Synthesis of fluorescent, dansyl end-functionalized PMMA and poly(methyl methacrylate-b-phenanthren-1-yl-methacrylate) diblock copolymers, at ambient temperature

Abstract

The polymerization of MMA, at ambient temperature, mediated by dansyl chloride is investigated using controlled radical polymerization methods. The solution ATRP results in reasonably controlled polymerization with PDI < 1.3. The SET-LRP polymerization is less controlled while SET-RAFT polymerization is controlled producing poly(methyl methacrylate) (PMMA) with the PDI < 1.3. In all the cases, the polymerization rate followed first order kinetics with respect to monomer conversion and the molecular weight of the polymer increased linearly with conversion. The R group in the CTAs do not appear to play a key role in controlling the propagation rate. SET-RAFT method appears to be a simpler tool to produce methacrylate polymers, under ambient conditions, in comparison with ATRP and SET-LRP. Fluorescent diblock copolymers, P(MMA-b-PhMA), were synthesized. These were highly fluorescent with two distinguishable emission signatures from the dansyl group and the phenanthren-1-yl methacrylate block. The fluorescence emission spectra reveal interesting features such as large red shift when compared to the small molecule. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012