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pubs.acs.org/doi/abs/10.1021/ma050998o

Thermo- and pH-responsive micellization of poly(ethylene glycol)-b-poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) in water was studied. Micellization of the triblock copolymer, which was synthesized by sequential atom transfer radical polymerization of 4-vinylpyridine and N-isopropylacrylamide, occurred with combined stimulus of temperature and pH changes to form various morphological micelles. The copolymer existed as unimers at pH 2.0 and then associated into spherical core−corona micelles when pH increased from 2.0 to 6.5 at 25 °C. The critical aggregation temperature of the copolymer was about 34.6 °C, which was a little higher than poly(N-isopropylacrylamide). When the copolymer solution was heated above the critical aggregation temperature, the copolymer first self-assembled into compound core−corona micelles or micellar cluster and then converted into core−shell−corona micelles with pH increasing from 2.0 to 6.5. When temperature decreased from 50 to 25 °C, the core−shell−corona micelles further rearranged into core−corona micelles.