In Situ Crosslinking of Nanoparticles in Polymerization‐Induced Self‐Assembly via ARGET ATRP of Glycidyl Methacrylate

Polymerization‐induced self‐assembly (PISA) and in situ crosslinking of the formed nanoparticles are successfully realized by activators regenerated by electron‐transfer atom transfer radical polymerization (ARGET ATRP) of glycidyl methacrylate (GMA) or a mixture of GMA/benzyl methacrylate (BnMA) monomers in ethanol. Poly(oligo(ethylene oxide) methyl ether methacrylate) was employed as macroinitiator/stabilizer, and a cupric bromide/tris(pyridin‐2‐ylmethyl)amine complex as catalyst. Tin (2‐ethylhexanoate) was used as reducing agent for ARGET ATRP, and simultaneously acted as a catalyst for ring‐opening polymerization of oxirane ring in GMA. The kinetics shows that the double bond in GMA was completely polymerized in 4.0 h, while only a 33% conversion of oxirane ring in GMA was reached at 117.0 h. Such a large difference would guarantee a smooth PISA and a subsequent in situ crosslinking of formed nanoparticles. The transmission electron microscopy and dynamic light scattering show spherical nanoparticles formed. With a feed molar ratio [BnMA]0/[GMA]0 = 150/50, 100/100, and 50/150, the nanoparticles formed in ethanol can dissociate or swell in toluene. When pure GMA was used, the solid nanoparticles were observed in toluene or ethanol. The ARGET ATRP provides an efficient strategy to stabilize the nanoparticles formed in the PISA of GMA‐containing system. Based on the dual function of tin (2‐ethylhexanoate) (Sn(EH)2) agent as reducing agent for an activator regenerated by electron‐transfer atom transfer radical polymerization (ARGET ATRP) and as catalyst for ring‐opening reaction, the polymerization‐induced self‐assembly (PISA) of glycidyl methacrylate (GMA) monomer and subsequent in situ crosslinking of the formed nanoparticles are successfully carried out.