DE1645064A1 - Polymerization process - Google Patents

Description

The invention relates to a process for the production of polyolefin resins, in particular a process for the production of practically homogeneous, branched-chain polyethylene resins with a broad polymodal molecular weight distribution, the characteristics as desired for electrical grade resins such as cable jacketing and similar coating applications for various electrical and mechanical components and Objects ο

It is known to use broad molecular weight polyethylene resins " Produce distributions, for example reaction systems tubular type or stirred autoclave type can be used, such a reaction can be carried out in a single reaction area be carried out at different reaction temperatures, as for example in the DAS ... ... (patent application

0098-20 / 1674 - 1 -

NDCO 21 ■ '- .. "..

message I 27 422 I? d / 39-e) is described as an alternative Polyethylene resins, which have a relatively broad molecular weight distribution have, are produced in reaction systems which contain two or more separate reaction vessels, which can be connected in series, or in a common receptacle or in a common separating device be emptied ». as described in U.S. Patent 2,868,762. -

Object of the present invention is an improved process for the polymerization of ethylene or other olefins in a plurality of reaction regions can be obtained thereby polyolefin resins with broad polymodal molecular weight distributions, and the production of Polyäthylenharzen, the superior crack resistance under ümgebungsbelastungen and superior processed ₌ beitungsmerkmale have what their Use for electrical grade coatings, blow molding, and film forming applications.

Polyolefin resins, preferably resins made from branched-chain polyethylene, with broad, polymodal molecular weight distributions, are made according to the present invention by initially a first stream of the olefin, for example ethylene gas, under a pressure of about 700 - 2700 at, lengthways is passed through a first reaction area, which is kept at temperatures of about 150 - 260 ° C »The polymerization

009820/1674

645064

NDCC 21

in the first Reiktioasberiiicii wire! starch addition ®ia <ss. © rsten catalyst-catalyzed, äes? © © in © HamptwiÄsastait 2Hr Catalysis of the reaction at temperatures of approx. 190 - 245 ° 0 "has ο an additional? Olgfingasstom wtoä glei @ lss @ iti * s? L @ htung aureh one gweit.
^ © i! Teffipsrateea f © a about 250
the .Gasstrom \ mt © r bridges T © a aiadestene 70 ®, t wsiäger than the pressure of the du ^ efe öen first Eso & tioiasber_ © ieii led G-asstr © ma _t . sVeetailsitzorweise l @ i Dri © k © & τοη © "Stm β50« 1200 at _f held v / irö _o The PolymeslQ © ¹ !!, ®® w ± r6 in ä®m w> v® ± t®n reaction area through access " be of a gwaitea
who his optimal © Üs & talytiseh® Akti ^ ä ^ iä ^ te © i. about 245 - 290 ° S © i

Daa at the end of the first
product is removed from it tmö in a gw @ it @ si loaktionsfee- vmich at a point in the middle of its lä & go ®iag @ .fütot »wo ea 3i-? i: with asm reaction mixture in the wide area in one? ^ff narrow proportion of about 3 * 3 - 20 parts by weight of a single reaction product®, per part 3ea reaction mixture® mixed Separated feed components.

It was found that the so-formed polyethylene harness was in the

3.-

■. 009820/1 ^ 14

NDOC 21

contain substantially homogeneous mixtures of polyethylene fractions which have broad 'polymodal molecular weight distributions', these distributions being broader than those which can be formed using heating systems5 which uraf © ss @ n _e the polymerization in a single reaction area. Moreover, the polymodal character improves The molecular weight obtained in this way makes the preparatory work of such a meager; The resin-like materials have smoother surfaces and show less fusion than similar © resins ^ which © continuous® partitions

Bs wu £ d © w @ lt§2? found * that through.-cli & ektee introducing Heaktioasproöu & tes from the first Rtatetionsisereieh in ä® & ι tea B © akti0 & @ b @; g * @ iciv tsriai? Use d @ s? special conditions given above _fl - an improved ©© Misehen the denominator harsartigen fractions ersielt tmisämn TiMn _9, by separate preparation of the -Hischtmgskomponenten * and f anschliaßen- the mechanical Hisehen the same can not be effected könnt®.

It is assumed} that under the high pressure mixed conditions, the in-oen second reaction area can be maintained A solution mixture (for bridges of about 650 - 1200 at) of the two components is achieved, which is essentially homogeneous! tat of the product mixture results. In contrast, lie the components - if, for example, similar, resinous grain *

A-.

009820 ^ 1674

■■■■■ ·. * '■■

NDCC 21

components produced in separate reaction areas and by They are emptied into a common separation vessel (such vessels are usually kept at less than about 200 atmospheres pressure) be mixed, in separate phases, without having to use the practical homogeneity achieved, which one after the invention Procedure achieved. By getting such a deeper blending of the polyethylene fractions of the resinous product, the inventive method eliminates the need for the separate treatment of such fractions in subsequently Process equipment used, for example in separation vessels, Extrusion presses or pelletizing devices «

It has also been found that polyethylene resins produced by the process according to the invention have exceptional resistance have against cracking under limging stress. This feature is of great importance for blow molding applications and for electrical grade coatings that are neither Form cracks, nor may they become water-permeable if they are used for insulation or similar purposes. made from resins using the present process also exhibit desirable flow properties, plastic recovery, and relative smooth extruded surfaces! »

Preferred forms of the device for carrying out the invention Procedures are shown schematically in the accompanying drawing, in which!

. "■ '■" - .. "■ Λ. Σ .009820 / 1674

21

FIG. 1 shows a schematic, partial flow diagram of a preferred system for carrying out the method according to the invention driving represents;

Figure 2 is a schematic diagram similar to Figure 1 showing an alternative system for performing the method; and ■

Figure 3 shows the flow diagram of a preferred overall process, which includes the reaction system of the embodiment of the invention shown in FIG.

The process according to the invention is preferably carried out by introducing a first ethylene gas stream through a line 11 into a first, longitudinally extending reaction area which is delimited by the basic resin reactor 12, while at the same time a second ethylene gas stream is introduced through a line 15 into a second, in The longitudinal reaction region is introduced, which is represented by the wax reactor 14. The feed rate and temperature of ethylene gas, and reaction pressure, temperature and catalyst parameters are determined, as will be specified in more detail below, so ₌ that a base resin fraction having a relatively high molecular weight and low melt index in the base resin reactor and a guard fraction with a relatively low molecular weight and high melt index in Wax reactor are formed.

- 6 ■■■ -. 009820/1674

ITDCC 21

According to the invention, the reaction product formed in the basic resin reactor is removed therefrom through line .15 and fed into the Waohsreaktor 14 ₀ ! The latter is, for example through the subdivision 16, in ice © obese zone ® & ® $? E @@ 2ctiosis- mmm 17 and an outer zone © or Misehsone 18 g ©% @ ilt teafalls camouflaged also in the Grundharsr® @ ^ gate. See s © in the _P the'this level © ia ®im
shares »Vorsisgeweiee vd ^ d das
reaÄtor in_iie frliachzone 18 of the. Waefesesistor®. @ & S © 2 »Stell © 19» as shown in Pigur 1. ₉ © ing © f®si? Te Mf tile ¥ © is © is

in the Waehsreaktor in .iss © E © a ^ ti © ii © S0a © 1?

it from ä © is Eeslsfes 12 iaad
soae formed wax resin is i © g Msehs @ m © fin®! © aSr ^ s © 14o a »ari so dim reaction aaxf den © Iqe ¹ © !! f © il ig® XfesüksgQefet © ^ ®

-liird, eiae \ 2nkont7ollisrt @ BiIi ¹ OiIg -if © a 1? @ Χ; ρ3 <! ^ © ΐΐ ait high 'takeIzindes in the Misehsone. "18 fes'kiaigsfts'» Jödmsak Sa © wieiit des ¹ products made from the WaehsrsE & te® -i ^ g @ h the 21 are removed _f g © nam regulated in the mafi S@3h.wankufigen from batch to batch in the final harsai'tigea Pro.dulst be brought to a minimum.

Alternatively, the giasiitesz removed from the reactor 12, the reaction zone 1? dea ¥ aehareaktors an ^ iae Stell® 22 _s as shown in Figure 2 of the drawing »is introduced -wered ©! ^ B @ i in such an embodiment, the Q-rmidharB-realtig ©

⁷ * 00982.Ö / 1S14

BAD ORfGlMAL

IiDCC 21 ₌

product of a further polymerization in zone 1? subjected to the formation of a larger fraction of the low molecular weight High melt index material leads. By having a larger proportion of the polymerization at the higher, Carries out reaction temperatures used in the wax reactor 14, the optical properties of the resinous product be improved.

Using either of the reaction systems shown in Figures 1 and 2, the length to diameter ratio (L / D) becomes each Reactor, the temperatures and pressures of the reaction mixture passed through, the type and the amount of the with the respective reaction mixtures mixed catalysts and the relative proportions of the base resin-containing reaction product removed from the reactor 12 and the waxy Reaction mixture that is formed in the reactor 14 and mixed with it, in the case of those specified below Values adjusted to give a resin blend which has the desired bimodal molecular weight distribution and shows the improved features set forth above.

The green resin reactor and the wax reactor are each with an L / D ratio of at least about 11: 1, preferably from about 15: 1 to 20: 1, designed for optimal conversion of the ethylene feed gas into the resinous reaction product to achieve and a further polymerization in the output lineeii of the respective reaction vessels or in the

■ '■.-._ 8 - 0098207 1 674

NDCC 21.

Separator, into which the reaction product is finally introduced will, to keep to a minimum, if. not to. impede.

The feed stream of ethylene gas going into the base resin reactor 12 is inserted through line 11, and the second Feed stream of ethylene gas introduced into wax reactor 14 through line 13 must be particularly elevated Pressures are maintained to prevent the formation of branched chain ethylene polymers known in the art Way to facilitate. In particular, the feed gas flow, which is fed to the base resin reactor is maintained at a pressure of about 700-2,700 at, while the feed stream of ethylene gas which is fed into the wax reactor, is kept under a pressure of about 650 - 1200 at the reaction mixture in the base resin reactor is maintained at a pressure that is at least about 70 atmospheres, and preferably etv / a 140 at up to 900 at above the pressure of the reaction mixture in the Waohsreaktor lies to the correct flow through to maintain the reaction system.

The ethylene gas feed stream introduced into the basic hara reactor is in these at a speed of about 5300-16500 kg / h. introduced while in the wax reactor introduced ethylene gas feed stream into these "with a Speed of about 325 - 4250 kg / hour. is introduced

* ⁹ "GO982 0/1674

NDCO 21

If desired, modifiers such as isobutylene, Propylene, η-butane or propane can also be added to the ethylene gas feed streams. The feeding speeds along with the reaction temperatures and pressures and the compositions and feed rates of catalyst, adjusted so that the required product quantities result in each reactor, which, at Mixing in the mixing zone of the wax reactor will result in a practically homogeneous mixture in accordance therewith.

It has been found that the conversion of ethylene to polyethylene in the two reaction areas decreases directly by 0.07 # changes per ° C difference between the temperature of the feed gas and the discharge temperature from the reaction vessel. In other words, when ethylene is introduced into the base resin reactor at a rate of, for example, 11,000 kg / hour per hour the conversion can be increased by 25 kg / h. for each 3 ° C Increase in the temperature increment (temperature difference). On the other hand, the application of degraded Feed gas temperatures to form resinous Products whose optical and other characteristics are not the same as those obtained when using higher feed gas temperatures can be achieved «In accordance with the above requirements For example, the temperatures of the ethylene gas feed stream introduced into each of the reactors 12 and 14 can be determined will be in the range of about 24 - 120 ° C.

■ - 10 -

0 0 9 8 2 0/167 / »

NDCC 21

Me reacting mass is kept at temperatures in the range of about 150-260 ° C. while it passes through the base resin reactor 12, while the reaction mixture passing through the wax reactor H is kept at temperatures in the range of about 230-275 ° C. In this way, a polyethylene fraction with a relatively high molecular weight and low melt index is formed at the relatively low reaction temperatures in the base resin reactor, while a relatively low molecular weight fraction with a high melt index is formed at the relatively high reaction temperatures in the "wax reactor a melt index of about 0.001 2.0 and a Waöhsfraktioa with a melt index of about. 10 ³ - ■ 10 ⁵ formed.

Dir in the base resin reactor uid maintained in the wax reactor Temperatures can be regulated by any convenient measure for example by external heat exchange means and / or suitable agitation means which provide radial and / or end-to-end mixing therethrough. The reaction temperatures can so in accordance with each predetermined Temperature profile are set, for example flat temperature profiles, vde they usually for '. Production, of Polyethylene resins with relatively narrow molecular weight distributions can be used, or split or other Profile designed to prevent the formation of a resinous To effect product with relatively wide molecular weight distributions.

009820/1674

- 11 - ■

»Ρσσ.21

Regardless of the special temperature profile in the base resin reactor and can be used in the wax reactor, if it is preferred, the mixing zone 18 at the outer end of the wax reactor 14 to provide a precise® control over the final temperature of the product mixture that comes out of this reactor through the line 21 exit, see below. This is necessary because the Enthalpy characteristics of ethylene are such that a pronounced temperature increase of the product mixture results when

* It flows from a reactor into a high pressure separator / which is kept at a significantly lower pressure. By feeding the reaction product at a relatively low temperature from the drum resin reactor into the Son® 18, as will be described in more detail, and thoroughly mixing the reaction mixture in such a 2on @ , a practically uniform final reaction temperature of no more than about 290 ° C is achieved set, and a further increase in temperature and consequently a continued © brought polymerization to a minimum When the outlet temperature of the reaction mixture.? in the wax reactor

' If not controlled in this way, the out-of-control temperatures in the exhaust line 21 from the reactor or the aneofol-containing separator could lead to continued polymerization therein or to explosive decomposition of the product streams8 *

can be a further © control of the temperature dee Abetroase, fior is removed from the guard reactor Einprit ** n τοη cold Äthyleni> * 8Chlc? Kuagaga8 in the lower part

12 *

00 9 820/187

45064

ίί

1B0Q 21

, Resistors can

To äi® im

i _t will mimd © strass zealous reaction gtsigöii mal® activity "bei Stmpe ^ atii ^ ea A go! rather latalysatos ¹ radicals for example one of the as special maxi *

is®tt®Kia ± ti ± 0r®iiäfE Kafei

ron

ö ^ © töff ^

⁽ oo <Scn feol

m GO <&, *

ORIGINAL INSPECTED

NXK3C 21

RaaktiSBSgemiseh is Waeheröaki © ;? 14 jpug-dsatzt to the

d. *. f f'Jlyiierdssstion ron Xth / Xen t) #i iö ^ ns ^ & tUTitJji ¥ sn about 245 26G * 0 expand »Eü Ratal? aato £ * ttr the ami -teosnsn * belong 3i« tert, - »butylp »2? O3qf? 1 ₉ peroxide, p-tert-butyl hydroperoxide and Henthanhydroperozyd. j Such a catalyst (or catalysts) in the same manner as di @ least öemiach added in the base resin reactor catalysts are added, and is (or are) useful in a Henga of about 0.05 to 1 * 35 "preferably about 0.2 1.1 kg / hour _t admitted.

In order to form a practically homogeneous resin mixture according to the invention, the basic resin-containing reaction product from the reactor 12 is added directly to the reaction mixture in the reactor 14 in an amount of about 3 ₅ 3 20 *, usually from about 10 to 18 (iew . -Parts of such a reaction product are introduced per part of the reaction mixture formed in the wax reactor. According to a preferred invention, about 850-26.0 kf * / hour, at Renktionepxokt from the base resin reactor eo with about 57 * 6PO kg / ^ t> ^ -> ί .. ·. ··. ~ 5-x- ■ WaoliP-t-fairtor gebil-

; · -; «* ·»>'■■ Ϊ if:' fi »ff« Twn · ί Γ? «"'•> ^J h.' - ''"If * ■■." * << ■■ ν efii'Si ' · "'· ^. w ^ "T * fl etviiyp ·«

* · 1.1 € - ■

. W 0.07 bi £ fi fet \ rfa S *> has u.:iu - · _^; ^c *; ■ 'ϊ ^ ν; .- ^ one?

· ■ 14 -

ι; Γ ν ^? 2 ^l '' - i »V 4

OFHGINAL INSPECTED

1845064 ff

lrooc 21

Waohefraktion includes, which has a Sohaelsln & ex tq «about 1Cr- to 10 -fold dü & Sehmelz & ndexes fav @r« ä3idha? 8fraktion thereof. The product _{tetrota 9} of such a mixture and not uiegesetrtos ÄthylenbeeeS & otasigSjgae »ath & lt, is withdrawn from the .Waohsreaktor, and <taa? Rod% kth & r2 is conveniently separated from it». ·

"""Sonder bevornuft ^ s Syst®® sur Burchführtmg DE® inventions £ ungsgem & 0ezi Terfahreas How is inclined 3 of reward lsi Hgur. Indicated there viwü ®ϊμ © ^ Contour Ithjlenga ^^ t ^ o ^ by! Line 11 in a ^ ryadfearsr ^ aslEto? 12 alt 3er introduction of a «¥« ites by Ti3itvjig 13 in d®.m V & eh & roaktov 14 · Bin eseeter Eatalyeator wi ^ l in the Grundhar.fivftakt ^? imraü «Inen Eial & S eÄer several des? SlalÄe33 23a, 23 * & odeff SSs introduced .., Äi © lisg® -iiseeelben at a distance aag ^ e ^ toe * siaä? ias · * Λ «^ olpisiS.se.'Sl®» in efiJMB

₀ ^ ShsrsnS eis swisltes catalyst 3-il; la i * R VasSiespeeucte »is introduced, about the reaction äm $ .m gm begttaetle-sa · 2-ira @ kB3i0igevweiee contains genäfi the authorized execution for @ rm de? Invention of the tert-butyl catalyst introduced into the basic hardening reactor in a kenge clay approx. 0.2-0.5 kg / hour. _e while the catalyst introduced into the Waohereaktor contains M-tert.-butylperozyd, the In such a Heakto? ta one henge of about 0.2 - 1.1 kg / hour. is introduced.

- 15 -

009820/1674

NDCC 21

Since the basic resin reactor 12 is formed reaction product Duroh line 15 removed and into the Waohereaktor U at the Position 19 in accordance with the reactor system of Figure 1 introduced. Such a reaction product is mixed with it the reaction mixture formed in the Waothereactor in the Mieehzone 18 of the same, which is formed below the subdivision 16. The composite reaction product is thereafter removed through the exhaust line 21 and the Hoohdruokseparator Eur pressure reduction and separation of the remaining Äthylenbeschickungsgasee through the return line 26 fed.

The stream containing the product is passed through from the Hoohdruokseparator the discharge line 27 is removed and introduced into the extruder hopper 28, which feeds an extruder and a pelletizing system 29. Residual ethylene feed gases will be With the resin-like product in the extruder hopper through the line 31 withdrawn

The ethylene gas recycled through line 26 and the exhaust gas removed through line 31 are passed through a number of reflux coolers and filters 32 and returned by the compressors 33 and 34 in the circuit to the individual reactors for further polymerization. Ethylene feed make-up gas and appropriate modifiers, if necessary, they are introduced through lines 35 and 36, respectively, and recirculated with the Ethylene mixed to the gas flow for the Reaktorbesohiokung

to build. ·

009820/1674 - 16 -

NDCO 21

The following examples explain preferred implementation foraen of the process according to the invention, which are carried out in reaction systems similar to those described above in connection with FIG. They explain the invention without restricting it.

Example ii

As shown in the above theme of FIG. 3, a first ethylene gas feed stream is fed at a temperature of 53 ° C. through line 11 into the base resin reactor 12 at a rate of 12,400 kg / hour. introduced. Simultaneously with this, a tert-butyl perbenzoate catalyst is used in an amount of 0.4 ^ 8 kg / hour. added to the heating mixture in this reactor through the Kc, alysatOTsufleitungen 23a, 23b and 23c. The reaction mixture v ^ rd Xm. Orun-iiiasm-s & ktöä * at giner seapsratur of 227 ° G and under aiiisp J3? Uek τα ,. - * ·;, β 1800 at gäteltef ^ A product stream of 1629 kg / h. a: i contains a 3 / olyäthylaaharzfraction with a Sohmelzindex of about 0.001, and 10 730 kg of ethylene gas / hour are withdrawn through the line 15 in the Misoh zone of the wax reactor.

A second stream of ethylene gas is passed through in a corresponding manner the line 13 is introduced into the wax reactor, this Stream held at a temperature of 57 ° 0 and in the reactor wit a rate of 1382 kg / hour. introduced will. 0.32 kg / hour of a Si-tert-butylperoxide-KfttalyMitor ·

* ¹⁷ ~ 009820/1674

VDCC 21

are added to the reaction regimen in the Waothereactor through the latalyeator inlets 24a and 24b. The pressure in the wahereactor is kept at about 820 at and the reaction mixture moves that a reaction temperature of 275 ° C in the reaction zone 17 above the subdivision 16, and a temperature of 255 ° C in the Wed very one 18 under this subdivision upright can be obtained. This results in 360 kg / hour. on a polyethylene fraction with an estimated sun melt index of 6000 and mixed in zone 18 with the polyethylene-containing product from the base resin reactor.

That "-: ~; Amme-set product is withdrawn from the awake reactor by ^T - *> m \ 21 at a temperature of 262 ° C. Dae Produir: ant SIt 11 730 kg / h. Of ethylene gas and 1990 kg / h. Ait eir-er i ^ lyäthy ^ enmieohungj einachließlich 1628 kg / hr. at the Grundfe ^ rzreaktor Polyäthylenfraktion formed and 360 kg / hr. on the Polyäthylenfraktion formed in the guard reactor. containing the aggregate mixture so formed 18.1 i> wax and has a composite solids index of 0.11.

The heating product is relaxed on a pressure ac ron 224 at in the Hoefadruckeeparator, whereby 25 545 kg of ethylene per hour and 1990 kg of the composite polyethylene-containing mixture 'per hour are removed through line 27 and fed to the extruder hopper, in which ethylene is is deducted. The remaining 1990 kg of product are then fed to the extruder and the pelletizer supply.

"18- 009820/167 £

KBCC 21

11 240 kg of ethylene gas per hour are fed through line 26 to the outside Koohdruokseparator in circulation «and old 2875 kg / 8td on top-up ethylene gas, which is introduced through line 35, is wrong τ - smells). The susamoengeetste stream becomes old la cycle βir ** speed of 14 100 kg / hour. surüokgeftthrt while he at a temperature of 17 ° C and a pressure of 224 at is held. Appropriate fractions of this current will be passed the compressor 33 and 34 and then through the Sinlafil lines 11 and 13 in the respective reactors «for others Reaction directed

Examples 2 - 5t

Further Eusanaene-set resin mixtures are produced in the manner generally described in Example 1. They are process parameters as shown in Tables X below and II accepted, varied, the value being fäfe? any greetings for the OrundharEreeJctor-Aaohereftk ^ orejiteile d «reaction system in that order.

Work catfish? ■ '. -. Examples 2, 4 and 1 * s - x ^ \ 9n using the In T * _ ': dselgten R ^ ktioiüsysteas eur formation of biaodal Uariitolekulemrgeifloht ^ distributions carried out. In example 3 there is £ % »n xird t ^ ;. Ea & ktlonssystea applied that • Ine subdivision - 4, ': ι »ϋ as> Endtn ö * s Srundhani? ®aktors points, unfi Getr« ¹ - i, - F% - alyretosetrtt = · sake i »-; oa« i; · ' - ) $

BAD ORlGlNA !,

N "OOG 31

Introduced into ami Kwei reactors' storage zones

A manufacturer / product with a verochi flat polymodal is obtained.

Table I X Process parameters used in Examples 2 and 3

Example 2 Catalyst A / B Catalyst ton amount (kg / hour) 0.47 / 0.7

A «tert-butyl perbeneoate catalyst B * Di-tert-butyl peroxide catalyst 0 * diifiopropyl peroxydioarlionate B «tert-ButylperieQbutyr & t.

C / B / B / B 0.96 / 0.2 0.11 / 0.2

Reactor outlet
temperature (° C) 226/274 1540/346. 264/283 Durable reactor
temperature ( ⁰ C) 226/274 18.1 193/278 Reaktordruok (at) 2090/680 25,000 1520/840 Beeohiokungegae-
temperature (° C) 48/48 0.12 106/103 Loading amount (kg / hour) 12400/1500 1170/2220 calculated product! one-
geeohwindlgkeit (icg / hour) 1560/335 formed Waohefraktion (%) 17.0 estimated Waohs-
Schaelsindex 6000 Product melt index 0.13

-20- 009820/167

NDOC 21

Table II

Process parameters used in Examples 4 and 5 example catalyst Amount of catalyst (kg / hour)

Heater outlet temperature (o C)

Average reactor temperature (° C)

Reactor pressure (at)

Feed gas temperature (o C)

Feed gas quantity (kg / h)

calculated production speed (kg / hour) formed Waohsfraktion estimated wax Sohmelzindex Product solimelt index

A / B 0.2 / 0.2

228/273

A / B 0.31 / 1.05

226/270

227/275 227/275 2100/860 2040/680 $ 49/4 51/49 12 160/1500 * 1fl 200/1310 ** 1930/335 1570/294 17.48 15.42 6000 30,000 0.14 0.13

B X

XX

tert-butyl perbenzoate catalyst Dl-tert-butyl peroxide catalyst

The fresh feed converted in this example contains $ 0.59 of cyolohexane modifier

The fresh charge converted in this example contains $ 1.45> vinyl acetate comonomer,

- 21 -

009820/1674

NDCC 21

The above description mainly concerns the homopolymers! aati on. of ethylene, but can the invention The method and the device according to the invention also in connection with the interpolymerization of ethylene or others gaseous olefins with any suitable ethylenically unsaturated compounds known to be interpolymerize with it. It is therefore evident * that the method according to the invention "although the The description relates primarily to the preferred homopolymerization of ethylene for reasons of duality, both the Homopolymerization as well as mixed or interpolymerization of ethylene and other gaseous olefins by the procedure described.

- patent claims -

- 22

00 98 20/167

Claims (3)

$ 2 21 J5. February Patent claims 1645 064 for the division of a polyolefin resin, such as ■ ',' .. "to a practically homogeneous polyethylene resin, with a broad roi ^ modal molecular weight distribution, characterized by the fact that" s a first stream of olefins under a brisk of 700 Ma U ^! UO at in the longitudinal direction leads to a first reaction area which is kept at temperatures in the range from 150 to 260.degree b) a first catalyst that catalyzes the polymerization this olefin is effective at temperatures in the range from 190 to 45 ° C., from the reaction mixture in the first Bireioh eugibtj A second fine stream under a bridge of 650 to 1200 at, this bridge being at least 70 at lower than the pressure of the olefinic aerosol led to the external reaction area, in the direction of flow through a second reaction bar which runs at temperatures in Range from 250 to 275 ° C is maintained? d) a broad catalyst, which catalyzes the polymerization This olefin acts at temperatures in the range from 245 to 290 ° C. in the reaction mixture in this s wide area sufficient? - 23 - 009820/1674 HBOC 21 β) the reaction mixture decreases from the end of the first region and this in the wide reaction area at one point «Wipe its ends introduces the reaction product from the first Bereloh and the reaction mixture in the second area mixed with one another in a proportion of 3.3 to 20 parts by weight of the reaction productβ per part of the reaction mixture8} and f) the composite reaction product at the end of the wide Reaction area decreases and the desired polyolefin resin separated from it - 2. The method according to claim 1, characterized in that the first catalyst to the reaction mixture in stage b) in an amount of 0.2 to 2.0 kg / hour, and the second catalyst to the reaction mixture in stage * d) in an amount '· Fön 0.05 to 1.35 kg / hour is admitted. 3. The method according to claim 1, characterized in that as the first catalyst methyl ethyl ketone peroxide, di-tert.- - ■ buty.peroxide, tert.-butyl hydroperoxide, tert.-butyl perbenzoate or tert-butyl peracetate and, as the second catalyst, di-tert. butyl peroxide, methyl ethyl ketone peroxide, p-menthane hydroperoxide or tert-butyl hydroperoxide is used. 4. Process according to claim 1, characterized in that each of the reaction regions of Ib is generally cylindrical in shape and has a ratio of length to diameter ron 24- 009820/1674 NDCO 21 has at least 1111, the erete QlefingaeetroM in the first reaction area at a speed τοη 5300 to 16,500 kg / hour. is introduced, while he ** * tfttiurt * pe * e at temperatures ranging from 24 Feie 120 ° C is maintained, and the "wide Olefingasstrom in the vast BeaJttionebereioh in a {Jeeehwineigkeit τοη 325 bi" 4390 WtfWtitt eia irtüireii! he l at temperatures i " Bereioh ti""4 We ^ is held. · ^f The method according to claim 1, because the second reaction is divided into four zones, one which the second olefin is introduced into, and one wide mesh zone, in we lohe the reiction "e" ieoh ou of the first area is injected · ■ 25- 009820/1 67A BATH ORIGINAL Blank page