STUDIES OF THE ADSORPTION OF HALOGENS BY POLYDIACETYLENES.

DSC kinetics measurements of the solid state polymerization of PTS distinctly show slow polymerization takes place during an induction period followed by a rapid transition to a fast polymerization regime which appears to obey first order kinetics over similar 20-95% polymer formation. Rate-controlling chain initiations in both regimes proceed with an activation energy E//A equals 22. 3 plus or minus 0. 9 kcal/mole. The ratio of polymerization rates in the fast polymerization regime to that in the induction period is k///k//o approximately equals 150, corresponding to final chain lengths of order 1-3 multiplied by 10**3 monomer units. The heat of polymerization DELTA Hp measured for single crystals is minus 31. 2 plus or minus 0. 9 kcal/mole, and consistently higher values have been observed for polycrystalline ( minus 38. 8 plus or minus 1. 5) and aged single crystal ( minus 38. 0 plus or minus 1. 5) samples which may be associated with extra contributions coming from thermal decomposition, crosslinking, or surface induced effects.