Polymers from 1,2-Disubstituted Ethylenic Monomers. IX. Radical High Polymerization of Methyl-tert-butyl Fumarate

Methyl-tert-butyl fumarate (MtBF) was found to homopolymerize in bulk in the presence of 2,2′-azobisisobutyronitrile (AIBN) at 50–80°C to give a high molecular weight polymer. From IR, ¹H-NMR and ¹³C-NMR spectra, this polymer was assumed to consist of alternating methoxycarbonylmethylene and tert-butoxycarbonylmethylene units, indicating that it was produced from MtBF through an ordinary vinylene polymerization mechanism. Consideration of a molecular model suggested that this polymer had a less flexible rodlike structure with the diameter of about 13.5 Å. The thermal properties of this polymer were also evaluated. Moreover, the bulk polymerization of MtBF initiated by AIBN was investigated kinetically at 60°C. The overall activation energy for this polymerization was determined to be 83.5 kJ/mol. The reaction orders with respect to the monomer and initiator concentrations were obtained as 2.0 and 0.33, respectively.