FREE-RADICAL SYNTHESIS OF ALPHA-OMEGA-PRIMARY AMINO FUNCTIONALIZED POLYISOPRENE THROUGH THE FUNCTIONAL THERMAL INIFERTER [BIS(N-(2-PHTHALIMIDOETHYL)PIPERAZINE)]THIURAM DISULFIDE

The primary amino functional iniferter [bis(N-(2-phthalimidoethyl)piperazine)]thiuram disulfide (PEPTD) was synthesized and characterized. Thermal polymerization of isoprene in the presence of the initiator afforded alpha,omega-functionalized polyisoprene with primary amino end-groups after cleavage of the phthalimido group with butylamine. The kinetics of polymerization of isoprene using this iniferter was studied at 80, 85, 90 and 100-degrees-C. Interestingly, isoprene showed a complex kinetic behavior. The different parameters, related to initiation, chain transfer and primary radical termination reactions, as well as the constants for thermal decomposition of the initiator, were determined. From the Arrhenius plot, the activation energy of the overall decomposition constant of PEPTD (2 f k(d)) was calculated to be 110 kJ/mol. The functionality of the telechelics was examined by GPC.