Phase behavior of semiflexible polymer systems

Date of Completion

January 1999


Chemistry, Polymer|Engineering, Materials Science




Phase behavior of semiflexible poly(n-hexyl isocyanate) (PHIC) and flexible coil poly(cyclohexyl methacrylate) (PCHMA) were investigated. Room-temperature solubility screenings showed that PCHMA behavior in various solvents agreed with that predicted by Flory-Huggins theory: solvents had interaction parameter values χ1 < 0.5, i.e., less than the critical value for incipient phase separation, while nonsolvents had χ1 > 1, well within the thermodynamically-poor solvency region. PHIC, on the other hand, had interactions which were not in accord with the simple enthalpic theory. A high-boiling solvent, 1-chloronaphthalene, was chosen as suitable for binary and ternary phase behavior work, as a result of the screenings. PCHMA was found to be soluble at all concentrations at room temperature. However, PHIC crystallized at about 5 wt.% a result not previously reported in the literature. The crystallinity, and degradation, interfered with liquid crystalline expression up to the PHIC melting point in binary solution. The novel room-temperature ternary phase diagram, PHIC/PCHMA/CLN, was developed. Particularly striking is its 5 wt.% total polymer solubility limit, which extended to 90:1 (w/w) ratios of PCHMA:PI-HC in CLN, as verified by serial dilution experiments. ^ Novel gels were prepared with PHIC longer-pendant-group homologs poly(n-nonylisocyanate) and poly(n-undecylisocyanate), to investigate their heightened solubility relative to PHIC, in high-boiling alkylaromatic solvents. Apparently homogeneous isotropic gels in two structurally similar solvents, were found. Lengthening pendant groups in the alkyl isocyanate polymers increases solubility in high-boiling solvents, although gelation occurs when the solutions are cooled to room temperature. Elongational flow apparati were constructed. Trumpet-shaped tube experiments indicated no flow-induced crystallinity of isotropic PHIC/CLN solutions. A planar-elongational flow system was constructed and tested, and its central stagnation point verified. A phase characterization apparatus was refined, providing sensitive detection of phase transitions and rheological data from hermetically sealed small samples. ^