Four-center photopolymerization. A heterogeneous topochemical solid-state reaction

The four-center solid-state photopolymerization of distyrylpyrazine (DSP) and of 2,6-naphthalene bis(acrylic acid-2,4-dichloro phenyl ester) (NBA–DCP) was investigated by x-ray and microscopic techniques. In both cases the polymer grows as a separate product phase topotactically well arranged with respect to the monomer matrix. In the case of polymerization of DSP the space group of the monomer (Pbca) is not maintained but the polymer phase has space group P2₁ca. Nucleation and growth of the polymer phase was observed by light and electron microscopy. Nucleation occurs at defect sites. The polymer grows at different rates in different crystallographic directions which were identified by electron diffraction in the case of DSP. Polymerization thus occurs in the transition region between monomer crystal and product phase and not in the bulk of the crystal so that the four-center-type photopolymerization is best described as a heterogeneous solid-state reaction.