碳酸钙粒子在水相raft聚合中的应用分析-application analysis of calcium carbonate particles in aqueous raft polymerization.docx

PDMA-b-PS-b-PDMA三嵌段共聚物。发现CaCO3/St重量比对RAFT聚合速率有影响，当CaCO3/St重量比提高时，反应速率增加，但是对产物的分子量分布影响不大。动力学研究表明，ln([M]o/[M])与时间呈线性关系，数均分子量Mn随着单体转化率提高而线性增加，CaCO3粒子存在时可以提高反应速率并降低共聚物的分子量分布。关键词：RAFT聚合，水相RAFT聚合，碳酸钙；苯乙烯；N-异丙基丙烯酰胺；N,N-二甲基丙烯酰胺ABSTRACTSinceinitialintroducedin1998,thereversibleaddition-fragmentationchaintransfer(RAFT)polymerizationhasproventobeperhapsthemostversatileofthecontrolled/livingradicalpolymerizationmethods.Uptonow,RAFTpolymerizationunderhomogeneouscondition(solution/bulk)hasbeenextensivelystudied,andvariouspolymersincludinghomopolymer,andblockpolymerwithnarrowmolecularweightdistributionhavebeensynthesized.However,theRAFTpolymerizationunderheterogeneousconditions,especiallytheaqueousRAFTpolymerization,isfarfrombeingperfectlyaccomplished.Anewmethodtoachievewell-controlledaqueousRAFTpolymerizationofhydrophobicmonomerandhydrophilicmonomerinthepresenceofCaCO3particleswereproposed.Polystyrene(PS)wassynthesizedbyaqueousRAFTpolymerization.Thesurfactantplaysthecrucialroletoensurestabilityoftheemulsion.However,thesurfactantbringssomesideeffects.Inthispaper,theRAFTagentofS,S-bis(α,α-dimethyl-α-aceticacid)trithiocarbonate(BDMAT)andStwereaddedintowatermediatedwithCaCO3particles,anditwasfoundthattheywereadsorbedonthesurfaceofCaCO3particlesandwell-controlledaqueousRAFTpolymerizationwasperformed.TheweightratioofCaCO3/StontheaqueousRAFTpolymerizationwasinvestigated,anditwasfoundthathighCaCO3/StweightratioledtofastaqueousRAFTpolymerization.TheaqueousRAFTpolymerizationkineticswaschecked,andthefastRAFTpolymerizationrateatlowmolarratioofstyrene/BDMAT/K2S2O8,thelinearln([M]o/[M])-timeplot,thelinearincreaseinthenumber-averagemolecularweightwiththemonomerconversion,andtherelativelylowpolydispersityindex(PDI)valuesweredemonstrated.TheaqueousRAFTpolymerizationwascomparedwiththegeneralemulsionRAFTpolymerizationinthepresenceofthesodiumdodecylsulfate(SDS)surfactant.ItwasfoundthattheaqueousRAFTpolymerizationseemedmorevalidthantheemulsionRAFTpolymerization,despitethataqueousRAFTpolymerizationran