1、Controlled/ “living” radical polymerizationA new tool for macromolecular designJunpo H高等高分子化学高等高分子化学Contentsconventional and controlled radical polymerization (CRP) brief history of CRP1.2.3.4.5.6.7.8.9.Kinetic feature: slow initiation fast propagation rapid terminationOORCtMnCWiMnConventional radic
2、al polymerization11d22ppptP*MMI ()fkRkkk三个问题：1) MMA端基；2) MMA+St；3)无ktNon-livingPolymn.LivingPolymn.NOControlled/ “Living”Radical Polymn. Conventional Radical Polymn.Conventional and controlledradical polymerization(ATRP)(RAFT)(NMRP)CuCl/bpyZSSRAnionicIdea for controlled radical polymerizationThe ori
3、gin of the non-livingness of conventional:Protecting the propagating radicals !1980s. Otsu: initiator-transfer-terminator: iniferter1987. CSIRO group: www.csiro.org.au Nitroxide in MMA Polymn.1993. Georges: Nitroxide in St. Polymn. Xerox in Canada1995. Hawker: Alkoxyamine IBM Almaden1995. Wang and M
4、atyjaszewski: ATRP Carnegie Mellon Sawamoto and coworkers: 1998. CSIRO group: RAFT-based Polymn. dithioesterHistory of CRPSFRPTerminology Names that have been used in the literature:Controlled radical polymerization; living radical polymerization;Controlled/”living” radical polymerization.IUPAC reco
5、mmendation:Reversible-deactivation radical polymerization (RDRP).IUPAC permitted:Controlled radical polymerization (CRP).IUPAC discouraged: Names with “living”Living radical polymerization; Controlled/”Living” radical polymerization;Quasi-living radical polymerizationSpecific nomenclature recommende
6、d by IUPAC:Stable radical mediated polymerization (SRMP); Nitroxide mediated (radical) polymerization (NMP or NMRP);Organometallic-mediated radical polymerization (OMRP);Atom transfer radical polymerization (ATRP); (RAFT) 见后Contentsconventional and controlled radical polymerization (CRP) brief histo
7、ry of CRP1.2.3.4.5.6.7.8.The first publication of a successful SFRPStable free radical polymerization (SFRP)1990 Xerox Research Center of Canada (XRCC)Radical polymerizationAnionic polymerizationSt, MA, butadieneM. K. GeorgesOther guyNo desired propertydesired propertyMW and MWDHigh costiniferterTEM
8、POBetter stable radical ? Discuss with ESR expert250 experimentssuccess“Stable radicals” eds. Robin G. Hicks, Wiley, 2010. p.407 NONONOOHTEMPOSome stable nitroxyl radicals1. Initiation: BPO/TEMPO, Alkoxyamine,etc.NORkdkcNOR+C O O COOC OO2C OOCH2CHO N+NOElementary reactionsAlkoxyamine: Unimolecular i
9、nitiator for NMRP.Elementary reactions2. Reversible equilibrium:3. Propagation:PiM+kpPi+1NOPikdkcNOPi+4. Termination:PiPj+ktPi+j/ Pi+PjTerminology Names that have been used in the literature:Controlled radical polymerization; living radical polymerization;Controlled/”living” radical polymerization.I
10、UPAC recommendation:Reversible-deactivation radical polymerization (RDRP).IUPAC permitted:Controlled radical polymerization (CRP).IUPAC discouraged: Names with “living”Living radical polymerization; Controlled/”Living” radical polymerization;Quasi-living radical polymerizationSpecific nomenclature r
11、ecommended by IUPAC:Stable radical mediated polymerization (SRMP); Nitroxide mediated (radical) polymerization (NMP or NMRP);Organometallic-mediated radical polymerization (OMRP);Atom transfer radical polymerization (ATRP); (RAFT) Vivid discussions on terminology“On the origin of NMP and RAFT”“On th
12、e origin of NMP and RAFT”Nitroxide trapping experimentWhy: to study the defects and reaction mechanism of radical polymerizationTerminal structure, Head-to-Head (H-H weak site?), initiation step and fragment? (kaolinite in paints increase viscosity, spontaneous ignition)Flory biradical mechanismMayo
13、 MAH mechanismNitroxide trapping experiment support MAH mechansim !Observation of dimer and trimer.possibility ofpolymerizationThe first patentContentsconventional and controlled radical polymerization (CRP) brief history of CRP1.2.3.4.5.6.7.8.9.Kinetics of living polymerizationConstant concentratio
14、n of propagating center.First order kinetics- dM/dt = kp RM- ln(M0/Mt) = kp tKinetic models: the pure alkoxyamine PolymerizationNORkdkcNOR+RR+ktPRiM+kpRi+1Fischer, H. Chem. Rev. 2001,101, 3581.Kinetics of SFRP: the persistent radical effectFischer, H. Chem. Rev. 2001,101, 3581.Kinetics of SFRP: the
15、persistent radical effectWho found the PRE ?1. Solomon et al.C. H. J. Johnson, G. Moad, D. H. Solomon, T. H. Spurling, D. J. Vearing, Aust. J. Chem. 1990, 43, 1215 (super computer).2. Fukuda et al.Fukuda, T.; et al. Macromolecules 1998, 31, 1064; Macromolecules 1996, 29, 6393.4. Hans Fischer et al.H
16、ans Fischer, Chem. Rev. 2001, 101, 3581; Macromolecules 1997, 30, 5666.5. Yan D and Mueller et al.Macromol. Theory. Simul. 1996, 5, 333 (simulation).6. J He and Yang Y.He, J.; Yang, Y.; et al. Macromolecules 1997, 30, 8010. (Monte Carlo)3. Matyjaszewski et al.Matyjaszewski, K.; et al. Macromolecules
17、 1996, 29, 5239 (the role of thermal initiation);Macromolecules 1996, 29, 7661 (simulation by Predici).J. Polym. Sci. Part A: Polym. Chem. 1997, 35, 1857 (speed up by DCPO).Macromolecules 1999, 32, 2948 (effect of termination).How to measure the kinetics of alkoxyamine Fischer, H. Chem. Rev. 2001,10
18、1, 3581.Linear Mn conv.;Inverse: Mn 1/TEMPO0;Independent ofradical initiator;Difficult to reach highMn;Kinetics of SFRP: the persistent radical effectAnalytical resolution by Muller, A. H. X, Yan, D.Monte Carlo Simulation by He, J and Yang, Y.PREDICIKinetics by Monte Carlo simulationHydrogen transfe
19、r, or decomposition of alkoxyamine:Thermal initiationof styreneHe, J.; Li, L.; Yang, Y. Macromolecules, 2000, 33, 2286.Kinetics by Monte Carlo simulation1. Monomer limits; styrene and derivatives copolymerization of acrylates and acrylonitrile with styrene2. Slow polymerization rate; 50-70 hours3. L
20、ow molecular weight. thousands to 20000 g/molLimitation of SFRP1. By organic acid such as camphor sulfonic acidVeregin, R. P. N.; Georges, M. K.; et al. Macromolecules 1996, 29, 4161Initial aim: to suppress the autopolymerization of styreneOCH2SO3HRate enhancement2. Initiators with small kd:Goto, A.
21、; Fukuda, T. Macromolecules 1997, 30, 4272O OHBHPRate enhancementSome new nitroxidesSG1or DEPNNONONOOHTEMPOArkemaSigma-AldrichGnanouR. B. GrubbsAlkoxyamines: Universal Initiators for SFRPO NAdvantages:1. Mn increased up to 200000;2. Polymn. Rate enhanced;3. PDI small: 1.061.2;4. Wider Monomer select
22、ivity: styrene, acrylates, acrylamide, acrylonitrile,etc.5. Block copolymers possible.Benoit, D.; Hawker, C. J.; et al. J. Am. Chem. Soc. 1999, 121, 3904.Benoit, D.; Hawker, C. J.; et al. J. Am. Chem. Soc. 1999, 121, 3904.Some new nitroxidesMain purpose:1. Increasing the range of monomer;2. Preparin
23、g end-functional and telechelic polymers;3. Enabling photoactivation of alkoxyamines.MMAacrylatesThermally labile polymersR. B. GrubbsSome new alkoxyaminesIntroducing functionalization:R. B. GrubbsMacromolecular engineering1. Syntheses of narrow disperse polymers: functional monomers;2. End function
24、al polymers;3. Block copolymers;4. Star and graft architectures;5. Highly and hyperbranched polymers6. Radical crossover and its applicationMacromolecular engineering 1. Narrow disperse polymers: introduction of functional groups, Halogen-styrene, chloromethyl-styrene, t-butoxy-styrene, actoxy-styre
25、ne, oligsaccharide-styrene, conjugated moiety containg styrene, etc. ClXOOONOOROOORROROORORORROcomonomers: acrylates, acrylonitrile, N-vinylcarbazole, 4-vinylpyridine, etc.Functional monomersR. B. GrubbsFunctional monomers for electronic industryThese monomers are not suitable for ATRP (copper conta
26、mination and chelating)!R. B. GrubbsMonomers only suitable for NMRPDienes:R. B. GrubbsBlock copolymers:1. Solely by NMRP: TEMPO-terminated macroinitiator: PS-TEMPO PS-b-P(S-co-AN), usually, 1st block PS, 2nd St+acrylates;2. By combination with other controlled/”living” radical techniques (ATRP and R
27、AFT);3. By combination with other polymerization mechanisms (non-radical polymerizations);4. By dual head initiators.Macromolecular engineeringR. B. GrubbsSynthesis of block copolymersSolely by NMRP: the select of stable radical depends on monomers.Stable radicalM1M2polymerTEMPO, TIPNO, SG1styrenics
28、tyrenicAll styrenicTEMPO, TIPNO, SG1styrenicacrylicPS-b-PATIPNO, SG1styrenicacrylamidePS-b-PAMSG1acrylicacrylicAll acrylicTIPNOstyrenicdienePS-b-P(diene)TEMPO, TIPNO, SG1styrenicAcrylonitrile, etcPS-b-(St-co-AN)R. B. GrubbsSynthesis of block copolymersNMRP and ATRP: High and low reaction temperature
29、s.U. Tunca, et al Polymer 2001, 42, 8489Synthesis of block copolymersNMRP and ATRP: High and low reaction temperatures.D. Gigmes, et al Macromolecules 2009, 42, 8604Synthesis of block copolymersNMRP and anionic: very difficult, only one exampleE. S. Tillman, et alSynthesis of block copolymersNMRP an
30、d ROP: double headed initiator.C. J. HawkerBlock copolymers by Long-chain attached TEMPO:OHOONOmnYoshida, E.; Sugita, A. Macromolecules 1996, 29, 6422.Synthesis of block copolymersMacromolecular engineeringEnd functional polymers:Hedrick, J. L.; Hawker, C. J.; Jerome, R.; et al. Polymer 1995, 36, 48
31、55.Architecture controlStar like polymers:KOH125 CAnalysis: no crosslinking degradationHawker, C. J. Angew. Chem. Int. Ed. Engl. 1995, 34, 1456. Well-defined graft copolymers:; ; .HOO NAIBN60 CNaHArchitecture controlGraft copolymersGraft ontoDendronized initiator: linear-dendritic block copolymersLe
32、duc, M. R.; Hawker, C. J.; Frechet, J. M. J. J. Am. Chem. Soc. 1996, 118, 11111.Macromolecular engineeringThe concept of SCVP: by Frechet and Hawker.Hawker, C. J.; Frechet, J. M. J. J. Am. Chem. Soc.1996, 118, 11111.Macromolecular engineeringHighly branched cleavable polymers: by polymerizablenitrox
33、yl radicalOONOONOcleaveVcLinearchainONO Li, C.; He, J.; Yang, Y. Macromolecules 1999, 32, 7012.Tao, Y.; He, J.; Yang, Y. Macromolecules 2001,34, 4742.Macromolecular engineeringContentsconventional and controlled radical polymerization (CRP) brief history of CRP1.2.3.4.5.6.7.8.9.Radical crossover rea
34、ction不同烷氧基胺之间的交叉反应，可以实现自由基片基和氮氧化物片基之间的互换！NMRP机理佐证！Application of radical crossover reactiondynamic covalent bonddynamic covalent bondA new concept of chain linkageA new concept of chain linkageDynamic macrocyclesDynamic graft copolymersDynamic networksLiving gel with controlled mesh sizeDynamic gels and amphiphilic conetworksSummaryNMRPchemistrykineticsapplicationNORkdkcNOR+Persistent Radical effect
