CA2010249A1 - Preparation of oxetane polyether polyols - Google Patents

Preparation of oxetane polyether polyols

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Publication number
CA2010249A1
CA2010249A1 CA002010249A CA2010249A CA2010249A1 CA 2010249 A1 CA2010249 A1 CA 2010249A1 CA 002010249 A CA002010249 A CA 002010249A CA 2010249 A CA2010249 A CA 2010249A CA 2010249 A1 CA2010249 A1 CA 2010249A1
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CA
Canada
Prior art keywords
bleaching earth
polyether
oxetane
monomer
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002010249A
Other languages
French (fr)
Inventor
Jonathan L. Schuchardt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lyondell Chemical Technology LP
Original Assignee
Arco Chemical Technology LP
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Filing date
Publication date
Application filed by Arco Chemical Technology LP filed Critical Arco Chemical Technology LP
Publication of CA2010249A1 publication Critical patent/CA2010249A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16Cyclic ethers having four or more ring atoms
    • C08G65/18Oxetanes

Abstract

ABSTRACT OF THE DISCLOSURE A process for the preparation of polyethers is disclosed in which an oxetane monomer, or a mixture of an oxetane monomer and an oxolane monomer, and a carboxylic acid anhydride are contacted with a bleaching earth catalylst. The process yields ester-terminated polyethers which may be saponified to obtain hydroxy-terminated polyether polyols.

Description

PF 50-01-2033~
PREPARATION OF OXETANE POLYETHER POLYOLS
Thi6 invention relate6 to a proce6s for preparing a polyether which i8 comprised of recurring unit6 of an oxetane monomer or recurring unlt~ of oxetane and oxolane monomers It 18 more particularly directed to a proces6 where an ox~tane and, optionally, an oxolane are polymerized u~ing a carboxylic acid anhydride and a bleaching earth cataly6t to yield an e~ter-terminated polyether The e~ter-termin~ted polyether ~ay be 6aponified to yield hydroxy-terminatcd polyether polyols useful as intarmediate~ in th- preparation of segmented ela~tomers BAC~G~OUND OF THE INVENTION
A variety of polyeth~r polyols are widely u~od a~ fioft, flexible ~egment~ in tha production of ela~tom~ric block copolym-r~ such a- polyur~thane~ and poly~ther e~tera In general, ~uch polyether polyola are low to m~dium molecular welght polymer~ havlng low gla~ tran~ltlon temperature~ and at l-a~t two hydroxyl groupa p-r polym-r chain The low gla~
tran~itlon temperatur~ provide~ high 01a~ticity and good low temperature performanc~, while the hydroxyl groups parmit thc polyother polyol to react with the other component6 of tho ~egmented ela~to~ers Exa~ple6 of commercially important polyeth-r polyol~ include poly~thylene glycol, polypropyl~ne glycol, ethylene oxide/propylene oxide copolyol6, and polyt~tra-methylenê ether glycol (poly THr)~
It i6 de6irable that a polyether polyol u~ed a6 a ~oft 2Q~t~249 ~-g~-nt hav- prl~ary hydroxyl group~ to provld- good r-actlvlty towardz tb~ ctrophll~c functlonal group~ ~uch as i~ocyanate or carboxylate pre~ent on the hard segment components Furth~r~oro, to dovolop optimu~ low t~perature propert~e- lt i8 gen~rally prof-rr-d that th- poly-th~r polyol b~ a~orphou~ and not cry~talllzable In addltlon, the polyether polyol should be hydrophob~c z~nc- the ~chanical properti~ of th~ ~egmented elasto~r product can b~ advor~ly aff~cted by ab60rpt~0n of wat~r The co-oonly u~ed poly~thor polyol~ generally are either hydrophlllc (poly-thylon~ glycol and thylene oxld~/propyl-n~
oxld- copolyol~) or cry~talll~abl- (polyt-tra~othylon- th-r glycol), or hav- ~-condary hydroxyl nd-group~ (polypropyl-n-glycol) ~ or th-~- r--~on~, ox-tan- polyol~ and ox-t-n-/oxolan-copolyol~ hav- b--n lnvo~tlgat-d az polyothor polyol~ of pot-ntl-l co~-rclal lnt-r-~t ~lnc- ~at-rlal~ whlch ar-~l~ult-n-ou~ly a~orphou~, hydrophoblc, and which hav- prl-ary hydroxyl nd-group~ ean b- obt-ln-d by th- ~-l-etlon of approprlat- ~ono--r~ How-v-r, untll now only a ll~lt-d nu-b-r of ~ynth-tlc ~-thod~ for th- pr-p-r-tlon of th-z- ox-tan--cont-lnlng polyol~ hav- b--n dovolop-d Con~--v-ra- t al t-ach th- proparatlon of polyoxytrl--thyl-n- glyeol by lth-r of two rout-~ In th- flrrt -thod, high ~oloeular wolght polyox-tan~ ynth~iz-d u~lng an alu-inu- eoordination cataly~t' thon ozonizod and r-duc~d wlth lithiu~ alu~inu~ hydrlde In the s-cond rout~, th~

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polyoxytrimethylen~ glycol i- obtalned directly by th- cationic polymerization of oxetane using boron trifluoride~ethyl ether as catalyst and a diol a~ co-initlator Toga et al teaeh a proc--r for producing a poly-ther polyol in which 3-methyloxetan- and tetrahydrofuran ar~ ccpolym~rlzed at low temperature u~ing a hydroacid cataly~t such a6 perchloric or fluoroeulfonic acid Motoi et al teach preparation of a 3-methyloxetane polyol u-ing a hydroaeid cataly~t to polymerize th~ ox-tan- ~onomer at eryog-nic temperatur-~
All of ther- ~nown m~thodr for producing oxotane-containing polyol~ involve either a t-diou~, indir~ct route or th- ure of vory low temperature- (<-40'C) 8uch ~ethod~ are not practical or eeonomieal to earry out on a eom~ereial ~eale In addition, th- known m-thodr for formlng th- polyeth-r polyol dir-ctly all mploy a rtrong acid eataly~t whleh 1~ ither ~xp~nriv-, dlffleult to handl-, or hlghly toxle Mort of the~o rtrong acld eatalyrt~ ar- rolubl- ln th- polym-rlzatlon ~ixtur- and thu~
dlffleult to r-~ov- and reeyelo ln ~ub~-qu-nt polymerl~atlon~
8UMMARY OF ~H~ INVINTION
In th- proe-~- of thl~ lnvontlon, whleh provid-r a poly-th~r eomprlr-d of from about S to 100 w-ight perc-nt ba~d on total poly-th~r of r-eurring unlt~ of at l~art one oxetan~ mono--r and from 0 to 95 weight pereent ba~ed on total polyether of rccurring unit~ of an oxolane monomor, a mlxture of an oxetane ~onou-r, an oxolano monomer, and a carboxylic acld anhydrlde lr contact-d 2~02~9 wlth an a~ount of a bl-achlng arth ff-ctlv- to accomplirh polymerization of the monomer6 Thi~ invention additlonally provlde~ a method for producing an ~ter-terminat-d polyether comprl~ing contaeting an oxetane mono~er (or a mixture of an oxetane monomer and an oxolane monomer) and a carboxylic acld anhydride with an amount of a bl-aching earth eff-ctive to accomplich polym-rization of the ~ono~-r~-) Th- ct-r-t-rminat-d poly-ther may be ~aponified to yi-ld a hydroxyl-t-rmlnat-d poly-th-r polyol ~uitable for u~- a~
an int-r--dlat- ln th- pr-paratlon of -gment-d elartom-r- ruch ac polyur-thaner D~T~IL~D D~SCR~PTION OF TH~ INV~NTION
Th- poly-th-r- produc-d by th- proc-~r of thir inv-ntion are co~prlr-d of fro- about 5 to 100 w-lght p-rc-nt bared on total poly-th-r of r-currlng unltr of an ox-tane onom-r and fro- about 0 to 95 w-lght p-rc-nt baa-d on total polyeth-r of recurrlng unltr of an oxolan- ~ono~ r Th- proc-r~ of thlr lnventlon ir thuc ua-ful for th- pr-paratlon of ox-tan- homopolym~rr or ox-tan-/oxolan- copoly--rc Copolya-r~ of two or or- ox-tane~
ay al~o b- pr-p-r-d Th- ox-tan- ~ono~-r ay b- any of th- four memb-r-d a-turat-d cycllc th-rr capabl- of polym-rization by cationic meanr The ox-tan- ~ono~er m-y b- ~ubrtltut-d wlth one or more alkyl, aryl, halo alkyl, o~ other ~ub~titu-ntr ~xample~ of ~uitabl- ox-tane ~ono~-r~ lnclud- oxetan-, 3---thylox-tane, 2-methyloxe~an-, 3,3-dimethyl-ox-tan-, 3,3-di-thyloxetan-, 3,3-bl~(chloromothyl)ox-tane, and ixture~ thereoi' In g-n-ral, , ,.,," ",, j,. . . .. . .

Z~ )24~

if th- poly-ther or it~ derivativer aee to be used a~ ~oft r-gmento in th~ preparation of ela~tomer~, it i8 preferred that th- ho~opolymer of the oxctan~ eaployed have a low gla~
tran~tlon t~mp-ratur~ and little or no cry~tallinity For the-~r-aronr, 3-~-thylox-tan- i- th- pr-ferred ox~tane monomer Th- oxolane mono~-r which ~ay optionally be pr-~ent in the proc-*~ of thit invention i~ ost preferably tetrahydrofuran, but ub~titut-d oxolan-~ capabl- of cationic polymerlzation ~uch a~
2-~-thylt-trahydrofuran and 3-~-thylt-trahydrofuran may al-o be u~-d In on- ~bodi~-nt of thi~ inv-ntion, a poly-th-r aay b-pr-par-d which contalnc prl~arlly t-trahydrofuran but which i~
non-cry-tallin- du- to th- incorporation of a ~ignificant a~ou~t of an ox-tan- ~uch a- 3-~-thylox-tan- The prop-rtie- and charact-rlrtlcr of th- poly-th-rc ~ay thu- b- ad~u-t-d a- d-rlr~d by v-rylng th- ~tructur- of th- ~ono--rr uc-d and th-lr r-latlve proportlow Mlnor a-ountc of alkyl-ne oxid-~ (for exa-pl-, thyl-n- oxld- and propyl-n- oxld-) ~ay alro b- copoly~erl~-d wlth th- ox-tan- ~ono--r~
In g-n-ral, th- poly-th-r produc-d by th- proc-~- of thlr lnv-ntlon ~ay h-v- a nu-b-r av-rag- ~olecular welght of fro-about 250 to 10,000 Mol-cular w~ightr of between about 500 and 4000 ar- partlcularly pr-f-rr-d if th- polyethers or their d-rivatlv-r ar- to b- ur-d ln r-guentcd elartomer~ The poly-th-r~ r- g-n-rally lln-ar, although branching may b-lntroduc-d by th- u-- of dli'unctlonal oono~err ~ h- earboxylle eld anhydrlde u--d ln the proe--- of thi~
inv-ntion ervor ar a promoter in combinatlon with th- bleaehing ~arth cataly~t Thc fragments derived from the anhydride generally become ineorporated a6 e~ter end-group6 on the polyeth~r The degree of poly~erization i~ influenc~d by the carboxylic aeid anhydride eoneentratlon of the polymerization mixtur- Th- low-r th- anhydrid- eone-ntration, the high-r the poly-th-r ~ol-eular w-ight obtain-d, and vic- v-rra How-v-r, cine- th- dogre- of polymerization ic al~o affeeted by the prop-rtl-r or aetivity of the bl-aching arth, it i~ normally n-e-r-ary to mpirieally determin- the anhydrid- coneentration which giv-r the de~ired ~ol-eular weight for any particular bl-aehing arth To pr-par- -t-r-t-rminat-d poly-therr having a nu~b-r av-rag- mol-eular ~-ight of from 1000 to 3000, for xampl-, a earboxylie aeid anhydrld- eoneentration of from about 0 5 to 10 mol- p-re~nt ba~-d on total monom~r i~ normally o-ploy-d Th- e-rboxylie aeid anhydrid- ay b- d-rlv-d from aliphatic oe ro~atle polyearboxylle eld- or ~onoearboxylle aeid- having 2 to 12 e-rbon to-- ~xa~pl-- of ultabl- anhydrid-r inelud-, but r- not li~lt-d to, butyrie anhydrido, val-rie anhydrid-, eaproie anhydrid-, phthalie anhydride, ~ueeinie anhydride, maleie anhydrid-, and, ao-t pref-rably, propionic anhydrid~ ~nd acetic anhydrlde Mlxtur-~ of anhydride~ o~y b~ u~d ~or rea~on- of eo-t and r-ady availabllity, aeetie anhydride i~ prefcrr-d Suitablo bleaehing ealth- are aluminum rilicate~ and alu-inum 2(~Z49 magn-~lum ~illcat-~, whlch ar- g-n-rally r-f-rrod to a~
montmorillonite clays sleaching earth~ of th~s type are commonly also referred to as "fuller~s earth" The ratio of silica to the oxide6 of divalent and trivalent metal6 in these minerals i~ in most case~ 4 1 It i~ preferred that the bl-aching earth be activated by treating with a min~ral acid such a~ zulfuric acid, hydrochloric acid, pho~phoric acid, or nitric acld Method~ of treatlng a bleachlng earth wlth a relatlvely concentrated mlneral acid ~olutlon which will yield cataly~t~
~uitable for u~e in the proc-~ of thi~ invention ar- d-~cribed in U S Pat No 4,127,513, the teachingz of which ar-incorporated her-in by ref-r-nce Alternatively, the bl-achin~
arth may b- acid-activated by tr-atlng with dilut~ (<15 w-ight %) mineral acid ~olution and th-n drying the cataly~t Th-bl-achlng arth u~-d i~ pr-f-rably ~ub~tantially anhydrou~ and contaln~ l-a~ than 3 welght p-rc-nt wat-r U S Pat No 4,243,799, th- t-achlng~ of whlch ar- lncorporated hereln by r-f-r-nc-, t-ach-~ th- pr-paratlon of ~ub~tantlally anhydrou~
bl-achlng arth~ ~ultabl- for u~- in th- proc-~ of thi~
lnvention Th- a-ount of bleaching earth employed 1~ not crltlcal, although the rate of polymerlzation is ~omewhat dependent on the cataly~t concentratlon The propertie~ of the polyether are not ~ub~tantially aff~cted by the quantity of bleachlng earth employed Advantageou~ re~ult~ are obtalned lf the bleachlng earth 1~ pre~ent ln an amount of from about 1 to 20 w-lght 2~

p-rc-nt b---d on th- total wclght of the poly~-rlzatlon m~xtur-The bleaching earth may be u~ed in the form of a powder 6u~pended in the mixture or a~ molded pellet~ in a fixed catalyst bed Unlike prior art method~ for prcparing ox~tan~ polyol~, the proce~ of the invention ha~ the advantage that the cataly~t can be readily removed from the polyether product and can normally be rcu~ed in ~ub~equ-nt polym-rizatlon~
Polymerization gcncrally may bc carrled out froa about -80C
to lOO-C ~owever, ~ince the rate of polym~rlzation may b~
fairly slow at low temperature~ and ~ince ~ide r~actlon~ or a broad-ning of th- mol-cular w-lght dl~tribution may occur at hlgh te~p-rature~, the tcmp-rature rang- of fro~ about 10 to 50 C i~
pr-f-rr-d Thc polymerization tim- required to achl~ve the d-~irod molecular weight and aonoa-r conv-r~ion will vary d-pendlng on th- aonoaer~, t-mp-ratur-, cataly~t conc-ntratlon, and anhydrlde concentratlon uz-d, aaong oth-r factor~ For the mo~t part, polymerizatlon tla-r of ~rom 0 5 to 1~ hour~ wlll be ~ufflcl-nt Oxet-n- aonoa-r~ g-n-rally polya-riz- mor- r-pidly than oxolan- mono--r~
In ord-r to k--p the poly -rizatlon ixtur- l~quid and to p-ralt fflcl-nt h-at r-aoval, it aay be d--lrabl- to u-e an inert ~olv-nt in th- proc-~ of this invention Non-protic ~olvent~ ~uch a~ chloro~ora and toluene are generally ~ultable When the polymerizàtion i~ carried out in ~olvent, the poly-ther obtalned appears to contain approxiaately equimolar aaount~ of hydroxyl and e~ter end-groupr - z~

~ -eau-- o~ th- g-n-rally hlgh-r r~actlvity of ox-tan~
monomer~ compared to oxolane monomer~, it i~ preferred when preparing a random copolyether to have only a portion of the oxetane monoaer charged to the reaction ve66el initially with the oxolan- ~ono~ar and to continuou~ly add the r~maining oxetane mono~-r to th- m~xtur- Th~ for~ation of oxolane homopolym~r may b~ avoided ln thi~ way Aft-r poly~-rization ha~ tak-n plac-, th- r-action i~ rtopp-d by r-~oving th- bl-aching arth cataly-t Thl~ ~ay b~ don~ by any of th- method~ known for r-parating ~olid- from a liquid ~-diu~, including flltratlon nd c-ntrifugatlon If unr-act-d ~ono~-r, carboxyllc acid anhydrld-, and/or ~olv~nt ar~ pr---nt, th-r- con~tltuont- ~ay b- r--ov-d by any appropriat~ dl-tlllation or rtrlpplng m~thod Th- ~t-r-t-r~lnat-d poly-th-r- obtaln~d by th- proc-r~ of thlr inv-ntion ~ay b- eonv-rt-d to hydroxy-t-r~lnat-d poly-ther polyol- by any of th- a-thod- kno~n to ff-et hydroly-l~ of a e-rboxylie rt-r functlon-llty Th- raponifieatlon ~ay b-aeeo~plirh-d, for xa-pl-, by h-ating th- ~tor-t-r~in-t-d poly-th-r wlth an alkall -tal or alkalin- arth hydroxld- or alkoxld- ln th- pr--onc- of wat-r or an aleohol Alternativ-ly, th- -t-r group~ ay be conv-rt-d to hydroxyl group~ by ~lth~r tr-at--nt wlth a hydrid- r-duelng ag-nt or by hydrog~natlon uring a ~trong ba~- and a tranrition ~tal eataly~t a~ d~6crib-d in U S Pat No 4,608,422 Th- t~aehingr of thi8 patent r-incorporated h~r~in by r~f~r~nce ZC~3249 Th- poly-th~r polyol~ thu- produe~d ~ay b~ uz~d ln th~ ~am-mann~r a~ any other eonventionally-obtained polyol, not only a~
the ~oft eegment eomponent~ of polye~ter6, polyamide6, polyur~thane~, and the like but alro a~ lubricant~, functlonal fluid~, adhe~iv-~, and zurfactant-Th- following exa~pler ar~ meant to illu~trate, but not ll~it, th- proces~ of thiz lnv-ntion ~hAMPL~8 G~NERAL PROCEDUR~
Th- 3---thyox-tan- wa~ pr-par-d from 3-ehloro-2-m-thyl propyl ae-tat- uzing known proe-dur-z (U 8 Pat No . 4, 599,460) and drl-d by dl~tillatlon fro~ ealeiu- hydrlde prior to u-e Th-e-taly~t war pr-par-d by placing 200g full~r~ ~arth (Aldrieh) in a colu~n and wa~hing with 400 ul 5~ (v/v) ~ulfurle aeld at 5-10 C Th- flow rat- through th- eolu~n war ad~uzt~d ~o that th- cld wa-h r-qulr-d ca 20 lnut-- Th- cataly~t waz th-n w--h-d wlth 000 aL wat-r nd 400 aL c-ton-, blown dry with a nltrog-n rtr-aa, and dri-d at 130 C for 16 hourr (100 ~) Th- 3-~-thylox-t-n-, eataly~t, ae-tie anhydrldo, and ~optlonally) chlorofor~ w-r- co~bined at roo~ ta~p-ratur- ln the aaount- ~hown ln T-bl- I A round bottou glar- ~la-k equlpp-d wlth nltrog-n bubbl-r and rtirr-r waz ured Poly~-rizatlon waz lnitlat-d ln th- n-at alxtur~ xa~pl~ 1-3) by warming zlightly Th- exa-pl-- u~ing ehlorofora a~ rol~ent (~xaapl~6 4-6) w-r-r-flux-d Aft~r 1-2 hour~, th- r-actlon product wa~ filt-c-d through a pad of diatouac-our ~arth filt~r aid and strlpp-d of 20~Z49 volatil-~ und~r vacuum on a rotary ovaporator Yi-ld~ w~r-calculated from the we~ght of polyethec obtalned compared to the welght of 3-mcthyloxetane charged Molecular w~ight and molecular weight dlrtribution (Mw/Mn) w-re determined by gel permeation chromatography u~ing poly(t~trahydrofuran) calibration ~tandard~
Analy~i~ by 13C NMR and infra-red spectro~copy determined that th- poly-thers obtained in Example~ 1-3 were e~ter-terminated, whilo the product~ of ~xampler 4-6 contained approxi~ately qui-olar amountr of hydroxyl and e~ter ~nd-group~

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Claims (28)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for producing a polyether comprised of contacting an oxetane monomer, an oxolane monomer, and a carboxylic acid anhydride with an amount of a bleaching earth effective to accomplish polymerization of the monomers, wherein the polyether is comprised of from about 5 to 100 weight percent based on total polyether of recurring units of the oxetane monomer and from about 0 to 95 weight percent based on total polyether of recurring units of the oxolane monomer
2. The process of claim 1 wherein the oxetane monomer is selected from the group consisting of oxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3,3-diethyloxetane, 2-methyloxetane, and mixtures thereof.
3. The process of claim 1 wherein the oxolane monomer 1-tetrahydrofuran.
4. The process of claim 1 wherein the oxetane monomer is tetrahydrofuran. and the oxolane monomer is tetrahydrofuran.
5. The process of claim 1 wherein the carboxylic acid anhydride is acetic anhydride.
6. The process of claim 1 wherein the bleaching earth is acid-treated.
7. The process of claim 1 wherein the bleaching earth is substantially anhydrous.
8. The process of claim 1 wherein the bleaching earth is acid-treated and substantially anhydrous.
9. The process of claim 1 wherein the bleaching earth is an aluminum magnesium silicate.
10. The process of claim 1 wherein the bleaching earth is a montmorillonite clay.
11. The process of claim 1 wherein the polyether consists essentially of recurring units of the oxetane monomer.
12. The process of claim 1 wherein the polyether consists essentially of recurring units of 3-methyloxtane.
13. The process of claim 1 wherein the polymerization of the monomers is carried out in the presence of a solvent.
14. A process of claim 1 comprising the additional step after polymerization of separating the bleaching earth from the polyether.
15. A polyether produced in accordance with the process of claim 1.
16. A process for producing an ester-terminated polyether comprised of contacting an oxetane monomer and a carboxylic acid anhydride with an amount of a bleaching earth effective to accomplish polymerization of the oxetane monomer.
17. The process of claim 16 wherein the oxetane monomer is selected from the group consisting of oxetane, 3-methyloxetane, 3-3-bis(chloromethyl)oxetane, 3,3-dimethyloxetane, 3,3-diethyloxetane, 2-methyloxetane, and mixture thereof.
18. The proess of claim 16 wherein the carboxylic acid anhydride is acetic anhydride.
19. The process of claim 16 wherein the bleaching earth is acid-treated
20. The process of claim 16 wherein the bleaching earth is substantially anhydrous.
21. The process of claim 16 wherein the bleaching earth is acid-treated and substantially anhydrous.
22. The process of claim 15 wherein the bleaching earth is an aluminum magnesium silicate.
23. The process of claim 16 wherein the bleaching earth is a montmorillonite clay.
24. The process of claim 16 wherein the polymerization of the oxetane monomer is carried out in the presence of a solvent.
25. The process of claim 16 comprising the additional step after polymerization of separating the bleaching earth from the ester-terminated polyether.
26. An ester-terminated polyether produced in accordance with the process of claim 16.
27. A process for producing a hydroxy-terminated polyether comprised of saponifying the ester-terminated polyether produced in accordance with the process of claim 16.
28. A process for producing a hydroxy-terminated polyether comprised of hydrogenating the ester-terminated polyether produced in accordance with the process of claim 16.
CA002010249A 1989-02-27 1990-02-16 Preparation of oxetane polyether polyols Abandoned CA2010249A1 (en)

Applications Claiming Priority (2)

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US07/315,956 1989-02-27
US07/315,956 US4970295A (en) 1989-02-27 1989-02-27 Preparation of oxetane polyether polyols using a bleaching earth catalyst

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US4970295A (en) 1990-11-13
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AU5051990A (en) 1990-08-30

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