苯乙烯-乙烯-1-丁烯共聚物功能化反应的选择性机制的研究.pdfVIP

苯乙烯-乙烯-1-丁烯共聚物功能化反应的 选择性机制研究 于海珠 苏圣钦 党智敏*胡国华 北京科技大学高分子科学与工程系，北京市海淀区学院路30号，100083 运用自由基反应对高分子聚合物进行功能化是制备功能高分子的重要手段，其中多组分 共聚物上的高选择性/可控功能化过程是实现这一目标的有效途径[1]。最近，意大利的Ciardelli 教授课题小组报道了过氧化二异丙苯(DCP)引发的马来酸二乙酯(DEM)对苯乙烯-乙烯-1- 丁烯的三嵌段共聚物(SEBS)的功能化反应。[1]实验发现通过调控DEM与DCP的配比，可 以使功能化过程主要发生在聚合物的烷基碳原子上[2]。 MechanisticOriginofSelectiveFunctionalization ofStyrene/OlefinCopolymers(SEBS) YUHaizhuSUShengqingDANGZhiminHUGuohua LaboratoryofPolymerMaterialsforNewEnergyandEnvironment,Departmentof PolymerScienceandEngineering,UniversityofScienceandTechnologyBeijing, Beijing100083 Abstract:Controlled/selectivefunctionalizationofpolymersisfundamentallyimportantfor preparationoffunctionalpolymers.Mechanisticstudiesonthesereactionscanbenefitthe clarificationoftherate/selectivity-determiningsteps,andalsoprovideimportantcluesforrational designofnovelreactions.Inthisstudy,mechanisticinvestigationontherecentlyreported,controlled functionalizationofstyrene-b-(ethylene-co-l-butene)-b-styrenetriblockcopolymer(SEBS)hasbeen conducted.Withtheaidoftheoreticalcalculations,effortsaremadetoclarifythemechanisticorigin oftheexperimentallyobservedpreferentialfunctionlizationonthealiphaticcarbonsofthe polyolefinblock.Basedonthecalculationresults,thereasonoftheobservedselectivityisidentified tobetwo-fold:boththeformationofthealiphaticandbenzylradicalsisirreversibleintheradical initiationprocess,whereasthefollowingtransformations(radicaltransferandterminationsteps)of thealiphaticcarbonsaremuchmorefavorablerelativetothoseofthebenzylradicals.Inotherwords, oncethealiphaticcarbonradicalsareformed,theyeasilyundergotheradicaltransferand terminationsteps,fromwhichthethermodynamicallymorestablefunctionlizedproductisformed selectively. Keywords:Controlledfunctionalization ; SEBS ; mechanisticstudy