Synthesis of polymer materials by low energy electron beam. IV. EB-polymerized urethane-acrylate, -methacrylate and -acrylamide

Abstract

The structure and properties before and after electron beam (EB) irradiation were investigated using urethane prepolymers with different terminal groups of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA) and N-hydroxymethyl acrylamide (HMAAm). The prepolymers were synthesized by reaction of HEA, HEMA and HMAAm with the isocyanate-capped intermediate, which was obtained by reaction of poly(butylene adipate)diol (PBAD) with 4,4'-diphenylmethane diisocyanate. The resulting urethane-acrylate (UA-251M), -methacrylate (UMA-251M) and -acrylamide (UNAA-251M) had the crystallinity arising from PBAD moieties, and UA-251M and UMA-251M had higher crystallinity than UNAA-251M. IR results indicated that UNAA-251M was larger in the fraction of free NH stretching absorption than UA-251M and UMA-251M regardless of the number of NH group per a molecule. Accordingly, it was assumed that the difference in crystallinity was attributed to the polarity of terminal group. Hence, the rate of gel formation for UA-251M and UMA-251M was higher than that of UNAA-251M. The crystallinity based on PBAD of the prepolymers was remained also after EB irradiation. Spherulitic texture was observed on the EB-polymerized gel film surfaces for UA-251M and UMA-251M, while it was almost destroyed for UNAA-251M. Mechanical properties of UA-251M and UMA-251M gel films were much superior to those of UNAA-251M gel film according to the phase structure. Especially, UMA-251M gel film represented most excellent mechanical properties. Schematic models of the phase structure for UA-251M, UMA-251M and UNAA-251M were suggested from all experimental results.