RAFT-polymerized poly(hexafluoroisopropyl methacrylate)s as precursors for functional water-soluble polymersElectronic supplementary information (ESI) available: Fig. S1-S32, Table S1 and Scheme S1 including additional spectroscopic and SEC data. See DOI: 10.1039/c3py01630g

Post-polymerization modification of well-defined precursor polymers is a versatile tool to obtain multifunctional water-soluble polymers that cannot be synthesized by common polymerization techniques. For the first time, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) based homo and block copolymers were synthesized via RAFT polymerization to provide precise precursors for the post-polymerization modification of the 1,1,1,3,3,3-hexafluoroisopropyl ester side chains with water-soluble amines (methoxy tri(ethylene glycol) amine, 2-hydroxypropyl amine and 3-(dimethylamino)-1-propylamine). Sequential aminolysis using Oregon Green cadaverine first followed by 2-hydroxypropyl amine enables access to dye-labelled poly(2-hydroxypropyl methacrylamide) and aminolysis with 3-(dimethylamino)-1-propylamine provides homo and block co-catiomers that complex pDNA in PBS. To this respect, poly(1,1,1,3,3,3-hexafluoroisopropyl methacrylate)s P(HFIPMA)s as precursor polymers may become an alternative route for the synthesis of multifunctional water-soluble polymers for advanced applications. RAFT-polymerized 1,1,1,3,3,3-hexafluoroisopropyl methacrylate homo and block copolymers can serve as well-defined precursor polymers to obtain multifunctional water-soluble methacrylamide copolymers via post-polymerization modification.