Computer simulation of end-linked elastomers. I. Trifunctional networks cured in the bulk

Abstract

The end linking of difunctional poly(dimethylsiloxane) with trifunctional cross linkers in the bulk has been simulated with a computer. A random array of primary chains with a Gaussian end-to-end distribution is generated in an image container on the computer. By joining chain ends at nearby junctions, inter- and intramolecular reactions occur in all species, allowing formation of cyclic structures of any size. At high extents of reaction, the sol components extracted from the spanning forest thus constructed consist of a substantial amount of cycles such as cyclic dimers. The effect of intramolecular reaction increases the extent of reaction by several percent for molecular weights in the range of thousands. Structural statistics of various types of network imperfections and the cycle ranks of the networks are reported. The gels obtained at complete conversions contain loop defects, their populations increasing with lower molecular weights of the prepolymers. The elastic activities of nonstoichiometric systems are compared and discussed.