Amine-Actuated Catalyst Switch for One-Pot Synthesis of Ether-Ester Type Block Copolymers  

作　　者：Hong Qiu Peng-Fei Zhang Jun-Peng Zhao 

机构地区：[1]Faculty of Materials Science and Engineering,South China University of Technology,Guangzhou 510640,China

出　　处：《Chinese Journal of Polymer Science》2024年第12期1925-1932,I0008,共9页高分子科学（英文版）

基　　金：This work was financially supported by the National Natural Science Foundation of China(Nos.52022031 and 21734004).

摘　　要：Organocatalysis has shown special potency for simplifying the construction of complex polymer structures.We are reporting here a one-pot synthetic pathway using amine as a selectivity-switching agent in the two-component catalytic system consisting of triethylborane(Et_(3)B)and a phosphazene base.We first modelled the interactions of a variety of amines with Et_(3)B by density functional theory calculations.The results indicate that the aliphatic diamines comprising both primary and tertiary amino groups,capable of forming stable intramolecular hydrogen bonds,undergo the strongest complexation with Et_(3)B.Accordingly,experimental results demonstrate that the addition of such amines promptly actuates the in situ selectivity switch from Lewis pair-catalyzed ring-opening polymerization(ROP)of epoxide(propylene oxide,n-butylglycidyl ether,or glycidyl phenyl ether)to organobase-catalyzed ROP ofδ-valerolactone,allowing one-pot continuous synthesis of ether-ester type block copolymers.We thus exploited the noncovalent interaction between amine and Et_(3)B to refine the catalyst switch strategy by exempting it from loading of extra catalyst.

关 键 词：Ring-opening polmerization Block copolymers ORGANOCATALYSIS 

分 类 号：O631.5[理学—高分子化学] O643.36[理学—化学]