Abstract
Polyester and polyether are two key oxygenated polymers,and completely alternative sequence of poly(ester-alt-ether)could efficiently combine the advantages(including flexibility,degradability,etc.)of both segments.Currently,despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides,perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs.Moving forward,synthesizing poly(ester-alt-ether)from commercially available and largescale monomers would be a significant advance.For example,successfully commercialized poly(glycolic acid)(PGA),which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle,would encounter a new paradigm if engineered into poly(ester-alt-ether).In this work,starting from the design of monomer with hybrid structures,we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide(GA)and epoxides using commercially available Salen-Cr(Ⅲ)and PPNCl catalytic systems.The new monomers underwent ring-opening polymerization(ROP)to form a series of poly(ester-alt-ether)with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base.The poly(ester-alt-ether)have significantly lower glass-transition temperature than PGA.Additionally,the poly(ester-alt-ether)can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU)as a catalyst in solution,thus establishing a closed-loop life cycle.From monomers derived from GA and epoxides,this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether)with chemical recyclability.
基金项目
National Key R&D Program of China(2021YFA1501700)
Science and Technology Development Plan of Jilin Province(20230101042JC)
Science and Technology Development Plan of Jilin Province(20210201059GX)
National Natural Science Foundation of China,Basic Science Center Program(51988102)
National Natural Science Foundation of China(52203017)
National Natural Science Foundation of China(52073272)
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