Copolymers of acrylonitrile with some furans and their Diels-Alder adducts

Copolymers of acrylonitrile with furan, 2-methylfuran and with 2,5-dimethyl furan have been prepared by free radical copolymerizations, and their ¹³C spectra examined for evidence of the three types of structure that formed, according to previous studies. We have characterized the Diels-Alder adducts of acrylonitrile with furan and with 2-methylfuran, and have found that they may also copolymerize with acrylonitrile by addition at their double bonds. The enchained adducts were most readily recognized in the ¹H spectrum by shifts at 4.8 and 4.6 ppm respectively from protons at the oxygen bridgehead. The ¹³C spectra of these various polymers have been assigned with the aid of model compounds. Below δ=60 ppm the nitrile shift was dispersed over a larger range of shifts than is found in PAN itself, and was joined by the shifts of unsaturated carbon atoms and of carbon atoms linked to the oxygen atoms within these structures. Above 60 ppm the shifts of carbons in acrylonitrile units were found to be perturbed systematically from their normal places by the presence of neighbouring structures formed from the different furan-containing molecules. In both the ¹H and ¹³C spectra shifts characteristic of the end groups from the AIBN initiator were noted. Fine structure in the spectra was attributed to monomer sequence effects and to the tactic structure of the polymer. Chiral centres appeared to be created from the furan rings at random, at least when protonated carbons were the site of initial attachment, but the mode of addition to the ring—whether cis, trans or both, was not certain. Assignments were made of bands in the i.r. spectra to modes of vibration of the units formed from the furan monomers.