Synthesis and properties of a novel (main-chain)-(side-chain) polymeric peroxide

A novel (main-chain)-(side-chain) vinyl polyperoxide, poly(dipentene peroxi de) (PDP), an alternating copolymer of dipentene (DP) and oxygen, has been synthesized by thermal oxidative polymerization of DP. The PDP was characte rized by H-1 NMR, C-13 NMR, FTIR, DSC, TGA, and EI-MS studies. The overall activation energies of the degradation from Kissinger's method were 28 and 33 kcal/mol, respectively, for the endocyclic and acyclic peroxide units. T he side-chain peroxy groups were found to be thermally more stable than the main chain. Above 45 degreesC the rate of polymerization increases sharply at a particular instant showing an "autoacceleration" with the formation o f knee point. The kinetics of autoacceleration has been studied at various temperatures (45-70 degreesC) and pressures (50-250 psi). (C) 2000 John Wil ey & Sons, Inc.