DE1520227A1 - Process for the copolymerization of ethylene and vinyl acetate - Google Patents

Description

PAIkNTMHWKLTI

DR. E. WIEGAND DIPL-ING. W. NIEMANN 15 20227

DR. M. KÖHLER DIPL-ING. C GERNHARDT MONKS HAMBUKG

PHONE. 55S47 « 8000 MÖNCHEN 15, 5, AUGUST 1969

TElEGRAMMEi KARPATENT NUSSBAUMSTRASSE 10

W. 10 545/61 11 / Nö / Loe P 15 20 227.4

Monsanto Company ■
St. Louis, Missouri (V.St.A.)

Process for the copolymerization of ethylene and vinyl acetate.

The invention relates to an improved process for the production of ethylene-vinyl acetate copolymers under high pressure in a tubular reactor.

It is known that ethylene is suitable for copolymerization with vinyl acetate. It has now been found that it is possible to achieve very high conversions in ethylene-vinyl acetate copolymer of good quality of a narrowly limited range

909881/1377

New documents (Art 7 | I Abe. 2 No. 1 Clause 3 of the inclination to amend K. V. 4. p. 10921

luolekulorgowiohto distribution, duroh Wioohpolynorioioron of ethylene and vinyl acetate in a tubular Roaktor under bentimciton conditions au received · The Ethylene-Vinylacotat-Miuohpolymorioation doesn’t require the presence of any Katerialo that takes over all vinyl acetate and the vinyl acetate takes over because of the function the appropriate conditions in the Uiuchpolyaerioat approximately in the gleichon speed v / i ο dan Äthylon enters "wherein die.Konzentration to Vinylaootat remains largely konatant · This Tatoacho can in advantageous or V / oiee with addition of more Katalyuator and andoron Arboiteweioen _f the Uioohpolyaerioation to be continued, auoßonuts & t · Da: »Ethylene-vinyl acetate-Kiochpolymerioat ochnilzt a little lower alo lolyUtliylen and the Vorwondung of reserve of the high HoaktionatoDperatui'on makes eo possible, a auareiohonde FlioOfiihigogkoit in the Hooktiona on poetro hea, oktiona onatro contains lymerisat, to rest upright

The polymer co-ax: mono-formation is almost independent Ten dor conversion, d # h. the copolymer produced in the laston Seil doo tubular reactor is proportionate dom in the front rope dos rohrförnigon Rooktoro produced almost equivalent

In the process according to the invention, a catalyst is introduced in order to achieve more than one reaction,

909881/1377

«AD ORIGINAL

dth · im to cause zwni odor mohr polymoriautionareaktionon to take place one after the other · To achieve this, a portion of the catalyst can be fed to the inlet end of the tubular Rcaktoro with one or both monomers odor dao monomers alone can be fed to the inlet end, while the catalyst can be introduced in two or more proportions at places read afterwards · The Auodruok "multiple introduction ^{11 used here} includes any two or several separate ο additions of catalysts, regardless of whether oino ooloho addition takes place with the tlonomoronbeuchiokung ·

According to one embodiment of the invention, the catalyst is introduced into an ethylene-vinylaootate copolymerization stream which contains at least 55% by weight of raw polymer and the crude polymerization is continued at temperatures above 200 ° C. in order to achieve high conversions. Or, as an option, one can consider introducing the catalyst into the polymerisation gas after any substantial degree of interpolymerization has taken place, that is, after about 15 to 20% conversion to interpolymer, and the micropolymerization may be continued in order to obtain high conversions "After the process of the invention jeraiiß _t, it is possible transformations to a Uloch-

909881/13 7 7

BATH ORIGINAL

heh sr, uality received from inahr αΐπ ^ w .j au 3ιιο ^ aur IJiüchpol ^ moriaatlon by / thj-lon \ inC. Vinylacotat, obtained v / ordeo _t atoht in auaecoprochonou. Coi; onaita au. ". RcobniaaoB, the boi before ^ chioclonon andorcachon ilochdrucion: - 2> ülynoriion ilochdrucion : ton v; ur «'on ·

trot to viclo i.önoaoro, woftn aio alt ^ thyloa who «on * in <iaa Liiach ^ olyaorit-iat ait

ice | the eo. Sohr is different from dor όοο Γ talons that the tsonoaoro iiuaauaonaofccuni; t; on aic? i öio aonotaero r.uaa ^ taenaotsuna doa himself öi'ccbonrlon "icohpclyiaoriaaüa» wonn dio .Volyiaoriaafcioa Xortacliroltot, v; o;: ontlich "innert, i70 <! urch es au ■ oronlörtlich cch..ioriß, v / onn not unKu ^ lic.Wrd, oin Pro ^ ulit constant SuCa ^ uOnOOt-UD ₁ * au orhalten, where an oino high Uaaanrilunis boi einoa konticuiorlichon VerahroD orw'iascht iat ·

l-'ornor üind the known VerXahron aur Polyaoriaationvcn PoI ^ i'i; liylon genrisaon Be ^ onKun ^ on · Beiopiolij-ν.ΰ.1αο int oä generally noti ^ i boi ^r thylon ~ Hochdruokpolyccriüationon in RohrXüraigen reactors I * ottonübort I. ; suittol to vor »; onden» ua daa molecular coi-vicht üea polyitliy · Ions cu toboggan; diea bocchrcinkt to oineo cewiasen Aue wet dlo applicability doa procedure and night 09 not possible,

909881/1377 ^ ORIGINAL

hcho Uauandlungen su received since the ciioiwtivc ICoiizeafcratioa co.j Kottcnubortraeunjoaifctolfl anateicti when dan Athylon polyaorislort, wan die Krzeucun ^ ac i'olyaorisata by andcroci I ocular weight; ia don hits or en Share £ co neaiitorrohros » ale ö3 in tion anterior parts dou noafctorrohros ce -.-, uv o, · Vülirend caused the KoaaentiMwion to ciinoa

j \ uoDa3 by dio EiniUhxon of zusHtzlichon "'.caktioQ3koüponontioa £ wordoa can 0Γ0 £ β1ϋ, this has a toö! usual Ärboitavorgane sur? ol ^ o and iat not iisaor sufritidonstollend · Auoscrüoa bostollt boi dos -'ciojciaatioQ the l.'oicunß that dor Heaktcr vorofcopit we.: when dia Konsentiration dor Polyneriaut ^ oapcaonto ita

so your cro will. Bio understanding eru'ihaton ^ on su & acacn ait ^ borloGungon, v / oloho dio PoIy-:.: Oriüafcqualitilt and anäore factors botrofXon, collected caeietontoilo at dor Ί1 · chdruckpoXyoorisation in rohrXür ^ ic ^ n! Factor ο α boscronsto 20th bsi £ 3> vihnliohon Arbeltäwoison and from about 20 to 25 .J wonn boaendorο Arboitewoiaon an ^ owondob wurdoa.

Boi dea ancestors revealed ErXinduns has a cross section of the population of a pipe located in an eich la operation Löraigon Keaktoro »see dit nittleran Teaperaturon at the end of the year, the reactor * is generally considered

909881 / T377 β. cn, G _1N AL

Xoapornturupitzon and -tälor on (as beiopioltwoieo in Pig "3 is beechriebnn below) · That process can be applied to the invention if a smaller amount of vinylncotate is used" in gooitfiotor Weieo by adding catalyst at such places dee fteaktoru at wolchon the penetrated oh A moderate temperature not higher than about 2 ^ O ⁰ C iut, thereby reducing any excessive tempurature of the resulting increased reaction, and the analyzer is usually added at such times, dJLo ßooij.-iut aiml, uu the durohuohnlichen "onpernturon during the polysierioation at all tunnels mindeetone about 200 ⁰ C high and vorzußcwoir.e raindeoter.o 220 ⁰ C high, inebeoondero if Eauorotoff is used as a catalyst.

The Vinylaootatmengo in the Polyaarioationcn'-ron has a considerable influence on the results obtained in the process of the invention, that there is sufficient vinyl noetate to lower the ohmic point and / or the results obtained In general, it is desirable to lower the melting point to 5 ° or more among the polyethylenes, which results in a proportionally much greater flow on the polyethylenes . The range from about 7 to 20

909881/1377

CAt i ORiGINAL

odor 25 Gow.:$ vinyl acetate »with respect to dac! iiooLpolynoriüat" iet ale 7 Gevj of beconderem Intoroßoe · Less.> acetate collected gowöhrlioh no Polyraerieationceigenschaften that differ significantly from those oioh that _f when ethylene is polyaoriuiert alone Wordon received.

In addition to the process of the invention, it is also directed to a verbocaerteo process for the production of chewable xthylon vinyl acetate polyacrylates. When the iJrfindunß is made in this way, high-quality lithium-vinyl acetate polymers with a vinyl acetate level of atapioleweioe 35 bio 75% by weight are converted to a high degree by polyaerieation in a tubular reactor under pressure at a temperature of not more than 200% ⁰ O left, duroh aelirf <8IE LinfUhrung the Polyiaeriaationokutnly8at.oren _t mä3ißen at Colch temperatures wirkeani oind heryoctellt, v.ie described below ·

In the procedures according to the invention, the working pressure has a monthly meaning. At pressures of 1055 or H06 to 2612 kg / cm ² (15,000 to 20,000 pei to 40 OCO pni) or higher, vinyl acetate and ethylene, at suitable working temperatures, enter about the same rate as mechanical polymorphism that are significantly below

90 988 1/1377

BATH ORIGINAL

■ · O "·

1055 kß / ca ^Z (15,000 püi), boiopiolewoiso boi 703 kg / cm ² (1t pOO poi) or less, the miochnonoraorons obviously do not polyraerioieren in dernelbon Qonchwinditjkoitf what a change in the concentration of the Vinylacotats and dou J'olekulnr ^ ewiohtoeieren the product causes and by which additional polyvinyl nootate is formed; One dor most significant effects of this is the reduction of the; .iolokular _t '; GWiohtQB.

The use of laindeutone 7 bio 10 percent; 5 Vinylnootat oei ancestor geaUß the invention verbοuοert dio inner Xomporaturoigonnoliaften polymerization wouontliohj Wonn enough Vinylacotat is vorwondot, dio Tonporatur iet to einor beotimiaten point in ^ oaktorrohr only ν ear periodiaohon lenperaturUnderungen subjected ± 5 ⁰ U or less, as is observed for a short period of time, boiepieleweioe an hour (although the temperature dn:; u nei ^ t, in the course of the polymerization, within a period of 20 bio 40 hours or more to deviate in greater AuBciaQ) t, moreover, the verboouorten. There is a deficit of the polyruorioationeiaicchuns nuo dom lower pressure levels above the reactor. '. The required proportion of vinyl acetate at the appropriate Polyznerieationetonperaturen is used, is

909881/13 7 7

BATH ORIGINAL

Pressure drop between the inlet and outlet of the oaktore (enjoy at the moment when the outlet of til woit is opened) not more than about 1/9 to 1/5 the working pressure or about 281 or 492 kg / on (4 OOQ bw 7 OuO pei) in the reactor used in Examples 1 and 4 "if the working pressure is approximately 2461 kg / cia (35,000 psi). You can expect the pressure drop at higher conversions to be longer wlrkoamon üeaktorrohrea da sur attainment hühuror Unwai ~ .d-1uncen necessary eats some increases · However, if wonn βor exceeds, the preferred "here beuohriobonen conditions are worked in particular with sufficiently high lemporaturon" ^ o, jar if higher conversions than anything described here and " The pressure drop across the reactor is about 0.25 to 0.5 A working pressure for every 1 / * of the monomers wrapped in at;. of the work druokeo for each of the catalyzed reactions taking place in dom lieaktor »ie for iode catalyzer addition or introduction not over orcohritton ·

How aua dom? Emperatur <iueruohnitt der H oak tion on, which in FIGS. 5 and 4 are illustrated or described in detail, the polyaorieation method according to the invention can be used as a working method

909881/1377 ' _{ΛηιΛΛ1ΑΙ}

BAD ORlGiNAL

-ΙΟ-

ί 'odor several individual ethylene vinylaootate r.inchpolyneriRationsroaktion d r ^ eetigte. ΰΐο KßtalyfmtorkonEentration, for any such reaction before ^ Oi-.ehon lot, eats α1ΐ £ θΏ0ΐη ütwa die !! tight, dio necessary lot, ur. comparable to get Krgübnlsoe for a ^ 'inzelroaktion, v.oauroh the Gcöantraongo on catalyst in the process go .ttß dor Invention about dna n-faohe of the crowd is »that at one individual reaction is used if η the reaction (or catalyst-liinfuhrunßen) deu Yerfahrono £ onUiJ the invention indicates; First of all, of course, that one a small number of hoops provided for Getaatnonge of the procedure ^ emUQ of the i.rfinduni; a pre-heated catalyst would be if the done monge were fed all at once or in only one part, cause a carbonization, but your method is true of the invention in spite of the use of such large The length of the catalyst does not lead to a small amount of decomposition.

The total amount of Katalyoatora used in the process according to the invention is generally la range from about Ϊ5 to 30 parts Jt million (molar · Baoia) of the Mono-Bitrenbetichiolcung ·

909881/1377

BAD ORJGf.VAL

Mo ZoIt awioohon don Katalyoatoreinführun ^ en roiolvt ßohnlioh auo uun ausulaofien that the honktion oino Cpitcentoaporatur orroioht and then cools to a temperature, which is low enough, in order to avoid high, so that the temperature does not increase before the catalyzer in front. The period of time for the individual reactions changes to a considerable extent with the diencions and the heat transfer in the individual reactor. Is typically introduced while the catalyst under 250 ⁰ C and 15O ⁰ untor O "** hen a higher proportion of vinyl acetate is used, it may have been introduced boi higher Toaperaturen when or in sufficient kloinen"';. ^ Is onßch oin efUhrt, although there was a boaohten that the catalytic converter also affects the molecular weight of the product

ι t

fluQt, what to consider to ßiohon iot ₍ '

The length doe imported Katalyeatore lot nll & onein equal to about 5 to 20 Toilon Jo llillion-Ieilon (nonouore Baaio) the Mononerenbooohlckunc, beiepieleweiee nindoutono about 5 parts by weight per million öo.uoretoff, boao ^ on to dao

Oqwicht der Uonomorenboaehiokung, iivt but not high gonug, to under the HochtomperaturpolytioriBationobedinGUn ^ on one Carbonization tsu causes · Boi some üeaktoron iat it but not feasible more elu 20 parts Jo Million to be used for every import, and go it

909881/1377 '

BATH ORIGINAL

generally necessary; «less alo 30 Üoilo per million Laueret off boi each introduction au use.

Sauoretoffiaongon in the Greetings from 10 to PY Gowichtoteilen per million, based on the nonomore feed, suitably be introduced and whether let often expedient at any introduction Uan ^ .Q dienolbe to use ·

In general, the catalyst is used before the introduction truohtlich vorUnntf among other things a suitable Abmetjwen Eusulaeoen, and can ontwoder with Oacen or FlUQoi (; koiten diluted become «SweoknUüiij; he becomes old in addition to the Konoaeronnioohung the Heaktorbooohloktion in concentrations of 100 to 1000 dinghies per million imported; the addition of a gienlioh large amounts of cool monomers, üuconaon with of the analyzer causes a slight drop in the inner i'onporatur on the adding part in the iieactor ^, but wan usually not harmful lot · »i'onn the Katalyr.ator in ' Form of a solution in colohen coal water, like n-pentane, η-hexane uow, eu ^^ e will be the catalyst allgenoin in concentrations of 0.5 bia 2 üew ^ or moor of the hydrocarbons used The catalyst is usually fed continuously at the inlet parts, however, it can be added cyclically, intermittently, etc.

90 9881/137 7

BATH ORIGINAL

The Xiitalyeatoroon # e, as well as the l'olyir.orioationotonporatur beoinflueaen dia iTolekulargewiohu doc a I ergobond on Uif> ohpolynorieate in the reverse fioiee "ie higher" Kntalyoatorkonaentrionen and higher tenporaturen cause a decrease in the Uolokulariuatorkiohte of the catalyzes The required ranges are used to generate the gain in molecular weights, which usually run within the range of about 0.5 bio 20% mm / oin. at 90 ⁰ O (Λ. ¹ DM 1) "1ϋ3β). In For some fillings, you may be able to use the later reactions at higher temperatures, all the ore are subject to loads, above goriziGore catalysts, uci receive a product that is highly conducive to high temperature, and yet the mobility of the high temperature is beneficial XOIymerlßationetromeß, which contains a high proportion of Polymerieat, have BU · General in the examples 1 bin 3 the completely indigo polymerisation is carried out at a relatively high temperature, and · »is usually recommended to keep the tempering door of the ülaantele at 170 ⁰ O and often above 20 ⁰ U 8U ·

Uno iOlynerisationsverfahren geaäS the invention requires "in · longer period of time and takes a QrtiQwQ length Onea given tubular ütaktore" in al "a polymer! -

909881/1377

* HO ORIGINAL.

Cntlonnreaktioni which is also carried out in a single location. Abnoi raised in a heater tube: aun £ jor. and V.ilrno-UmertragungaeigonBohaften »in which, for example, the Kfttalycator an] ni, tellon was introduced, botm-cen oowohl the side of the aohrlUnge, dio voa Boginn dor Polyr.ori cation bio suia linde (biw ttie stops) were ganotuen (^ There is a bolBpielö \ vel-, e from the point in time of the initiation of the sanction, which a teaporaturanetiog to a certain \ Vert vorurcaohtf bit sua back under a co-ordinate. «/ place where the reaction stops) the n -fno near the values for ο in ο a ~ fnolio i-olynerioation in the ßloiohon heaktorrohr under doncclbon

The method according to the invention can be carried out in a tubular ioactor which is suitable for carrying out the continuous polyaerionation of ethylene. However, Γ, ΰ has an additional answer. Exploitation of the changes is desired and often a practical necessity, the ivoaktionectrom Druek-Strunungolnpulre aufuerlegon and which can be done in a geoigneteten in a Koaktor »the for autonatiaohon oyolinchen operation oelnoe drain valves (" let down ¹¹ valve) at £ ndo Doü itoaktionorohree iet, Se is often necessary »to give the flowing KtaktionBmiuohunß considerable flow impulses in boütixonten 2 titint ervallen β oil oh · η Frequtn · uM Qviiä · bu» that

9 0 9 8 81/137 7 BAD ORIGINAL

The tube of obstructive signs of olympic at the inner vnnds in the weekly froi is not allowed, while a suitable mean temperature through the indirect V. urn from thaw inside the reaction tube during oinor dwell time, which is the time during which the xolyraorination elapses The frequency of the tinting impulses imposed, the duration of the various phases of a single cycle, and the size of the impulses are of course subject to the various types of reaction and conditions, but they are selected by an appropriate series of tests to irregular changes to pressure drop iatrönungsgenchwindigkeil which Ansaranlungcn would dcü lolymerientu verureaohen and to prevent · to fill in most frequency mindeotenu einnal the 2 minutes and Võrnu _f: eeiee einraal each fraction of a 'ünute as only 45 seconds each am once per tekun.e amount n · Kinnal all panr "Okunden, aB» once every 3 to 10 seconds, it is the preferred frequency ^ emti3 the form of execution and ^ ig superior! results than those obtained when the iretiuene once every 20 expresses entered · Ho is preferred a irequens νοη less every 20 ieconds · J ¹ Ur Joden ^ trOKun ^ BimpulB is intended to increase the speed of reaction through the pipe, lasting 2 to 10 times

^909881/1377 BADORIG.NAL

Or multiple of the standard operating speed ooin · Before the Utrümunßsimpuloe accompanied by corresponding DruokimpulBon, oils can be called in dieueza Pail al ο Eruckstrünungoimpulse, and the size can, as angogoban, by the increase in speed and / or the Xndorung doa pressure (like ale um introductory deo reactor · rohrο9 ßcmoou η will be measured) and ooll door every Druok-utrönunceiapule about 5 bie 25 ¹ ^ dee standard Betriebsdruokes concerned "

X) Ie Druok-Strömunße-Inpuloö been voreugswoioe by Botrieb doo let down valve & α AuelaBende deo Keoktionsrocrea rediolated. It should be mentioned that daa Also see air compressors, pumps and / or pressure pumps, a device to bring the ethylene reaction components up to the extraordinarily high reactlon pressure for thorough training of the rooted Kengen of united Catalyst and vinyl acetate with the ethylene, a device for conducting the coupling of them and ethylene through the tubular reactor "a preheater which is used first and / or the front rope of the reaction tube" which is used as a preheater, and a xifafyua The outlet end of the reaction tube, through which the endro-action tube of ethylene and vinyl acetate plus polymer flows into a polymer t ^ ennione old low pressure.

909881/1377

BATH ORIGINAL

The pressure on the ignition reaction device can be wetted out and is usually applied as a precautionary measure at the time on the AuelaO valve. _f beiopieleweiee from the standard ^ iteaktionbdruolc within doo ranges of etna 1050 kg / on (1,000 pal) or before & u ^ awaiaa about 175ö kg / cm (25,000 pol) to 3515 kg / eta (SQ 000 pel) nbcolut la reaction tube only A print of 35 bi "> 3Ü7 k ^ oa ² (§00 am 5000 pci) in the Tronnaone" Wi "above mentioned ongectb" nt the rtrünun ^ oisiyula "voroilhnft durob Geeißnato handling dou Ablaüvontile causes iüin Pnoluaann iut due to the loiclitiroibung in the Lc ^ e, varoohledena working conditions dioooe Vontile tmcuijebon, in order to give the Jieaktionaayatem dia ßewUnoohton Druok-Strudun ^ aiapulae su · Xn all PuIlOn ₉ in which by Üettitißung b / w «handling dee Vintilo In can be opened .pulca can be opened .pulca no, in order to cause a rapid drop in pressure in the electron tube. Diasa naturally causes "Ina appealing increase in pressure over those parts of the body", in which the current is restricted by polyether leaks and a reduction in the flow rate of the reaction through the body through all parts. üaohdam diee in a given Auenafl etatt _c efundon »the valve is then unvarsUeXioh partly or completely geoohloaen · ooenld the pressure in the beaction tube

909881/1377

BATH ORIGINAL

eich auf don friihuron pressure suriiok forms »volohoa dor ktandard-oesriebedruok doo Verfahrene iot _f odor if lying under it, the A.blaSvontil wlosäorum suddenly becomes far wio suor ^ t ^ eOffnot» and en boßinnt οin neuor ** roislaufos · The bosohriobone can Ar boliubi ^ i'or,; ocotzt cordon. Dio Soit, dia from οincm go ^ above 2ell dua K-rcißlcuIoo bia sun gloiohon * oil doe nahohoten K veratroich ^, will ula the jffoqucms do »'' Üreiulnu bözoichnot.

ttQnl £ Qr before ^ oilhaft »but quite sulä ^ ois can similar« Impuleo duroh Aufreohtorhalton öinoo ßloici.nii'ii Auola.ictroaeo <iuo düa Houktionerohr and Voründerur.g dor inlet »tröraungü-üedinijunßon, which dl are "ileaktioneoibohung in όαβ JXohr drove" imposed "Other aspects diooeo L'trönunec-Ispulu-Üerkiaaloi dao at dca ancestors geaü3 the invention useful lot" Xn dor Patent application P 14 20 595.9 describes "... *".

909881/1377 BAD ORIGINAL

The dimensions of the tubular reactors in which the "process according to the invention is carried out" can change to a considerable extent. continuously through a long-distance pipe, which allows rapid removal of the heat that is set free by the high-hexothermal polymerisation of ethylene and vinyl acetate, so that the heat transfer that takes place in the other parts of the world is reduced were, that dl · jfolymerlsatione-

909881/1377

BATH ORIGINAL

reaction oino hoohexotherme reaction solder and carefully. be regulated now, aaohen eo orw.lnooht, daoa dna reaction tube olnon vorgleiohavrelee klcinon Durohneocer, and this especially when the transformation jo passage very high let «J2n let therefore be that the ratio of the length of the reaction tube sum of the inner durometer junction Reaction ^ rohree eeJ; r hooh ie t ₍ boicpiolnwelee at least about 300 t 1 to $ 00: 1 and often bia su 1 000 ι 1 and higher 3 na (1/8 inoh) and a length of about 240 α (800 ft.) And longer than about 12 a (40 ft.) Can be used

909881/1377

BATH ORIGINAL

The invention is explained below with reference to the drawing beiopiolowoiao explained in more detail.

In the drawing, FIG. 1 shows a device for the practical execution of the method suitable let according to the invention "

Figure 2 let a flow diagram, welohoa the reactor, the Supply lines, the catalyst introduction pumps and the Re-run system ahead of the noo.

Figure 3 is a graphical representation of the clay poratures obtained at various locations in the reactor are applied as reaction temperature against dwell * since line A represents the temperatures for the batch with repeated introduction of Example 1, while line B su Verfiel oho purposes a graphical representation of the temperatures tinea Verauohee with a single introduction is ·

FIG. 4 is a graphical representation of the temperatures obtained at different points of the boaktors are »plotted as tactlon temperature versus time ·

Zn Figure 1 is «in the polymerization reaction tube with This tube is shown in a sinuous form, however, it can also have a different form »for example Being straight · Sin «vertical · position of the tube supports the polymeric acid flow. It is to be noted that this is a high Pressure equipment is and suitable "steel" and construction conditions are used · The reaction tube 10 is shown surrounded by 3 successive jackets, by each

. 909881 / 13.77 BATH ORIGINAL

diooer Müntol is goloitet by means of the binlos and Auo «· IaG at oll on oin WUrnoauatauoohiaittel · Dor oroto Mantol alt don Bosugzeiohon 12, dor zv / oito Kantol nit don Besugsoiohen 14 and the third mantol nit dom Bazugsoiohon by three can optionally be arranged can be considered on the other hand in the Zonon dee reactor · Usually the WUrneauetauschnittol, which is passed through the dumbbell 12, hotter than the monomers which enter the reaction tube 10 »while the Würneauetauachaittel, wolohos through which the jackets 14 and 16 is passed, is cooler than that Eo-action anisohung in the corresponding zones deo reactionary ear θ a 10 lot »oo the exothermic heat of reaction is removed ·

You mono & erenmieohung is withdrawn from a source via a line 10, in which elno kloine Menno catalyst is introduced (if the catalyst is added before the heating) , brought to the Roaktionodruok · Dioae can *, B. Boetohen from two or nohrorcn cylinders, which are connected to the suction and conpreaoion, which takes place by means of the Kolbon located therein, and are 180 ° phase shifted Temperature, β.3. is increased to 7 $ to 150 ⁰ O ₉ · The · reaction mixture is then passed through the dl · line 28

909881/1377

^B AD ORIGINAL

Duroh etn Reguliorventll 30 for the inlet of the RoaktionBrohres 10 out · Dao valve 30 is in gooignotor Woloo ouGßabildot and an actuation is brought into harmony with the actuation of the Druckvoretilrkor 22 »then it ο smelled konatantor Druok of the ileoction malfunction entering the valve This constant Druok is going to lie, un Overcoming the pressure drop at the valve eu and also the standard work pressure in dpa reaction tube 10 during that line of the Krela run in which the indulgence or Relaxation valve 32 is geeohloesen or modulated to to maintain this standard arboitsdruok. Other methods of submitting the reaction mixture Einiao ο dos Reoktionerohree 10 with the desired speed and the mentioned pressure su orholten, atohen naturally available »like the Weglasaen des Vontilo 30 and a regulation of the geo-speed of the pumps 22 »to a constant flow geohwindiokeit of the Maaao BU aohaffen · Das Ablass- odor Entopannun ^ avontil 32 iot am AuQlaßcndo dos reaction tube 10 arranged »around the Druok dor endro-action, hearing the most unconverted honomors and Lower Polyneriaat eu and their PIuS in the separator 34 The rules below · A separation of the polymers from the monomers takes place in the separator 34 * as a precautionary measure above the temperature at which the polymer is kept so that the polymer is soothed from gssohmolssnsm Xthylen *

909881/1377

BATH ORIGINAL

Vinyl acetate product by spraying out the Vontil 36 and the line 30 is obtained. The separator 34 is shown eohooatieoh, and can be any suitable It goes without saying that the drawing is not to scale and that the separator 34 is large is enough, including a considerable amount of dos gooohmoleonen To keep polymerizates · The monomers will be removed duroh dna valve 40 and line 42 recovered

The AbIaO or entopension valve 32 can be done by hand be humiliated · For non-existent extension of the extension long zoitabaohnitte should jodooh the valve with suitable Coats that are not marked with 44 are autoxaatieoh betriobon and been regulated. While the veroohiodonon aeohonioohon and eloktrioohon arrangements necessary to obtain the gowUnoohton oyolioohen actuation dos Bntopendungaventila 32 can be applied, eahlreioh oind, and can be rooted entepreohend by Faohlouton, becomes a simple one and preferred arrangement eohematieoh in Figure 1, wherein actuation of valve 32 in response to pressure from the loading end of reactor 10 occurs suitable or pneumatic dam line 46 takes place Valve actuationaeohanisBUS 44 lat eo set »that he has a constant pressure within very close Oreneen at the pressure regulator at the inlet end the Beoktorrohra 10 sustains * Hit other words when dar Druok dar

909881/1377

BATH ORIGINAL

Pressure regulation tunnel over the pre-approved and previously - put Stondardarbeitsdruok rises, opens sioh dao Valve 32 automatically otwos, sodau on dieae Weioo joder further increase in pressure is avoided and the pressure is dropped somewhat untor the standard arboitedruok falls, oohließ sioh dao Valve 32 automatically to adjust the pressure to the preselected value by a small amount. This modulation process is known to the person skilled in the art. For example, a work load of 13 6QO kg (30 English fund per square inch) can be preselected and the system can have sufficient sensitivity to keep this pressure within 45.3 kg (100 English pounds per square inch) according to a special mode of operation to induce flow impulses in the ancestors According to the invention, the control of the Arvtriobaeinrichtung 44 for the drain valve 32 under anoproohen on the guided by dlo line 46. Druokolgnalo subject to anticipation by means of a timer Circuit the response of the motor 44 to the on the Line 46 takes place. Druakon shows advance or prevents a response and causes the drain valve 32 wtit is opened · An · Sud · the previously set period of time, which · gtwöhnlioh is less than one second.

909881/1377

BAD ORiGlKiAL-

causes dia Zoitvorriohtun ^ 40 that di; a Vontil 32 is immediately goachloaoen or littleatena goes into oino Droasolo division · The valve 32 is oo had, bia the pressure within doo Hoaktionooyatotaa aich again on the standard work pressure can surUokgebildot so ·! The time nohaltayatcm Be booohaffon that on the other hand you can then acfort lait an onderon üffnon dos valve 32 started, among other things oinon relaunchon pressure drop and pressure flow / ioinpula su result or the Kroielauf can not coechlofiDon coin »but oo can nornnlca Working deo drain valve v / ilhrond a short zoitdauor in front of the dncle doa circuit sugolaoson ooin » Mutai dna Ictstoro the Pail is, as soon as the standard arboitodruok has been reached at the Eruckrogelstolle iot, the line 46 carries the signal BU to the motor 44» which valve 32 The modulating begins to maintain the standard working pressure and continues until the timer registers the circuit uf start again IUQt.

In FIG. 2, the designations of the flow picture do not require any further explanation. The circulating system shown works virkoam in spite of the Tatoaohe, because one could expect that the vinyl acetate will lead to the unpolyoored oono & oron polyneriaiort and an impurity to the return pipe horboie #. ViB lines from the Katalyeatoroinführunße- or Siuopritapump · can be connected to the reactor at suitable points and a rope d * · Xatalysatoro can

90988.T / 1377

BAD ORiGINAL

of course also at some tunnel in the supply line to the reactor either before or after the EompreaBionotufe introduced bcw injected

In Fig. 3, line A illustrates the Iomporaturspitzon and -täler deo process gomUß Beiopiol I ₉ while line B a comparable process with an olnsigon introduction into the same Roaktorrohr at 2461 kg / cm (35,000 pai) and using 12 to 14 lines per Hillion of oxygen as a catalyst to achieve a conversion of 13 «5 ^. A comparison of lines A and B clearly shows that the different peaks of the curve for multiple introduction are similar to the single tip of the curve for a single introduction.

According to a further feature, the invention includes the use of a ttolaufsyotema in ethylene vinyl acetate Mioohpolyaorieation and the essential conditions for effective use "in such a system. It is easy to see that vinyl acetate, even at moderate pressures, tends to ^{polymerize with free radicals at elevated temperatures in the presence of} catalyst, and that the avoidance of such a polymerization in omlaufe systems is a considerable possibility. However, it has been found that a βolohe polymerization can be daduroh avoided that non doa Polynerioationoatron can gonügond Zoit and Röalrtorraun, vm to about 230 ⁰ O or absukühlon including, before it is discharged from the reactor and further

909881/1377

BATH ORIGINAL

in that one vorwendot oin Ablaßgofüß to separate the Polynerioatprodukt from the unreacted monomers. By providing sufficient cooling space against the dispenser, not only is the material allowed to cool down, but sufficient refrigeration time is also left to allow the catalyst to be used up and any remainder of the catalyst to be used The polynoron product is separated off into the drainage vessel, so that the monomers are released into the circulation through the Unlaufoysteia in a catalyst-free state dea catalyst is consumed (a fürVAbgabo suitable naxiaale Temporatür is about 250 ° C) · Usually, the last SinfUhrungspunkt before Abgaboonde of the tube to a Xemperaturabfoll from 40 to 6O ⁰ C or more in the tube to allow, after the 8pit & ontomperatur orraioht is · One could allow further cooling within the pipe according, but this would not be the most effective utilization dos reactor space representing · moreover is os weüontIich to maintain a certain Mininoltenporatur * to a mobility dos a hohon proportion of polymer product-containing stream to ensure · Daa polymer tronngefüß or discharge vessel in which doe product

909881/1377

BATH ORIGINAL

απ Endo dea Keaktors is geoancielt, is in • under oinon! pressure Uor zwiaohon Ataoaphärondrucic odor 141 (1000 or 2000 p3i) wilhrond of Lauioa reads at don beginning of a Polyisoriaationalaufea to 70, daa is jodoch ssweoka & Ug ^ ei oinon pressure of OTWA 105 ko / cn '

poi) botrioDcn and the Tanporatur in dca lot hooh enough »uc a loiohteo Auostcuon of the Pülymoriaats from iha au permit and lies in general in the Beroioh from 100 ° to 200 ⁰ C.

The invention will next be chondzmhancl of Boiopiolon whispers.

909881/1377 BATH ORIGINAL

Boioplol 1

Its polymerization was carried out in a reactor, where there was 1 lot of ice cream, but 5 different ulaantelsonons and a device for feeding the catalyst to the pre-diodic position along the course of the reaction tube / 16 inch) and an IUn ^ o of 50 "5 ei (192 ft.)" Sauorntoff was heated to the Hononoron before heating and the raw tube on two crochiodenon Stollon. You naoiietehondon V / or to vorochauliohon dlo liedendungon and Srßobnieao deu Voreuchoa;

Gooontatrununc kß (lba) hr 10.2 (4O ₁ C)

Scuiorotoff Consontration

Gov.Seile per Million & introduction to "A"«" «15 introduction to » B « » · «· 15

Inner tone temperature

Spitzontomperatur after inlet ⁰ O 250

tonality at ⁿ A ^w 215

Gpitzontonperatur according to ^M A ^N 240

Temperature at * B "'200

Spiteontonporatur naoh "B" * 280

Oil notol clay porature ⁰ O

Zona 1 11.8 B 39 ft) 215

Zone 2 11.5 x 38 x 190

Zone 3 11.5 »30" 180

Zone 4 11.5 x 30 "185

Zone 5 Ut? · 30 ■ J 180

About dta Beoktor kg / on ² (pal) 211 (3000)

57 # O

909881/1377

BATH ORIGINAL

Vinylaootat Gew, £ dor Monömerenbesohung 10 »Ο

Polyacrioateigonsohaftone

Diohto cVml «0.9270

Tensile strength at break kß / c = r (poi) 120 (1820)

Elongation at break i * 670

Sohnelzindex Deoigranm / Hinute at 190 C 3.7

The product of a qualitative kit is comparable to that obtained by feeding it on a single point under the same conditions. The inlet tube ¹¹ A ¹¹ was about 23 »4 π (77 it ·) from the inlet end of the pipe and the point" B "about 4 ^ 8 m (144 ft.) From the loader. The inlet tube was 12.1 bic 15 | 2n (40 to 50 ft ·) below the tunnels at the Spitzontenporatur · The piloted feed point was about 1512 α (50 ft ·) from the end of the pipe, so that the raw action temperature was about 6.0 η (20 ft «) lower than before the exit from the beaction tube »The polyxaerization was carried out at a pulse frequency of 5 seconds and a drop in pulse intensity of 105 kg / cm (1500 p8i) at the inlet of the heating tube.

Example 2

An experiment was carried out approximately under the same conditions as in Example 1, with the exception that somewhat lower temperatures were used for the acid off-supply or tollon, and the vinyl acetate represented 15% of the honomoric concentration. The conversion was 46 ^ ₉ and that The mixed polymer had a density of 0.9317.

909881/1377 ", .." ..

BATH ORIGINAL

take lot »with cuton result from the Kroislauf to be carried out again«

Example 3

was a Anaatz with 10 wt _# jS vinyl acetate in the IlonomQronbosohiokung and without oxygen in Hononoron-Sinlaßstrom, however, an oxygen introduction at 4 studs along dos Itoaktionarohrea executed. In 22s a change of 46; £ i £ O was achieved.

One of the advantages of the ancestor monopoly of the invention lot the fact that the need for the Vorliogono any UuQeror chain means of transmission and therefore the disadvantageous Ergobnleee undorso different concentrations thereof, and the need to regulate the concentrations can be avoided · Jedooh it can in particular Cases desired οein, transfer nlttol from different Reasons to introduce and such chain transfer agents as low saturated hydrocarbons, in particular those which contain at least 3 carbon atoms, and acetone can be in minor congeners or higher Kengen, such as 0.3 to 15 hol weight, based on the ethylene, uses word on. The method according to the invention is Mainly due to a dry ancestry or a method without solvent, geriohtot, and although small amounts of solvents or water may occasionally be present, requires the ancestor, according to the invention disclosed

909881/1377

BATH ORIGINAL

oiohtlioh not dio large IIongen an Bonaol odor arideren Lönungomittoln or Waoaor, dio for voroohiodono Polynerisationaroaktionon characteristicoh oind, wio I-Icngon grüßor alo 10 Gow, # dor Ethylenbossohiolcung.

Mo voratohondon Beiopiolo advance the Verboooorunscn boi dor with oxy-acetylene titration Hoohdruol; -Kioohpolynoriaation of Xthylon and Vinylaootat »jodooli iat dio invention also on Vorbosaorun ^ on boi dar I <Iiaohpolyno-

• trization of Ethylon and Vinylaootat, which by any other Eatalysatoron with free radicals, via usually used in the Itoohdruok Polyöorioation of Xthylon v / ground »inaboGondoro those Peroxyeauorstoffverbindungen which ^{have, which Zohcnunsatonporaturon 0} in the area of oxygen dio äthylenpolymerioationon initiates, goriohtot. Boiapiole of poroxy compound, which has often been used in such PofyRoriaations, or 2,4-biohlorbon-

Caprylyl peroxide
EqylperoacydfY lauroylperoacyd, t.-butylporosyioobutyrate, bonzoylperoacyd, p-chlorobenzoylporoside, di-t.-butyldiporphthalate, t.-butylporaoqtate, t.-butylporbenzoate, t.-butylporbenzoate, dporicunylporoxide, di-oxyloxy-butyl peroxide, di-butylperoxy p-Monthanporoacyd, Pinenporoxyd _t Cumonperosyd, and 2,5 Diuothylhexan-2,5-Dihydroporoxyd · Dio Katalyaatorcn were allGonein in oolohon Honconvcrwondot, un Polynoriaationowirkungon au result, which are equal to those oind _f dio in the vorotohondio beaohroniebonon

909891/1377

^ D ORIGINAL

gen been received »woloho In den aolaten Püllon nolnro Prozontottts are like those that are used by Gauoratoff

VühroJid eioh dio Boioplelo 1 bio 3 on VorboGOorungon der lilaohpolynerioation boziohon, woloho riodrigoro hormone, \ / lo otwa 10 bio 20 # vinyl acetate »boaogon on UIo conanto Mononorenbeoohlolaing unfaeoon _y lot dio nchrfaoho I at 1'J.tJOhpolynorlQationon, voloho hühoro Atitoilo an Vinylaootat, wio 2? ble 75 Oou · ^ dor Konoaeronbosohlokun ^ before »vondon, useful, although it is necessary to add the reaction conditions to special cases . ündom · Boiopiolavreino lot oo aufßnmd dor Kottonübortraßuncovdrlcunß the high VinylaoetatkonvontrAtlon necessary, with nlodoron tenporatures you can work »and a product with goniiccnd high molecular weight to ßrrlcunß, and the use of solo lower tone constructions. Catalysts with a sufficiently low 2er0otzungatenporaturon _f such as those mentioned in advance are selected köimon, vorauo.

The invention counteracts this tendency to reduce the molecular weight, while the catalysts are added in proportions that are not too high Ttawwanderung without higher tenperturopitson eu similar tone, which is usually present and when there is a high unwonding üUflroiohender catalyst is added to tinnal · So let

909881/1377

• ORIGINAL BATHROOM

been found that the continuous Polymerisationootron "polymerization in oinom tubular reactor of small diameter auoroichond remains flowable even Venn or oinon high Peststoffgohalt from the hohon conversion and having relatively moderate temperatures angowendot vordon ·

The Hiachpolynoriaationoniaohung is, even in the absence of remedies od. ^ Gl. gonügond iließfUhiß to the Polynerioation in oinor flowing Hioehung at Unvandlungen of 35 'and zuzulaooen / about "cofjar if only näßige PoIynoriaationatonperaturon in Boreich of 150 ° bia 200 ⁰ C are present · Eq iat to beaohton that the aforementioned üienpcraturen low eind ala those! which generally lead to considerable conversions in a tubular reactor in the naaaenpolynoriaation of ethylene or ethylene, which contains small amounts of vinyl acetate, as in Examples 1 and 3. In order to obtain a Mioohpolymerioat von brauohbaroa hohon Hololculargewioht su'er "Allgomoin is ea he" wishes to carry out the polymerization for the formation of Kiechpolymerieat with average Kolekularcawichtdn (as they are determined by oomotiooho (osmonetrio) working methods) in the range of 20,000 to? Q,000. at temperatures that are much more than 200 ° to 250 ⁰ C, is to

909881/1377

BATH ORIGINAL

Presence of large moons of vinyl acetate which liaisunc »form a microlynorioate of undesirably low molecular weight su · If a continuous polync-rioation by using effective cooling odor V / ünao-Auotauochnittcl and multipleo! is, ao that the liaouo of the Polyncrioation on i'cnporaturon is kept below 200 ⁰ C and only a corinßor CL'oil dor Polyncrication the Gpitsentonporatu? · ron in Boroioh of about 200 ° bio 225 ⁰ O orroicht, is co, however, too high Unwandluncon in Ethylon-Vinylacctatlliochpolynorioate hohon liolekularßowichta nit Vinylaoetatcohalton of 35 tio 75 Gew. ^ i or the like. cu orhaltcn.

909881/1377

The reference to the vinyl acetate base of polymers also refers to the polynomials that are present in the polymers and also include vinyl acetate before the international market for the production of ithylon-vinyl acetate-rtinchpolyncrioatcn with rubber-like sigenaohafton, ie. Wioderauar.rancnziohon naoh Auadehnung und gorinso "permanent rormanderuns · With» virlc · --lich low-lasting porn and crunsuei ^ onachafton it is necessary to have a vinyl acetate content of 4σ. ", And it may be desirable to stay ranging from 4o ^£ / to 6of4 vinyl acetate, UQ to get the best ZuaamnensiehunCQoißGnoohaftQn. Abgooehen of aoincr effect on the Sigenschaften Polyneren the Vinylacetatgohalt has to be applied also a direct influence on dio Polycorieatlonabedingungon "un high .'lolekularge \ 7ichte zusantmon high conversions received au. Since both hoho i ^J olymerieationatomporaturen and high Vinylacotatgehalto the liraeußung of Polynoron low molecular weight support, has been found, DAT orforderlich is to find a means of Aufroohterhaltung verhHltnioniiDij low Polynorieationetenporaturon in the invention,

909881/1377

BATH ORIGINAL

at wolchon the Vinylaootatgohalto in don Beroich of 35 bio 75 Gow ^ i ran

The main advantage of the laehx-fachon Katalyoatoreinführung Iiojt in its efficacy, v / onn aio £ oiuU3 dor invention for the scouring of verbouuorton Itovandluason of Athylon-Vinylaoetatniochpolyr & erioatkuutuchuk au £ 0-wculndot is in it: zuzu suotltzlio) ia ^ Katalyuator obon and dio right Umcobungatonporatur voriuoohon, un suaützlicho Polymorioation door hoho Unv / andlun ^ s zuzulaaoon · 3 cl einor beoonderon Auoführung is zuoätzliohor Katalyoator doa flowing Polymerleationootroa to ^ oHüßt after 2o ^ odor Nohr dos bofindliohen in r.onoaoron in oin liiachpolynerioat ucgow & ndolt been oind «

According to this Auofühnuxß doa ago a "rolynorioationükatalyoator" containing free radicals is used for low tenporuturon. Ea IaX to bonorkon that here the Auadruok "low tone quality" is used relatively in relation to the Polyuorioationokatalyeatoron «un ICatalyaatoron, want to introduce the poljaioriaation in the Boroioh from about loo ° or 12o ° to 1 (So ⁰ C ₁ anotatt in hühoron Tonporaturboro There is a high degree of polyaerieation tone poraturon by adding the catalyst in separate proportions, and the exotherms resulting from the constant polymerization

909881/1377

tie ^ to rejoin, vormiedon

Dio Tenpernturkurve οineο in operation ^ cn Hoaktora wciot, beao ^ on on dio middle Tcinperaturon at different points doo P.oaktoro general Tcmpcraturapitzon and -tiller on (wio p.3. In the Fitf.4 üo ^ oi ^ t iot described below ), Diooo Auoruhrunc doa Vorfahrona lcann feei ^ notor.veioo through don Zuaata doo Katulyeatoro at Stollon doo reactors, at which the average temperature is not higher than about 16o ° C, and allcoraoin at tunnels, at donon dio Z) urohschnittotcitiperatur untor ISo ⁰ C let ^ t, craiolt, whereby joclicho excess tenparaturon of the ßich er ^ obonden increased conversion are voriodon. VoriJU ^ Qv.'oiaQ place of the v / oaentliche part of Polyraorioation at temperatures higher niclit alo 2oo ° C otatt and the Spitaontenperatur in Roaktar not higher than 225 ⁰ C. 2oo to

been or ^ aniucho roroxykatalycatoren with theoor execution G ⁰ ^ UB of the invention, beaondora those poroxykatalyoatoren, v / which © ino polynorisation at xonporaturon not higher alo 16o ° C. The bcj aondero temperature at which the catalyst is filled, Khan ^ t of course depend to a gowioüon Auenaß of the booonderea catalyst liogt aboratory allßenoin in the range of 15o loo ° bie ° C, usually at about 12o ° to 14 ⁰ C.-O.

909881/1377 _BA D

can for example be introduced very well at 12o ° bio IJo ⁰ C · With a catalyst with a hühuron £ inloitun £; atenpcratur »beiopiolswoico t ^ Butyli ^ racotut, ea erv / Unaoht coin, boi about l6o ° C can be introduced · Preferably Vforden leroxydkatalycatoron before; vondot, wolcho oleh at temperatures not higher than alo 16o ° C zoruotzon, whereby the decomposition temperature ala dio 2QGperatur, if the half-ortzoite affects one minute, becomes anconoi ^ rion. To diooon Katolyaatoren gohüron bobeispielDv / oioo 2 _t 4-2ichlorbonaoylperoxid, Caprylylporoxid, Lauroylporoxid »t-2utylporoxyioobutyrat, Denzoylporoa ^ d, p-Chlorbonzoylperoxid, Dl-t-Butyldiperphthalat and t-Butylporacetat *

One of the door parts of the application oinea thin-walled, lan ^ soBtrockton tubular Roaktoro with kloincm JXirch-KOaaor let the smoke distribution of the exothermic Heuktionov / ärxae · Dipping the reactor in an oil bathtub contributes to the heat dissipation by immersing the reactor in an oil windshield. Dio Badtonperatur uoll jodoch not be so low to vorliindern or absubroohon the polymerization "to effect the i ^ olynorisation (jeraäß this AuofUhrung the invention, it is erv / Unocht, bath temperature on la Boroioh of loo ° to 14o ° E au use·

Xn Pig "4 illustrates dio line C dio ~ Tonporatur acute and -tälor a method, v / olohes zwoi catalysis

909881/1377

BATH ORIGINAL

oatoreinführunson uofaoat, while dio Linio D οία represents pre-Gloichbaroo procedure with olnor oinzigon Sinfuhruns. The zoIt is divided by the location dos Hohrabachnittos. (Pipe number) in the aua 2o pipe on beotohonde reactor. Dan's ancestor, which is shown by the Linio C, had a 32 ⁱ / 4. Sin Vorgloich dor lines C and D 3oi {jt _t that the peaks "with a multiple introduction of the eluaigou peaks of a curve with an οinsicon addition ο very similar ·

The following Boiopiele explain nahhor diooo Auaiülininssfora the invention·

Example 4

A J? Olyno ± ination was transformed into one similar to Pis · I Reactor carried out, but not with 5 verochiodonon (51mantol3onen of equal length and with facilities for the Introduction of the catalytic converter on various greats lengthways deo reaction tube auo ^ eatatted. The reactor was from ßowundenor Porm and had 2o ala "pipes · * boaeichnete Abechnitte, with 4 pipes for each of the ülnantelzonon. That Reactor tube had an internal DurohneoQor of 7.9 approx (5/16 in oh) and a length of 58.2 m (192 ft.) was put into the reaction tube at two tunnels The catalyst was not added to the monomers

909881/1377

BATH

lanoonde dos reactionarohroo give up Dio following V.'crto explain the terms and Ersebniooo doa attempts;

Oeaantoturung kg (lbs) / pc. 10.5 Bon.-ioyl peroxide concentration

? - ^T ol / mole monomorea

Introduction boi "A", ropes per pillion, 12 LinfUbxunß boi "B", parts jo Willion 9

Internal temperatures, ⁰ C

2ani> erature at "A" 125 °

Peak Entcpnporatur after "A" 21o ° Toilet at "B" 12o ° Spitaentenperatur after ^M B "2oo °

oil cantol torature, ⁰ O

Zone No. 1 132 °

Zone Kr. 2 132 °

Zone Kr. 3 12o °

Zone Xr * 4 125 °

Zono Kr. 5 125 °

Vorweilseitboroiohe, seconds 15o - 3oo

2

Pressure drop across the reactor kg / cm (pai) 281 kg / cm (4ooo) Impact size, kg / on ² (pai) Io5 kg / om ² (15oo)

Transformation, ^

Vinyl acetate, f »oow. the mononore bust

909881/1377

BATH ORIGINAL

- 43 -! bZUZ / /

LIo polymerization was continued continuously for more than 17 hours. The guide a part "A ¹¹ was about 7» 6 m (25 ft) from Sinlaaaendo dos Ilohroo and the import unsoatollo "B" about 33 π (125 it) from liinlaaoondo · Probon doe aich ergcboiidon Atr Vinylucctat-Iiiuchpolyncrioats has ton oinon Viny Iac ο tat; johalt from 45 to 46 Gow.i ', a Scaolzindox (Doci ^ raan / lUnuto "boi ISo ⁰ C) of 13" bio 15 tuid ο ine 2ichto of about o, 97 · you good quality and that c ° öiti ^{ne <t} e hoho MololculorßG \ Ticht dos Vl Qchpolynorisata is represented by the following ISiijonBchafton oinoe preaoßoformton woiDon Ilatoriala

5oo ⁱ ;> Kodult kß / cm ² (poi) Io5-115 (1500-I600)

Tensile strength, kg / ca ² (pai) 162-169 (23oo-24oo)

Stretching, # 57o

Permanent change in the pore size l _t $ 7-8 I ₁ percentage of the expansion that was not recovered within minutes after the breakage.

The molded mass was subjected to a heat treatment of 3o minutes. at 16o ° 0 (32o ° P) of the following Zuu oma onü et aurig formed t

909881/1377

BATH ORIGINAL

GoY / .Toile

Uiaohpolynerioat 400

Rutile titanium dioxide 2oo

AuojcfiiHtco Silioiumdioxyd Ao

Dicunylporoside on calcima carbonate 16

Beiopiol 5

Using daa in Bqiopiol 4 "bopchriobonon Roaktoro vrurdo a polyaerization as follows by & aführungi

Gooamtotrömuns, kß (lba) / hour 18.5 (41.2)

Douaoyl poroxide concentration,
Mol / i.iolniononicrea

Introduction to "Λ", Toile Je Liillion 9-16

2inTührun £ i boi ^W B ^M , Toilo Jo Millioa 9-16

Iiuiero Xcapcratur, ⁰ C

i'enperj-tur boi "A ^w 125 °

Top temperature according to "A" 215 °

ieräiporatur at "B" · 13o °

3pit2Gntcmperatur after "Β" 21o °

ülcaatoltönporatur, ⁰ C

Zone 1 132 °

Zone 2 132 °

Zone 3 12o °

Zone 4 132 ° - 123 °

Zone 5 90988Ί / Τ377 132 ° - 123 °

BATH ORIGINAL

15ο - 3οο 352 (5οοο) 1ο5 (15οο) 31.6 4 5

Lingering soitboreich, seconds

Pressure drop at dom Heaktor, kg / on (pai)

GtoD size, kg / cm ² (pai) conversion, f5

Vinyl acetate, fi wt. Of the monoraeron

boachickung

The resulting Hi uchpolyineriaat had hardened oinon U indox (dooigrann / klinute boi ISo ⁰ C) of 13-17, oino density of about ο »97 and a vinyl acetate content of about 45: V / onn eo, as in case 4 or wilmebehandolt wurdo, the zucfeati ^ koit was 15o kß / oia (22oo poi), the elongation 54oji and 5οο? ί ilodul 125 kg / cni (Ιθοο pai)

In the case of a polynerioation with doroolben Hononoronboacliiolcung and under approximately the same conditions, Jodooh Edt Siniuhrung the Katalyeatoro was carried out in only one place ₉ the conversion was only about 19 ^, and the effective reaction extended oioh over a much smaller space in Reactor.

As stated above ,, the method results in high conversions to enjoy some of the invention kautschukartlgon ethylene-vinyl acetate Uiochpolymorieaton of good tensile strength and good properties with other · -It is erwünacht that Polynerloution β auoauiühren ο that can cure at a _t vale in Beiepiel 4 , Tensile strengths of at least Io5 kg / on

909881/1377

BATH ORIGINAL

(I5oo pol) and Dehmm ^ on from nindoatc: uj £ oo; ' gets · Dio :: itichpolynoriaatkautoch. '.. kartcn nit ^ eel ^ notcn TU ^ on ^ chafton have all ^ or.oin znhlcnnuOlgo Surehnohsittnnolelralarsev.-ichto in the range of 2o ooo bio Jo ooo (by 0 »r.oao £ cr. e; i!.: cn) and oind by da «woaontlicho foals, borrowed Polynoriöato ait niodrißen Itolokula ^ cewlcht Bit übercrdurohoclinittliohaa Vinylacetattfchalt β koruizoichnot. Beiü ^ iolo7 / oiDo has oin Äthylen-Vinylacotat-Kiüch ^ olyniorißat! Cautnc}: uk jutor quality in Beroioh from 4o - 6o $ vinyl acetate with extraction nit "ethanol oinon. Gewiohtavorluat vonnjcht r.chr alo 5"'· A eolchor can easily foat ^ ootollt v7Grden _t inden nan ο, 25 g Kautochukktfrnor oine Utundo long in 75 nl "otlianol kooht, and then oino sv / oito Kxtraktion nit friochom ZSothonol and then at Ho ⁰ O trooknot ·

With a bonus on the Solinolzindicoo iat footzuätoilon, that I also keep the KiachpolyitiGrioatkautochulcarton due to their pre-periodic VinvrlacotatgohaltQ similarly vcrochiedcn. In the case of Kautachukarton not 4o bio 6o Go \ r ^ Vinylacetat iat oa Jodoch allgonoin erv / Un3oht _v 3chnolalndiooo not higher alo 2o Dooißrana / ^ iinuto (boi 15o ° C) su have, and dioae Sohmelzindiooo will usually be above 5 -Deo "Furthermore, the use of Räuigon Senporatures in the process of the invention of ethylene

909881/1377

BAD ORlGfMAL

su orsou ^ en, "at wolchon π ohr v / onij Vcrav / ol ^ unc außor dor ^ onlson inXolfjo ^ cr Acotat- (jruppon occurs; as a result, dan /d.ichpolyneriaat liijön— ccharton, dio aioli auo hochlcriotalliaiorton Aboclinittcn, dio in. Abotündon by Acotatcruppon uatQi-brochon are, raised.

909881/1377

BATH ORIGINAL

Claims (9)

Claims ■ ί) Process for the copolymerization of ethylene and Vinyl acetate in a tubular reactor at temperatures from about 2oo to 3oo ° C and high pressure in the presence of a Catalyst, characterized in that the catalyst is used in the polymerization without a transfer agent introduces in at least two different places. 2) Method according to claim!, Characterized in that that oxygen or a peroxygen compound is fed continuously as a catalyst in such a way that a polymerization is brought about and at least a peak ■ temperature occurs in the flowing reaction stream, the reaction stream is allowed to cool, and then more Catalyst is introduced to bring about further polymerization. 3) Process according to claim 1 or 2, characterized in that vinyl acetate is used in an amount of about 7 to 2o %, preferably 1ο to 2o % _{9 of} the monomers, based on the polymerization in the presence of about 5 to 30 parts of oxygen per million on the weight of the monomers, and introducing a similar amount of additional oxygen downstream from the peak temperatures while maintaining the reactor temperature above 200 ° C. 909881/1377 Documents (Article 7 SIAbS ₁ ZNr-VSaIZ3 BATH I vJ Z. U JL £. I. 4) The method according to any one of claims 1 to 3, characterized in that additional oxygen, preferably in at least three substantially identical Kengen, is introduced into the reaction stream where the temperature is in the range of 2oo ° C to 25o ^c C. , 5) Method according to claim 1 or 2, characterized in that there is vinyl acetate in an amount of 35 to 75% by weight of the monomers applies, with the main " part of the polymerization takes place at temperatures that should not be higher than about 2oo ° C. β) Process according to one of claims 1, 2 or 5, characterized in that 4o to 6o wt .-% vinyl acetate containing monomers is reacted in the absence of solvents with a peroxygen catalyst with a decomposition temperature not above 16o ° e, with peak temperatures not ^C are obtained over 225 C, allowed to cool, the current flowing bouquet and additional catalyst at temperatures not related about 15o ° C and in an amount of 5 parts by mole to 2ο the MII lion * to the monomer feed, introducing. 7) Process according to claim 5 or 6, characterized in that the catalyst is introduced after about 15 to 35 % of the monomers have been polymerized, the residence time being 150 to 300 seconds. 909881/1377 .BAD ORIGINAL - 5ο - 8) Method according to one of claims 1 to 7, characterized characterized in that the reaction is carried out at pressures above 1050 kg / cm. 9) Method according to one of claims 1 to 8, characterized in that the separated volatile Monomers returned to the inlet of the reactor without substantial Polymerization can be returned on their way. 909881/1377 Read more