简介:Theuseofliving,alkyllithium-initiatedanionicpolymerizationtopreparechain-endfunctionalizedpolymersandheteroarm,star-branchedpolymersisdiscussed.Thescopeandlimitationsofspecificterminationreactionswithavarietyofelectrophilicspeciesareillustratedforcarbonation,hydroxyethylation,amination,andsulfonation.Themethodologyofusingsubstituted1,1-diphenylethylenestoprovideageneral,quantitativefunctionalizationprocedureisoutlinedandillustratedwithexamplesofamineandphenolend-functionalization.Amethodologyisdescribedforthesynthesisoffunctionalized,star-branchedcopolymerswithcompositionallyheterogeneousarmsofcontrolledmolecularweightandnarrowmolecularweightdistributionusing1,3-bis(1-pbenylethenyl)benzene.
简介:Lamellarcrystalsofdiblock,triblockandfour-armpoly(ethyleneglycol)-b-poly(ε-caprolactone)(PEG-b-PCL)crystalline-crystallinecopolymersweresuccessfullyobtainedfromtheirsolution.Morphologyandstructureoflamellarcrystalsofcrystalline-crystallinecopolymerswereinvestigatedusingtapping-modeatomicforcemicroscopy(AFM)andselectedareaelectrondiffraction(SAED).Allofthesesamplesshowedthetruncated-lozengemultilayerbasalshapeswithcentralscrewdislocationorcentralstack,whichwereallobtainedsimultaneouslyfromtheoilbath.ThediffractionpatternofPEGblocklamellarcrystalisattributedtothe(120)diffractingplanesandthepatternofPCLblocklamellarcrystalisattributedtothe(110)diffractingplanesand(200)diffractingplanesaccordingtotheSAEDresults.Four(110)crystalgrowthplanesandtwo(200)crystalgrowthplanesarediscoveredforthePCLblocks,butthe(120)crystalgrowthplanesofPEGblocksarehidedinthefigureofAFM.Thecrystallinestructureofthefour-armcopolymers(FA)ismoredisorderandconfusedthanthatofthediblock(DI)copolymerandthestriatedfoldsurfacestructuresoflamellarcrystalsoffour-armcopolymers(FA)aresmootherthantheseoflinearanalogues,owingtotheconfusedcrystallizationofblockscausedbythemutualrestrictionofblocksandthehindranceofthedendriticcores.Inaddition,theaspectratioofFAisgreaterthanthatoftheothers.Itishypothesizedthattherearetworeasonsforthechangeofaspectratios.First,the(200)diffractingplanesofPCLcrystalsgrewslowlycomparedtotheir(110)diffractingplanesbecauseofdifferenceintheenergybarrier.Secondly,edgedislocationsonthe(200)diffractingplanesarealsoresponsibleforthevariationoftheaspectratio.Consequently,thecrystallinedefectsareaugmentedbythecompetingblockscrystallizedsimultaneouslyandthehindranceofthedendriticcores.