Incorporating glycidyl methacrylate into block copolymers using poly(methacrylate‐ran‐styrene) macroinitiators synthesized by nitroxide‐mediated polymerization |
| |
Authors: | Benoît Lessard Milan Marić |
| |
Institution: | Department of Chemical Engineering, McGill Institute of Advanced Materials (MIAM), Centre for Self‐Assembled Chemical Structures (CSACS), McGill University, 3610 University Street, Montréal, Québec, Canada H3A 2B2 |
| |
Abstract: | Methyl methacrylate/styrene (MMA/S), ethyl methacrylate/styrene (EMA/S) and butyl methacrylate/styrene (BMA/S) feeds (>90 mol % methacrylate) were copolymerized in 50 wt % p‐xylene at 90 °C with 10 mol % of additional SG1‐free nitroxide mediator relative to unimolecular initiator (BlocBuilder®) to yield methacrylate rich copolymers with polydispersities w/ n = 1.23–1.46. kpK values (kp = propagation rate constant, K = equilibrium constant) for MMA/S copolymerizations were comparable with previous literature, whereas EMA/S and BMA/S copolymerizations were characterized by slightly higher kpK's. Chain extensions with styrene at 110 °C initiated by the methacrylate‐rich macroinitiators (number average molecular weight n = 12.9–33.5 kg mol?1) resulted in slightly broader molecular weight distributions with w/ n = 1.24–1.86 and were often bimodal. Chain extensions with glycidyl methacrylate/styrene/methacrylate (GMA/S/XMA where XMA = MMA, EMA or BMA) mixtures at 90 °C using the same macroinitiators resulted frequently in bimodal molecular weight distributions with many inactive macroinitiators and higher w/ n = 2.01–2.48. P(XMA/S) macroinitiators ( n = 4.9–8.9 kg mol?1), polymerized to low conversion and purified to remove “dead” chains, initiated chain extensions with GMA/MMA/S and GMA/EMA/S giving products with w/ n ~ 1.5 and much fewer unreacted macroinitiators (<5%), whereas the GMA/BMA/S chain extension was characterized by slightly more unreacted macroinitiators (~20%). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2574–2588, 2009 |
| |
Keywords: | block copolymers copolymerization functionalization of polymers methacrylates nitroxide‐mediated polymerization (NMP) |
|
|