Poly(1,3‐cyclohexadiene‐alt‐α‐fluoroacrylonitrile): Synthesis and structural analysis of a new alternating copolymer

Abstract

AbstractPoly(1,3‐cyclohexadiene‐alt‐α‐fluoroacrylonitrile) [poly(1,3‐CHD/α‐FAN)], an alternating copolymer of α‐fluoroacrylonitrile and 1,3‐cyclohexadiene has been prepared in bulk using varied monomer feed ratios and AIBN as initiator at 65°C. Elemental and 1H‐NMR analyses indicate that the copolymer contains an equimolar composition of α‐FAN and 1,3‐CHD as observed for alternating copolymers with donor‐acceptor polymerizations. A 2‐D 1H‐COSY NMR experiment indicates that the copolymer contains 1,4‐linkages across the cyclohexene unit while more reliable 13C‐NMR spectra suggests the copolymer to contain both 1,2‐ and 1,4‐linkages. Poly(1,3‐CHD/α‐FAN) exhibits improved thermal stability relative to the alternating copolymer of 1,3‐CHD and α‐chloroacrylonitrile due to a higher resistance to HF elimination relative to HCl elimination.