The synthesis by reversible addition‐fragmentation chain transfer (RAFT) polymerization of three phosphonated terpolymers with tailored architecture has been studied. A phosphonated methacrylate (MAUPHOS) was copolymerized with vinylidene chloride (VC2) and methyl acrylate (MA) to prepare a gradient terpolymer poly(VC2‐co‐MA‐co‐MAUPHOS). Besides, hydroxyethyl acrylate (HEA) was used as a functional monomer in RAFT polymerization to prepare a statistical poly(VC2‐co‐MA‐co‐HEA) terpolymer and a diblock poly(VC2‐co‐MA)‐b‐poly(HEA) terpolymer. The HEA‐containing polymers were then modified with a phosphonated epoxide to introduce the phosphonated group. The control of the polymerization was proven by kinetic studies (evolution of molecular weight vs. conversion) and by a successful block copolymerization. The architecture of the terpolymers was determined by the reactivity ratios of the monomers: terpolymerization of VC2, MA, and HEA leading to an ideal statistical terpolymer (no composition drift) whereas terpolymerization of VC2, MA, and the phosphonated methacrylate led to a gradient terpolymer. These terpolymers were characterized by size exclusion chromatography, 31P NMR and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 13–24, 2006

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Summary: The living radical terpolymerization of vinylidene chloride (VC2), methyl acrylate (MA), and dimethyl‐2‐methacryloxyethylphosphonate (MAPHOS) was performed at 70 °C in benzene by a reversible addition fragmentation chain transfer (RAFT) process to yield a gradient terpolymer of controlled molecular weight ($\overline M _{\rm n}$ = 5 800 g · mol−1, Ip = 1.53) with a molar composition of 75:14:11 (VC2/MA/MAPHOS). Such terpolymers, hydrolyzed (phosphonic acid groups) or not, were used as polymeric additives in coating formulations based on a poly(VC2‐co‐MA) copolymer matrix ($\overline M _{\rm n}$ = 63 300 g · mol−1, Ip = 1.99, VC2/MA = 80:20 molar ratio). The formulations were spun cast on stainless steel surfaces and the coatings were observed by scanning electron microscopy (SEM) coupled with X‐ray analyses (EDX). The hydrolyzed additive was shown to both segregate and migrate towards the metal interface, leading to a preferential organization of the coating. Hence, the matrix at the air surface acts as a barrier to gas while the additive ensures adhesion at the polymer/metal interface.SEM photograph of a section of the coating with formulation 4 [poly(VC2‐co‐MA‐co‐MAPHOS(OH)2) (75:14:11)].magnified imageSEM photograph of a section of the coating with formulation 4 [poly(VC2‐co‐MA‐co‐MAPHOS(OH)2) (75:14:11)].