TY - JOUR
T1 - Reversible addition fragmentation chain transfer polymerization of 3-[tris(trimethylsilyloxy) silyl] propyl methacrylate
AU - Saricilar, Sureyya
AU - Knott, Robert
AU - Barner-Kowollik, Christopher
AU - Davis, Thomas P.
AU - Heuts, Johan P.A.
PY - 2003/8/7
Y1 - 2003/8/7
N2 - 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%).
AB - 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%).
KW - Living radical polymerization
KW - Polymerization kinetics
KW - Reversible addition fragmentation chain transfer (RAFT)
UR - http://www.scopus.com/inward/record.url?scp=0041528347&partnerID=8YFLogxK
U2 - 10.1016/S0032-3861(03)00520-2
DO - 10.1016/S0032-3861(03)00520-2
M3 - Article
AN - SCOPUS:0041528347
SN - 0032-3861
VL - 44
SP - 5169
EP - 5176
JO - Polymer
JF - Polymer
IS - 18
ER -