RAFT polymerization of dimethyl(methacryloyloxy)methyl phosphonate and its phosphonic acid derivative: a new opportunity for phosphorus-based materials

Asymmetric neutral, cationic and anionic PEO-based double-hydrophilic block copolymers (DHBCs): synthesis and reversible micellization triggered by temperature or pH

“…Other phosphonated PEO-based DHBCs are also prepared in our laboratory using dimethyl(methacryloyloxy)methyl phosphonate as a monomer; 29 and their synthesis which relies on a different synthetic pathway will be reported elsewhere. Thermo-sensitive block copolymer 1 is directly obtained by polymerization of N-isopropylacrylamide (NIPAM) while cationic block copolymer 2 and anionic block copolymer 3 need an additional chemical modification of the new polymerized block: polymerization of vinylbenzyl chloride (VBC) followed by quaternisation with triethylamine (TEA) leads to a poly(quaternized vinylbenzyl chloride) (PQVBC + ) cationic block, and polymerization of vinylbenzylphosphonic diethyl ester (VBPDE) followed by deprotection reaction with trimethylsilyl bromide ((Me) 3 SiBr) and methanol leads to a poly-(vinylbenzyl-phosphonic di-acid) (PVBPDA) polyacid block.…”

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.…”

Synthesis and characterization of innovative well-defined difluorophosphonylated-(co)polymers by RAFT polymerization

“…Although thermal-initiated and photo-initiated free-radical polymerization of pCF 2 -monomers have been previously reported, 29, 31 the synthesis of well-defined polymers containing the pCF 2 moiety with controlled architectures have not been previously investigated. Canniccioni et al 32 reported the reversible addition-fragmentation chain-transfer (RAFT) polymerization of dimethyl(methacryloyloxy)methyl phosphonate (MAPC1) using dithioester-based chain transfer agent and trithiocarbonate-based chain transfer agent to afford well-defined phosphorous polymers with low dispersities (Đ M = 1.23-1.35). Well-defined phosphorous block copolymers having a thermo-responsive poly[N-(n-propyl)acrylamide] block have been prepared with potential value for drug delivery.…”