Copolymerization kinetics of a model siloxane system

Using ²⁹Si NMR, we monitor the copolymerization of trimethylethoxysilane and dimethyldiethoxysilane (model compounds for more complex sol-gel copolymer systems) in a batch reactor. Under the chosen conditions, the extents of self- and cross-condensation reactions are readily determined. Using a nonideal polycondensation kinetic model, we show that the copolymerization rate coefficient for a pair of sites of differing functionality is bounded by their homopolymerization rate coefficients, lying closer to the larger one. This reactivity pattern generates a heterogeneous monomer distribution in the copolymerization products.