Radiation crosslinking of poly(vinyl chloride)

The mechanism of the electron irradiation crosslinking of poly(vinyl chloride) (PVC) with polyfunctional acrylic monomers has been investigated as part of a program to develop an insulation for distributing‐frame wire. These monomers were found to undergo rapid polymerization to form a rigid, three‐dimensional network onto which PVC was grafted. Polyfunctionality was necessary for crosslinking to occur, since butyl methacrylate, containing only a single unsaturated bond, did not crosslink readily. On the other hand, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, each containing three unsaturated groups, gave extremely rapid crosslinking. Trimethylolpropane triacrylate showed 40 times the radiation sensitivity of tetraethylene glycol dimethacrylate, a diunsaturated compound. The rate of disappearance of unsaturation was related inversely to the rate of gel formation. This was attributed to immobilization of unreacted pendant double bonds in the rigid crosslinked network. In the triunsaturated monomers, half the vinyl groups were left unreacted when all of the PVC was insoluble.