Homopolymerization and diblock copolymerization of 2-hydroxypropyl acrylate (HPA) has been conducted using reversible addition fragmentation chain transfer (RAFT) chemistry in tert-butanol at 80 degrees C. PHPA homopolymers were obtained with high conversions and narrow molecular weight distributions over a wide range of target degrees of polymerization. Like its poly(2-hydroxyethyl methacrylate) isomer, PHPA homopolymer exhibits inverse temperature solubility in dilute aqueous solution, with cloud points increasing systematically on lowering the mean chain length. The nature of the end groups is shown to significantly affect the cloud point, whereas no effect of concentration was observed over the PHPA concentration range investigated. Various thermoresponsive PHPA-based diblock copolymers were prepared via one-pot syntheses in which the second block was either permanently hydrophilic or pH-responsive. Preliminary studies confirmed that poly(ethylene oxide)-poly(2-hydroxypropyl acrylate) (PEO45-PHPA(48)) and poly(2-hydroxypropyl acrylate)-poly(2-hydroxyethyl acrylate) (PHPA(49)-PHEA(68))diblock copolymers formed well-defined PHPA-core micelles in 10 mM sodium nitrate solution at 40 degrees C and 70 degrees C with mean hydrodynamic diameters of 20 nm and 35 nm, respectively. In contrast, most other PHPA-based diblock copolymers investigated formed larger colloidal aggregates in 10 mM NaNO3 solution at elevated temperatures. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2032-2043, 2010