Synthesis of phosphonated copolymers with tailored architecture by reversible addition‐fragmentation chain transfer polymerization (RAFT)

Abstract

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

Living Radical Polymerization by the RAFT Process—A First Update

“…Other examples are the terpolymer of styrene, MAH, and NVP [200] and various copolymers based on phosphonated monomers. [201] A detailed study of the kinetics of RAFT copolymerization of styrene and MMA with dithioacetate RAFT agents has been reported. [34] Transfer constants (C tr = k tr /k p , where…”

Ab initio emulsion RAFT polymerization of vinylidene chloride mediated by amphiphilic macro‐RAFT agents

“…On the basis of the aforementioned results, the kinetics of ab initio emulsion polymerization were investigated using PAA‐ b ‐PS‐TTCA as the CTA and VA044 as the initiator at 50°C, in which NaOH was added to adjust pH value to 5 after polymerizing for 60 min (entries E7 , E9–E11 ). In all cases, the RAFT emulsion polymerization of VDC was much faster than RAFT solution polymerization reported previously . A conversion greater than 70% could be achieved after polymerizing for 300 min.…”

“…Severac et al pioneered a work on RAFT copolymerization of VDC and methyl acrylate (MeA) using ditiobenzoates as the chain transfer agents (CTAs). Lately, the preparation of phosphonated VDC copolymer and CeO 2 /PVDC hybrid latex via RAFT copolymerization was reported by the same group . Velasquez et al synthesized the VDC–MA and VDC–acrylic acid (AA) copolymers by RAFT polymerization using a trithiocarbonate CTA, and obtained the PVDC‐based amphiphilic block copolymers using the hydrophobic poly(VDC‐ co ‐MeA) and hydrophilic PAA macromolecular RAFT agents.…”

Synthesis of NR based Polyurethanes containing phosphorylated polymers as chain extenders

“…In contrast, RAFT methodology does not require any metal catalyst and thus we focused on this methodology to target such phosphorylated polymers. Successful RAFT polymerizations with phosphorus based monomers have been already described in the literature using some dithioester and trithiocarbonate RAFT agents [33][34][35][36][37]. We thus focused on the synthesis of a new trithiocarbonate based RAFT agent requiring a diol end group in order to incorporate the phosphorylated polymer in a covalent way in the backbone of the Polyurethanes.…”