Catalytic oxidative polymerization of 1,1-diphenylethylene at ambient temperature and potential application of peroxide macroinitiator

Abstract

The Co(II)TPP(Py) complex was used as an efficient dioxygen carrier for the radical polymerization of 1,1-diphenylethylene (DPE), which has a low ceiling temperature, at ambient temperature and low oxygen pressure. The mechanism of polymerization is discussed on the basis of kinetic data, UV-vis, ESR, and ¹H NMR studies. The rate of polymerization (R_p) and number-average molecular weights (M_n) of poly(1,1-diphenylethylene peroxide) (PDPEP) are higher and the polydispersity is lower than in 2,2'-azobis(isobutyronitrile) (AIBN) initiated polymerization. PDPEP was further used as a macroinitiator for the polymerization of MMA. The polymerization obeys classical kinetics. The K² value of the PDPEP has been determined from the slope of R_p² vs [M]²[I], which reveals that it can also be used at higher temperature for the polymerization. An "active" PMMA was also synthesized, containing initiating segments in the polymer backbone.