Chapter 4-Living Radical Polymerization - Living Radical...

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Living Radical PolymerizationIntroduction: Importance of block copolymersComparison between ionic and radical polymerizationsStable Free Radical Polymerization (SFRP)Atom Transfer Radical Polymerization (ATRP)Reversible Addition Fragmentation Chain Transfer (RAFT)1
Living Radical PolymerizationIntroduction: Importance of block copolymersComparison between ionic and radical polymerizationsStable Free Radical Polymerization (SFRP)Atom Transfer Radical Polymerization (ATRP)Reversible Addition Fragmentation Chain Transfer (RAFT)2
Living Ionic PolymerizationFree Radical Polymerization-Well-defined polymers (PDI < 1.2)-Block copolymers-Functionalized polymers Living polymerization enables one to generate:Polymers produced by free radical polymerization are:-Poorly defined (PDI > 1.5)-“Dead” polymers-No block copolymersLiving Radical Polymerization3
Polymer-Polymer Phase BehaviourBates, F. Science1991, 251, 898-905.4
Polymer-Polymer Phase BehaviourBates, F. Science1991, 251, 898-905.Effect of varying composition on the ordered-phase symmetry in polystyrene-polyisoprene (PS-PI) diblock copolymer; fSrefers to the overall volume fraction of polystyrene.OBDD = ordered bicontinuous double diamondBody-centered cubic latticeHexagonally packed cylindersOrdered bicontinuous double diamondLamellae5
6Polymer-Polymer Phase BehaviourRuiz et al. Science2008, 321, 936-939.Block Copolymers
THE DAWNING ERA OF POLYMER THERAPEUTICSDuncan, R.Nature Rev. Drug Discovery 2003, 2, 347-360a. Polymeric drugb. Polymer-protein conjugatec. Polyplex: polymer-DNA complexd. Polymer-drug conjugatee. Polymeric micelleHydrophilic blockDNACationic blockTargeting residueHydrophilic blockDrugHydrophobic block7
Discher and Eisenberg Science2002, 297, 967-973.Polymeric Surfactants8
Living Radical PolymerizationIntroduction: Importance of block copolymersComparison between ionic and radical polymerizationsStable Free Radical Polymerization (SFRP)Atom Transfer Radical Polymerization (ATRP)Reversible Addition Fragmentation Chain Transfer (RAFT)9
Living Ionic PolymerizationFree Radical Polymerization-Well-defined polymers-Block copolymers-Functionalized polymers Living polymerization enables one to generate:Polymers produced by free radical polymerization are:-“dead” polymers-poorly defined (PDI > 1.5)-No block copolymersImportant for NANOTECHNOLOGYLiving Radical Polymerization ?But ionic polymerizations are hard to do!

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