Alkoxylation process using dipyridinium catalysts

Abstract

Alkoxylations are performed by reacting a cyclic oxide with a starter in the presence of certain dipyridinium catalysts. The dipyridinium catalysts are highly active and effective in such small quantities that it is often unnecessary to remove catalyst residues from the product. The dipyridinium catalysts are very effective in alkoxylating even low molecular weight starters such as glycerol and sorbitol.

Description

[0001]ono a ssnvenon reaeso an aoxaonrocessn wc a ccc oxes ae oareer ceorms aorunorouce an eer oroeer. exame, are anmerouceoanareuanes.oeeroos,or ns,e ar oran raw maeraorroucnoureanes.mon oer are use,ore ex uasmeoe, m aase surac raenssen acn, mnouesr, oar r sovenoasm,s a.moone oer monos aronae- an eser-moe aene oxeomers ason er uses. acaons. usesnese an oern wco ane acerve m soneo osn ane soaos arerouce va aoxaon o a sarer comoun, e acve se o rer reacs w a ccc oxen a rn-oenn reacon. arox oroer soaur.er coem moaunnusn acornous o conea snanre arn c aomcvoeun aroreeno, surocv as moecuar we conro ano esase numer o roxrouse aox e rouc wave ae common c uasaes. caas nsese aere aoa o maena econormoxcaes soucme arzaon raes. e mos e so-caeoue mea cane caas cosmoeaxsesumroxe an exacanocoaae caas comexes aree mos co s, o wc znc a mea roxesroveeenes omomwe cracaasm coorane. aoxaon raes.e are versaenae eecveo ss an acceae oxes.oneeess, aa mea roxesave we merze man aene aoxaerouc muse neuraze, an caas -nownrawacs. e esensn ses a reaoo caa a resues scruuous remove. aona wase sreamsa muse cean n oeran coss anrouce caassrove ra omeer uza anono rraesso cosem oar. caass, even wen use a verow caas concenr eo aa mea o caass over aa mea roxess noaons.nmoran avanae caas resues oen caneenero neurazaon ses neee.e roxes are use aseomerzao uc, unee case wen aa mea roucon coss.oneee n caas.s can resun sncanower eenoerormoss,e caassave sncansavanaes as we. an esecaneresoerncen ooew mreoseecnucear o we c sonacrenerr caomonosu onsreoxcerroun osr, -- sonreroesae coanveonsr,oxe caroausssne,- or,-osons w reseco eac oer. eacvaeeoreeomerzao anres ccoumeo aec.vae,ser reormres seunss a s an oen maon one wesre ncan aan aoon o caass. aoxrnum sas as r escre-aoxunonum or- omerzaons areerormooem usemne ara sruorneoocaa sossor eoxeomerzaons. snvenons an ao urce a roomemeraure. mx xaonrocess comrsnse ormn a reacon a mouerceu coamr wresn a o a saorer commooun aavenas a oeas onerox ororou an eecve amoun o a rnum caasavn enee crc oc oex seru acnur ces: a caaca neene - s arnunmrouro wcare orrnoevrso suas anueworroocuars maonoeo a caron aom o moe, eac xs a numerro1 1eerorm avaen rou, eac2s mo,s annrou, eac s avaennnner susueneenen,e zns a nurmoeenr, arom,noer, an su esacue3asn,eenen or rocar orner susue rocar oneo a caro en rou anse reacne ccc oxe w e n aom o arnum o o°neresen sarer comoun a aemeraure n av ce oernum caasoorm an aoxaerouc. oane usnan veare s omae amrooucensss o oeenvenronnus ver aoxaon raes are caas resues ca m caass an,ora reason, reucn neeneroucune aa mea roxes,ere caass, or eevseen co emmonuanns a craease eacecvaveon a an a remova ses.ne moecuar we naors an are aso eecven aoxnan ox sraanreesrs on wo v eereonwe -- o axoex.aneow morecnuuamr we caa ssasreress wcreoere onxa areenaer ucnuasrer a ucsevueor ac, resen, maeneen se. sus en a eseca1-4a,ner moeue a, ar orner susue ar.nworous maorm avaen ar coounsu aareaoonrmes. a runc s ar runcu srerucoueree mra worm,eoerenr wumroeusron wumcroues, 4-1-, me wa arom eree,a no erc a e r cxnam ss 4se,e n am.vaen racaavne srucure –42q- or -- en2q orner susueeneenen roen, a,ner susue a, reera.ac4reerasn, ans aeas one,reera o an mos o1r3ousncue meene eenen roen or me.ecc exames a-c --22r-e-e,r -a- - s2n2e-e-n,2- -, en- eene3ro--2en2- or-,2m --, -3-2-, -3- e-.3- 3--. mosreera .ecc exames o2rousncue me reeras or, -2a2-c, -3,3resen2- an -3-2 3-. ene-2-, eene susue a, ar orn,er ma seneenen a eseca1-4a,ner oxe unnenrere su cosnueonnss o oneus e aau osx neo a a rreoanc. revaec wone sarer comoun or ccc susuensncue non-ccc eersuc as se.xames oner uox anee, eser, a nc meox, eox,soroox, n-uox,- aen, nro- anaoen unnear,rance anor ccc a, ar, ea coeo arnnon2ans a an woenas ar ceo.orosnea wno aseno conoranaaosn a voaenece o n-, nen or. weaerana oe surrounn soven moec assocae caonss conveneneermne o ues.oornaon sren o an anon e san caro rmn ar-n-ocammonum sa oe anon,ssovn secrosco, usnne ara mceoroe a,s anesc mreaesu,ronr exaem-e, snre.cmn.reemuencoc.nrare -.n- srecnreuenc o cm-1orreaer, eseca c,-1, reaer,sncave o a we m or xames o w a coornan anon. eras,-sruoeraome coorneanno arnaoen,sncruueoroemreasaneesruuoonroaeenroraaee,, -- 334——,, 11e56——,12122—, 1156——, e54—, e56—, e3c34c exames o324r annum caas3snc3u24e:. -- w—ea roeno arase,eras,-sruorome a men avaen aseraseruo oraone s auc ruoromeanesuo n eos useunaoerae. o rrearne rnum caas areeneraescre, corm exoaumnes, cnonveenme.nur c.on.vere,oe.- s saarn rae sa oe rnum orm+3- or+3-.ss convene2noneeanc ao snu wae a so covmenou onr ouene -- s suucc a assoroumene oor ac°eo.nre, an caneerorme a aroxmae roomemeraure, wereaarennoes aranoumen, caanee saresareavnnee r searuccounre o , coam-o1unavne sruc aeavne srucure or exa-ma re,, weroea°s. a an eevaeemeraure o, ouene o s reacon caneerormen a suae soven suc as ar acenonre.rnum ae sas avn e srucure canerearen a reacon o an-oxe com2ou-na,a wvnereea srsuc auraeo a a aen eaevvnaeee smruecraurea- or e2xnazem ore,o°. s ure o, oue e n a suae soven suc as e saree a r aceo comonxr ouae no.nass oenreo orrmeneresence o one or more sarer comouns. mae,or exame,rm morerox anororous. roxrous or ar, seconar orerar rox.reerre sarer conans an m moare conaronx as a mnanor aso orrou mosr,ereerroax an oro mroreorroouxs. anororous, -- em n ceran emomens,eunconarous are a roxrous.n some rouos,mens,e sarer comoun waveo,o,o,o oro rox rous. wc roxrous mosreera arermar anor seconar rox a oe sarer comounas an euvaen we erunconarouessan meonoeeer suroauec. sas aormua moecuar we o o mo. acrc ac,roxe aarers are vn acoo,roen acoo, a acoo, a aano,eno, ccrae,roxe meacrae, a1-16 aanoeseca re1-12eneco,r coexano, an a eno, eeneco,eeneco, o,,-exaneoo,ene,co,roeneco,rroeneco,,-uane rmeoroane,rmeo-oecane o, ccoexane meano, cern, manno, mao, sucr ane,enaerro, soro, sucrose, xo, rsroxen aose,eno, aoenoc sarer suc asseno- or,,- e useoeereane, anee.nwo or more oeoreon sarers ma srucuree cac cocn oaxes nsere as. n c oxaraecne arozmenneav rnn s arueacsur oen.es-,ec- or- memer rn oxes are oxranesaave aree-memer, oxen areerre ccc mae,or exame, eene oxe,,-roe conann rn.e ccc oxes “roene oxe”, oxeane,, ne oxeenera reerreoeren as oxe,erarouran -uene oxe,-me-,-uene oxe,,-uene vnenze , ecororn,exene oxe, ocene oxe, srene oxe, ecoronren or ooxeer,o amerc eer suc asseno- c eer,s,-roene oxe zae oxrane.n some emomens,e aene oxe mxure o , eene oxe, or a mxureereo,ncun,or exame, a corresonn ae uaso rreeeerraa a ueoas we roene oxe an emomens,wo or more aene oxes are we eene oxe.n some ranom coomers, anore comos omerze smuaneousoorm mes, or even connuou on oe aene oxes cane one or more anor ranomoc cs,rououe course oeomerzaonoormoc caa e aoxaoonosmeerrso.rme comnne sarer ane rnum reacs w e ccc oxes an oona comonomer an suecne resun sovenon. muxcure a soo rveeanconre ceornaonss.nere u canaers mea cone aonse o as ae s aouoxonanon a -- r uesaecuo sno.venesor eer,coromeane an rocarons suc asouene orexane are e aoxaeonrrocenum caas. º, aeas °, aeaess a aº reaconemeraures aeas°, aeas omerzaonemeraurereera o oers n ao eexas °, an uo °. e no excee º.nmoran avanae oceee º, an morereera oesnvenonseerorm we a eremeraures,rnum caass usene °.e eremerauresromoeaser reac esonesca °o° or°o oerae aese eremerauresermserocesso.e usona,e a o ccc oxesaave somewa menemerauresse w sarers anor manno, mao, sucraose anor wc are vsc uc as soro, xo, e soro ancern,aveme so ous aoweremeraures, or wc, e aoxaon reacon usuausene ccc oxe aoweremeraures. caneerorme a amose rorme a a sueramosercressureu aoxaon rea rcressure or even a suamosercressure.e eecromanec racoan maeerorme wou exosn e reacanso waveens o nmonne uravoe an vse secrasuc as raaonavn a cose reacorao nm.e aoxaon maeerorme,or exame,n vse secra an oes no am eecromanec raaonne uravoe an n oes no conan annerna source o uravoe an vse raaon. aoxaooun r rnum caass useorove a commerca reasonae w reasonaaee a,uoxasoenn rearaes, aessraseoo u rseeu acsesee coesreoor aseo csasaes con asns cean emnaee neeo remove caas resuesromerouc. e amounn rnum caas mae,or exame, o we o rnum ca sucenorove o, m emomens,e amoun oasranseum one we oe sarer.n secc m, aeas m or aeas cma caaas msa one seucenorove aeas , m or uo m caas, aan oneoreonoraesso.neas ws, an uo rnum caasncuese we oo e oe e aox caon an assocae anon. ncun aon reacon caneerormeac-wse, sem-connuous connuou w connuous aon o sarer asescren ,, or orerees ss a. uroexs anaonem reaecraounre csan enceounereorrem.ene a renacore s oou vessee euase su wa ae -- meea mnas onarnoev wn annore re rmeouvrne reaan, seo.eueameera meuarnes onceu reeac vaorn mxure canacenorermaus, varouses onerna or exernaea ouses o coo-own seerorme on connuous wrawnrouc ers, anee.n a reacorarevens sncanac-mxnr s convenen conuce ae oruuar reacors areerre m om occurrn.uow oeraonn e cruerouc oanenaenn aero oerormn suc a coo-own se. ccc oxe, smauanes oe sa xaonrocess ma conan unreace orancmures anor waer. rer comoun an smauanes o oer ccc oxes souease oroaemuresncun mosure an unreace rouc ca conans caas r sesrueerome aoxaerouc.e crue rouc,uese cane remove esrs.scaoeaveese resuesne a erocess oenvenons useeu.orrearn aoxaeroucsa can eveuvaernox, eouvaen wes o euvaen or more, eseca o rox euvaen weesu ova aenox,aeoreuvaen or o euvaen. raon meos suc as -,o wuccs aree con aveneneermne usn ram oooa cane convereo euvaen werox usn numeer rn m euvaen we =, ÷rox num eaon maerasoxorareouconosorourueceannes ac acoerr.ance w envenon are useu raw aoxaeoo w aosocanae.nese oroerucomers mae reacne an non-ceuar maeras, wc ma var sncue a we vare o ceuar exe. e aoxaeroucsn are essceacaroe ursesrom ver r o oureane anoureane-socanuraeoams.oxaeeuor man r accorance w envenon are useu as suraca monosroucen oer uses.oxaeoos an mon ns or asnusra sovens, amon amne-ermnae maera os cane amnaeoroucee corresonn maerasnc s, wc arenurn useu raw maerasor man varous narucunar eomuoreamse anns, curee s earoxe resns. we o mo oress, eseca mros or aesos ooravn arox euvaen aoxaons connue un o, eseca o, eveno ormoo oress, ane oxe are aeerroxrou one sarer.e numer avera uns o ccc oe aoxaerouc mae,or exame, o mo,e mooecuamr woe, -- aooemero s oarnaro mo, as measure eermeaon cromaora aans roene oxe, e.enne su oxcarcuar emomens,e ccc oxesreera ,- or a mxure o anwo or moer,e,-uene oxe,,-uene oxe, ecororn mxureereoenarcuarerreeoe,rr w ,-roene oxe, eene oxe or a reeras one or more ocern,rmee.ore sarern suc emomens mos enaerro, soro an sucrose.ucroucso aane,rmeoeane, erro, r oureane anorosocanuraeomers,re useu raw maerasor man or moren c soomoe emmerozameen msonoem cecrsc oxae asreo nome crn czceu c wn oxe oo sram .ns. xeamreseesnc oe o su once c aoomerzae monomersncue caronaerecursorsa coomerze w an recuernseor osxnecuoero caurceon carooxnaee,nosaeense,nneearro caurco.naxeasm anes c oc succ ca crarononae er coomerzae monomersncue caroxc ac anres, wc coomeaes. w ccc oxesorouce esernae rze eoown exames arerovsnerouc. neneome scoeereo. earso anuserraceenaeesnvenonu are no oerwsencae. are we uness aas roceure eac . . , w.ere , . - -- were eac caa—ssesna-oens “ ma-e acacror”navone sruc . , . 653 e meo caas esnae “r - ” avn e srucure - ,- eea ac a—:s:r euaveaeonnsreare comnn eano° overn raon aceonre, an rmesraen ac.eone rreseu ann srae sas recovere an comne w rouceenarouc. re a roomemeraureor mnueso were eac caa—sesnae “r - ”avne srucure :: sraesreare comnnrne an,- a eeu savaesn re rcaovon aceonre, aneano° overn.e resun srre a roomemeerraeur aenor com mnneue wsorromuecesenarraoeucn. aceonre an xamesra-m asn o saomaraveames- a saness see semrersoronx.,ceron a oer cases are careno ee an mono -ac reacor eue w srrer,emeraure conros, nroen amoun o caamser aeree asnnes an a ven.aass ae as a so.ee an eaeoeemeraurencacaeennaaee. we reacorsure w nroen an nroeno remove an sovenrome caas a sonr.rn,ee mnure aan w emeraure,roene oxeensenoe reacor onemaannanone same manan aareroene oxeara aemo --ressure asncaenae.eare a,m aonun oroor seonre oox aeooxea aonesne aeccero aoxaonss aroxmae eme reureo ua amounse arencaenae. com eeeroene oxerunmesncaenae.on o°e uonn oer m nonroomeenreuer,e.e reaecronsese a °orours anen cooe roucsers coec urn w nroen a°or mnues,e o e, anes cacuae. eroucs anazeorn an es acvees oermeea caona csrsom araeo cormaar aansosrene sanars. n eacnsance. reecse numere oro caceunea oxne a muorencouveersreuenc er caac seer un me, asoows:convere er vaues^ ^ ^^ ^^nen aerc ,nauem ceasanasess aroe aasssnumcaernae. ruoree eerae. e an3·2esnaesoron -- ae recsesruoresne sea rreaecronr aur oner. ceaseos.merzaa.rona.reessuurnesmeenarcaeesearma reouurne ooroeeenee onxceaee aumronune onr e am ocaeen reu onxme.e. “ “”es”unrnocvaeresreeuenoca erase meooecuasr weres.neox,ec.ue.,a wre we avse . av arraee m meaosuecruear we aavnseo nsumreneer sanars. acve comsnarecaeoe coneroasa.neanece,roen caae ssasr oer,uernnovveenrorne aure exreme are aroxmae o mesreaerana o.ereaer caaences rane easorasca reuce runmes, eecvencreasnerouco c acv e manuacurn eumenroorona.oecuar we anon csaear o smaroose oanene-ca s are e exceen acv o raze runom.. raaon are excuerome sanes- s noae, as uravoe an vse nownouncon as aoonaor wes see reacor.r - wasrevous as caas ecenomerzesnr eoxoesnee oo xameemonsraes ne asence o an vse raaon. xe a eevaeemeraures even -- eecveo amoaraveameemonsraesa no a rnum comouns are eroxex craa ouaon ss c asa re oas res man. rve.nonerou ccaea asox,a ceroucsn wc- o wc on oeroxrous arermar onras,roucesroucsn roxrous correaeo sncan er . erroorons ormarnvenon no onrovesoras, reacv wosocanaesuse rouces aoxaeroucsavn s ecen aoxaons,un aon ene -ar anen-narcan caarsease arre re uascv. moecuar we ro unere sameen aera en an aoxaon o a aoxaonrocees sus ane caas ea crosnoeoancs ovae.xames-,e xames araerese a snn uere oxeeacoomerzaons areerorme usn a-wemxecnooes weeassnseravrn an.neac oe wess eue w annvua e wes eac conan an o rna wornu voume o aroxmae m. sarer.s c mar oe ao eaccerove ocr mae uaasa e mnxe seu s rrserr .ceorn. sa mnxnur aroxmae. oe we o caasase one comne we o sarer aeroves aou m omerzaon run.ac wesressurz n eene oxe usene eaeoeomerzaonemerauree o w°s .a nroen anen emeraure,. m o eene oxesn .on reacneomerzaon sarerneassnser. eceno eac we, were reacs w e enernaressureneeasace o eac wes monorenvuanreorunaouressuereosm oesrezraveo,n a.naceourre assuerrene anrsanecon o eene oxe,e s. a, anoer. m oe eene oxersncuar weasaeneow aere seconour oomerzaon.our ece.ssone aan e wes are aoweo cooo r s aerers eene oxenecon, aoweo san oomemeraure an vene.eassnsers are voaze, aer w uncer nernoseerns a are w-e°e oveorneermon aeowe r aemsouuna e oroenuec oxeo wne reesuermnearoonu ccrsom araeo arnaaze aaonrs m aoeocusarr wenee san anar.os.ers -- oomoerr,xraomue,e caassen- . oe eene oxes convereose cn aroucavn a numer averae moecuar we o an a ors o.. oomerr,xraomuce,e caass -ar. oe eene oxes convereosers o.n. aroucavn a numer averae moecuar we o an a --

Claims

: comrs.n a an s aaroexr caomonounrocesasv cnom arsenase ormn a reacon mxure moecuar we o o umm coaas aaevas onerox ororou an a eecve amoun o a rn sn o ene cerc oc oxe seru acnur ces: a caacaneenen -rocar orner susue rocaroneo a caron aos arnumrou w erovsoa anworous maoeer m o moe, eac xs a numerromo, eac1orm avae2nneenen roen, a orne s avaennnrou, eac s eac3sneen r susue a, zs a numerromo, an caron aom o arennumrrooucar an osrener rea scunsuee ccc oroxcaer wonee saro a comoun a aemeraure o o°neresence oe er orm an aoxaerouc. rnum caaso seece.romee arouox coansosnnro oce csosm oo cuanmsa wvnerene sreucurersnum caass----- o.r a mxure o anwo or moreereo, weren eac e .roue c aonsoxsnaon orocess oer caamser oruor woer oee nnn ea ae.ocrae,-s seecerom sruorome enorae anruoromeanesu eras,- comoun.as noer amoaxra amonnorroocuesss a on a nno secroencearn am cnaomro wuesr.ene sarer comoun.aseo aoxroaxonrourosc.ess o anrecen cam werene sarer comoun.s onee or a moorxe oaoncerroo,cerssm oe anororecaene,nr cam werene sarer soro. eoroane, sucrose an an oxran.e. e aoxaonrocess o anrecen cam werene ccc oxes eene. oxe,,e- arooxeaneon oxreo,ces,s- ou ceanem ox we aenren,-eu oxenrean oexse. one or more o erorme. a aeem aeraoxurae oonroocess° o. anrecen cam weren se s --wou ex.osnee a reoxaonrocess o anrecen cam wcserorme vse secra. acon mxureo eecromanec raaonne uravoe an --

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