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Preparation of PNVCL controlling its molecular weight and maintaining low dispersities by using a trithiocarbonate RAFT agent was achieved. Typical RAFT kinetics were not observed, nevertheless the prepared polymers were reactivated to grow a second hydrophobic poly(hexyl acrylate) block. A series of statistical copolymers of NVCL with N‐vinyl pyrrolidone, n‐hexyl acrylate, methacrylic acid, 2‐(diethylamino)ethyl methacrylate and 2‐(methacryloyloxy)benzoic acid with controlled dispersity were also prepared. By this copolymerization method the cloud point temperature of PNVCL was varied from 27 °C to 42 °C depending on comonomer type, content and pH of the aqueous solution.

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The design, synthesis, and use of two new, stable, functionalized chain transfer agents (CTA's) containing OH and amine end groups for the RAFT polymerization is reported: 2-hydroxyethoxy-carbonylphenylmethyl dithiobenzoate and 2-(2-(tert-butoxycarbonyl)ethylamino)-2-oxo-1-phenylethyl benzodithioate, respectively. The RAFT polymerization of n-hexyl acrylate (HA) using those CTA's, were compared to several other functionalized dithiobenzoate esters reported in the literature containing COOH and Ester groups. The performances of the dithiobenzoates were compared in terms of kinetics and molecular weight distribution control. Good control in polymerization of n-hexyl acrylate with a linear increase of M n with conversion mantaining polydispersity indices (PDI) below 1.1 was obtained by use of the new functionalized CTA's developed and also by use of some other CTA's tested,

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