DE1645481A1 - Process and apparatus for polymerizing ethylene - Google Patents

Description

KOaI ¹ BU IiJDIföTKIES * INCORPORATED., ^[ Tokyo

Process and apparatus for polymerizing ethylene

The invention relates to polymerization devices for use in the case of air pressure polymerization of ethylene and processes for .application of these devices.

Two types of polymerization devices for so-called high-pressure polyethylene production through polymerization of ethylene at high pressures, for example 1000 to 3000 atmospheres, are known. One consists of an autoclave reactor and was manufactured by Imperial Chemical Industry, Ltd. developed and further developed by Dupont. The other is a tubular reactor type developed by the Badische Anilin & Sodafabrik. Polymerizers for the production of high pressure polyethylene all over the world are among them

BAD OBIGiNAL

β fleas * / 1 ο /. c

one of these groups. - ■

In practice, as will be described below, the conventional devices have both advantages and considerable disadvantages on. As is well known, there are many ways to influence to improve such disadvantages on the quality of the polymer product and on the yield of the polymer "

In the case of the known, customary autoclave reactor, there is theoretically a uniform, complete mixing in this type of reaction it is necessary to mix the constituents forming the content by means of a stirring device operating in the reactor. An advantage here is to be seen in being wet as long as it is the reaction temperature in a relatively uniform direction im. generally held, the polymerization ηάΐ a relative constant reaction rate takes place. "

On the other hand, freshly added fresh food is constantly being added Polyethylene is evenly dispersed, -order the possibility for a large part of the fresh ethylene mentioned, as it is or as polymer "-low molecular weight carried out to graze, which is a significant disadvantage in terms of the condition of a perfect Durcixmischunt is. I.e. at entire reaction process by autoclave polymerization fluctuates although the reaction temperature is kept uniform the reaction time from molecule to molecule of the .Ätthylens- in a wide range, uass a gimsti.i-r; , influence animal more experienced ones are canceled out by the unfavorable influence of the latter will. . ""; ..- ■

0 0 9831/1846 badoriginal

■ _> - ■ '■■

In the hex position of high molecular weight polyethylene for]? Ilme, wotei uie xachte aes polyethylene product "is increased", a process is known in which the reaction temperature is reduced ν * Iaα * use isan iedoch the usual autoclave reactor for cifcSfu-Zweuk, v. . ill aie Eeaktionszeit of liolekül to 1-iolekul un ρ It ic hf öjLüii§i, and s 'is aie likelihood aa; fs_ein jrOlydtrr.len _^r: ± v low molecular weight era made' / _o vill in rut · .: Rhi η from tediiig the disparity of the reaction control erotur a considerable change in the quality of the polyethylene produced.

Veiv.enu "et ^ η direct the olDen mentioned" well-known, tubular KeoKtor, fo ii.tt ^ n advantage to see that the reaction time from ... molecule to luolecule of ethylene is equal "; uv» ei: na ere .rosse ITa cü χ hurry to appear beer-ei jeoocü. The eluc- u ^ tcM dai ^ n that the '! - «. eactibnsseit not about the jes £ <.. ιte ^ olymeriüiitiprisreektion is the same. · ilat' Surely ou-rcii use of a wäxne a ue exchanging keüium for cooling, iijcifci.i üiesbs circulated in a shackle around "as itohr, aie iteakxi onste -'- ii-ej-ötur in fe ^ issem degree evenly graze, .- As i, ii i / ctxuelbitun- 'through a small pipe, a perfect partial operation control cannot take place. ^first! erature uurch aas o'bengenanrite thick J ^ -ear more than 5> 0 ° Ii ti in Ü. Temceratuien the ..fU-sen along the tubular reactor VJU ,. UG. eiutiden, UASs aie Reai.tions teaiperatur an extreme l, jjxi - um in a "certain shorten 1'eil dea - ^ ohres." su ± * points and Pier, ΐ · ίι- · .'-. Li on one :, lower level in front of and behind or al esani

009831 / 184B

BAOORtGiNAL

Part is located. The quality disadvantages that result from this are that, while the polymer is once passed through the part with the exceptionally high temperature, it branches out and creates peaks, and when the oxygen is used as a catalyst or initiator aas polymer absorbs the oxygen, creates a carbonyl residue and forms bridges, thus deteriorating the quality and sometimes ^ leading to explosions ο

^ in another large part of the tubular reactors is that, since the preheating part and the cooling part are separated by the high temperature zone, the heat of reaction cannot be effectively exploited; i.e. the advantages of a thermally independent type of reaction in which the high exothermic Heat accompanying the polymerization of ethylene, cannot be obtained. In the case of an autoclave reactor, for example can determine the so-called thermally independent system type where the cold ethylene is used directly for cooling una to the thermal iiusglbich for the product, which the exothermic Reaction is accompanied, introduced "« In contrast, in the first part of the tubular reactor, ethylene is heat exchange ends medium down to a temperature of 1 ^ 0 ice 200 G preheated, at which ethylene begins to polymerize, and in the second half we then use the heat of reaction of a cooling, heat-exchanging medium eliminated ,, ücLch & in bystem is thermally very uneconomical and - you wish to recover the heat of reaction - a very complicated device is required,

■; v ;;;. 009831/1845

BATH ORIGINAL

The invention now creates a polymerization device and a Method "at α one the above-mentioned disadvantages of both the usual" ■ Autoclave reactor and the tubular reactor eliminated and at the same time their advantages are retained. When using the The device according to the invention is said to be non-uniform the reaction time that occurs in a conventional autoclave reactor, considerably reduced '. JYes the according to the invention e-device for thermally independent type, this results in thermal Savings, and no local ones, too, are unusual high temperature zones, as they are the usual tubular Reactor are peculiar. The quality of the polymer produced becomes significant compared to that which is obtained in the usual autoclave reactor ina / or tubular reactor and, / at the same time, is increased oie yield of the polymer product.

In the device according to the invention, the polymerization of Ethylene are carried out by

.1. a process is used in which the pressurized.

Ethylene is first passed through a tubular part

and then in an autoclave reaction chamber and 2. a process in which the ethylene is first passed through the autoclave «

reaction chamber and then into the tubular part, »/ Fclchfes special failure is applied, si oh from the final use for the product,

Beisj7ieleweiae auu leadership, ^c ; Forms of the Jirfindung will now be explained using αer drawings in which

009831/184 6

1 shows a section through two reaction chambers according to the invention shows.

- ⁰ Ig. 2 is a section through a typical conventional reactor with two reaction chambers. .

Pig. 3 is a schematic cross-section through a typical usual tubular reactor and

Fig. 4 is a graph showing the relationship between the pipe length and the temperature distribution, compared to conventional tubular d-eiL Reactor shows as shown in Fig. 3, compared with the reactor according to the invention shown in FIG. 1.

In -Big. The device for the polymerization of ethylene according to the invention consists of a tube 8 which is arranged inside an autoclave · reaction kaiiimer = 1, the autoclave machine chamber 9 of which is attached to the upper end one end on the outside of this autoclave reaction chamber 1, an opening 6 at the outer end of the tube is located inside the autoclave reaction chamber 1, so that it is separated as far as possible from an opening 4 in the autoclave reaction chamber 1 «, The The opening 6 points in a direction opposite to that of the opening 4. The tube 8 is preferably designed in the form of a screw "A stirrer 2, which is connected to the motor 3 and is driven by it, is rotatably mounted within the helix of the tube", Die Motor chamber 9 contains the motor '5 for driving the stirring? 2 and has an inlet opening 7 which is closer to opening 6 than opening 4. The Kainmer 9 stands with the above mentioned]

009831/1845

BAD OR / QiN _AL

Ixeakticusk-iammer etui cn a small opening 10 in connection, through. o.the shaft of the iüihrers 2 is also guided _o

The openings 4 and 6 and the opening 7 are preferably arranged, the spacing between the openings 4 and 6 and a distance between the opening 4 and the inlet opening 7 being as large as possible. It is very desirable the B.ohr öffnun ~ _t 6 UNU the opening 7 to separate as far as possible from each other TJt-;.! to make the reaction as complete as possible and at a favorable reaction temperature to be obtained by preheating it iüt vvichtic, iii ^ length of Jxohres δ from opening 5 to opening b long _; "to be made enough so that an effective length of the .cöhrenfürri: ii / eii i'eils is given", the position of opening 5 in the Auto! icven S reaction chamber is independent of the lay of the opening 4 una ο er .-, usleuoffnung 7.

..ie as: .tig this arrangement is, ergiot from the below schrtibenden to L ^, ^T ei finuungs-emässen method and the fact üass vie ^ ii chieile aes conventional autoclave reactor una of 'röhreni-tn. ".-eSi.tox-: niciduxch eliminated

ν i-; i ', u: _. ij. oak 4, i ;. and ^; b · in? ig-1 sin., tit openings. instead of i..it ijii-li; .. unu .auslad denotes, including them - as described below. ^ ei ·. «Earth. - "in other procedures both as inlet • -Is - Io ^ u, iltji;> can enter puncture. i, s and thus two new tirfihuun ^ ue methods for using the inventive nasal I ¹ Ol ₄ / u.txib ';. tion device re, fcbf.n. bie ', .- earth in the following it ), e- / AXr ·. ui'i'ig. 1 explained.

0098 3 1/1845

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In the first method in which the device according to the invention is used, compressed ethylene to be polymerized is introduced into the autoclave reaction chamber 1 through the opening 4. In the normal state, practically complete mixing takes place inside the autoclave reaction chamber 1 through the action of the stirrer 2, which is driven by the motor 3, and the inside of the autoclave ^{reaction chamber 1 is at a temperature in the range from 150 to 300 °} C. (favorable for the reaction) held. The compressed ethylene introduced through opening 4 begins to react immediately. The catalyst can be added and introduced into the reaction chamber in a defined concentration, which is suitable for initiating the polymerization, through the opening 4 together with the already mentioned compressed ethylene or through a separate inlet opening, not shown, which is located inside the chamber 1 in the Near the opening 4 is provided.

Part of the compressed ethylene to be polymerized is also fed into the chamber 9 through the inlet opening 7 in order to cool the motor 3 therein, i.e. to reduce the temperature increase to regulate in the motor chamber and to prevent the occurrence of a reaction there. Therefore preferably no Catalyst added to the compressed ethylene introduced through the inlet port 7. That introduced into the motor chamber 9 Ethylene passes into the autoclave reaction chamber 1 the opening 10 and is there by the ethylene polymerization reaction consumed. The reaction product enters the tubular

009831/1845

- «. 9 -

shaped part 8 through the opening 6 within the chamber 1 and is withdrawn from the autoclave reactor through opening 5 and then into the polymer and the unreacted ethylene separated according to usual procedures after a compression ^ reduction has been made to a desired pressure (e.g. 400 to 40 atmospheres) in operation.

The reaction system is evenly distributed and through the The stirrer 2 is mixed while the reactant material is led from the opening 4 to the opening 6. The reaction temperature is smoothed out and regulated more precisely, whereby the quality of the product is considerably improved * The polymerization reaction takes place in the tubular rope 8 between the opening 6 and the opening 5 is completed. Due to the uniformity of light the reaction time, which is the case with the usual autoclave reactor occurs, caused tile parts are essentially eliminated. using the method according to the invention is also the disadvantage of the usual autoclave reactor which the imported raw material ethylene is short-circuited and as unreacted or low molecular weight polymer, that is still completely polymerized, escapes, is eliminated » This improves the polyethylene yield and production of the low molecular weight polymer becomes more remarkable Wise regulated and reduced in scope, while at the same time maintaining the advantages of the conventional autoclave reactor.

Pig. 2 shows an example for. the usual autoclave reactor, which does not have a tubular part similar to the pipe 8 according to the

0090 31/1845

- ro -

finding as it is shown in Jig ,, 1 possesses. That condensed Ethylene to be "polymerized" is placed in an autoclave reaction chamber 11 introduced through an inlet port 14 together with a catalyst. Part of the ethylene without that Catalyst is introduced into a motor chamber 17 through an inlet port 16 for cooling a motor 13 and then into the reaction chamber 11 given through a narrow opening part 18, ^ so that it takes part in the reaction ».

In the normal state, the above-mentioned, compressed polyethylene, which was introduced through the inlet port 14 is at a temperature of 150 to 300 ⁰ C, which is favorable for the reaction., Held and uniformly mixed by a stirrer 12 and begins to react immediately. The reaction product is withdrawn through outlet 15,

A comparison in the use of the device according to the invention and procedure (illustrated in Fig. 1) and the usual "autoclave reactor (illustrated in Fig. 2) is given in Table 1.

009831/1846

Table 1

conventional auto-slave reactor device according to the invention

Reaction temperature in G

240-250 '

Reaction pressure in atmospheres 1500-1600

produced polymers

density

0.921

Production yield of polymers with a low molecular weight of 1.9 in f>

240-250

1500-1600

0.922

middle mole
gross weight 27 800 29 200 Total yield
of polymers in fa 12, 3 15, 1 Yield on that
desired poly
meren with high mole
gross weight in% 10, 4th H, 8th

0.3

According to the table above, in both cases

1. During the polymerization, a di-tertiary butyl peroxide is used as the catalyst related,

2. 600 parts of a solution of a 5? ° strength di-tert-butyl peroxide, which was dissolved in a white spirit was used in a million parts of the raw material ethylene.

3. The catalyst was then premixed with the raw ethylene, and the mixture was then through the opening 4 (Fig. 1)

0 9 8 3 1/18 4

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after. Invention introduced and through the inlet pipe 14 after Pig. 2 in a conventional autoclave reactor "

In the experiments mentioned above, the capacity of each autoclave reactor was 2 liters; the capacity of the _{polymerization device shown in lig o} -1 was reduced by 6.57 ° by the thin-walled tube 8 contained therein »

In any case, the results shown in Table I are after Invention noteworthy. By using the inventive Polymerization device can prevent leakage in the short circuit of the freshly added ethylene, and in particular the problem of the short reaction time for parts of the ethylene that are introduced into the system is eliminated, whereby extremely favorable results have been obtained.

The second method according to the invention is explained below with reference to FIG.

o ¹ . '"- / ■

First, the compacted, with a catalyst of a given, concentration suitable for the polymerization is introduced into the tube 8 through the opening 5 and by heat exchange preheated with the reaction product on the outside of the tube 8 inside the autoclave reaction chamber 1 is guided in the first parts of the tube 8 and reaches the reaction temperature in the latter parts of the tube 8

00 98 3 1/1846

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and starts to react there. The ethylene is then released into the autoclave reaction chamber 1 through the opening 6 before the reaction temperature inside the tube 8 is greater than a temperature in the range from 150 to 300 ⁰ C, which is particularly favorable for the reaction Motor 3 driven stirrer, a reaction takes place in the reaction system while the above-mentioned temperature is uniformly maintained,

Part of the compacted, not mixed with the catalyst Ethylene is fed into the motor chamber 9 for the same purpose as in the above-described first method according to the invention introduced.

The most important factor in the second process is that in the last half of the tube 8, before the reaction temperature is higher than a predetermined maximum, ie, still at a favorable temperature of 150 to 300 ⁰ C and before the reaction temperature reaches local maximum temperatures, the unfortunately occur in the short, tubular part of the usual tubular reactor, # £ * # the reaction system is released and discharged into the reaction chamber through the opening, 6 / This allows a flat course of the reaction temperature within the autoclave reaction chamber, as shown by curve b in Fig. 4 should be retained. This regulation of the reaction temperature towards a flat curve is achieved,

9831/1846

By reducing the amount of ethylene in the engine chamber the inlet port 7 is adjusted. If the above-mentioned, favorable reaction temperature exceeded "before the compacted Ethylene exiting through the pipe 8 from the opening 5, the Reached opening 6, the course of the reaction temperature can be made flat by increasing the amount of compacted, through the inlet port 7 introduced ethylene is reduced and the Amount of compressed ethylene introduced through opening 5 is increased. Becomes the mentioned favorable reaction temperature is not reached before the compressed ethylene, which is passed through the pipe, reaches the opening 6, the amount of compressed, 'introduced through the opening 7 of the motor chamber 9 The amount of ethylene increased and the amount of compressed ethylene continuously introduced into the - "ear 8 decreased, so that one can reach the mentioned favorable reaction temperature. A A flat course of the reaction temperature within the autoclave reaction chamber 1 can therefore be obtained and also a constant one Course can be achieved by the relative amounts of compressed, introduced through the inlet port 7 of the motor chamber Ethylene and that introduced through the opening 5 are adjusted by observing the temperature of the ethylene passed through the tube 8 before it reaches the opening 6. A An example of the usual tubular reactor is shown in FIG. In operation, it is first compacted, with a catalyst at a given concentration, that the polymerization is able to introduce mixed ethylene into a tubular Reactor 21 introduced through an inlet 19 Sin heat

00983I / 184S

Exchange medium for heating -stt a jacket 20 around the Reactor 21 passed through a thick pipe, so that the first half of this tubular reactor up to a point can be preheated above the initial reaction temperature, and so that the temperature inside the reactor 21 so the Reaction exit temperature can reach «, therefore becomes a heat-exchanging Medium for cooling passed through the jacket 20 before the preselected, favorable reaction temperature above the initial temperature is reached, so that the heat of reaction can be discharged within the tubular reactor 21. The reaction product is passed through the tubular reactor the outlet 22 withdrawn. Results of comparative experiments, which once in the just described second method according to the invention, explained in? ig. 1, and once under Use of the usual, shown in Fig. 3 and explained above, tubular reactors are given in Table 2.

0098 31/1845

Table 2

Usually, tubular reactor Pall 1 case 2

inventive Vorrich tung

Capacity in 1,
in the reaction tube

Ke
xn

temperature
temperature

maximum
_32Q

maximum

^ Reaction pressure in
P atmospheres

2400 2500

1500-1600

_{1 (} - _nn J ^puu "

density 0, 1 918 0.925 0, 921 average molecular
weight 29 500 31,000 29 100 generated
Polymers Total yield
of polymers in fo 3.7 9.8. H , 2

Yield on that
desired polymet with the high molecular weight in fo

Yield of PoIymeren m.niedrigem Molekulargew.in fo

1.4

8 Q

0.9

0.3

In the table above, in both cases: 1. The catalyst used for the polymerization was a

di-tert-butyl peroxide,

2-, 600 parts of a solution of a 5% strength di ~ tert-butyl peroxide, which were dissolved in a white spirit , were used for one million parts of the ethylene supplied as raw material .

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3. The catalyst was fed in with the raw material used Ethylene premixed and then through the opening 5 in Fig. 1 in the case of the invention and introduced through the inlet pipe 19 in Fig. 3 in the case of the conventional tubular reactor.

As can be seen from Table 2, 'was the average molecular weight essentially the same as that, which one after the invention Process received, though, a reaction pressure difference of about 1000 atmospheres occurred after Case 1 of the conventional tubular reactor. Also the yield of polyethylene was higher and the amount of low molecular weight polymer produced was lower in the process according to the invention.

In the first as well as in the second method according to the invention, a short-circuit course of the reaction could be prevented, while the desired properties of the usual tubular Reaction tube were obtained. Also, according to the invention, the reaction system does not become extremely high temperatures exposed, and there is therefore no risk that a large amount of polymers with relatively low molecular weight will

is -

be procreated. As shown in Table 2 / although there is a pressure difference of about 1000 atmospheres compared to the pressure required for the usual tubular reactor. (Case 1), is present, the average molecular weight is essentially the same and the present of the desired polyethylene product

higher «Ϊ * in the method according to the invention.

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It is possible to use high molecular weight polyethylene for films or Foils and the like to create while the leisimgkosten for High pressure operation, separation and recirculation are reduced.

The relationship between the pipe length and the area of temperature distribution in the conventional tubular reactor shown in Fig. 3, and on the other hand according to the second invent The method according to the invention will now be explained with reference to FIG.

In Fig. 4, curve a shows the relationship between pipe length and Temperature in the event that a common tubular reactor is used, and curve b shows this relationship, where, in the second inventive method, before reaching a temperature above the favorable reaction temperature, the ethylene serving as the raw material into the autoclave reaction chamber through the opening 6, Fig. 1, is dispensed.

The temperature difference at the outlet of the reaction systems after the Curves a and b are probably based on the fact that in case a Heat was not effectively removed by indirect cooling from the outside using a cooling medium, whereas in the case b, i.e. the invention, ^ a thermally independent reaction took place »

The curve c shows the case in which the amount of ethylene supplied to the motor chamber 9 was incorrect, which led to the " Temperature inside the tube 8 the favorable reaction temperature

00983 t / H4B

-. 19 -

for heading and also the temperature inside the autoclave reactor 1. The course of curve c can be corrected to that of curve b by increasing the amount of compressed air in the motor chamber 9 supplied ethylene is reduced, and by the Opening 5 the amount supplied is increased «

Both in the first and in the second method according to the invention the spread of the distribution of the molecular weights of the polyethylene produced is considerably smaller than in the conventional autoclave reactor or the tubular reactor. This is also the distribution area in the case of the second method according to the invention less than the first method. The first process is particularly suitable for the production of polyethylenes, which have a narrow molecular weight spectrum «,

A comparison of the molecular weight distributions between polymers produced with the usual autoclave reactor, the data of which is given in Table 1, and polymers produced by the first and second processes according to the invention, explained in Tables 1 and 2, is given in Table 3 , - ■; _Tab - _elle 3

Distribution of the mean molecular weights in ° ß>

Mean usual

Molecular weights of the autoclave reactor

fewer 000 · as 000 18 * 8 10 000 - 000 22.6 10 000 - 20th 000 15.1 20th 000 - 40 000 14.1 40 000 - 60 12.3 60 more than 100 17 1 100,000 1 I , 1

invention 2. Procedure 1. Procedure 11.9 13.5 29.3 27.6 18.5 17.2 14.4 14.3 12.9 13.1

14.3

13.0

100.0

05 98 3 1/184

100.0

100.0

BATH ORIGINAL.

In the polymerization of ethylene, the yield by any method is usually low and it is necessary to recirculate the κ unreacted gas. Thus, the K ₀ Sten of Veräichtungsleistung are relatively high compared to other costs. The invention in which the reaction pressure is lower by about 1,000 atmospheres as shown in Table 2 and in which. the yield of the polymer produced is high and there is also little variation in the quality of the polymer produced has considerable practical importance.

In Pig. 1 shows a coiled tube as tube 8. The pipe 8 does not need to be a screw or spiral-shaped J-tube, but can also be a straight tube, the connected by U-tubes above and below and parallel lengthways the inner walls of the reactor 1 is arranged. Since the pressures inside and outside the tube 8 are the same, a suffices very thin tube, which makes the h-ohr 8 very easy to use Manufacture and shape is.

It can be any catalyst that is suitable for the polymerization of Ethylene is suitable, can be used according to the invention, as is oxygen, the known peroxides and the like. It can be any Reaction pressure are used. Lower reaction pressures are preferred, as this saves compressor costs. Suitable reaction pressures are in the range from 1,400 to 2,800 Atmospheres. All values for the given product yields

00983 t / 1845

relate to the total weight of the ethylene fed into the respective system. The proportion of ethylene introduced through the opening 10 can be varied over a wide range in accordance with the given description. The best results are obtained when going through the ^U opening 1Ö 10% to 50% of the supplied into the chamber 1 by the first method the entire Äthyüens zuführtjund 10% to 20% in the second process. "

0 0 9831/184 p

Claims (16)

Pat e η t a n s ρ odor 1. Device for the continuous polymerization of ethylene, consisting of a pressure reaction chamber with first and second opening "", through the ethylene in and Reaction products carried out of this chamber are marked through a tube with two open ends arranged within this reaction chamber, mine being these ends with the first opening and the other open end is arranged at a distance from the second opening and in a direction away from the second opening points and through facilities with which the content of the Chamber is stirred. 2. Device according to claim 1, characterized in that the pipe is serpentine, and that these devices are a stirrer which is arranged inside this chamber outside the pipe and rotates between the serpentine pipes and this pipe * 3. Apparatus for the continuous polymerization of ethylene, consisting of a reaction chamber with first and second openings through which the ethylene is fed into and the reaction products are passed out of this chamber, characterized by a motor chamber and a motor for a stirring device mounted therein. .08383 1 / 1SlS ORIGINAL plant, a stirrer arranged inside the reaction chamber, which is drivably connected to this motor, one under considerable distance from the second "opening, which creates a connection between the chambers, through which this stirrer extends and through which the ethylene is passed is, an inlet in this motor chamber for introducing the Ethylene and a tube which runs within this ^ reaction chamber is arranged. and has two open ends, one of which open ends is connected to the first opening and the other open end is spaced from and in a direction from said second opening in the second direction. 4. Apparatus according to claim 3 * characterized in that this pipe is serpentine, and that this one Stirrer outside the pipe and between "these snakes is arranged « . 5. .A process for the continuous polymerization of ethylene, - _<■:, - characterized in that ethylene is supplied to a first high-pressure high-temperature zone to form a reaction mixture of polymerized ethylene and unpolymerized ethylene; that this mixture is passed through a second high-pressure, high-temperature reaction zone, one of these reaction zones being arranged within, but separate from, the other reaction zone, and wherein both reaction zones are connected to one another for the passage of this reaction zone 009831/1 * 45 mixture * related; and that the reaction mixture - is kept in stirring movement over the entire other reaction zone; and that this reaction mixture is withdrawn from the second reaction zone _o 6, process for continuously polymerizing ethylene, characterized in that ethylene in a first high pressure, high temperature reaction zone is introduced, wherein a reaction mixture, the polymerized ethylene and unreacted Contains ethylene} that this reaction mixture is set in stirring motion in this zone, and that this reaction mixture is passed through a second reaction zone within and separate from this first zone "becomes, the second zone with the first zone to the passage this reaction mixture is in communication and is exposed to the heat and pressure of the first zone; and that this The reaction mixture is withdrawn from the reaction zone. 7. A process for the continuous polymerisation of ethylene, characterized in that ethylene is preheated through a high pressure and high temperature zone to be led; that the resulting preheated ethylene in a high-pressure, high-temperature reaction zone is supplied, which comprises this preheating zone and is separated from it, this reaction zone with the preheating zone communicating therebetween for passage of the material and wherein the ethylene forming a reaction mixture contains polymerized ethylene, and that this reaction 0 0 9831/184 5 mix subtracted from this Beaktionszone 8. Method according to Anaprueli 7 * daduroli gelcennzeicifanei; that Itn ^ ylen directly to this heaktionszone and also to this Yorwärmzoaae zag efülari; will. 0098 3171845 9. Autoclave reactor according to one of the preceding claims for the continuous polymerization of Mhylen, consisting of an autoclave reaction chamber and attached autoclave motor chamber connected via a passage for a rotor shaft, with the outside of the downwardly guided rotor shaft
Eührer is provided, characterized by a tube (8) in the reaction chamber (1), which is directed downwards from an opening (5) in the reactor jacket and then back upwards from the bottom opening (4) and there near the motor chamber opens into an opening (6). 10, reactor according to claim 9 / characterized in that the Eohr (8) a snake tube with a na.ch upward straight end is. 11. Reactor according to claim 10, characterized in that the Sole rod is passed around the motor shaft and stirrer. 12 · Reactor according to claim 11, characterized in that the Coiled pipe is concentric, is guided. 13 / method, in particular for the application of the device according to One of the preceding claims, characterized in that the ethylene is in a first high-pressure, high-temperature reaction zone leads to the formation of a reaction mixture of polymerized and unpolymerized ethylene, then the mixture is passed through a double reaction zone being, with one of these cells within the other, but gt .009831 / 1845 separated from this and the zones for the material transfer are in connection with one another _f that ^: the reaction mixture in the second reaction zone is through-: stirred and is withdrawn from this reaction zone " 14. The method according to claim 13 »characterized in that the Reaction mixture is stirred in the first zone, and that the second zone within the first zone the pressure. and the Temperature of the first zone is exposed, and that the reaction mixture is discharged from the second zone » 15 · Method, in particular for application to the device according to one of claims 9 to 12, characterized in that that the ethylene is continuously passed through a high pressure high temperature preheating zone, then into the "reaction area surrounding the preheating zone", and that the mixture forms stirred by polymerized ethylene and from the reaction zone is deducted. 16. The method according to claim 15 »characterized, that ethylene is also introduced directly into this reaction zone. ORIGINAL fMSF £ CTED 0098X1 /; i? Ai5.-.-. ·: