A Minimal Amount of Acrylonitrile Turns the Nitroxide-Mediated Polymerization of Methyl Methacrylate into an Almost Ideal Controlled/Living System

作者：Nicolas Julien^*; Brusseau Segolene; Charleux Bernadette

来源：Journal of Polymer Science Part A: Polymer Chemistry , 2010, 48(1): 34-47.

DOI：10.1002/pola.23749

• acrylonitrile
• block copolymer
• copolymerization
• kinetics (polym.)
• living radical polymerization (LRP)
• methyl methacrylate
• nitroxide-mediated polymerization

Nitroxide-mediated controlled/living free-radical polymerization of methyl methacrylate initiated by the SG1-based alkoxyamine BlocBuilder was successfully performed in bulk at 80-99 degrees C with the help of a very small amount of acrylonitrile (AN, 2.2-8.8 mol%) as a comonomer. Well-defined PMMA-rich P(MMA-co-AN) copolymers were prepared with the number-average molar mass, M(n), in the 6.1-32 kg mol(-1) range and polydispersity indexes as low as 1.24. Incorporation of AN in the copolymers was demonstrated by (1)H and (13)C NMR spectroscopy, and its effect on the chain thermal properties was evaluated by DSC and TGA analyses. Investigation of chain-end functionalization by an alkoxyamine group was performed by means of (31)P NMR spectroscopy and chain extensions from a P(MMA-co-AN)-SG1 macroinitiator. It demonstrated the very high proportion of SG1-terminated polymer chains, which opened the door to block copolymer synthesis with a high quality of control.

• 出版日期2010-1-1