The free radical polymerization controlled by 2,2,6,6-tetramethylpiperidine
-N-oxyl (TEMPO) was carried out in a water/oil suspension at 120-135 degree
s C. Suspension polymerization is a polymerization reaction with high conve
rsion and allows high-molecular-weight polymers to be synthesized. The poly
merization was started by a styrene macroinitiator. The block length is det
ermined by the level of conversion and the initial macroinitiator concentra
tion. A kinetic model is introduced which predicts a drastic reduction of p
olymerization time (at ca. 90% conversion a reduction from ca. 20 h to 5-3
h) and improved polydispersity through selective addition of initiator. The
agreements between the simulated results and the experimental findings are
surprisingly good. From model calculation, the percentage and molar mass d
istributions of the dead polymers can also be derived.