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Osmotic Compressibility of Poly(propylene imine) Dendrimers in Deuterated Methanol.

The inverse osmotic compressibility of the poly(propylene imine) dendrimers in deuterated methanol has been measured as a function of concentration with small-angle neutron scattering. The experimental results reveal three different regimes. First, there is a dilute regime going up to a maximum in the inverse osmotic compressibility. This region can be subdivided into a very dilute region, where the behavior is hard-sphere-like, and a denser region, where the solvation layers overlap. The maximum, occurring around volume fraction 0.30 for each generation, is found to be the concentration where the distance between the centers of two dendrimers is twice their radius of gyration. It designates the crossover to the second regime of a semidilute phase with shrinking dendrimers. Interpenetration of the dendrimers does not seem to take place. Finally, for the higher generations, at high concentrations, the dendrimers are collapsed and the inverse osmotic compressibility starts to increase again. As dendrimers are regularly and very highly branched molecules, they can be considered as ultimately hyperbranched polymers. For both types, the experimental inverse osmotic compressibility shows similar features. The dendrimers seem to be more compact, however. Copyright 2000 Academic Press.