A novel method for the synthesis of macrocyclic graft copolymers was developed through combination of anionic ring-opening polymerization (AROP) and atom transfer radical polymerization (ATRP).A linear α,ω-dihydroxy...A novel method for the synthesis of macrocyclic graft copolymers was developed through combination of anionic ring-opening polymerization (AROP) and atom transfer radical polymerization (ATRP).A linear α,ω-dihydroxyl poly(ethylene oxide) with pendant acetal protected hydroxyl groups (l-poly(EO-co-EEGE)) was prepared first by the anionic copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE).Then l-poly(EO-co-EEGE) was cyclized.The crude cyclized product containing the linear byproduct was hydrolyzed and purified by being treated with α-CD.The pure cyclic copolymer [c-poly(EO-co-Gly)] was esterified by reaction with 2-bromoisobutyryl bromide,and then used as ATRP macroinitiators to initiate polymerization of 2-(dimethylamino) ethyl methacrylate (DMAEMA),and a series of pH-and temperature-sensitive macrocyclic graft copolymers composed of a hydrophilic PEO as the ring and PDMAEMA as side chains (c-PEO-g-PDMAEMA) were obtained.The behavior of pH-and temperature-sensitive macrocyclic copolymers was studied in aqueous solution by fluorescence and dynamic light scattering (DLS).The critical micellization pH values of macrocyclic graft copolymers and their corresponding linear graft copolymers (l-PEO-g-PDMAEMA) were measured.Under the same conditions,the cyclic graft copolymer with the shorter side chains gave the higher critical micellization pH value.The c-PEO-g-PDMAEMA showed the lower critical micellization pH value than the corresponding l-PEO-g-PDMAEMA.The average hydrodynamic diameters (Dh) of the micelles were measured by DLS with the variation of the aqueous solution pH value and temperature.展开更多
基金support from the National Natural Science Foundation of China (20874013)
文摘A novel method for the synthesis of macrocyclic graft copolymers was developed through combination of anionic ring-opening polymerization (AROP) and atom transfer radical polymerization (ATRP).A linear α,ω-dihydroxyl poly(ethylene oxide) with pendant acetal protected hydroxyl groups (l-poly(EO-co-EEGE)) was prepared first by the anionic copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE).Then l-poly(EO-co-EEGE) was cyclized.The crude cyclized product containing the linear byproduct was hydrolyzed and purified by being treated with α-CD.The pure cyclic copolymer [c-poly(EO-co-Gly)] was esterified by reaction with 2-bromoisobutyryl bromide,and then used as ATRP macroinitiators to initiate polymerization of 2-(dimethylamino) ethyl methacrylate (DMAEMA),and a series of pH-and temperature-sensitive macrocyclic graft copolymers composed of a hydrophilic PEO as the ring and PDMAEMA as side chains (c-PEO-g-PDMAEMA) were obtained.The behavior of pH-and temperature-sensitive macrocyclic copolymers was studied in aqueous solution by fluorescence and dynamic light scattering (DLS).The critical micellization pH values of macrocyclic graft copolymers and their corresponding linear graft copolymers (l-PEO-g-PDMAEMA) were measured.Under the same conditions,the cyclic graft copolymer with the shorter side chains gave the higher critical micellization pH value.The c-PEO-g-PDMAEMA showed the lower critical micellization pH value than the corresponding l-PEO-g-PDMAEMA.The average hydrodynamic diameters (Dh) of the micelles were measured by DLS with the variation of the aqueous solution pH value and temperature.
基金supported by the National Key R&D Program of China(2021YFE0201400)the National Natural Science Foundation of China(61890940)+5 种基金Chongqing Bayu Scholar Program(DP2020036)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB30000000)the Program of Shanghai Academic Research Leaders(23XD1420200)China Postdoctoral Science Foundation(2019M661353)the National Postdoctoral Program for Innovative Talents(BX20190072)the State Key Laboratory of Molecular Engineering of Polymers and Fudan University。
