Free radical synthesis of α,ω‐primary amino functionalized polyisoprene through the functional thermal inferter [bis(N‐(2‐phthalimidoethyl)piperazine)]thiuram disulfide

Abstract

AbstractThe primary amino functional iniferter [bis(N(2‐phthalimidoethyl)piperazine)]thiuram disulfide (PEPTD) was synthesied and characterized. Thermal polymerization of isoprene in the presence of the initiator afforded α,ω‐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°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 kd) was calculated to be 110 kJ/mol. The functionality of the telechelics was examined by GPC.