Polymeric reaction of acrylic polymer–monomer system irradiated by low energy electron beam. I. Effects of molecular weight of polymer and polymer‐to‐monomer ratio

Abstract

AbstractPolymeric reaction of the poly(n‐butyl acrylate) (PBA)–benzyl acrylate (BzA) system induced by a low‐energy electron beam was investigated. In order to elucidate the reaction behavior of the PBA–BzA system, the gel fraction, molecular weight of soluble part, and molecular weight distributions were examined by means of gel permeation chromatography (GPC) equipped with both ultraviolet (UV) and refractive index (RI) detectors. RI‐detected GPC curves represented the molecular weights and their distributions of the total polymers, graft polymer, homopolymer, and unreacted PBA, while UV‐detected curves only corresponded to the benzyl groups of graft polymer and homopolymer. Thus, the reaction behavior of the system was able to be followed by GPC. The molecular weight of the added PBA and the mole ratio of PBA/BzA were varied. The crosslinking, the graft reaction and the homopolymerization of BzA proceeded competitively during the polymeric reaction. The proportions of BzA unit incorporated into the crosslinked, graft and homo polymers were estimated by combining of measurement of gel fraction, UV‐detected GPC curves, and infrared (IR) spectrum of gel. It was revealed that in the system containing PBA with high molecular weight, the grafting, and the crosslinking reactions predominated. The main reaction was the grafting in the system with a high mole ratio of PBA/BzA, while it was the homopolymerization in the systems with the low mole ratio of PBA/BzA. The reaction mechanism is discussed on the basis of reactivity and mobility of polymer radicals.