聚乙二醇-PEG-聚乙烯醇-PV-省略--温敏水凝胶的制备及温敏特性研究-孙大辉

(PEG)/(PVA)＊孙大辉1,崔　艳2,疏官胜2,马荣堂3,张　梅2(1.,130021;2.,130062;3.,130023)　:　温敏水凝胶作为一种智能高分子材料已成为一个研究热点,由于它的温度敏感性在生物医学、生物工程等领域具有良好的应用前景。通过分子设计利用接枝共聚法将低熔点的结晶性,不同分子量的PEG接枝到高熔点的PVA高分子骨架材料上,获得具有可逆相变特性、不同相变温度的功能高分子材料,在此基础上制备温敏性水凝胶,对其温敏性能及影响因素进行研究;用DSC方法对干凝胶的相转变行为进行研究,在此基础上探索PEG在相变温度的结晶熔融性能与水凝胶温敏行为之间的关系。结果表明,水凝胶相转变温度可控制在38.5～40℃,在高于相转变温度20min内水凝胶失水60%以上。此研究可在医学人体体表创伤创面药物控释方面得到应用。:　;;:　TQ423.21;O648:A:1001-9731(2009)-0493-041　　。、(),,(LCST)。(),、[1～5]。,,,。PNIPA,31℃[6～9]。PNIPALCST、,。-PEG。,PEG,PEG,PEG,PEG。,、、,PEG38.5～40℃,。2　　2.1　(PEG),Mw=1500～4000,,;(PVA),,;-2,4-(TDI),,;(DMF),,;,。2.2　TDIPEG,。PVA,。::,N2,(n(PEG)∶n(PVA)=9∶1),PEGDMF,70℃TDI,,1h,TDI,TDIPVA。:PVA5%PVA-DMF,,,4h。10h,,24h,,。PEGPVA,-,PEG,PEG,PEG。7d,12h,,,。493:(PEG)/(PVA)＊:(20070513):2009-05-04:　:　(1971-),,,,。2.3　2.3.1　METTLERTOLEDODSC821e,100ml/min,-30～100℃,10℃/min。2.3.2　,,,,。SR=[(me-md)/md]×100%,me,md。2.3.3　LCST20min,,,。WR=[(mt-md)/med-md]×100%,mtt。3　3.1　[10],PEG,PEGPVA1。1　PEGPVA-g-PEGTable1PhasetransitiontemperatureofPEGandPVA-g-PEGpolymersofdifferentmolecularPolymerGraftratio(%)DSC(℃)Tm(on)TmTm(end)Tc(on)TcTc(end)PEG1500-46.8154.5858.732.4325.6921.03PEG2000-54.3154.7459.1237.1434.4630.57PEG4000-58.1260.8965.4238.5335.0530.30G150036027.7635.540.58-7.04-13.86-28.07G200068026.6336.0340.441.3-6.6320.20G400057033.4849.4655.4924.7519.181.2G(2000-4000)20032.4739.5242.9813.96-8.45-22.81　　　　G=PVA-g-PEG　　1PVA-g-PEGDSC。图1　不同分子量PVA-g-PEG的DSC图Fig1DSCcurvesofPVA-g-PEGpolymersofdifferentmolecular　　1,PEG。,,38.5～40℃,,,;,。。,,;,,,4942009(40)。,,。,,。PEGPVA,,PVAPEG。(PEG2000∶PEG4000)=9∶1。3.2　PNIPA,31℃。-PEG。2DSC。图2　G(2000-4000)不同温度下溶胀率与其DSC图的比较Fig2DSCcurveandSRtemperaturedependenceofG(2000-4000)2,G(2000-4000)39～40℃,,PEG,。G(2000-4000)60℃20min,,,2。2,20min60%,,,,。2　G(2000-4000)60℃20minTable2WaterretentionofG(2000-4000)at60℃af-ter20min溶胀平衡质量me(g)20min退胀后质量mt(g)干态凝胶质量md(g)WR(%)0.780.390.1637.14　　、PVA-g-PEG,,DSC,,PEG,38.5～40℃,PEG,。20min60%,。:[1]　BokiasG,HourdetD.[J].Polymer,2001,42:6329-6337.[2]　ShiXY,LiJB,SunCM,etal.[J].JApplPolymSci,2000,75:247-255.[3]　,,.[J].,2002,18(1):98-101.[4]　LeeWF,YuanWY.[J].JApplPolymSci,2000,77:1760-1768.[5]　MelekaslanD,OkayO.[J].Polymer,2000,41:5737-5747.[6]　,,.[J].,2000,13(2):380-384.[7]　KratzK,HellwegT,EimerW.[J].Polymer,2001,42:6631-6639.[8]　ZhangXZ,YangYY,ChungTS,etal.[J].Langmuir,2001,17:6094-6099.[9]　ZhuoRX,LiW.[J].JPolymSci,PartA:PolymChem,2003,41:152-159.[10]　　,　,.[J].,2005,26(1):170-174.495:(PEG)/(PVA)Studyonpreparationandsensitivepropertiesofpolyethyleneglycol(PEG)/polyvinylalcohol(PVA)thermo-sensitivehydrogelSUNDa-hui1,CUIYan2,SHUGuan-sheng2,MARong-tang3,ZHANGMei2(1.FirstHospital,JilinUniversity,Changchun130021,China;2.CollegeofQuartermasterTechnology,JilinUniversity,Changchun130062,China;3.CollegeofChemistry,JilinUniversity,Changchun130023,China)Abstract:Thermo-sensitivehydrogelhavebroadapplicationprospectsinbiochemistry,medicineandotherfields.Inthispaper,PEGaslowmeltingpointpolymerwasgraftedatPVAwhichwasaspolymermatrixmate-rialofhighmeltingpointbycopolymerization,aserialsofnewreversiblephase-changematerialswereobtainedandthermo-sensitivehydrogelwerepreparedbecauseoftheirswellingproperties.Thehydrogelswellingbehav-iorwasanalyzed,thermo-sensitivepropertiesanalysiswasmadebyusingDSCmethod,xerogelphasetransitionbehaviorwasalsostudiedandthroughwhichsearchtherelationshipbetweenPEGphasetransitiontemperatureandthermo-sensitiveactsofthehydrogel.Theresultsshowedthatthethermo-sensitivehydrogelphasetransi-tiontemperaturewasin38.5-40℃,in20minthehydrogelvolumechangesinmorethan60%.Thestudycanbeappliedindrugdeliveryofthemedicaltraumawoundaspects.Keywords:polyethyleneglycolmonomethylether;polyvinylalcohol;hydrogel;thermo-sensitivemechanism4962009(40)