Synthesis and properties of a Novel (Main-Chain)-(Side-Chain) Polymeric Peroxide

摘要

A novel (main-chain)-(side-chain) vinyl polyperoxide, poly(dipentene peroxide)(PDP), an alternating copolymer of dipentene (DP) and oxygen, has been synthesized by thermal oxidative polymerization of DP. The PDP was characterized by ~1H NMR, ~(13)C NMR, FTIR, DSC, TGA, and EI-MS studies. The overall activation energines of the degradation from Kissinger's method were 28 and 33 kcal/mol, respectively, for the endocyclic and acyclic peroxide units. The side-chain peroxy groups were found to be thermally more stable than the main chain. Above 45 deg C the rate of polymerization increases sharply at a particular instant showing an "autoacceleration" with the formation of knee point. The kinetics of autoacceleration has been studied at various temperatures (45-70 deg C) and pressures (50-250 psi).