A pH-and temperature-sensitive macrocyclic graft copolymer composed of PEO ring and multi-poly(2-(dimethylamino) ethyl methacrylate) lateral chains

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.