LAUSR

Furfuryl isocyanate (FIC), allyl isocyanate (AIC), and n-hexyl isocyanate (HIC) that have different β-carbon substituents were employed as monomers in living anionic homo- and copolymerization. The rate constants of the self- and cross-propagation reactions were determined, and their comparison showed the electrophilicity order of isocyanate as FIC > AIC > HIC. The kinetic analysis revealed that the anionic copolymerization of FIC:HIC, AIC:HIC, and FIC:AIC generated three different sequence-controlled polyisocyanate copolymers, poly(furfuryl isocyanate-block-n-hexyl isocyanate) (P(FIC-b-HIC)), poly(allyl isocyanate-tapered block-n-hexyl isocyanate) (P(AIC-tb-HIC)), and poly(furfuryl isocyanate-gradient-allyl isocyanate) (P(FIC-grad-HIC)), respectively. The homogeneous sequential anionic copolymerization of the binary isocyanate mixtures generated the polyisocyanate copolymers having repeated monomer sequences. A series connection of P(FIC-b-HIC), P(AIC-tb-HIC), and P(FIC-grad-HIC) segments in the copolyme...