零价金属催化raft聚合物末端硫代羰基去除及修饰-removal and modification of thiocarbonyl at the end of raft polymer catalyzed by zero-valent metal.docx

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2018-05-27 发布于上海
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零价金属催化raft聚合物末端硫代羰基去除及修饰-removal and modification of thiocarbonyl at the end of raft polymer catalyzed by zero-valent metal.docx

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零价金属催化raft聚合物末端硫代羰基去除及修饰-removal and modification of thiocarbonyl at the end of raft polymer catalyzed by zero-valent metal

Zero-ValentMetalCatalyzedRemoval/ModificationofThiocarbonylthioEndGroupsofRAFTPolymersAbstractDuringthepastdecades,reversible-deactivationradicalpolymerization(RDRP)hasbeenwelldevelopedaseffectiveandrobustsynthetictechniqueforitspowerfulcapabilityofdesignandsynthesisoftailor-mademacromolecules,whichincludingatom-transferradicalpolymerization(ATRP),reversibleaddition-fragmentationchain-transfer(RAFT)polymerizationandsingle-electrontransferlivingradicalpolymerization(SET-LRP).RAFTpolymerizationusingathiocarbonylthiocontainingchaintransferagent(CTA)isundoubtedlyoneofthemostversatileRDRPtechniquesforitsmildpolymerizationconditions,widerangeofavailablemonomersandgoodcontrolovermolecularweights.ButRAFTpolymerspossessahighdegreeofthiocarbonylthiospecies(S=C(Z)-S-)attheωchainend.However,problemsthusarisesincethepresenceofthiocarbonylthiogroupcancolourtheresultantpolymerwithviolet,redorpaleyellowdependingontheCTA‘sstructure.Also,theRAFTpolymerssometimesreleaseanodorduetodecompositionofthethiocarbonylthiogroupsandtheevolutionofvolatilesulfur-containingcompounds.Inaddition,theRAFTpolymercanundergodegradationbyaminolysis,hydrolysisorthermolysis.Thepurposeofthispaperistoremove/modifyofthiocarbonylthioendgroupsofRAFTpolymersbyusingzero-valentmetal/TEMPO.Thedetailedworkareasfollows:SynthesisofRAFT-madepolymerspoly(methylmethacrylate)(PMMA),poly(styrene)(PS),poly(methylacrylate)(PMA)andpoly(vinylacetate)(PVAc)fortheremoval/modificationoftheirthiocarbonylthioendgroupsbytheutilizationofzero-valentmetal(Cu(0)orFe(0))/2,2,6,6-tertamethylpiperidinyl-1-oxy(TEMPO)atambienttemperature.At[PMMA]0/[Cu(0)]0/[ligand]0/[TEMPO]0=1/5/5/1.5,the1HNMRresultsshowedgraduallyweakenedsignals(7.3–8.0ppm)ofthiocarbonylthiogroupswithtreatedAbstractZero-ValentMetalCatalyzedRemoval/ModificationofThiocarbonylthioEndGroupsofRAFTPolymerstime,andthemolecularweights(MW)graduallyincreasedtothetwofoldoftheprecursor,duetothepolymericradical-polymericradicalcrosscoupling.While,theMWkeptunchangedat[PMMA]0/[Cu(0)]0/[lig