DE1520320A1 - Process for esterification in solution of polyoxymethylene - Google Patents

Description

PROF. DR. DR. J. REITSTÖTTER r OL · υ ο c u DR.-ING. WOLFRAM BUNTE

8 MUNICH 18.HAYDNSTRASSE 5. FERNRUF 53 47 12

Munich »19» * ftai 1965 a / 6938

ron siur Merest β rung In Xtisttng of

t CiBSMBtM CiDCTCHM SStVMIt

The ürfliadaag acts on the esterification: from A '

Innbonondcrö let ^ genetanä dor invention oln VoxdToliron snr Veroöteruno la Χΰβοης «that loicht kontlnuiorlioi. is durcuf'iiirbar and Gloh boson <loro for ^ alyox ^ otnylene iait iioäor iCrietalliiiitttt (About 90 #) nacii weloi _; .isa .Vostuhseft ▼ tire-ateit * Polyoas ^ aetlLylene with stability orüolteii can be

As is well known, itUnnon Polyca ^ motbyleiiOt ornalten aus oöer Hrloxan.naoh Vörsciiioänen & n PolymeriQationoveria ^ rea iait äer fol ^ ondon 'älooaolne

HO -

y / eräön, where ß «aee or stoff or oi & e ijeaeuiGt the Polsriaerioation ala Thorminator or olo Xronef eralttel elnöebraciit v? Urde ·

Tsar Verfaeeoorun ^ the tiiexsiiaclien -ötabilltllt of Ions aUoaon Ue ondotäniHsen% dröÄylena |> p © odor one of the bokanntcoton methods helps to be-in of the esterification at the end of the period

909 815/10 2 2 ~ -

BATH

organic anhydride, 2.1. Acetic anhydride "

Can contribute to the DurohfUhrunß reaction of this wide variety of Vorfahrcnobedin 3unson applied v / erdenj may, in a heterogeneous system worked been v / oboi that feote polymer ββ in contact with dom liquid or gaseous anhydride * · introduced V7ird _v or in a homogeneous system "wherein dos Polymer dissolved in anhydride v.ir-3 »in the presence or absence of Katalyoatoron and VerdLinniin ^ oiiittoln xara at 2eraperaturon between 60 and 200 ^ 0»

The olyO3symeth; ylonG with high Kriotallinit'it (over 90 *>) the boiepiclswoino from trioxane or by iOlyaerieation of xorualdQhyd in a large podium are ochuierig zn in front of ο at cm; In order to recover a holien iroreatoruni3ssrad ssu erroichon and hinroiciond stable iOlymere tön, the polymer must be dissolved

■ Venn 3 · Ε. Acetic anhydride οίο Voreetorun ^ oiflittol r; ird _f the polymer can be aoetylated in I »Uouns by: irLitaen der idiBchunc on oino ^ emi> er £ itur to over 170 ⁰ C,

33oi implementation of the procedure »inobcoondore im (jroaoon However, the difficulties differ to make the seduction uneconomical "

The main difficulties can be resolved as follows

1 · During the cooling-off period, the polyoxymethylene solution is crystallized the polymer) forms a deposit on the In the interior of the apparatus, after a certain period of time ■ 7'lrmeaustQuech prevents what would cause frequent discomfort

necessary v / ird ^ .. -, - -.

909815/1022 BADORfQlNA ^

2. Ee let difficult dl "Granuloaetrie dee crystallizing polymers regulate ssu! νιβηχι dee polder in eoLr fine ε given and swollen ^ orm crystallized »the filtration land dae subsequent washing difficult.

3. B is notwendiß high Verijliltnioson of J ^ itis eigkoit bu solid work au dor suspension of the polymers, in particular Äio naoh dor crystallization leiciit ¹ OXN toh hardly flieesbaron swollen Maoeen anninnt "adequate fluid it ät verloltion au ·

Ee mirdo now £ <j £ undeni that all clioßo naciitoile which can be avoided at dor etyliorung in reading auitroton, if one is the fr alii oat ion dos X ^s oly.aers (auo der Löounc) at high temperature (laugh at 100 - 135 ⁰ C) duron and the ^ öcurv; from the Äoetyliörunsotßiaijeratur jaur Krlatallißierunßotemperatur duroh iuiechen with a cold riUoßir; coit cools and dos cooling dor warm LUawic at don iuotallflüciion des Kriotallieators τ avoids.

The lCriotallioation dea SolysiexB from the Löeung at temperatures awieoiien 100 and 13O ⁰ C allows to obtain eo crystalline aggregates, which are hardly swollen and easily decanted from the liquid phase kßnneni the product is filtered and without any iJöhwieriakeit sev / ash _t the drying takes place Soneil and dae received iailver lot hoaaoc; en and

Di © tiriotallioation tiOi niodrißon l'cüaperaturon leads andororoeits su fcinvortöllten i'rodutctoni lie otark ßequollon SAre and only oohr lanssara or at all nioht from the flüacißen phase by Dokantloiron cetronnt werdon könneni Piltration and washing oind Bch ^ ^ lcvlß and Wiihron of -'rooknono iverdon compact

, 909815/1022 '

BATH ORIGINAL

hard agglomerates formed j aid ale jPlUeiitlßifraktion «ar soar lüiiQBoa. hand over·

Cooling the warm foliage tables with a cold interior tempts the formation of drainage runs on the inner veneer of the crystallization organ. This is easy to explain if the solution is to be exchanged over a cold motall value, it is πβηα. ^ ia ^: ~ rietallieati on bofinnt v / ird the formation of oiner pol ^ aerablar ^ runc on the Italton ü & aäeti it form Qlcli dalior films on the inner wall en dea ßatore which quickly wacüsoa until the vuintieaustaueoli miochcn der and the warning polymer lion ^ is completely undermined.

Duroii geeisneto i.nderun ^ der Semperotur der Kdten Fluid or dee Veriiilltnißoeo von Imlter HUeoi ^ oit sm warner liöeruno ifeann the Kriotalliöationstoaiporafiiir loioht and externally controlled «earth

Mixing the warning air with the cold ..FlttoBlgteelt can Vortoiliinftcr.7cioG by drying the polymer during the Hand filtration of the separated fluid is carried out dieoe .cioe v. is not contaminated with alcohol.

KUhlfltiooigkelt can also be used other fluids, β «Β · aliphatic, cycloaliphatic or aromatic üoiiloavaoo'rotoffc, AtIiOr ₁ ethers and ketones»

Dae erfinaunßsseciaooe Verfaiiren can entrroder chargeiwoioe or are carried out continuously "it eißnet custody but be" sondere FTIR ^f "the kontinuiojfllciie Ärbeitewoioe the aue komaerei ·" rush ^ rwäßuncen intoreoeanter is.

909815/1022 BATH ORIGINAL ~ ⁵ "

2UR beoseren Illustration dea öegenjjfeainlGS dor present invention lot in the drawing, the äobeoa a continuous process indicated · XQtua nan bolopi9ls>r; EIGE ait rclnea Aoetanhydrid and Pol ^ o ^ Aoth ^ lenpulvor operates the anhydride 1 and the polymer 2 are continuously supplied to the Vischer 3 fed

The suspension obtained -iirr! in a ^r .'imea'iotauonhsr 4 Q in which the mixture is set to a temperature above 17O ⁰ C,

175 wid 210 ⁰ C er ^ llnat wlrd _f and in it ainreiehend long for complete dissolution of the polymers vorbloibtj la its can dle & e tent sv / iociien 1 and 15 min oGisianhcn, depending on the granuloiaetrie and the urology of the

then arrives at don ^ Gaktor 5, which at a peratixr Above the ^ riotallioat Ions temperature deo Polymers auo the solution held v; lrd

Since the crystallization of the iolyiasr3 unto? 135 ⁰ C begins näxa-IICL at a temperature 'lie noticeable borrowed is lower than that but I <6sanc bon ^ tirjte MinlrialtGoiperattii ·, J: ann; üe Acet ^ iiorunßo response in Xgoun ^ even with ^ enperaturen durongefUhrt verden _t under the J ^ sunuetcaporaturen

It therefore icann the Acet ^ lierunsßtGaperatur la section 135 and 210 ⁰ C can be selected and the economic accounts # eilzcit in neaktor can Depending on the ^ rbeitsteaporatur 1-30 min concerned ·

It is clear that the dissolution and reaction:;; loiciiceitlss instead of * »can take place. Bs can i? duration exchanger 4 and reactor 5 through <ettae> elneicc apparatus Terl: be f3rpcrt ·

BATH 909815/1022

The LUouns ^ i * a ^ ociporatur from 135 - 21O ⁰ O becomes in the 6 old that from dea l ': aik 9 kaaiuoMen cold VerSUnnungaaittel

2m »^ Gr ^ ilionang dor feistallioationsteaporatar Sa bischer 6 can ontv / ödor dac relation of the iiciosen Locuns si & i Vordtlnni oittel or dio SGuperatur des Verüilnaingcalttclo j ground.

On; ieae i * iee can sowoid the i

alß öBch daa TTerhilltnis von i? oototoff au Piaooigkeit Im Kriotalliaator changed independently according to uasöh tuii

/ onn partig aviGioc el ie hot & oe £ 83unc ^ with an isupcratrir lie a little over -3er KriDtallisationoteaperatur lies in the ii β {jelan ^ t, can doo cold ver-iOnmin ^^ ittel in the 10th low to a temperature vorer.vilrmt, ila for example under "uvli> der fMr die Kriotallioation ser / üJalten I'eaperatur lie ^ t · dnf this -oieo lot it evidently ^ uch ^ ron se Vbltciina an before" · ätinnun ^ aalttel au use un3 Hq Bol ^ -aerLiunponcion after su fluid meieren

.Vände doe Kristallioatoro afXcoen -vara kept cordon around the crystallization dos Polymers to the. "Tadon and the formation of? Ilms and deposits to vermeil cn; lies can aerden achieved by £ pte Ioolntion the * ppaxutur or lurch circulation in one !!. Usoickcitanantol a Fl Ils sicke it under the same or a etwae htSheren ^ eaperatur "^ ie they f: ir crystal ·" ation £ chooses *; urde to the / irneaDf all in liavn ssu koapenoi "r" n *!

BAD ORIGINAL 7 909315/1022

The precipitation dec polymer a * ds of IiB-Bunc can, in a one * his Krlotallicator or UEI several ravstordneten in series crystallizers a IOC "· are held 135 ⁰ C ile at cloieher oäor verecMeßcnen temperatures in the range swisciien eta? Be performed. If aeiirore i-ristallioatOren are available in series' that cold VoKliiftmmoffliittcl ssu uinom oinsi- ^ n KriGtollisatör s'efüiirt or it can v / srden in the Vorocliiedenen tlrietollicatoren v / srden

Sfach-4r: r Kri ^ tallirintlöh "inV-3ie J ^ ol ^ aepcuDpcanion in cinon Sank 7 gebraeiitf dßr ^ o ^ oboiienfails provided with & incm Spüloystraa isti da-'dte Kriet alii oat ion deo iOl ^ morB berrita _t Iot iot The opening continues after any Bystoa ßekUiilt ν / earth "exampleseweioo iibcr oinen" iimeauatauDcher or because the suciel tank rushes to an EUblsciiliingo or oinoni iCU

tel is voreehen or pierce dor yu £ 5ponsion approaches a ETIT a lower 2 © nperatur.

3> ie Sticicnaion can on ^ artntei ^ eratur odor ai2f rine. etsrae höiioro i'föäperötttr brought ti orden · JSs fecötn ^ oßü di "AuCN at high temperature leieiit filtered ^ erdenj EÖ Jcann therefore äuspeneion after crystallization directly without intermediate cooling are z \ w filtration ßebraciit.

The Polgomer was from the önopeneioii-in dor Piltoroinriohtuni; that with the Aetylian "resolution iopr ^ gnated -H . xitvd waiter ßewaaohen vatä, ßetrooknet ·

The filtered Aeetylieruncolosanc ^: is an ^ amraoltank 9 ι from Nolchaa a 2c ü sirr - iod orco ^ Innung 12 geeohiokt ₉ and another ^ oil zvm Kriotalliaator 6 for the cooling

909815/1022 'BAOOmG ₁ NAt. * -

"is returned" to the return-led! faction canoe in exchanger 10 to the ^ ice emergency ^ temperature $ ··· cools or desires · orden ·

Ün a niedriüoo VerLülinia from ΡοοΐβΐίοΓί au £ Iüeüi $ coit im

au erhultien ₉ iauct: a ^ rooee ^ ence to Äeety «· riickßorUhrt» whose seapcratur ooll niciät weeantlich imter der g

ni ondorcroc-itc mnec 'ie be scktUilt on niodrisö Sompcrnturen, call the r ^? iokge rUirto üence noriivi ict. In the oooa i'all vcrUn & ort not evidently the pre-cover from solid to fluid, ~ l: cit in the crystallization stage c®ri »ß. Above it primarily to the Aeety-30füjtirton S

The & ii £ lsoQJiu tloo I'ol ^ TierD in dor Acetylienxn ^ lOminc will be v / io obon seoai.! Tb © i high Sompöraturon, but 170 ⁰ C durenge »leads y insbeqondore at 'ienporaturön which itbor lie to the boiling point of AoetanJaydridß and < The apparatus is * therefore the pressure is operated on

However, © γ pressure is not a critical factor for carrying out the demonstration been det, the higher plumb ale the uompfdruok of the flueaigen Phaee

It is, of course, not necessary that the apparatus be operated under Or -ick be carried out under atmospheric pressure

909315/1022 "bad ori ^ l" -9-

Dao beseliriebone may eolbatveroiiamllioii durclige.fUb.rt are made using i ^ otanhydi ^ id either roiii odor In ülechun alt organiealien I * i8ungöiaittelii oovrio in the presence or absence of esterification catalysts or onäoren

Ißoungsaittol kUaaen aLipitatiocliö, or a-rotaatisciie ^ OiilösHRraßösi »

nod ketone ©! a * B · iloptaa, 3on3ol _f toluene, xylene, r, ekaline _t methololctyl] coton _f but ^ lasetat vorv / oMot

Other cr ^ anic acid anhydrides (in all ^ cmoinen the anhydrides Ton alipiiutiocriGn odor aromcv-tlschen Karbonaluren «s * B · i) ekan— acid anhydride,

kannnan anotello of acetic anhydride used wordonj in case © uvlqb jedooß deua ^ ov /: üilte anl ^ drid sins jute for the ^ ol ^ jaor at 2 caperat vr en about 17O ⁰ G

The in voriierüOäüzidGn beecürieböne kontuaiuorlioiiG offers the advantage ₉ that the formation of abla ^ oases in apparatus is avoided, because the granules of the acetylated polymers can be regulated and that the anlijrdridiaen ^ required for the preparation can be reduced. which means an economic advantage to the man

Di "aar Verestorung the terminal Iiydroxylgruppen the Polyoxyaotnylen & ettea needed AnhydridmenßO eats auoeorordent" · LiOH i'jQTinc (some Gov.'iohteprojaille with - ^ eauo on the polymer).

BATH 909815/1022

~ io ~ 1B2Ü320

^ s iet, Jodooh necessary with hoiuon Iforiüiltniaoen von ^ keit to I ^ eatsto? f au work from etvia 10 ι 1 to tier IiUaung dine ixinreioliönde Fluiäifcit, oo then this auroli BoIipö, pumps u »d {; l» ordered viexii I

TTor «lor ^ ootylierun ^ viovden Ήο iiociilcriotallinen (90 * »100; ■) in aoetic anhydride only came fuiaoqnolloa and eo bohalt dalier .lio üuapenaion auoh ait soia? .'serlngon YgriiUltnisoon of i'lüsni ^ eit su ^ oobsäoff (a.B. ItI or below) oine relatively low viscosity

T) Io naeii Auilusong 3eö Pol ^ ueve Ta ^ i -tiiaperati ^ on iibor oriiültenon lüsun ^ cn 30i _H ; Gii at high Scuperatures ^ß i ^ relatively low viscoeiK / lt imßh with very low VoiciUlltnieoen from? Ltt0Diotokoit au r »IjoiopiölGwelso from 1 ι 1 odor also including ·

Haoh crystallization seist äaa precipitated XoIj ü «a Oueßanjspolyaor sino niadriGsrc Bristollinität (about 80 5» less koapakte crystallino A ^ re / jatoj ola Polge iiiövon

ös bewiichtliciio ^ lLtcaifjkoitoaongen tind oa are therefore high fluidity for the bus boarding house Ratios of H, llcsi: ^: clt to Feetatoff 2 · Ώ. about awioolien IQ t 1 and 30fl

Been Goait ^ Uo iiQlien TorhJilSnisso of I ^ ^ Usüi teit su dtoff mainly fe <9n0tlgt "" a, the 3ueponsionon in Rpiotalllsationnstufe and AEEN fol / jsnilen Stuf on nioderviokoö and fliesefllhig sft Nachon.

Haoh erfinduncogenäasen the method may include TorMltnis of pills l _t 3k3it stu solid nacii .Vunach wHhrond dor Kriotallioation

9098 15/102 2 _ßAD

- 1B20320

des Pol? iiiera ßeändart who & on, unabhliftjic; from don at dsr Liaison level

IvS is therefore possible sur ^ cotyliürun /; oino ^ noponoioa nit a low denomination of fl'dosi ^ inlt su Fcctetoff ₉ for example about Aryan Iu t 1 and υ, 5: 1 au oondon and iiacli.; unecii in dor ^ riatallioationsstufc üas Vcriaiiiiiis from jteeit au j-Oötstoff Juroh Vordtiamuit. lait dor naoh ü & r ^ rücltgei'lüirton «PlUssigkoit su eriiüLonj on cliose .eise fourden the boi öon procedures üonUtisten kongon Aootiuihyüria noticeably reduced ·

Di "foloQJoden öoiöpiole SOLION explain the vorliecondo ^ rfiaduos without daoo this, however, should have been limited to} the uodin specified therein. '^ Ungon have lcMrXlcL · illustratiTen word because sahireiche.-OdifilNationen Mur ^ ioh gind _t without the nature and advantages doa Vorfatocns differ and lie depending on the useniletoa tol ^ iaör and veriioMeter flUesifrJcGit acüwanlcon can «»

The acetyloxymethyl used was manufactured by Polyjaeris & tlon from i'orLiuldchyd in v. & eaer also düiu in the Itulieiiiocnüo, patent » echrift 646 437 written Voi-fohren received ·

The iirietallinitiit dee ϊοΙ ^ ίιογο, beetioist by Kontßenanalye · is about 100 ^ (beetimrat after that of G, P. Liataaer _t T.Ä.Koch and Jrutiitney, J. Appl, Pol ;; AöR ϋο1 · l ^ ₉ and 11, Ur ₉ 2, Selten 169 - 17B ₉ 1959) described method; the l

beotlütat aa acotyliortoi; l'olynot at 15O ⁰ C in with a concentration of 0 _f 5 g / 100 oil amounts to 0 _f 8 * the

909 8 15/1022 -12-- ^

BAD ORlGiNAl.

Loss of attention at 16O ⁰ C at the £ & ft bot rises 40 - 50 $ based on the AusG% 0 £ cpxo (clock per hour

Basically the polyester is suspended in pure acetic anhydride with a volume of 1 ι 5 of polymer and anhydride. The suspension is continuously under a bridge of about 5 atm ledι 'lie with D on 18) ⁰ C suffered lot.

The Verwoilnoit dor uiGohun? in the iSoiilange was 15 min Oil the cloaks verlacoenäo l ^ Jminc ^ ird ilber üin i <osu3.1erre til, dtcroh weloliöc the r> i * uok from 5 to 1 ata cosonkt küxin, in an old oinoa saiiper provided crystalizer brought*

In the Kjfiotulllostor the üieaperatw by supplying Aoetaa · iiydrid at lOCPc swiechen 125 uaö 130 ⁰ C {rolialten, Y / obei that Teriiilltniß 2r,; ioc.iien tier uemon PolyuerltSoun ^ and aea as kai ton Vr-röittclnni. irkenden Aoet & nitsrdrlä about 1 t 1.7 botretzti the ro-formed Pol ^ fnercnapenoiOA liat a preJulnis of Feetstoff sir. TÜ.üsoiγΜit of about 1 t 15 and their TemeSleelt in Kristallieator is about 30 min »

The PolTuermiepenoion then wipfl in DNEA v / oeeermaatol provided Tc "r. 40 -? 5 ^ ⁰ C gefcUlilt- wnd ßolilicöolioh in a centrifuge filtration ·

After drying, the "ossongo product" is "bumped", • tv / Q 95 & ew "5" aoctyliortos polymer is obtained, since the ethylated polymer obtained from this gives about 30% criotollinity

• 13-

90Π815 / 1022 '*

BATH ORIGINAL

by ßuntgenanalyee and aeigt a <* ev? iohtsverluDt at 16O ⁰ O at the loft of less than * 0 _f 2

The olj-mer used in the foresighted Belopiel is suspended in T&M acetic anhydride with a weight ratio of about 1 tonne of polyer to anhydride of about 9 kg / h. Suspension is continuously fed under a pressure of 5 atm to a stainless steel drill snake which has an inside diameter of about 6 ma and is heated to 190 ⁰ with steam.

The lingering time of the Miöchun ^ in dor Uchianße affects 3 ^ the solution etrikat after the uchlanoe in oinon ro ^ irformigen -Heactor made of stainless steel with an internal temperature of 30 OBt ₁ which is kept at 160 ⁰ C by an Ola coat ι the «Since the Xtä & anQ im. Reactor took about 20 minutes.

The view of the reactor sseMe i «6etttns i7irä about oin ite j til, whereby the pressure can be reduced from 5 to 1 atm, in brought one with an HOhror to θ © honon crystallizer

Xa Eristsllioator, the temperature is ^{kept at about 120 0} C by adding acetic anhydride at IuO ⁰ C. The ratio between the warm Polyjaerlüaunß and the anhydride acting as a cold TordUnunmittel is about 1 I 21 the formed polymer soup has a ratio Peetetoff su Liquid of about 1 t 11 and its residence time ^ crystallizer is about 15 sin.

BAD OFHGlHAt

909 8 15/102 2

· 152Ü320

The polymer ouopono ion V7lrd in a tank provided with an air sirculation * »jacket is further cooled to 100 ° C and then filtered in a centrifuge *

When dry, about 97 # (especially on the product) of an acetylated polymer is obtained which, as determined by X-ray analysis, has a crystallinity of 80 # and which at IGO ⁰ C on the i "uf | hour has an ev / ichtoverlat of less than $ 0.2> suffers

Bob Polymer of the *? Ype? / Ird used in Example 1 in an acetic anhydride-xylolcilaGi-un ^ at a ^ cv.'lciitßvorliciltnlo von Poller au anhydride of 1 t ?. and olnom ^G ov / lohtsrorhaitnis von Anüydrld au xylene of 1 t 4 suspended «

The temperature and times of the Löouiv; » Aoetyliorunn and Kriotollleatlon eowle the other terms and conditions and the meat as described in Example 1 "

The olymersuopenoion formed in the Mrlotal11οator has a ratio of solids to a solubility of about 1 t 27

Bach cooling, centrifugation and drying under the game in case of 1 · specified conditions are 96> (besoden the kxmgüneß product) of a aoety 11 locate polymer obtained dae

• ine crystallinity, determined duroh BCntgenanalyee of TTWA 80 / has i and a ^ e ^ iohteverluat at 160 ⁰ C in the air per hour · of wtnlger than 0.2 Gev? ./ suffers "

ßAD ORIGINAL 909315/1022

Claims (1)

Claim Γ1} method aar esterification in Luouns of Polsroxyniethylen nit by a certain fiöntgenanalyoo Kristallinit'it of Möhr than 90 ₉ cekennzoichnot by the polyoxymethylenes äaoß dom in the Voresterunßomittel containing liquid medium at a ^ oraporatur than 170 ⁰ C and 210 ⁰ 175 vorsusswoiee swiachon C 0u with oinem VorhUltnis of Peatotoff PlUssißkeit jzTC7iocli "i ETAA 1 t 0.5 and 1 ι 10 ßoLüst v» ira c _t! ie esterification l> ei a iomperafcur übor dor Kriotallioationotomperatur ööb polymers vorzuGßwoioe awiochen 135 and 210 ⁰ C is performed and the solution, which comes from the acetylization, is the crystallization of the polymer at oiner caperature Otiochon etcva 10u and 135 ⁰ C, the cooling from the melting temperature to lethality temperature by mixing with hot polymer solutions a with a speed that is a Soa perattir K ^ isoiien about 0 and X30 ° C beoitst is durohgefUhrt _f. 2 · Ancestors according to claim I _{9 are} characterized by the fact that the various stages of the ancestor are completely or partially continuously carried out " 3 «Method according to Ansgrach 1 and / or 2, characterized in that that as Voreaterungozalttel an anliydrld of an aliphatic Carbonoiiuro with 2 · 4 carbon atoms is used. -16 » ■■ · 90 ^ ° -15 / 1022 BAD ORIGINAL -16- 1b20320 4 · ancestors after änaprucii 3 $ thereby fjokonnsoicimot, daun alo l acetanhydride used - is used · VcrfaUron aacii cinaii or iaehreron dor vorüeiv ^ cbondon An · OpV [IQIiQ ₉ tladurcU ^ okonnsolciinotf dtinf; UEAs Vorcoterunßaiaittol In i.iiDoiinn;. ■ lr with "m or _(^ 'iniou i * s i" _f 3L3iinc'nittol üie alipiias.yJcloalipiiTitiaciiO wul aroaaticoue Koulonv / aßoorotorfe, ιΛ I otono, vcrvVendet wlrcU..! Γ> · VOr _- C '; -, ran: iuoii cinou or uchrcrcn the voriicri; oiicr * dcn Ληπηϊ''.- ouoi thereby ^ o'ionnsoirjiinot »then; ilo KfUiIfIU oi ^ koit: CUr clio lOl. ^ Aorl .Cntm ^ aorlCntm ^ aorl rlor hrlsta.llinatlon ate; lc-ioiio Vorentcrunn ^ l ^ ntmc used -is used the vota verootorton u $ A ltvictalliniortcn AOlyaor ab ^ ctron-st and üit a Xoj.ii-oratat toivialb dor urioialllnuoionoto; irdfu rirtü rirt 90 9 ° i 15/1022