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Reversible addition fragmentation chain transfer polymerization of 3-[tris(trimethylsilyloxy) silyl] propyl methacrylate |
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| Authors: | Sureyya Saricilar Robert Knott Christopher Barner-Kowollik Thomas P DavisJohan PA Heuts |
| Affiliation: | a Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia b Australian Nuclear Science and Technology Organization, PMB 1 Menai, NSW 2234, Australia c Cooperative Research Center for Polymers, 32 Business Park Drive, Notting Hill, Vic. 3168, Australia |
| Abstract: | Reversible addition fragmentation chain transfer (RAFT) bulk polymerizations of 3-tris(trimethylsilyloxy)silyl] propyl methacrylate (TRIS) have been carried out at 60 °C, employing cumyl dithiobenzoate (CDB) and 2-cyanoprop-2-yl dithiobenzoate (CPDB) as mediating agents at concentrations ranging from 5.0×10−3 to 2.0×10−2 mol l−1. The monomer conversion vs. time evolution was followed via dilatometry and 1H NMR spectroscopy. The CDB mediated polymerization displays RAFT agent concentration dependent inhibition and rate retardation phenomena, whereas the CPDB mediated polymerization process is less susceptible to rate retardation and inhibition effects. The different behavior of CDB and CPDB in TRIS polymerization is most likely due to the increased stability of the intermediate macroRAFT radicals in the CDB mediated process. The generated RAFT polymers were analyzed via size exclusion chromatography indicating linear macromolecular growth with respect to monomer conversion and low polydispersities (PDI<1.15) up to high monomer to polymer conversion (>90%). |
| Keywords: | Living radical polymerization Reversible addition fragmentation chain transfer (RAFT) Polymerization kinetics |
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