Functional Polymers Synthesized Via SuFEx Click Chemistry And Their Applications

In 2014,Sharpless and his colleagues reported a new click chemistry reaction,Sulfur(VI)Fluoride Exchange(SuFEx),for the synthesis of organic molecules.This click chemistry reaction depends on the extremely outstanding reactivity of the S(VI)-F group and it has attracted widespread attentions due to many advantages,such as easy operations,fast reaction rate,high yields,and high tolerance to various functional groups and reaction conditions.This thesis focuses on the applications of SuFEx click chemistry in the synthesis of functional polymers,taking full advantage of SuFEx click reaction to prepare functional polymer materials with high yields and excellent performances.A series of various polymers were synthesized and modified via SuFEx click chemistry,and their applications in organic electronic storages and water treatments were studied.In addition,this article also explores the possibility of applying click chemistry to the preparation of bottle brush polymers and porous polymer frameworks.The main work of the thesis includes the following aspects:(1)A triphenylamine derivative monomer TDA containing an azophenyl group was synthesized via SuFEx click chemistry,and a polytriphenylamine polymer PTDA was obtained by redox polymerization.Interestingly,TDA has a strong affinity with Fe(?)ions and a polymer metal complex PTDA-Fe was prepared by a one-pot reaction with TDA and FeC13.It is shown that the sandwich-structured memory devices with PTDA film as the active layer exhibits a binary storage performance.However,devices taking PTDA-Fe film as the active layer exhibits a unique ternary storage behavior.(2)A cross-linked polysulfate were synthesized via SuFEx click chemistry with two trifunctional monomers,TPC-OSO2F and TPC-OTBS,by two-solvent interface extraction method.Different from the commonly obtained cross-linked polymer powders,SuFEx click chemsitry cross-linking polymerization using a two-solvent interface extraction method results a cross-linked polysulfate solvent gel unexpectedly.This kind of gel can form polymer materials with macroporous structure(d>80nm)after solvent exchange.In this paper,regulations and influences of the pore-forming of this polymer were studied.And its adsorption and removal effects on POPs(such as bisphenol A)in water was investigated.(3)The styrene-based living polymerization monomer,sulfuryl fluoride-based styrene(PSF),which can carry out SuFEx click reaction and an ATRP polymerization initiator TBSO-HEBr with silicone ether group were synthesized.The sulfuryl fluoride styrene was explored as the main chain of the polymer,and the synthesis of the bottle brush polymer by SuFEx click chemistry was tried to make the post-modification of the polymer.Further attempts have been made to prepare porous polymer frameworks by crosslinking with side-active blocks.