| Summary: | The self-emulsifying acrylate-based emulsions with solid content 45 wt.% were prepared in 3.5 h by reverse iodine transfer polymerization (RITP), and the polymer molecular weight (<i>M</i><sub>n</sub>) could be 30,000 g·mol<sup>−1</sup>. The influences of methacrylic acid (MAA) amount, soft/hard monomer mass ratio, and iodine amount on polymerization and latex were investigated. A moderate amount of ionized MAA was needed to stabilize the emulsion. Glass transition temperature (<i>T</i><sub>g</sub>) was decreased with the increasing mass ratio of soft/hard monomer. A higher iodine amount resulted in lower <i>M</i><sub>n</sub>. The increased <i>M</i><sub>n</sub> after chain extension of the polymer with water-insoluble monomers in iterative one-pot method proved the living of polymer. Compared with conventional emulsion polymerization, molecular weight (<i>M</i><sub>n</sub>) could be controlled, and <i>M</i><sub>n</sub> of polymer synthesized in RITP emulsion polymerization is higher; emulsion of polyacrylate-containing hydroxyl monomer units prepared by RITP emulsifier-free radical polymerization is more stable. Good properties, such as hardness, water resistance, adhesion, and increased value of maximum tensile of films modified by reaction of polyacrylate with melamine−formaldehyde (MF) resin, indicated potential application in baking coating.
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