CA2010249A1 - Preparation of oxetane polyether polyols - Google Patents
Preparation of oxetane polyether polyolsInfo
- 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
- Authority
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular 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
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
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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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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2 ~ ~3~ ~
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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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~
Zcr~ 9 o`o o o ~ g o o `
_~O O ~1 _~
ooo o o c~
c~
o ~ ,~ 8 æ ~,0 UO ~
~ O ~ O O
~ I O ~ O I U~ o ~
v b4 O V O .~ C~
v ô d O
Claims (28)
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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
Publications (1)
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CA2010249A1 true CA2010249A1 (en) | 1990-08-27 |
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CA002010249A Abandoned CA2010249A1 (en) | 1989-02-27 | 1990-02-16 | Preparation of oxetane polyether polyols |
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US (1) | US4970295A (en) |
EP (1) | EP0385632A3 (en) |
JP (1) | JPH02248426A (en) |
KR (1) | KR900012972A (en) |
AU (1) | AU616370B2 (en) |
BR (1) | BR9000848A (en) |
CA (1) | CA2010249A1 (en) |
MX (1) | MX166251B (en) |
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US5807977A (en) * | 1992-07-10 | 1998-09-15 | Aerojet General Corporation | Polymers and prepolymers from mono-substituted fluorinated oxetane monomers |
DE4243722A1 (en) * | 1992-12-23 | 1994-06-30 | Basf Ag | Process for the preparation of polyether glycols |
US5468841A (en) * | 1994-04-13 | 1995-11-21 | Aerojet General Corporation | Polymerization of energetic, cyclic ether monomers using boron trifluoride tetrahydrofuranate |
US5543200A (en) * | 1994-12-19 | 1996-08-06 | Gencorp Inc. | Abrasion-resistant article coated with a coating compositions based on fluorinated monohydric alcohol |
US6235948B1 (en) | 1998-08-18 | 2001-05-22 | E. I. Du Pont De Nemours And Company | Process for the purification of 1,3-propanediol |
CA2379371A1 (en) * | 1999-07-16 | 2001-01-25 | Aerojet-General Corporation | Amorphous polyether glycols based on bis-substituted oxetane monomers |
MXPA02005943A (en) * | 1999-12-17 | 2003-01-28 | Du Pont | Production of polytrimethylene ether glycol and copolymers thereof. |
JP4638646B2 (en) | 1999-12-17 | 2011-02-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Continuous process for the preparation of polytrimethylene ether glycol |
US6599625B2 (en) | 2001-10-31 | 2003-07-29 | E. I. Du Pont De Nemours And Company | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and trimethylene ester hard segment |
US6562457B1 (en) | 2001-10-31 | 2003-05-13 | E. I. Du Pont De Nemours And Company | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment |
US6852823B2 (en) * | 2002-08-09 | 2005-02-08 | E. I. Du Pont De Nemours And Company | Polyurethane and polyurethane-urea elastomers from polytrimethylene ether glycol |
JP4273876B2 (en) * | 2003-08-25 | 2009-06-03 | 旭硝子株式会社 | Polyether monool or polyether polyol and method for producing the same |
WO2013049154A2 (en) * | 2011-09-28 | 2013-04-04 | Henkel Ag & Co. Kgaa | Oxetane-containing compounds and compositions thereof |
JP7300830B2 (en) * | 2018-12-28 | 2023-06-30 | 出光興産株式会社 | Polyalkylene glycol compound |
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US4034015A (en) * | 1973-12-10 | 1977-07-05 | Monsanto Company | Ester terminated terpolymers |
US4131740A (en) * | 1977-04-20 | 1978-12-26 | E. I. Du Pont De Nemours And Company | Alkyl perfluoro-ω-fluoroformyl esters and their preparation |
US4127513A (en) * | 1977-11-09 | 1978-11-28 | E. I. Du Pont De Nemours And Company | Method for preparing polyether glycols |
US4243799A (en) * | 1978-01-14 | 1981-01-06 | Basf Aktiengesellschaft | Polymerization of tetrahydrofuran |
US4189566A (en) * | 1978-01-14 | 1980-02-19 | Basf Aktiengesellschaft | Polymerization of tetrahydrofuran |
US4228272A (en) * | 1979-03-27 | 1980-10-14 | E. I. Du Pont De Nemours And Company | Method of catalytically preparing tetrahydrofuran/alkylene oxide polymerizates using a montmorillonite clay as the catalyst |
US4303782A (en) * | 1980-01-21 | 1981-12-01 | Mobil Oil Corporation | Polymerization of cyclic ethers |
JPS58126828A (en) * | 1982-01-22 | 1983-07-28 | Daicel Chem Ind Ltd | Novel polyalkylene ether glycol |
JPS59189120A (en) * | 1983-04-13 | 1984-10-26 | Daicel Chem Ind Ltd | Novel polyalkylene ether glycol copolymer |
JPS6026025A (en) * | 1983-07-25 | 1985-02-08 | Daicel Chem Ind Ltd | New lactone-modified diol |
CA1292011C (en) * | 1985-10-25 | 1991-11-12 | Susan S. Romm | Storage stable (meth)acrylate plastisols |
DE3606479A1 (en) * | 1986-02-28 | 1987-09-03 | Basf Ag | METHOD FOR PRODUCING POLYOXIBUTYLENE POLYOXIALKYLENE GLYCOLES WITH A NARROW MOLECULAR WEIGHT DISTRIBUTION AND A REDUCED CONTENT OF OLIGOMERIC CYCLIC ETHERS |
DE3613106A1 (en) * | 1986-04-18 | 1987-10-22 | Basf Ag | METHOD FOR PRODUCING POLYTETRAMETHYLENE ETHERGLYCOL DIESTERS WITH A LOW COLOR NUMBER |
DE3730888A1 (en) * | 1987-09-15 | 1989-03-30 | Basf Ag | METHOD FOR REDUCING THE CONTENT OF OLIGOMERIC CYCLIC ETHERS IN COPOLYMERS FROM TETRAHYDROFURANE AND 1,2-ALKYLENE OXIDES |
-
1989
- 1989-02-27 US US07/315,956 patent/US4970295A/en not_active Expired - Fee Related
-
1990
- 1990-02-16 CA CA002010249A patent/CA2010249A1/en not_active Abandoned
- 1990-02-19 EP EP19900301770 patent/EP0385632A3/en not_active Ceased
- 1990-02-22 BR BR909000848A patent/BR9000848A/en not_active Application Discontinuation
- 1990-02-26 AU AU50519/90A patent/AU616370B2/en not_active Ceased
- 1990-02-27 KR KR1019900002742A patent/KR900012972A/en not_active Application Discontinuation
- 1990-02-27 JP JP2044692A patent/JPH02248426A/en active Pending
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AU616370B2 (en) | 1991-10-24 |
MX166251B (en) | 1992-12-24 |
EP0385632A3 (en) | 1991-04-17 |
KR900012972A (en) | 1990-09-03 |
US4970295A (en) | 1990-11-13 |
EP0385632A2 (en) | 1990-09-05 |
BR9000848A (en) | 1991-02-05 |
AU5051990A (en) | 1990-08-30 |
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