含氟聚合物的合成进展

:2011-03-08;:2011-04-20;:(No.20474041,20974047,21074078);;;;:(1987-),,,;*:E-mail:[e-mail].王海蓉,张明祖,倪沛红*(苏州大学材料与化学化工学部,江苏省先进功能高分子材料设计及应用重点实验室,苏州215123):,/,:(ATRP)-(ATR-SCVP)-(RAFT)(NMP),:;/;;引言(398),(0132nm)C-F(540kJ/mol):[1~5],[6~11]Krafft,[11~15],,,1可控/活性聚合制备含氟聚合物//(ATRP)[16,17](NMP)[18](RAFT)[19],11ATRP1995Matyjasewski[16](ATRP),ATRPATRP,R-X,R,RMR-M,R-M,R-Mn-X,,,(ATRP)4111,,,,1998,ATRP[20]1[17]Figure1Mechanismofatomtransferradicalpolymerization[17]Hvilsted[21]ATRP,(3FM)(8FM)1,1,2,2-(17FM),(MMA)-2-(MEA)(PEGMA),,ATRP,(PDI)13,/,,BrittainATRP(MA)-(2,2,3,3,3-)[22,23],[22]ATRP,ATRP,[23],,,,,;,,ATRP,ATRP,,(ARGET-ATRP)[24~26],2,,,,,,[27]ARGET-ATRP,MMA,(HPA)(HFBA),,,P(MMA-co-HPA-co-HFBA),,95%,,,,Beuermann[28]ARGET-ATRP,(MMA)(tBA)1H,1H,2H,2H-(AC8),CO2422011112ARGET-ATRP[27]Figure2MechanismofARGET-ATRP[27],,AC8,,,,CO2,PAC8,PAC8,CO2,PAC8CO2,,,,ATRP,ATRP(SCVP)[29,30],ATR-SCVP,SCVPFrchet1995SCVPAB,A,BB*,B*,(B*,A*)B*A*(3),,,(SCVP),SCVP,,BFrchet3-(1-)-,(Mn100000)[29]3[29]Figure3Basicconceptofself-condensingvinylpolymerization[29],Wang[31]ATR-SCVP,(CMS)(CTFE),4311CMS,CTFE,(CTCs)SCVP(inimer),,Wooley[32~34]ATR-SCVP,2,3,4,5,6-(PFS)(TEG),-ATR-SCVPPFSATR-SCVCP()(4)[32],175210,,TEG,HBFP()HBPF()(DA-PEG),,4ATR-SCV(C)P12[32]Figure4Synthesesofhyperbranchedfluorohomopolymer1andfluorocopolymer2byatomtransferradicalvinylself-condensingvinyl(co)polymerization[32],Wooley(PDMSMA),ATRPATR-SCVP,5[34]Poly(PFS-co-PDMSMA),;Poly(PFS-co-PDMSMA-co-CMS),PDMSMA;HBPF,PDMSMA3,2Tg,,Huang[35][4-(4--)][4-(4-p-tolyloxyperfluorocyclobutoxy)benzylmethacrylate],ATRPPEG,6,12RAFT,,,,,-(RAFT)[19]1998,Rizzardo37Tailoredpolymersbyfreeradicalprocesses,-(RAFT)RAFT,,442011115[34]Figure5SchematicrepresentationsofPDMS-graftedfluorocopolymers[34]6PEG{[4-(4--)]}[35]Figure6PEG-b-PTPFCBBMAamphiphilicdiblockcopolymer[35]Pm,,,R,,7,,,/RAFTBoutevin[36](VC2)(MMA)RAFT,poly(VC2-co-MA),1,1,2,2-(FDA)RAFT,poly(VC2-co-MA)-b-PFDA,,,;,,X(EDX),Ishihara[37]:2-(MPC)-2,2,2-(TFEMA),RAFT,,,,MPC,MPC,Tg,Tg,Tg,,[38]-b-(-2,2,3,3,4,4-)(PBMA-b-PHFBMA)RAFTPHFBMA45117-(RAFT)[19]Figure7Mechanismofreversibleaddition-fragmentationchaintransferpolymerization[19],BMA,,BMA,2,2,3,3,4,4,5,5-(OFPMA),BMA,,,,PBMA,,,Patrickios[39]-2,2,2-(TFEMA)-(2-)(DMAEMA),(EGDMA),,,DMAEMADMAEMA(THF),;DMAEMA,BttcherLaschewsky[40]RAFT,-()(OEGA)-2--(1,1,2,2-)(FA),,,,13NMP(NMP),,[18]NMP,CO2[41]Lacroix-DesmazesNMPCO246201111(8)[42]8NMPPS-b-PFDSPS-b-PFDA[42]Figure8SynthesisofPS-b-PFDSandPS-b-PFDAbynitroxide-mediatedpolymerization[42],CO2PSCO2CO2,PS,142080[43],,,,,,,,Lodge[44~46],,-()()()(-EOF),OPEO,EPEE,FPFPOPFPOPEE,(multicompartmentmicelles)[44](9)SEC[45]-Py()1-(NFH)[46],PEE-b-PEOPyNFH,PFPO-b-PEONFHPy,-EOFPyNFH,,Nagasaki[47],(ROK)(RO-),,,:,,,,[48],[49~55](MePEG),,-2-()(DMAEMA)-(2,2,3,3,4,4,5,5-)(OFPMA),,MePEG-b-DMAEMA-b-OFPMA[49]3--3-471191%-EOF(2-9-5)[44]Figure9Cryo-TEMimageof1wt%aqueoussolutionsof-EOF(2-9-5)[44](HP),KH,DMAEMAOFPMA,,HP-star-PDMAEMA-b-POFPMA(10)[50],,PDMAEMA,DMF/,PDMAEMA,,,(NFHOH)KH,,,10HP-star-PDMAEMA-b-POFPMA[50]Figure10PreparationoftheHP-star-PDMAEMA-b-POFPMAcopolymersviaoxyanion-initiatedpolymerization[50]DMAEMA-2-()(DEAEMA),pH/NFHO-PDMAEMA-b-PDEAEMANFHO-PDEAEMA-b-PDMAEMA[51],,NFHO-PDMAEMA30-b-PDEAEMA10DEAEMA,PDMAEMA,,pH,,,NFHO-PDEAEMA10-b-PDMAEMA30(LCST),pH,LCST,,PluronicF127(PEO100-PPO65-PEO100)KH,K+O--(PEO100-PPO65-PEO100)-O-K+,OFPMA,POFMA-PEO100-PPO65-PEO100-POFMA[52]OFPMAPOFPMA,,,,48201111,:(TFMA)(OFMA),DMAEMA,pH/,[53],,,(LCST),,,LCST,,pH/,,MePEG16-b-PDMAEMA-b-POFPMA[54]PDMAEMA-b-PDEAEMA-b-POFPMA[55],,,,15,,,,,Matsuoka[2-(2,2,2-)](PTFEOVE)[2-(2,2,3,3,3-)](PPFPOVE)[2-(2,2,3,3,4,4,4-)](PHFBOVE),(2-)(PHOVE),(11)[56],,(SANS)X(SAXS)(DLS),,,,,11[56]Figure11Preparationoffluorinatedcopolymersviacationicpolymerization[56]2常规自由基聚合QuakeDeSimone[57](PFPE),2,2--2-,PFPE,,,,PFTEDNAPFPEPEG,1-(HCPK),[58],PEGPFPE,,,4911,Amduri[59],,,200,,,,,,,,,Xu[60],PEGSPEG,(HFMA)(MOTAC),PHFMAPMOTACPSt,PEG,(50~95nm),,,,(cmc),cmcHFMADNA,DNAHFMADNA,3乳液聚合制备含氟聚合物,,,,,,,[61]Soo-Bok[62,63],,80~90%,(FA),(PSt),(PFA)-,,PStPFA,-,FA,PFA,Cheng[64],,-,83~115nm,,,,,Wang[65]PMMA,,-,,,-,-[66],,Ling[67](BA)(MMA),(TFEM)(HFBM)(DFHM),-;,,502011114结束语,,,,,,,,参考文献:[1]ReisingerJJ,HillmyerMA.ProgPolymSci,2002,27:971~1005.[2]AmeduriB,BoutevinB.JFluorineChem,2000,104:53~62.[3]LeeKS,LeeJS.Chem.Mater,2006,18:4519~4525.[4]NeilsonAR,BudySM,BallatoJM,SmithDWJr.Macromolecules,2007,40:9378~9383.[5],,,.,2009,21:2183~2187.[6]MazzolaM,FredianiP,BracciS,SalviniA.EurPolymJ,2003,39:1995~2003.[7]ImaeT.CurrOpinColloidInterfaceSci,2003,8:307~314.[8]BerretJF,CalvetD,ColletA,ViguierM.CurrOpinColloidInterfaceSci,2003,8:296~306[9]GaoJZ,WangXM,WeiYX,YangW.JFluorineChem,2006,127:282~286[10]DuWJ,XuZQ,Nystrm,AM,Zhang,K,LeonardJR,WooleyKL.BioconjugateChem,2008,19:2492~2498.[11]KrafftMP.AdvDrugDelivRev,2001,47:209~228.[12]KrafftMP,RiessJG.ChemRev,2009,109,1714~1792.[13]Gonzlez-Prez,ChristopheC,KrafftMP.SoftMatter,2007,3,191~193.[14]KrafftMP,RiessJG.JPolymSci,PartA:PolymChem,2007,45,1185~1198.[15]KrafftMP.JPolymSci,PartA:PolymChem,2006,44,4251~4258.[16]WangJS,MatyjaszewskiK.JAmC