Backbone Stretching of Wormlike Carbosilane Dendrimers

Abstract

Wormlike dendrimers made of flexible and noninteracting segments were synthesized. Starting from a poly(methylhydrosiloxane) G0 and using short propylsilane branches, the synthesis did not go beyond the second generation, as predicted from steric congestion. The starting polymer and the G1 and G2 dendrimers synthesized were studied by small-angle neutron scattering. The molecular-weight dependence of their radius of gyration (Rg ∝ Mν, ν growing from 0.53 for G0 to 0.94 for G2) showed the backbone conformation to go from very flexible for G0 to nearly rodlike for G2. This was supported by the growth of the persistence length from 12 to over 200 Å, as deduced from an analysis of the data according to Benoît−Doty's law. The dendrimers being made of flexible parts, their stretching was attributed to the congestion of the peripheral branches. The absence of liquid crystallinity was imputed to the dynamical flexibility of the molecules.