33二磺化44二氟二苯砜二钠盐的合成与表征

6011Vol160No111200911CIESCJournalNovember20093,3c--4,4c-毕慧平,陈守文,高智琳,张莎,王连军(,210094):4,4c-(DFDPS),,,,3,3c--4,4c-(SDFDPS)HPLCUV1HNMRFTIR,:(SO3BDFDPS)310B1,110e20hDFDPS/,75%SDFDPS60%,,SDFDPS:;;;:O625175+2;O631:A:0438-1157(2009)11-2937-06Synthesisandcharacterizationof3,3c-disulfonated-4,4c-difuorodiphenylsulfonedisodiumsaltBIHuiping,CHENShouwen,GAOZhilin,ZHANGSha,WANGLianjun(SchoolofChemicalEngineering,NanjingUniversityofScienceandTechnology,Nanjing210094,Jiangsu,China)Abstract:3,3c-Disulfonated-4,4c-difluorophenylsulfone(SDFDPS)wassynthesizedfrom4,4c-difluorophenylsulfone(DFDPS)withindustrialgrade1ThestartingmaterialDFDPSwaspurifiedbysublimationbeforeuse1ThereactionconditionwasoptimizedbyvaryingthemolarratioofSO3toDFDPS,reactiontemperatureandreactiontime1ThepurityandyieldoftheproductwasdeterminedbyusingHPLC,UV,1HNMRandFTIR1TheoptimizedreactionconditionwasfoundasthatthemolarratioofSO3toDFDPSis310B1withareactiontemperatureof110efor20h,underwhichneithermonosulfonatedproductnorDFDPSresiduewasdetected1TheproductSDFDPSwasobtainedwithatotalyieldof75%uponrecrystallizationtwicefromethanol/water1Poly(aryleneethersulfone)copolymerwith60%sulfonationdegreepreparedfromthesynthesizedSDFDPSshowsahighrelativeviscosity,whichalsoindicatesthehighpurityofthesynthesizedSDFDPS.Keywords:sulfonationreaction;difluorodiphenylsulfone;sulfonatedpoly(aryleneethersulfone);protonexchangemembrane2009-05-05,2009-06-03:,:(1978)),,:(BK2007211);;Receiveddate:2009-05-05.Correspondingauthor:CHENShouwen,associateprofessor,[e-mail]1WANGLianjun,wanglj@mail1njust1edu1cnFoundationitem:supportedbytheNaturalScienceFoundationofJiangsuProvince(BK2007211).[sulfonatedpoly(aryleneethersulfone),SPAES],[1-5]SPAES3,3c--4,4c-(SDCDPS)3,3c--4,4c-(SDFDPS)SDCDPS,[6-8]SDFDPSSDCDPS,,,[9]SDFDPSSDCDPS[10-11],DFDPSDCDPS,SDCDPSSDFDPS,SDFDPS,DFDPS,DFDPS11114,4c-(DFDPS),,;(SO330%~35%),;(DMSO),;4,4c-(BP),,;,;BP,DFDPS,DMSO1124,4c-DFDPS200mlDFDPS(20g,010787mol)60ml,,DFDPS,,80e,18g,90%110e1133,3c--4,4c-100mlDFDPS(SO3GB1119811)89)DFDPS,110e120e101520h3,200ml,,NaCl,,200ml,10%pH7,120e10h(7B3),,75%114,,116500gSDFDPS(3160mmol)17mlDMSO,SDFDPS,016102gDFDPS(2140mmol)111173gBP(6mmol)019530g(6190mmol)17ml140e4h,/165e,15h,(500ml),,,120e24h(95%)1151HNMRBrukerAvance400,DMSO-d6,10%;FTIRBrukerVector22Waters2996[RP18(5Lm,319mm@150mm)],6B4,1100ml#min-1,30eWaters2996,,Gr,35e,015%()DMSO#2938#602211DFDPSDFDPS,4,4c-(DCDPS)4,4c-(DFDPS),DCDPSDFDPSDFDPS1(a),418minDCDPS,DCDPSDFDPS1(b)1(b),HPLC,418min,DCDPS,DFDPSDCDPS1DFDPSFig11Three-dimensionalHPLCspectraofDFDPSwithdifferentpurificationmethods212SDFDPSHPLC11,(SO3DFDPS115210215),DFDPSSO3DFDPS210,,,,SO3DFDPS310DFDPSDFDPS,SO3[7],SO350%[7],DCDPS110e,110e120e1,SO3DFDPS310,20h,(110e120e),110e1Table1SulfonatedproductsunderdifferentreactionconditionsSO3/DFDPS(molarratio)Reactiontemperature/eReactiontime/hMolarratio¹ofrawmaterialDFDPStomonosulfonatedDFDPS(disulfonatedDFDPS)115/111020014B3614B6312210/1110200B2419B7511215/1110200B218B9712310/1110100B215B9715310/1110150B016B9914310/1110200B0B10010310/1120200B0B10010315/1110200B0B10010¹DrawnfrompeakareanormalizationmethodofHPLCspectraat198nm.1,310B1,10h15h,,20h,2#2939#11:3,3c--4,4c-110minSDFDPS,113min,217minDFDPS,115210,,DFDPS,310,2adDFDPS,bcDFDPS,adDCDPS,DCDPSDFDPS,,,DCDPS2Fig12HPLCspectraofproductswithreactionconditionsof110e,20ha,d)recrystallization;b,c)sublimationmolarratioofSO3toDFDPS:a)115;b)210;c)310;d)3103110e20h,310B1215B1SDFDPSHPLC,,215B1,,310B1,231,DFDPS,310B1,,,DFDPSDCDPS,SO3/DFDPS310B1,110e20h3SDFDPSFig13Three-dimensionalHPLCspectraofSDFDPSwithreactionconditionsof110e,20h213SDFDPS,95%/,75%1HNMRFTIRUV4DFDPSSDFDPS1HNMR,4DFDPS(DMSO-d6),D8106(m,4H),D7146(t,4H),CDCl3DFDPS,[12],DMSO-d64SDFDPS(DMSO-d6),D8117(m,2H),D7197(m,2H),D7143(t,2H),[13]5SDFDPSDFDPS#2940#607SDFDPSFig171HNMRofdisulfonatedpoly(aryleneethersulfone)copolymersynthesizedwithSDFDPS,19517nm23516nm20217nm24011nm,,6SDFDPSFTIR1035cm-11103cm-1SO,1144cm-1SO214DFDPSSDFDPS,SDFDPSDFDPS6B4,60%,311,,SDFDPS78126c,g7191ab619871833,DFDPSDCDPSSO3/DFDPS310B1,110e20h,SDFDPS/,75%SDFDPS#2941#11:3,3c--4,4c-60%,,SDFDPSReferences[1]MaierG1Sulfonatedaromaticpolymersforfuelcellmembranes1Adv.Polym.Sci1,2008,216:1-62[2]HarrisonWL,HicknerMA,KimYS,McGrathJE1Poly(aryleneethersulfone)copolymersandrelatedsystemsfromdisulfonatedmonomerbuildingblocks:synthesis,characterization,andperformance)atopicalreview1FuelCells,2005,5(2):201-212[3]RoyA,HicknerMA,EinslaBR,HarrisonWL,McGrathJE1Synthesisandcharacterizationofpartiallydisulfonatedhydroquinone-basedpoly(aryleneethersulfone)srandomcopolymersforapplicationasprotonexchangemembranes1JournalofPolymerSciencePartA:PolymerChemistry,2009,47(2):384-391[4]NakabayashiK,MatsumotoK,UedaM1Synthesisandpropertiesofsulfonatedmultiblockcopoly(ethersulfone)sbyachainextender1JournalofPolymerSciencePartA:PolymerChemistry,2008,46(12):3947-3957[5]WangZhe(),LiXianfeng(),ZhaoChengji(),LuHui(),NiZhuo(),NaHui(),QianYaqin().Novelprotonexchangemembranesusedforfuelcel-lsulfonatedpoly(aryleneethersulfone)withtert-butylgroups1ChemicalJourna