Emulsifier-free polymerization of n-butyl acrylate involving trithiocarbonates based on oligomer acrylic acid

Emulsifier‐free reversible addition–fragmentation chain transfer emulsion polymerization of alkyl acrylates mediated by symmetrical trithiocarbonates based on poly(acrylic acid)

“…However, according to our previous data, the insertion of several units of alkyl acrylate into the PAA chain results in enhancing the surface active properties of the polymer . After reaching the critical micelle concentration, which is typically below 0.1 wt% (it corresponds to ca 1% conversion of polymeric RAFT agent), the amphiphilic block copolymers form micelles.…”

“…In the case of the batch regime, our studies of BA emulsion polymerization initiated by PSK and mediated by PAATC were supplemented by additional investigations of the influence of the PSK and PAATC concentrations on the kinetics and MWD of the products. The range of concentrations was chosen on the basis of our previous results …”

“…symmetrical trithiocarbonates that enable the synthesis of ABA triblock copolymers, have attracted much less attention. In our previous studies of emulsion homopolymerization and copolymerization of n ‐butyl acrylate (BA) in the presence of poly(acrylic acid) (PAA) based macroRAFT agents containing the trithiocarbonate group within the chain, we have analyzed the influence of monomer(s) to the medium volume ratio, the polymerization degree and the chemical nature of the co‐monomer in the macroRAFT agent on polymerization kinetics, particle size and morphology, and the molecular weight distribution (MWD) of the polymerization products …”

“…In contrast, emulsifier‐free emulsion polymerization of acrylates mediated by the same macroRAFT agents A–S–C(=S)–S–A, based on for example PAA trithiocarbonate, leads to different results . In contrast to products of solution or dispersion polymerization, the products of emulsion polymerization are typically characterized by a bimodal MWD in a wide range of monomer conversion.…”

“…The kinetic features of BA emulsion polymerization mediated by a macroRAFT agent with a similar nature of a leaving polymeric substituent, PAA, but a different locus of the trithiocarbonate group in the chain are also different . In particular, the induction period on the kinetic curves is longer, the number‐average particle diameter is smaller and the rate of consumption of macroRAFT agent upon increasing monomer conversion is higher in the case of PAA with terminal trithiocarbonate group …”