Well-defined multi-arm star thermoresponsive block copolymer nano-assemblies of [poly(N-isopropylacrylamide)-block-polystyrene]n [(PNIPAM-b-PS)n] with n = 1, 2, 3 and 4 arms were synthesized by RAFT dispersion polymerization via polymerization-induced self-assembly.

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Thermoresponsive poly(2-(N-alkylacrylamide) ethyl acetate)s with different N-alkyl groups, including poly(2-(N-methylacrylamide) ethyl acetate) (PNMAAEA), poly(2-(N-ethylacrylamide) ethyl acetate) (PNEAAEA), and poly(2-(N-propylacrylamide) ethyl acetate) (PNPAAEA), as well as poly(N-acetoxylethylacrylamide) (PNAEAA), were synthesized by solution RAFT polymerization. Unexpectedly, it was found that there are induction periods in the RAFT polymerization of these monomers, and the induction time correlates with the length of the N-alkyl groups in the monomers and follows the order of NAEAA < NMAAEA < NEAAEA < NPAAEA. The solubility of poly(2-(N-alkylacrylamide) ethyl acetate)s in water is also firmly dependent on the length of the N-alkyl groups. PNPAAEA including the largest N-propyl group is insoluble in water, whereas PNMAAEA and PNEAAEA are thermoresponsive in water and undergo the reversible soluble-to-insoluble transition at a critical solution temperature. The cloud point temperature (Tcp) of the thermoresponsive polymers is in the order of PNEAAEA < PNAEAA < PNMAAEA. The parameters affecting the Tcp of thermoresponsive polymers, e.g., degree of polymerization (DP), polymer concentration, salt, urea, and phenol, are investigated. Thermoresponsive PNMAAEA-b-PNEAAEA block copolymer and PNMAAEA-co-PNEAAEA random copolymers with different PNMAAEA and/or PNEAAEA fractions are synthesized, and their thermoresponse is checked.

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