POLY(4,4'-OXYBIBENZOATE) - POLYMERIZATION, MORPHOLOGY, TRANSITIONS, AND CRYSTAL-STRUCTURES

4-Acetoxy 4'-carboxy biphenyl has been polymerized from solution, the bulk melt, and in constrained thin films, all below the melting point of the monomer as measured by differential scanning calorimetry (DSC). An isothermal sublimation-recrystaIlization-melting (and chemical change)-polymerization-crystallzation process is proposed. From solution and in the thin films, single crystals consisting of ca. 100 Angstrom thick lamellae are observed, with evidence for monomer addition-reaction on the end (top and bottom) surfaces. The bulk samples are fibrous, the ''fibers'' consisting of whisker-like single crystals. The polymer is highly heat and radiation (electron beam) resistant, with numerous successive electron diffraction (ED) patterns from the same crystal or sheared sample permitting comparison of the changes in ED patterns with transitions seen by DSC at ca. 350, 530, and 590 degrees C. Phase I (a = 7.8, b = 5.5, c - 10.8 Angstrom), a possible phase II (a = 15.6, b = 3.6 Angstrom, c = unknown), and a phase III (a = 9.0, b = 5.2 = root 3a, c = 10.8 Angstrom). Phases I and II are seen in samples polymerized at temperatures at and below 310 degrees C; phase III is observed in samples polymerized at and above 350 degrees C and in sheared samples. (C) 1993 John Wiley & Sons, Inc.