One-Pot Synthesis of Poly((diethylamino)ethyl methacrylate-co-styrene)‑b‑poly(methyl methacrylate-co-styrene) Nanoparticles via Nitroxide-Mediated Polymerization

• Published in: Macromolecules Vol. 48; no. 7; pp. 1952 - 1958
• Main Authors: Darabi, Ali, Jessop, Philip G, Cunningham, Michael F
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14-04-2015
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.5b00258

Poly­((diethylamino)­ethyl methacrylate-co-styrene)-b-poly­(methyl methacrylate-co-styrene) nanoparticles were prepared by one-pot process via nitroxide-mediated polymerization (NMP). For synthesizing the first block, the SG1-mediated copolymerization of 2-(diethylamino)­ethyl methacrylate (DEAEMA), a pH-sensitive monomer, and a small percentage of styrene (S) was performed in water at 90 °C using 2,2′-azobis­[2-(2-imidazolin-2-yl)­propane] dihydrochloride (VA-044) as a positively charged stabilizer and initiator. The resultant macroalkoxyamine was then employed without any purification in the protonated form as both macroinitiator and stabilizer in the same pot for the surfactant-free emulsion copolymerization of methyl methacrylate (MMA) and styrene at 90 °C, which proceeded via polymerization-induced self-assembly (PISA). Latex particles had monomodal size distribution, narrow size polydispersity, and small average size. The polymerization kinetics, the control over molar mass and molar mass distribution, the effect of the charge density on the particles size and latex stability, and the colloidal characteristics of the in situ formed block copolymer micelles were studied in detail.