胺存在下自由基聚合与活性自由基聚合

319873,3,(,100871)50!:,,P,:;;;;(),,,,,,5080,,,,(ESR)80,,90,;,;P,[13],,[3,4],1[1c,1d,4,5][5],(BPO)2N,N2(DMA)BPO2N,N22(DMT),[6,7],;(CHP)DMT,[8],,2N,N,N,N2N2(NIPAM),PNIPAMBPO2DMA,CHP2DMT2,11122[4,5],Horner324[9]BPODMA,Imoto[10],Walling[11]DMABPO,,DMABPO,NBPOO,,(Quaternaryhydroxylamine),()(Aminiumradical),(Aminomethylradical),11Figure1Reactionmechanismofdiacylperoxidewithtertiaryaromaticamine(X=H,DMA;CH3,DMT;R=C6H5,BPO;C11H23,LPO)1,ESR()Latowski[12]DMTCCl4,[1a,1d]O2,(Aminiumradicalchloride),,C6H5COONaC6H5COO-,,,BPODMT,,:BPOLPO()DMA(MMA),BPOLPO,DMTN,N2()24220058(DHMA)DMAp22N,N2(NDMA)p2N,N2(DMAB),,,,,BPOLPOBPO[7,13,14],N2222N2(HMA)N2222N22(HMT)N,N2(22)2(DHET)N,N2(22)2(DHPT)N,MMA,11BPO2MMATable1MMApolymerizationinitiatedwithBPO2aromatictertiaryaminesystemsRp104(molPLs)RrEaP(kJmol-1)BPO2DHET9130a1174315BPO2DHPT8131a1154416BPO2DMT5145a1103914BPO2DMA2119a0144515BPO2HMT9107b1164113BPO2DMT5178b1103914BPO2HMA3130b0164314BPO2DMA2134b0144515a[MMA]P[]=1P145,[BPO]=[]=21010-2molPLbMMA40,[BPO]=[]=21010-2molPLESR:N2C,,UVPMMA,2,ESR,1122[1518](ROOH)(TBH)(CHP)(THFHP),DMADMTN2(NMP)N,N,N,N2(TMEDA)BPO2,ROOH2,MMA(RP),RPBPO2,25242ROOH2BPO2MMARrEaTable2RrandEaofMMApolymerizationinbulkinitiatedwithROOH2aromatictertiaryamineandBPO2aromatictertiaryaminesystemsTBH2CHP2BPO2RrEaP(kJmol-1)RrEaP(kJmol-1)RrEaP(kJmol-1)DMT110751171132381921433519DMA110052171100451511004417NDMA019357141107551701325414DMAB018650140157621401315019NDMA:NDMA:2ROOH2:[ROOH]=[]=21010-2molPL50BPO2:[BPO]=[]=11010-2molPL45113ROOH2ROOH2BPO2,BPO2DMT,1ROOHHN[16]TBH2,TBH2DMTCHP2DMTIR,ROOHOH,,ROOHTBH2TEATBHOH,3120cm-1TBH2DMTOH3336cm-1,CHP2DMT3257cm-11:MNP(222)ESR,N22,[15]ROOH2:NOH,OH-(H+),OH-,H2ON22TBH2DMT,H2ON22,UV,1142[1923]2(AAM),,R,Rr=1,R2NH(Rr=2168)RNH2(Rr=1147)R3N(Rr=1120);N2(NMMP)Rr118,2,,,,:(CH3)2NCH2CH2N(CH3)2(Rr=4192)CH3NHCH2CH2NHCH3(Rr=3147)NH2CH2CH2NH2(Rr=1137)6220058CH2CH2,(CH3)2NCH2CH2N(CH3)2,(Rr=4192)CH2CH2CH2,(CH3)2NCH2CH2CH2N(CH3)2,(Rr=4107)CH2CH2CH2CH2,(CH3)2NCH2CH2CH2CH2N(CH3)2,(Rr=3157)(CH3)2N,TMEDA,(Rr=4192)(C2H5)2N,TEEDA,(Rr=3147)2TMEDA,115ESRUV,,,NH,NHTMEDA[21,22],,:,,BPO,,,,,,,26070,,(VCZ)[24]VCZ(CTC),(AN)(MA)(AAM),,,CTC,[25,26]DMADMT(PHZ),MMAAN22(MEMA)(HPMA),2,DMADMTPHZ,2,724PHZ,,MA[27]AN[28,29]211ANAN[28,29],,,,:DMTDHETDMAN,N2(DMB)N,N2(DNA),,,[30]DMTANRpDMT0166,1PDPDMT015,,,[29]DMTAN,:Rp=K[AN]1162[DMT]0162RpAN1162DMT0162;ANN,N2(DMF)32164kJPmol17157kJPmol,,,:DMF212AN[31],ANAN(Exciplex),DMTANCTC,CTC365nm,CTCDMT313nm,AN,AN,,:p2CH3C6H4N(CH3)2C6H5N(CH3)2p2HOCH2C6H4N(CH3)2p2CH3C6H4N(CH2CH2OH)2,ANSteren2VolmerCTC:p2CH3C6H4N(CH3)2p2CH3C6H4N(CH2CH2OH)2p2HOCH2C6H4N(CH3)2C6H5N(CH3)2,CTC,,,,:8220058213AN[32]AN,33ANTable3PhotopolymerizationofANinitiatedbyaromaticamines(at313nm)a(313nm)cb10-4(molL-1)Rp105(molPLs)kqcd(ns)kq10-8C6H5N(CH3)2180021231446102132100C6H5NH286051221644152131193C6H5NHCH3176021321348102171178p2CH3C6H4NH2124031021144102151178p2CH3OC6H4NH2230011611848102191166m2CH3C6H4NH2103031811727132151109a313nmDMF2AN,[AN]=318molPL.b,01401cStern2VolmerI0PI=1+kq[AN],,[]=210-4molPL.d,[]=210-4molPL.:C6H5N(CH3)2C6H5NH2C6H5NHCH3p2CH3C6H4NH2p2CH3OC6H4NH2m2CH3C6H4NH2kqAN510-2molPL,ANCTC365nm,DMF,,365nmCTC,C6H5N(CH3)2C6H5NHCH3C6H5NH2C,N,N,:,[33](BP),BP2MMA,BP,N,PMMABP,ANPMMA2b2PAN[34],BP,2CAN,32080,90(Iniferter)[35,36](NMP)(SFRP)[37](ATRP)[38,39][40,41](RAFT)[42],,,,,,NMP924,ATRPRAFT(),,P(LivingPcontrolledradicalpolymerization)P(ControlledPlivingradicalpolymerization,CRP),,MwPMn113ATRP,311N,N2(DC),[4345]22N,N2(TDCA)22N,N2(EDCABDCA)22N,N2(BzDCA),,,PStDC,,DCPSt2DC,,MMA,BAAB[46,47](PEG)(,PTHF)DCPEG2PTHF2,St,MMA,BAABA[48,49]DC[50]22:22N,N2(2)(MAEDCA),MMA(PMMA2macromer)MMAMAEDCA,Mn=700032000PMMA2macromer,MAEDCASt,,MAEDCAPSt2macromerMAEDCA(Hyperchainbranchpolymer)[51,52]312ATRP1995P[3841,53],(RX),Cu(),Fe(),Ru(),Ni(),2,22(bpy),(PPh3)(L),,(NormalATRP)RXMtnXnLm,RXXXMtn+1XnLmR,RP,XMtn+1XnLmPXMtnXnLmATRPStMMAMAANATRP,,ATRP,,ATRP(RATRP),P2,22(AIBN),,ATRP,2(Lm)31211CCRATRPRATRPCC,1,1,2,2221,22(TPED),2,3222,32(DCDPS),2,3222,32(DCDTS)CC,Fe()Cu()MMASt[5462],,,,,MMA03200582Figure2TheprocessofnormalandreverseATRP[54]TPEDPFeCl3PPPh3MMA,(Mn=171,800,MwPMn=1113),2H2ClPMMAH,ATRPClTPEDPFeCl3PPPh3St,Mn=25004500,MwPMn=113115PSt,,Mn[55]DCDTSPCuCl2PbpyMMA,(DCDTSPCuCl2=1P2)MMA,RATRP[56];AIBNPCuCl2Pbpy,MMA[63],,(MwPMn113),CuClPbpyStATRP,PMMA2b2PStDCDPS,DCDTS,CuCl2Pbpy,FeCl3PPPh3NiCl2PPPh3MMA,St,RATRPDCDPSATRP:Cu():DCDPSPCuCl2PbpyPSt[57],DCDPSPCuCl2PbpyPMMA[58];Fe():DCDPSPFeCl3PPPh3PSt[59],DCDPSPFeCl3PPPh3PMMA[60];Ni():DCDPSPNiCl2PPPh3PSt[62]31212(Pseudo2halogentransfer)ATRP[6467]Cu(S2CNEt2),Cu(S2CNEt2)ClATRP,S2CNEt2ATRPATRP2S2CNEt2(p2TsCl)Cu(S2CNEt2)bpy,[p2TsCl]P[Cu(S2CNEt2)]P[bpy]=1P1P3MMA,,,(MwPMn1115),S2CNEt2ATRP,p2TsClCu(S2CNEt2)Cu(S2CNEt2)Cl,S2CNEt2,ATRP[64,65]AIBNPCu(S2CNEt2)ClPbpy100MMA[67],AIBNPCu(S2CNEt2)ClPbpy=1P2P6,[MMA]0=914molL-1.MMAPAIBN200P1500P11000P1,,,220min80%PMMA,48000,(MwPMn1125),S2CNEt2,RATRP,134ATRP:MMAPBPOPCu(S2CNEt2)Pbpy[68,69],MMAPBPOPCu(S2CNEt2)ClPbpyStPBPOPCu(S2CNEt2)ClPbpy[70],MMAPDCDPSPFe(S2CNEt2)3StPDCDPSPFe(S2CNEt2)3[71,72]313(I