Controllable synthesis of new polymerizable macrosurfactants via CCTP and RAFT techniques and investigation of their performance in emulsion polymerization

We reported herein the synthesis of poly(methacrylic acid)-A-poly(butyl acrylate) (PMAA-A-PBA) block copolymers (surfmers) and their performance as novel polymerizable macrosurfactants in emulsion polymerization. The surfmers bearing terminal unsaturated carbon-carbon double bonds were first successfully designed and sy thesized via catalytic chain, transfer polymerization (CCTP) and radical addition-fragmentation polymerization (RAFT) techniques. The structures of surfmers were characterized by Raman spectra, nuclear magnetic resonance (¹H NMR), and gel permeation chromatography (GPC). The critical micelle concentration of surfmers was determined. Subsequently, the surfmers were used as emulsifier to prepare polyacrylate latexes (PA-surf). The influence of the surfmer concentration as well as PMAA and PBA chain segment ratios of surfmer on their performance in emulsion polymerization was discussed thoroughly. The particle size, amount of coaguium, and stability against electrolyte solutions of the latexes were evaluated, Also, the relations between, monomer conversion in emulsion polymerization, polymerization rate, emulsion particle size, surface tension, and reaction time were investigated, which showed, some interesting information for the probable mechanism underlying this emulsion polymerization system. Atomic force microscopy (AFM) and attenuated total reflection Fourier transform infrared spectra (ATR FT-IR) were performed to investigate the surface morphology and component distribution of the latex films. The results show high efficiency of these surfmers in emulsion polymerization, suggesting that the resultant PMAA-A-PBA block copolymers act not only as the emulsifier but also as the stabilizer of monomer droplets as well as the so-called comonomer.