| Abstract: | The homopolymerization and copolymerization of butadiene-1-carboxylic acid (Bu-1-Acid) (M1) were studied in tetrahydrofuran at 50°C with azobisisobutyronitrile as an initiator. The initial rate of polymerization was proportional to AIBN]1/2 and Bu-1-Acid]1. The overall activation energy for the polymerization was 22.87 kcal/mole. For copolymerization with styrene (M2) and acrylonitrile (M2), the monomer reactivity ratios r1, r2 were determined by the Fineman-Ross method, as follows; r1 = 5.55, r2 = 0.08 (M2 = styrene); r1 = 11.0, r2 = 0.03 (M2 = acrylonitrile). Alfrey-Price Q-e values calculated from these values were 6.0 and +0.11, respectively. The Bu-1-Acid unit in the copolymer as well as the homopolymer was found from infrared and NMR spectral analyses to be composed of a trans-1,4 bond. The hydrogen-transfer polymerization of Bu-1-Acid leading to polyester was attempted with triphenylphosphine as initiator, but did not occur. |
