PLLA-PEG-PLLA三嵌段共聚物的合成及性能

31420108()JournalofQingdaoUniversityofScienceandTechnology(NaturalScienceEdition)Vol.31No.4Aug.2010:16726987(2010)04039505PLLAPEGPLLA,*(,266042):以萘钾和聚乙二醇形成大分子引发剂,在超声波震荡下引发L丙交酯开环共聚,合成出不同EO/LA物质的量比的PLLAPEGPLLA三嵌段共聚物利用FTIR和1HNMR表征了三嵌段共聚物的结构通过接触角和吸水率测试表明共聚物的亲水性是随着EO含量的增大而增强采用DSC和POM研究共聚物的热性能和结晶形貌表明,共聚物各段熔点比各自均聚物低且有一个Tg,由于共聚物中EO/LA物质的量比的不同,表现出某段的单独结晶或两段都不结晶因此,可通过改变嵌段含量,制备不同性能的材料,扩大聚乳酸的应用范围:L丙交酯;聚乙二醇;PLLAPEGPLLA三嵌段共聚物;亲水性;结晶性:O633.14:ASynthesisandPropertiesofPLLAPEGPLLATriblockCopolymersCUIGuozhen,HEJidong(KeyLaboratoryofRubberplastics,MinistryofEducation,QingdaoUniversityofScienceandTechnology,Qingdao266042,China)Abstract:TheringopeningpolymerizationofLlactidewasinitiatedbymacromolecularinitiatorwhichwasmadefrompotassium/naphthaleneandpoly(ethyleneglycol)attheconcussionofultrasonicwave.PLLAPEGPLLAtriblockcopolymerswithdifferentEO/LAmolarratiosweresynthesized.ThestructuresofthesecopolymerswerecharacterizedbyFTIRand1HNMR.Contactangleandwaterabsorptionbehaviorsweretested.ItisfoundthatthehydrophilicpropertyisenhancedwithincreasingthecontentofEO.ThermalpropertiesandmorphologydevelopmentoftriblockcopolymerswerestudiedbymeansofDSCandPOM,theresultsshowthatmeltingpeakofeachblockwaslowerthanitshomopolymerandonlyoneTginthecopolymer.Dependingonthecomposition,onlyoneblockcrystallizedortwoblocksdidntcrystallize.Therefore,aseriesofcopolymerswithdifferentpropertiescouldbesynthesizedbychangingthecontentofthesegmentandtheycouldbeusedinvariousapplications.Keywords:Llactide;poly(ethyleneglycol);PLLAPEGPLLAtriblockcopolymer;hydrophilic;crystalline:20091105:(1982),,.*.()31(PLA),[1](PEG),,[2]PLAPEG,PLAPEG,[34],PLAPEGPLAPEGPEG,PEG,,Zhu[5],PDLLAPEGPDLLA,,PLAPEGPLA,LL,L,EO/LAPLLAPEGPLLA,11.1L(LLA):,3;4000(PEG4000),,;,,;(THF),,;,,,TENSOR27,BRUKER;,BRUKERav500,BRUKER;,JC200C1,;,DSC204F1,;,OlympusBX51,OLYMPUS1.2PLLAPEGPLLAPEG4000,,60!,N23,,THF,PEG4000,THF,LTHF,LTHF,,25!2h,,1.3:,,,,:(2cm∀1cm),015mm,(m0),8h,,(m1):=(m1-m0)/m022.1,[6],L,,,,,,,[7]L,,PEGEOPLLALA,,11,EOLA3964:PLLAPEGPLLA1LTable1ResultofcopolymerizationofPEGandLLAn(EO)#n(LA)n∃(EO)#n∃(LA)aPEGbPLAbMnc/103A4.004.0191115.6B1.711.7391267.7C1.301.3591338.7D0.920.95914710.8E0.690.72916313.1F0.400.449110619.3G0.220.279116928.3:a.1HNMR,PEG366(CH2CH2O)PLLA158(CH3);b.PEG=4000/44=91,PLA=PEG∀(n(LA)#n(EO))/2;c.Mn=PEG∀44+2∀72∀PLA2.21PLLABFFTIR1,FTIRPLLAPEG,1756cm-1,1100cm-11186cm-1CO,LA1100cm-1PLLA,COC;2882~2998cm-1CH,PLLA,(CH2CH2),PEG;3500cm-1(OH)1bc,2882cm-11100cm-1,PEG,PEG,(CH2CH2)(COC),a.L,b.B,c.F1LFig.1FTIRspectraofPLLAandcopolymer2.32F1HNMR,158516PLLA,366EOPEG,272,41~44PLLAPEG,PLLAPEGPEGPLLA,2(F)1HNMRFig.21HNMRspectrumofcopolymer(sampleF)2.4PLLAPEGPLLA,PLLA,PEG,,33Fig.3Testedresultsofcontactangleandwaterabsorptionofthecopolymer3,n(EO)#n(LA),,PEG,PLLA397()31,PEG,,,[4,8]2.54PLLAPEGPLLADSC,,-60!DSC,APEG,PEGTg-65![9],A,,Tg,Tg,,,TgPEGPLLA(Tg59![10])n(EO)#n(LA)PEG,,,DSC24DSCFig.4DSCspectraofthecopolymer2DSCTable2ThermalpropertiesofthecopolymersdeterminedbyDSCTg/!Tcc/!Hcc/(J%g-1)Tm/!Hm/(J%g-1)A---48.3106.0B-42.3-16.9-38.745.275.9C-32.915.6-48.943.352.24D-4.6----E12.748.8,91.5-33.4128.7,142.835.9F21.961.9,93.5-22.5159.933.2G30.794.5-27.3165.525.9n(EO)#n(LA)&13,PEGPLLA,,PLLA,PEG,,PLLAPEGn(EO)#n(LA)=09,PEGPLLA,,,,,,n(EO)#n(LA)∋07,PLLAPEG,PEG,,,,[11][12]MPEGPLLA,55POMFig.5POMpicturesofthecopolymers5(a)(b)(c)ABC36!5(a)(b)(c),PEG3984:PLLAPEGPLLA,PLLA,PEGPLLAPEG,PLLA,,DSCD,,DSC5(c)(d)(f)EFG100!,PLLA,n(EO)#n(LA),,PEG,n(EO)#n(LA)∋07,EO,PEGPLLA,(),PLLA,,,,,PEG,EO31)(PEG4000)LEO/LAPLLAPEGPLLA;n(EO)#n(LA),,,L2)PEG4000PLLAPEGPLLATg;PLLA,PEG,n(EO)#n(LA);PLLAPEG,PLLAPEG;PLLAPEG,PLLA,n(EO)#n(LA)[1],,,.[J].,2006,3:4651.[2]LeeWenChuan,LiYuanChung,ChuIMing.Amphiphilicpoly(D,Llacticacid)/poly(ethyleneglycol)/poly(D,Llacticacid)nanogelsforcontrolledreleaseofhydrophobicdrugs[J].MacromolBiosci,2006,6:846854.[3]DongKeunHan,JeffreyAHubbell.Lactidebasedpoly(ethyleneglycol)polymernetworksforscaffoldsintissueengineering[J].Macromolecules,1996,29(15):52335235.[4]AndreaLucke,JrgTemar,AchimGopferich,etal.Biodegradablepoly(D,Llacticacid)poly(ethyleneglycol)monomethyletherdiblockcopolymers:structuresandsurfacepropertiesrelevanttotheiruseasbiomaterials[J].Biomaterials,2000,21:23612370.[5]ZhuZhixue,XiongChengdong,DengXianmo,etal.Preparationofbiodegradablepolylactidecopoly(ethyleneglycol)copolymerbylactidereactedpoly(ethyleneglycol)[J].EuropeanPolymerJournal,1999,35:18211828.[6]TatsuroOuchi,HidetakeMiyazaki,HidetoshiArimura,etal.SynthesisofbiodegradableamphiphilicABtypediblockcopolymersoflactideanddepsipeptidewithPendantReactiveGroups[J].JPolymSci:PartA:PolymChem,2002,40:12181225.[7],,,.[J].,2005,24(1):5358.[8],,,.[J].,2002,5:695698.[9]ShuaiXinTao,HeYong,NaYangHo,etal.Miscibilityofblockcopolymersofpoly(caprolactone)andpoly(ethyleneglycol)withpoly(3hydroxybutyrate)aswellasthecompatibilizingeffectofthesecopolymersinblendsofpoly(caprolactone)andpoly(3hydroxybutyrate)[J].JApplPolymSci,2001,80:26002608.[10],,,.[J].,2006,27(4):745748.[11],,,.L[J].,2005,26(5):956959.[12],,,.[J].,2006,27(11):21932197.(责任编辑林琳)399