Radical polymerization of butadiene‐1‐carboxylic acid

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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.