SOLID-STATE SYNTHESIS AND MORPHOLOGY OF POLY(FERROCENYLDIMETHYLSILANE)

Poly(ferrocenyldimethylsilane) (PFCDMS, 2) was synthesized by gamma-irradiation of the crystalline monomeric [1]ferrocenophane, Fe(eta-C5H4)(2)SiMe(2) (1), in the solid state. The resulting degree of polymerization showed a dependence on the initiating radiation dose. The morphology of the polymer films obtained by solvent casting was examined and compared with PFCDMS samples made in the thermally induced polymerization of the molten monomer. Wide-angle X-ray diffraction and differential scanning calorimetry indicate a typical crystallite size of 77 Angstrom, a degree of crystallinity of about 50%, and a corresponding enthalpy of fusion of 7 J g(-1) (1.9 kJ mol(-1)) for the as-cast film samples. Additionally, using these analyses, comparison of the polymer obtained by solid-state polymerization with that from melt polymerization shows that the degree of crystallinity following film casting was similar in each case. Optical microscopy revealed numerous, small regions of birefringence. Emanating fibrillar aggregates of width 90 nm were observed by atomic force microscopy. On the basis of the structural characteristics as a whole, the polymer films show a sperulitic morphology.