The in situ atom transfer radical polymerization of MMA using the TD-FeCl3-PPh3 initiating system

Well-defined poly(methyl methacrylate) (PMMA) with very low polydispersity and with alpha -Et2NCS2 and omega -Cl end groups was synthesized via in situ atom transfer radical polymerization (ATRP), using a tetraethylthiuram disulfide (TD)-FeCl3-PPh3 initiating system. The in situ ATRP of methyl methacrylate (MMA) was a "living''/controlled polymerization and the polydispersity indices of PMMA were very narrow (M-n=7100 and M-w/M-n=1.04). The presence of the Et2NCS2 and the chlorine atoms as end groups in PMMA was determined by H-1 NMR, FT-IR and UV spectroscopies. The presence of an omega -chlorine end group on the polymer chain was used to chain extend the PMMA using a conventional ATRP initiation system.