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Aqueous dispersion polymerization systems mediated by reversible addition–fragmentation chain transfer (RAFT) process have been less studied in comparison with other heterogeneous polymerization systems due to limited number of monomer/polymer pairs that are suitable for such a condition. We report a novel dispersion polymerization system based on 2-methoxyethyl acrylate (MEA) which is highly water-soluble, but its polymer is not. Using a hydrophilic polymer, poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA), as the macromolecular chain transfer agent (Macro-CTA), both solution and dispersion polymerization of MEA were studied. Chain extension by MEA from PPEGMA was successfully realized in DMF solution polymerization. In dispersion polymerization of MEA in water, PPEGMA was used as both a RAFT mediating species and a steric stabilizer for the formed nanoparticles. The dispersion polymerization of MEA in water was highly efficient using a redox initiator, potassium persulfate/sodium ascorbate, at low temperatures. Simultaneous control of both colloidal stability and RAFT process was realized. Block copolymers with small polydispersity indices were efficiently produced up to complete monomer conversion at solids content up to 32% w/v, in the form of nanoparticles of 40–60 nm diameter.

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The bifunctional role of hydrazine as a potent nucleophile and antioxidant was investigated for the rapid aminolysis of RAFT polymers within minutes in air with effective suppression of the formation of disulfides. Using both dithioesters and trithiocarbonates as model compounds, we showed that hydrazine exhibited a significantly improved aminolysis rate when compared with a commonly used primary alkyl amine. On the basis of the exellent results with CTAs, we further studied the aminolysis of RAFT polymers prepared with either dithioesters or trithiocarbonates. In accord with the aminolysis results on CTAs, hydrazine aminolyzed RAFT polymers in an impressively short time and, more importantly, it significantly suppressed the formation of disulfides as comfirmed with GPC.

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