnC/1・4H20, KMgCz,・6H20t N
I CZ 2.6H20-like halide hydrate, 3Mg0.MgC1! - Hydrate of double salt containing oxide and halide such as 4H20, 3Mg0-28i02
- Hydrates of double salts containing divalent metal oxides such as 2H20, hydrates of double salts of carbonates and hydroxides such as 3MgC01.Mg(OHh.3)(,0), and Mg5
Examples include hydrates of hydroxide carbonates containing divalent metals such as A/z(OH)tscOa.4H20.

Solid product 1) Fi, obtained by reacting a trivalent metal/metal halide and a divalent metal compound. In order to cause this reaction, it is preferable to mix and grind in advance for 5 to 100 hours using a ball mill or 1 to 10 hours using a perturbation mill, and then heat the reaction after thoroughly mixing. It is also possible to react. The mixing ratio of the trivalent halide and the divalent metal compound is usually 0.05 to 0.05, expressed as the atomic ratio of the divalent metal to the trivalent metal.
20 is sufficient and preferably ranges from 0.1 to 10. The reaction temperature is usually 20-500°C, preferably 50-300°C.
It is 00℃.

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. (1).

The polysiloxane is a linear or cyclic siloxane polymer represented by the general formula, in which each R represents the same or different residues that can be bonded to silicon, and among them, hydrogen, an alkyl group, an aryl group, etc. Hydrocarbon residues, halogens, alkoxy groups or aryloxy groups, fatty acid residues, etc., and those in which 2111 or more of these are bonded in various ratios within the molecule are used.

Octamethyltrisiloxane CHs (' + (CHs
) zo) z81(CH,)3. Diphenyloctamethyltetrasiloxane (CHs) ssio (81(CH
s) (CsHs)0)zsi(CHs)s, octanylcyclotetrasiloxane (8i
(CzHi)to)4m Cyclic polymers such as hexaphenylcyclotrisiloxane (81(C@HshO)n, dimedelporinloxane [5I(CH3)!O)n, methyl ether polysiloxane (8i(CHs)( CxHs)
0) n + methylphenyl polysiloxa 7 (S i
Chain polymers such as (CHs ) (C@Hs )O:)n, methylhydrogen polysiloxane (8iH(CHa)O)
n-phenyl hydrogen polysiloxane (S 1H (C4H6
)0) n, etc. In addition to chain alkyl hydrogen siloxane polymers, chain aryl hydrogen siloxane polymers, etc., chloromethylpolysiloxane (8ic/ (CH3)O) n,
, , methyl ethoxy polyi10xay (84(CH
s) (CzHsO)0)n, chlormethoxypolysiloxane (81C/(CHsO)O)n, methylacetoxypolysiloxaney (8i(CHs)(CH3CO2
)0)N and other linear polysiloxanes. It is desirable that the polysiloxane used be liquid, and viscous (
25° C.) is 10 to 10,000 centistokes, preferably 10 to 1000 centistokes.

Examples of the halogen-containing transition metal compounds of (Group A) include titanium, vanadium halides, oxyhalides, alkoxyparites, and acetoquinolides, such as titanium tetrachloride, titanium tetrabromide, and trichloromono Isopropoquine titanium, dichlordiisopropoquine titanium, monochlortriisopropoxytitanium, trichlormonobutoxytitanium, dichlordibutoxytitanium,
Dolichloromonoethoxytitanium, vanadium tetrachloride,
Examples include vanadium oxytrichloride, but titanium tetrachloride is most preferred.

(Group B) halogen-free transition metal compounds include alkoxides of titanium and vanadium, such as tetraethyl orthotitanate (tetraethoxytitanium), tetraisopropylovir orthotitanate (tetraisopropoxytitanium), and tetran orthobutanoate. - Tetraalkyl orthotitanate (tetraalkoxytitanium) such as butyl (tetraalkoxytitanium), vanadyl triethylate, panadyl triisopropylate, vanadyl trin-
Other polytitanate esters can be used, such as nadyl trialcholates such as butyrad. This product can be represented by the general formula RO + T Todoroki (OR) 2-0-), R, 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, and it is not necessary that all R's are the same type of group, and they may be mixed. The number of carbon atoms in R is preferably 1 to 10, but is not particularly limited.

Specifically, they include polymethyl titanate, polyethyl titanate, isopropyl polybutanoate, n-butyl polytitanate, n-hexyl polybutanoate, and the like. In the general formula, some of the alkoxy groups may be hydroxyl groups.

The solid product +11 is obtained by mixing the solid products (i.e., polysilochitin, (group A) transition metal compound and (group B) transition metal compound, but the mode of mixing is such that it can be mixed in any order under a nitrogen atmosphere. However, it is preferable to add the solid product +11 to the mixture of polysiloxane and transition metal compound.The mixing temperature is suitably between -50°C and +30°C, but preferably between -20°C and +20°C. 1. There is no restriction on the presence or absence of a solvent.

Solid product (1), polysiloxane, (AN) and (
Group B) The mixing ratio of transition metal compounds is as follows: solid product (1)
polysiloxane is 10 to 10
,000f, preferably 20 to 000'f.

The total weight of the transition metal compound (the sum of (Group A) and (Group B)) is 10 to 10,000F, preferably 30 to 4ooor, and the total weight of the transition metal compound is 100 tons of polysiloxane. , 10 to 1,00Of, preferably 30 to 500f.

(Group A) (Group B) The proportion of each transition metal compound (total amount if two or more from one group are used) is (
The weight ratio of 1#) to (group B) is 0.5 to 30.
Preferably it is 1 to 2 degrees.

After mixing, heat at 40°C to 30°C, preferably 5°C while stirring.
The reaction is carried out at 0°C to 200°C for 10 minutes to 50 hours, preferably 10 minutes to 30 hours.

Although it is not necessarily necessary to use a solvent in mixing the solid product (1), polysilochitin, and transition gold compound and in their reaction, it is preferable to react uniformly, so any or all of the above may be mixed in advance. The components may be dissolved or dispersed in a solvent and then mixed.

The total amount of solvent used is approximately 10 times the total amount of each component above (
Weight) or less is sufficient.

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

After the above reaction is completed, the unreacted transition metal compound, bo9v, and loxane are separated using a solvent such as aliphatic hydrocarbon or aromatic hydrocarbon at room temperature, preferably 60°C or higher, according to a conventional method. Washing is repeated until no more is detected and dried to obtain a solid product (seal).

The catalyst of the production method of the present invention is obtained by combining the above solid product +I) and an organoaluminum compound. Examples of organoaluminum compounds include trialkylaluminiums such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminium heptatubalides such as diethylaluminum monochloride, ethylaluminum sesquichloride, etc.
There are alkoxyalkyl aluminums such as monoethoxy diethyl aluminum and jetoxy monoethyl aluminum.

The catalyst thus obtained is used in the production of polyethylene. As α-olefins for co-monomers of ethylene,
Examples include linear monoolefins such as propylene and butene-11hexene-1, branched monoolefins such as 4-methyl-pentene-1, and diolefins such as butadiene.

Polymerization reactions are usually carried out in hydrocarbon solvents such as hexane, heptane, octane, decane, and the like. Polymerization temperature is 30
°C to 150 °C, preferably 60 to 120 °C, and the polymerization pressure is normal pressure to 50 Icf/cd.

Preferably it is carried out at 5 to 40 4/cd. During polymerization, the molecular weight can be adjusted by adding an appropriate amount of hydrogen to the polymerization system.

In the method of the present invention, a portion of the slurry in the polymerization system is continuously removed in order to circulate the inert solvent and unreacted ethylene, hydrogen, and organoaluminum compound.

The polymerization process will be explained below with reference to the drawings.

The figure is a flowchart of a polymerization apparatus related to a polymerization method showing one embodiment of the present invention. First, continuous suspension polymerization of ethylene in the presence of an inert solvent according to the present invention is carried out as described above. A solid product (I) diluted with a solvent, an organoaluminum compound diluted with a solvent, a replenishing solvent, hydrogen, ethylene and A predetermined amount of α-olefin other than ethylene (Note 4 in case of copolymerization) is fed.

By keeping the temperature raised to the polymerization temperature and maintaining the predetermined polymerization pressure and hydrogen partial pressure, the slurry concentration in the vessel (polyethylene portion/total slurry) gradually increases, but it is difficult to remove the next slurry and remove the solvent, ethylene, etc. With new supplies,
The slurry concentration in the vessel should be 50% by weight or less, preferably 5 to 5%.
Maintains 0 weight well. The most preferred concentration is 25-4
It is 5% by weight. If it is less than 5% by weight, the manufacturing capacity will be significantly reduced, and if it exceeds 50% by weight, operation management will be difficult and fluctuations in product quality will likely occur.

A part of the slurry containing polyethylene in the polymerization vessel which has reached a predetermined slurry concentration is continuously taken out to a flash drum 9 by a control pulp 8 installed in a withdrawal pipe. The gaseous parts, ie, ethylene and hydrogen, are separated from the slurry whose pressure has been reduced in the drum, and these are returned to the polymerization vessel 7 through the ethylene and hydrogen circulation piping 10 (the blower necessary for the piping 10 is not shown). ). The residence time and temperature of the slurry processed in the flash drum are not limited, but are usually 5 minutes to 1 hour and 20°C to 50°C. The slurry from which ethylene and hydrogen have been separated is sent to the next centrifugal separator 12 via a withdrawal pipe with a pump 11, where it is continuously separated into a solvent portion and a polyethylene portion (wet cake). In addition to the solvent, the solvent part contains most of the organoaluminum compound used for polymerization and a small amount of soluble low-molecular-weight polymer (
Note: Contains so-called polyethylene wax). This portion is entirely circulated through the pipe 13 to the polymerization vessel 7 by the pump 14, but a portion or the entire amount may be extracted from the pipe 15 as required for operation. On the other hand, the separated wet cake consists mostly of polyethylene, a small amount of solvent, very small amounts of solid products, organoaluminum compounds and soluble low molecular weight polymers.

This part is dried by contacting the wet cake with heated nitrogen gas in the flash drying pipe 16 by means of a flash drying device consisting of an inert gas heater 23 and pipes 24, 16 and 18, which are directly connected to the centrifuge 12. , dry polyethylene powder (
(Note: dry powder) and solvent vapor (Note: Diluted with nitrogen). The dry polyethylene powder (note: containing solid products, organoaluminum compounds, and soluble low-molecular polymers) obtained by the cyclone 17 is obtained through the polyethylene collection pipe 22 and subjected to a necessary known catalyst deactivation step. , sent to the discharge process and turned into pellets.

On the other hand, the solvent vapor passes through piping 18 and is cooled countercurrently with the solvent (note 20 is a solvent cooler) that has been cooled in advance by the scrubber 19, the solvent in the solvent vapor is condensed and separated, and the separated nitrogen gas is again inert. It is sent to the gun heater 23 and is heated.

In the above method, the solvent separated and recovered by the centrifugal separator 12 and the organoaluminum compound in the solvent are each 60 to 90% by weight of the portion contained in the slurry extracted through the aforementioned valve 8, and are separated and recovered by the scrubber 12. 1
The solvent collected in 9 is the same <30 to 5 wt.

Therefore, in the polymerization system, the amount of solvent and organoaluminum compound that is insufficient by circulation alone is continuously supplied to the polymerization vessel 7 from the aforementioned pipes 3 and 2. On the other hand, since the entire amount of the solid product (seal), which is the main catalyst component, is carried away by the polyethylene product after one use, the required amount must be constantly replenished from the above-mentioned pipe 1.

The characteristic effects of the method of the present invention over known methods are as follows. That is, the purpose of solvent circulation by a known method is to reduce the cost of recovering the solvent and save the amount of organic aluminum compound used, but the present invention not only achieves these effects, but also
Regarding polyethylene itself, which is the product to be manufactured, the following three points must be met:
The effects of this can be obtained. The first is that the polyethylene yield per unit amount of catalyst component is dramatically improved.
The second is that the melt flowability of the obtained polyethylene is improved, and the third is that the high bulk specific gravity of polyethylene, which is an effect specific to the catalyst used in the present invention, can be maintained. This third effect is extremely important because it enables long-term, stable continuous operation with a high slurry concentration within the polymerization vessel. Another advantage is that there is no limit to the circulation rate of the recovered solvent. That is, the recovered solvent according to the present invention does not contain any harmful substances that reduce the polymerization activity of the catalyst or otherwise interfere with the polymerization of ethylene in the polymerization vessel.

The present invention will be explained below with reference to Examples, Comparative Examples, and Reference Examples. The meanings of the terms used in these are as follows.

MI: Melt Index A8TM D-1238 (
190°C, load 2 to 16 noodles, f/10 minute units) FR: Flow ratio, refers to the ratio of the above MI (load 1i 2.164) to MI (load 108 KF), and is a measure of the melt flowability of the resin. The higher the flow, the better the flow.

Ep: A measure of polymerization activity, -coalescence (f)/(transition metal catalyst component (f) x average residence time (hr) Xα-olefin pressure (b/CI/1)) BD: bulk specific gravity tensile strength [: Unit 2/Denier Control Example 1 according to JIS Z1533-19701m (1) Production of solid product (1) 5.0 kg of magnesium hydroxide and 12 k of aluminum trichloride (anhydrous) were preliminarily heated in a vibration mill with a capacity of 60 mm for 2 hours. After mixing and pulverizing at room temperature, the contents were transferred to a firing reactor with a capacity of 11 t30/ml, and reacted at 150°C for 5 hours. Thereafter, the cooled reaction product was again transferred to the vibration mill and pulverized to obtain 15Kt of solid product (1).

(2) To a reactor equipped with a stirrer with a capacity of 100 liters for producing a solid product (seal), add 2 ounces of toluene while stirring.
01. Chain dimethyl polysiloxane (viscosity 100 centistokes) 1014, titanium tetrachloride 9.0! and tetrapdel orthotitanate 4.0 odor and mixed at room temperature, then the solid product +1110- was added and then 80°C.
The temperature was raised to 1, and the mixture was allowed to react for 3 hours. After the reaction was completed, the reaction mixture was filtered using a filtration device, and the solid product remaining after the filtration was diluted with hexane 80
Washing and filtration were repeated using / until unreacted titanium compounds and unreacted polysiloxanes were no longer detected in the washing solution. The washed solid product was then dried under reduced pressure to obtain solid product +11. The content of titanium atoms in the solid product (carbon dioxide) was 55 mF.

The above operations +11 and (2) were all performed in a nitrogen gas atmosphere containing no moisture. The same applies to the following Control Examples, Examples, and Comparative Examples.

(3) Production of polyethylene Ethylene was homopolymerized using a continuous polymerization apparatus shown in Figure 44. However, only purified n-hexane was used as the solvent supplied to the polymerization vessel 7, and the entire amount of n-hexane separated after polymerization was extracted from the system without being circulated to the polymerization vessel 7. An n-hexane slurry containing 0.160 t/hr of solid product (1) was added from pipe 1 to a polymerization vessel with an internal volume of 100/h, and an n-hexane solution containing 0.80 f/br of triethylaluminum was introduced from pipe 2. Supply n-hexane from pipe 3, and the amount of n-hexane supplied is 18
It was set to h/hr. Furthermore, the melt index of the polyethylene powder finally obtained by supplying ethylene from pipe 5 to 10/4/hr and hydrogen from pipe 4 is 0.
．． Continuous polymerization was carried out for 72 hours at a polymerization temperature of 80° C. and a total pressure of 144/cd while adjusting the amount of hydrogen supplied so that the amount of hydrogen was 7 to 0.9 (note: hydrogen and ethylene were circulated through pipe 10).

The polymerization slurry 9-, which reached a certain concentration in the polymerization vessel ψ, was continuously extracted to a flash drum 9 by a control valve 8. Unreacted ethylene and hydrogen separated in flash drum 9 were circulated to polymerizer 7 as described above. Flash drum9. The polyethylene slurry from
Separated into hechitin moieties. The wet cake is brought into contact with heated nitrogen gas at about 100° C. and is flash dried in pipe 16.
Dry polyethylene powder is transferred to pipe 2 by cyclone 17.
2 to 9.8 h/br. This polyethylene powder was separately subjected to a known catalyst deactivation treatment and then subjected to the physical property measurements described below.

The polyethylene powder obtained as above is M I
O.80, PR9.8, BDO047. Moreover, Ep was 3060. Next, add 50% of the above-mentioned polyethylene powder to 2,6-di-tertiary-butyl-para-
Cresol 25F and calcium stearate 100t
were mixed and made into pellets according to a known method. This pellet was extruded from a nozzle with an inner diameter of 2 mm using an extruder with a diameter of 65 mm, and the tensile strength of a monofilament obtained by drawing the pellet 10 times was measured and found to be s, or/denyl.

In addition, the load current of the extruder during extrusion was 77
It was ampere. Table 1 shows some of the main manufacturing conditions and results.

Example 1 N-hechitin (note triethylaluminum 2.4
0 Kg/hr) and n-hexane condensed and absorbed by the scraper 19 (Note: 15.0 b/hr in total, via the pump 14 and the pipe 15 together with the pipes 13 and 21, respectively) are circulated to the polymerization reactor 7, 1.3 Kg/hr of purified n-hechitin from 2 and 3 were fed in the same manner, and the feed rate of the solid product il+ was 0.10'Of/kr.
, 00SO new supply of triethylaluminum!
Polyethylene was produced in the same manner as in Comparative Example 1, except that the reaction time was changed to /hr. Polyethylene powder is taken out from pipe 21 at a rate of 9,9114/hr, and the supply amount of solid product +11 necessary to stabilize the critical conditions inside the polymerization machine is 0.100 b/hr as described above, and sBp is 4950
The polymerization activity was significantly improved compared to Control Example 1.

Furthermore, the obtained polyethylene powder is MI o,s
l,' pRi5. o, B D O, 47, and the tensile strength of the extruded monofilament obtained in the same manner as Control Example 1 was 8. at/denyl, the extruder load current was 68 amps. As described above, when this example is compared with Comparative Example 1, the strength of the molded article is maintained while the PR is improved, and the flowability during melting is improved as seen in the decrease in the load current. The main manufacturing conditions and results are shown in Table 1.

Comparative Example 2.3 N-hexane was circulated in the same manner as in Comparative Example 1, except that the feed rate (f/hr) of triethylaluminum was changed as shown in Table 1. I did it. The main manufacturing conditions and results are shown in Table 1 (=
Indicated.

Example 2.3 Circulating n-hexane (recovered in centrifuge 12 and scrubber 19) as part of the polymerization solvent to n-hexane recovered in centrifuge 12 as part of the triethylaluminum Example 3 was carried out in the same manner as in Comparative Example 2, except for using the following. The main manufacturing conditions and results are shown in Table 1.

Control example 4 Control example except that in '(3) Production of polyethylene' of Control example 1, the amount of ethylene supplied was 9.7 [1/hr], and butene-1 was separately supplied from piping 6 at 0.3 Tht/hr. It was carried out in the same manner as in 1. The main manufacturing conditions and results are shown in Table 1.

Practical side number Circulating n-hexane as part of the polymerization solvent 1 Centrifuging as part of triethylaluminum I! The procedure was carried out in the same manner as Control Example 4, except that the substance contained in n-hexane recovered in No. 1112 was used.

The main manufacturing conditions and results are shown in 1st fi.

Table 1-1 Polymerization conditions and results (partial) Note Pair: Control example, Actual: Example, n-C6; n-hexane, TBA; ) Riether aluminum, PE; Boriethelene Table 1-2] 1i polymerization Results (partial) Note: Pair (actual@n-C@%T) 13A, PK has the same meaning as in the table above.

MONOFIL ; Monofilament, *; Ampere,
As is clear from Table 1, the majority of n-hexane and triethylaluminum (about 831% of n-hexane)
Example 1 in which approximately 500ml of riether aluminum was circulated
- 3, the Ep was significantly increased compared to the corresponding control example, regardless of the amount of triethylaluminum used. This fact shows that in terms of PE yield, both the Example and the Control Example make full use of their respective equipment capacities, so there is no difference in this aspect, but the Control Example has a 'P B 10! The amount of n-hexane used per container was about 6 times that of the example, and there was no difference in the MI and BD of the polyethylene obtained. Moreover, the extruder load, which is an index of the melt flowability of the obtained polyethylene, is reduced by about 10%. In addition, in Examples 1 to 3, the concentration of triethylaluminum present in the polymerization system is higher than in Control Examples 1 to 3, but it is considered that the improvement in Ep is mainly due to this effect. Although there was still room, ethylene and butene-1 were copolymerized (Example 4 - Comparative Example 4)
), even though the triethylaluminum concentration in the polymerization system was kept the same, the difference in Ep was large as in the case of (Examples 1 to 3 vs. Control Examples 1 to 3), and the difference in Ep was large, even though the triethylaluminum concentration in the polymerization system was This indicates that this is not caused by a concentration difference (note: see Examples 5 to 7 and Control Examples 5 to 7 described later).

Comparative Example 1-A A final solid product corresponding to the solid product (Violet) was obtained in the same manner except that tetrabutyl orthotitanate was not used in "Production of Comparative Example 1'+21 Solid Product (Violet)". Polyethylene was produced in the same manner as in Control Example 1, except that this final solid product was used in place of solid product (1).The main production conditions and results are shown in Table 2.

Comparative Example 1-B Using the final solid product obtained similarly to Comparative Example 1-A, with recycled n-hexane as part of the polymerization solvent and recovered in centrifuge 12 as part of the triethylaluminum. It was carried out in the same manner as Comparative Example 1-A except that the substance contained in n-hexane was used. This example is a solid product (seal)
This is an example in which n-hexitine and triethylaluminum were recycled in the same manner as in Example 1, except that the final solid product was used instead of the final solid product. The main manufacturing conditions and results are shown in Table 2.

Comparative Example 2-A A final solid product corresponding to solid product +11 was obtained in the same manner as in Comparative Example 1', except that linear dimethylpolysiloxane was not used in the production of solid product (seal) '+21'. Polyethylene was produced in the same manner as in Control Example 1, except that this final solid product was used in place of solid product (1).

The main manufacturing conditions and results are shown in Table 2;

Comparative Example 2-B Using the final solid product obtained analogously to Comparative Example 2-A, circulating n-hexane as part of the polymerization solvent and centrifugation li1! as part of the triethylaluminum! ! It was carried out in the same manner as Comparative Example 2-A except that what was contained in the hechitin recovered in s12 was used.

In this example, n-hexane and triethylaluminum were circulated in the same manner as in Example 1 except that the final solid product was used instead of the solid product +11. The main manufacturing conditions and results are shown in Table 2.

Comparative Example 3-A Comparative Example 1 A solid product (!) was produced in the same manner except that titanium tetrachloride was not used in the production of '+21 solid product'
A final solid product corresponding to . Polyethylene was produced as in Control Example 1, except that this final solid product was used instead of solid product +1). The main manufacturing conditions and results are shown in Table 2.

Comparative Example 3-B Using the final solid product obtained analogously to Comparative Example 3-A, circulating n-hextin was added as part of the polymerization solvent to L7 in a centrifuge 12 with part of triethylaluminum. The same procedure as Comparative Example 3-A was carried out except that the recovered n-hexane (;) was used.

This example is an example in which n-hexitine and triethylaluminum were recycled in the same manner as in Example 1 except that the final solid product was used instead of the solid product (11). It is shown in Table 2.

Table 2-1 Polymerization conditions and results (partial) Table 2-2 Polymerization results (partial) MONOF I L, wood** The meanings of MONOF I L and wood are as shown in Table 2, which is the same as Table 1-2. , Comparative Examples 1-A, 2-A, 3- using final solid products different from those for the solid products of the present invention
In A, Ep was wider than either of Control Example 11 and Example 1.
is decreasing. The reason for this is mainly attributed to the difference in the solid product (seal). However, Comparative Example 1-B; 2-
B and 3-B are the corresponding comparative examples 1-A and 2-A, respectively.
.

Using the same final solid product compared to 3-A
- Contrary to the case of Control Example 1 vs. Example 1, gp is significantly reduced due to the circulation of a portion of hechitin and a portion of triethylaluminum. Furthermore, although the load on the extruder in terms of the melt properties of the obtained polyethylene has decreased, the tensile strength of the monofilament has significantly decreased. Moreover, Example 1 and Comparative Example 1-B.

Comparing 2-B and 3-B, the difference in manufacturing conditions is only the use of the solid product (soda) or the final solid product, whereas in addition to Bp, BD (Comparative Examples 2-B and '3- In the case of B), in order to enable the circulation of the solvent and organoaluminum compound without causing a decrease in Ep, etc., and thereby improve Ep, the present invention (: ) has become essential.

Control Example 5 (1) Preparation of solid product +11 Magnesium oxide 5. OK4 and aluminum trichloride (anhydrous) 11- were mixed and pulverized in advance at room temperature for 3 hours in a vibrating mill with a capacity of 601 cm, and then the contents were transferred to a firing reactor with a capacity of 1160 cm and reacted at 200°C for 2 hours. . Thereafter, the cooled reaction mass was again transferred to a vibration mill and pulverized to obtain a solid product +1114-.

(2) Production of solid product Tll In a reactor equipped with a stirrer with a capacity of 1001, 2 toluene was added under stirring.
011 chain methylhydrogen polysiloxane (viscosity 50 centistokes) 9.0-titanium tetrachloride and tetraethyl orthotitanate 3.0- were added and mixed at room temperature.
At the same time, 10- of solid product (1) was added, and then the temperature was raised to 110°C and the mixture was reacted for 2 hours. After the reaction is completed, the reaction mixture is filtered using a filtration device, and the solid product remaining after filtration is washed and filtered repeatedly using 80% hexane until no unreacted titanium compound or unreacted polyV cuquitin is detected in the washing solution. Ta. The washed solid product was then dried under reduced pressure to obtain a solid product (seal). The content of titanium atoms in the solid product (seal) It was 50 gJ.

(3) Polyethylene was produced in the same manner as in Control Example 1, except that the solid product (1) obtained in (2) above was used. Table 3 shows some of the main manufacturing conditions and results.

Example 5 Circulating use of hechitin and triethylaluminum separated in the centrifuge 12 and n-hechitin recovered in the scrubber 19 as a polymerization solvent, and the use of triethylaluminum supplied from the pipe 2 ，
Polyethylene was produced in the same manner as in Control Example 5 except that the flow rate was 2 t/hr. Table 3 shows some of the main manufacturing conditions and results.

Control Example 6 (1) Production of solid product (1) Hydromagnesite (3MgC'0.・Mg(OHh・
3H20) 6.0- and iron trichloride (anhydrous) 9.0- were mixed and ground in advance in a vibration mill with a capacity of 6C1 at room temperature for 2 hours, and the contents were transferred to a calcination reactor with a capacity of 1160/cm.
The reaction was carried out at 300°C for 1 hour.

Thereafter, the cooled reaction mass was again transferred to a vibrating mill and pulverized to obtain a solid product +El 1 3-.

(2) Production of a solid product In a reactor equipped with a stirrer with a capacity of 200 tons, 4 liters of toluene was added under stirring.
01s linear dimethylpolysilochitin (viscosity 100 centistokes), 10% titanium tetrachloride, and 4.0% n-butyl titanate (trimer) were added and mixed at room temperature, followed by the above solid product. II) 10 It
was added, the temperature was raised to 110°C, and the mixture was reacted for 3 hours. After the completion of the reaction, the reaction mixture was filtered once through a filtration device, and the remaining solid product was washed and filtered repeatedly using 100% hexane until no unreacted titanium compound or unreacted polysiloxane was detected in the washing solution. . The solid product after washing was then dried under reduced pressure to obtain a solid product (it).The content of titanium atoms in the solid product (11lf) was 30lf.

(3) Polyethylene was produced in the same manner as in Control Example 1 except for using the solid product (11) obtained in (2) above. Some of the main production conditions and results are shown in Table 3. .

Example 6 n-hexane separated in the centrifuge 12, triethylaluminum, and n-hexane recovered in the scrubber 19 are used as polymerization solvents by circulation, and the amount of trinium aluminum supplied from the pipe 2 is reduced to 0. =-2
Polyethylene was produced in the same manner as in Control Example 6 except that the heating time was 1/hr. Table 3 shows some of the main manufacturing conditions and results.

Control Example 7 (1) Production of solid product (corrosion) Hydrotalcite (Mg5A/z(OH)tscOs・
4H20)6- and 9Kf of aluminum trichloride (anhydrous) were mixed and pulverized for 2 hours in a vibration mill with a capacity of 60/cm, and the contents were transferred to a calcination reactor with a capacity of 60/cm and reacted at 120°C for 4 hours. After cooling, the cooled reaction mass was again transferred to a vibration mill and pulverized to obtain a solid product +11144.

(2) In a reactor equipped with a stirrer with a production capacity of 200/ml for solid product (seal), 3 xylene was added under stirring.
0/linear dimethylpolysiloxane (viscosity 100 centistokes) 30% titanium tetrachloride 15- and panadyl tributyl) 5.0- and solid product (1) 1
After adding 0- at the same time and mixing at room temperature, the mixture was reacted at 150°C for 2 hours. After the reaction is completed, the reaction mixture is filtered with an f-filtration device,
The remaining solid product was washed and filtered using 120% hexane until no unreacted titanium compound or unreacted polysiloxane was detected in the washing solution. The solid product after washing is then dried under reduced pressure to obtain a solid product (summer).
I got it. The content of titanium atoms in the solid product (111f) was 33-.

(3) Polyethylene was produced in the same manner as in Control Example 1, except that the solid product Il+ obtained in (2) above was used. Table 3 shows some of the main manufacturing conditions and results.

Example 7 The n-hexane and triethylaluminum separated by the centrifuge 12 and the n-hexane recovered by the scrubber 19 were circulated and used as polymerization solvents, and the amount of triethylaluminum supplied from the two pipes was 0,2
Polyethylene was produced in the same manner as in Control Example F except that the reaction time was 1/hr. Table 3 shows some of the main manufacturing conditions and results.

M(JNυFIL% Tree forest has the same meaning as Table 1-2.
As is clear from the table, Example 5 in which n-hexitine and a portion of triethylaluminum (about 831% of n-hexitine and about 75% of ethylaluminum) were recycled
Although most of the organic aluminum compounds in these solvents were recycled, they were used in different ways, so there were no differences in this respect. In the control example, the amount of n'-hexane used per PH1O was about 6 times that of the example, and the amount of TEA used was about 4 times the same.
There is almost no difference in the physical properties of the obtained polyethylene, except for the fact that it has a high PR (note: this is a positive effect).

Moreover, the extruder load, which is an index of the melt flowability of the obtained polyethylene, was reduced by about 10-10 compared to the control example, as in Examples 1 to 4. The above facts indicate that even if the types and reaction methods of the solid product, trivalent metal halide, divalent metal hydroxide, etc. used in the production of (1) are different, they are still within the scope of the present invention. and also shows that the effect of circulation of the solvent and organoaluminum compound in the continuous polymerization of ethylene is maintained as long as the reaction leading to the solid products (1) to (11) is also within the scope of the present invention. There is.

[Brief explanation of the drawing]

The figure is a process diagram of a continuous polyethylene polymerization apparatus using solvent circulation used in the present invention. In the figure, 6 to 6 are supply pipes for various reaction raw materials, 7 is a polymerization vessel, 9 is a flash drum, 1O is an ethylene and hydrogen circulation pipe, 12 is a centrifugal separator, 13 is a solvent circulation pipe, 16 is a wet cake flash dryer Piping, 17 is a cyclone, 18 is a solvent recovery pipe, 1
9 is a scrubber, and 22 is a polyethylene collection pipe. Above is the description of the L case fIB Wa 57 Year 411 Permission 1 [No. 11114562 Polyethylene manufacturing method (as amended today) 1 Amendment case and OII Permit applicant 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka Prefecture No.('?530
) (20 ma) Chisso Co., Ltd. Kinsha Substitute Mitsugu Nogi ζ generation layered person Tokyo S Shin-ku Shinjuku 2-8-1 (〒160) a@ Number of inventions increases due to date correction of positive instructions None Subject to correction■ Application form. ■ In the 1st part of the specification, there should be a point "Detailed explanation of the invention JO+ column. a Contents of amendment■ Correct the application as in the attached correction application. (The name of the invention stated in the application should match the name of the description ) ■ The specification will be corrected as follows: α) “Exit process” on the last line of page 24 will be corrected to “granulation l1.” ＠ Delete "and piping 15" on the 6th line from the bottom of page 31. (2) [Correct "Piping 21J" in the first line of page 32 to "Piping 22." (4) Insert "," next to "Example 2" on page 33, line 8. (5) IIIE page 49 line 9 or Kooai Teha Jt'r
In terms of px yield, it has been corrected to ``. α 9 brass correction application of sealed documents 1 or more copies

Claims (1)

[Claims] (1) A trivalent metal halide is reacted with a divalent metal hydroxide, monooxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. The final solid product supported with a transition metal compound prepared from polysiloxane and a transition metal compound of group 4a or group 5a is combined with an organoaluminum compound. In a method for producing polyethylene by polymerizing ethylene using the obtained catalyst, in the presence of polysiloxane, solid product (1) and (group A) a halogen-containing group 4a product are produced as the final solid product. Maku is a group 15a transition metal compound (hereinafter referred to as a halogen-containing transition metal compound) and (group B) a halogen-free group 4a or 5a transition metal compound @c hereinafter referred to as a halogen-free transition metal compound. ) using a solid product obtained by reacting at least two transition metal compounds selected from each group of A part of the obtained slurry containing polyethylene is continuously taken out and separated into a gaseous part, a solvent part and a polyethylene part outside the polymerization system, and the gaseous part and solvent part are circulated into the polymerization system. (2) The manufacturing method according to claim (1), wherein the halogen-containing transition metal compound is a titanium or vanadium halide, oxyhalide, alkoxyhalide, or acetoxyhalide. ( 3) The halogen-free transition metal compound ?I is an alkoxide of titanium or vanadium.
The manufacturing method described in item 1). (4) The halogen-free transition metal compound is a tetraalkyl orthotitanate (tetraalkoxytitanium) or a vanadyl trialcollade (Claim 1)
The manufacturing method described in section. (5) The manufacturing method according to claim (1), characterized in that the polyethylene concentration in the slurry is maintained at 50% by weight, 5:1 klS or more. (6) Claims * (Production method according to item 11. ) The wet cake is air-flow dried to separate it into a solvent vapor and a dry powder, and the solvent in the separated solvent vapor is condensed and liquefied to form a polymerization system (Claim IJ+6).
Manufacturing method of Section 1. (8) The production method according to claim (1), in which an amount of organoaluminum compound lacking in the organoaluminum compound in the circulating solvent is newly supplied into the polymerization system. (9) The production method according to claim (1), in which the amount of hydrogen gas insufficient in the gas portion to be circulated is newly supplied to the internal pressure of the polymerization system.