Polymerization of diethynyldiphenylmethane: DSC,FTIR, NMR,and dielectric characterization

4,4′-Diethynyldiphenylmethane thermally polymerizes by a free radical mechanism to a highly crosslinked structure of interest as a high temperature composite matrix resin. The polymerization reaction was characterized by differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, and microdi-electrometry. The predominant reaction mechanism appears to be linear polymerization through the acetylene end groups, which follows first-order kinetics. However, during the early stages of reaction a second, more rapid polymerization mechanism is evident; it is postulated that this is the formation of a cyclic trimer, which is kinetically favored but sterically prohibited as the crosslinked network grows. Formation of a liquid crystalline trimer is hyppthesized; such intermediate formation is supported by intensity increases in the aromatic region of the NMR spectra, by FTIR difference spectroscopy comparisons with model compounds, and by enhancement of conductivity as observed by microdielectrometry.