Functionalization of PMMA by a functional “iniferter”: Kinetics of polymerization of MMA using N,N′‐diethyl‐N,N′‐bis(2‐hydroxyethyl) thiuram disulfide

Abstract α,ω‐Dihydroxy‐terminated‐PMMA was synthesized by the bulk polymerization of methyl methacrylate in the presence of a functional “iniferter,” viz., N,N′‐diethyl‐N,N′‐bis(2‐hydroxyethyl)thiuram disulfide (DHTD). The kinetics of the polymerization were studied by determining the polymerization rate as a function of the “iniferter” concentration at 60, 70, 85, and 95°C. Evaluation of the data by a computerized multiple regression analysis led to calculation of the various kinetic parameters and the activation energies of the related phenomena. The maximum observed in the Rp–initiator concentration curve was found to shift to lower initiator concentration as the temperature increased. The formal reaction order with respect to the concentration of the initiator decreased with increasing temperature and concentration of DHTD. The chain transfer constants of DHTD with MMA were calculated from the molecular weights of the resulting polymers. The functionalities of the oligomers were calculated from the elemental analysis of the chain end groups. Thermogravimetric analysis revealed that the polymer chain ends were devoid of unsaturated groups and that the polymer underwent degradation only by random scission.