Effect of the medium on the homogeneous radical copolymerization of unsaturated carboxylic acids with vinyl monomers

Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous–organic, and aqueous media via RAFT polymerization

“…For example, for the copolymerization in bulk r AA ¼ 0.15 and r S ¼ 0. 25,48 in N,N-dimethyl formamide (DMF) r AA ¼ 0.05-0.08, r S ¼ 1.03-1.60, 49,50 in 1,4-dioxane r AA ¼ 0.13, r S ¼ 0.25. 51 The RAFT copolymerizations of HFBA with acrylic acid as well as 2,2,3,3,4,4,5,5-octauoropentyl acrylate (OFPA) with acrylic acid were conducted in the polar solvent DMF (50 vol%) using dibenzyl trithiocarbonate (BTC) as the RAFT agent and azo-bis-isobutyronitrile (AIBN) as an initiator at 80 C. The nal aim of these experiments was the synthesis of water-soluble narrow dispersed amphiphilic copolymers with the MW below 10 kDa for the further application in the emulsion and dispersion copolymerization of uoroalkyl acrylates.…”

Synthesis and pH- and salinity-controlled self-assembly of novel amphiphilic block-gradient copolymers of styrene and acrylic acid

“…The reactivity ratios of styrene and acrylic acid obtained earlier by different groups [33][34][35][36][37][38][39] were determined for copolymerization in different solvents where each initiator was a lowmass substance of a different nature (AIBN, BPO, MONAMS, Blocbuilder). As is pointed out in ref.…”

“…In other works the reactivity ratios for styrene and acrylic acid were determined for classical radical polymerization under various conditions. [35][36][37][38][39] Knowing the reactivity ratios, one can obtain statistical 34 or gradient copolymers 16,33 of styrene and acrylic acid by tuning the initial proportion of monomers.…”

Control over the relative reactivities of monomers in RAFT copolymerization of styrene and acrylic acid

“…A typical example is styrene (S)–acrylic acid (AA) copolymerization: the higher the polarity of the solvent, the more pronounced the difference in monomer reactivity. For example, for copolymerization in bulk r AA = 0.15 and r S = 0.25, 24 in DMF r AA = 0.05–0.08 and r S = 1.03–1.60, 25−27 in benzene r AA = 0.13 and r S = 0.30, 27 and in 1,4-dioxane r AA = 0.13 and r S = 0.25 for conventional radical copolymerization 28 and r AA = 0.27 and r S = 0.72 for a stable free-radical process. 29 …”