Effect of fluorinated substituents on hydrodynamic and conformational properties of hyperbranched polycarbosilane in solutions

Fractions of hyperbranched polycarbosilane modified with fluorine-containing end groups are studied by the methods of molecular hydrodynamics and optics in dilute solutions in hexafluorobenzene, methyl tert-butyl ether, chloroform, tetrahydrofurane, and toluene. The results are compared with the data available for the original polymethylallylcarbosilane. The incorporation of fluorinated groups leads to a change in the hydrodynamic parameters of the hyperbranched polymer. In this case, in thermodynamically better solvents, the patterns of the molecular-mass dependence of intrinsic viscosity for fluorinated and original hyperbranched polycarbosilanes coincide since the macromolecules of the polymers under comparison are characterized by similar shapes and almost the same hydrodynamic sizes. In a thermodynamically worse solvent (toluene), the above-mentioned changes in hydrodynamic parameters and the character of the molecular-mass dependences are related to compaction of macromolecules and a decrease in their shape asymmetry. This tendency is probably associated with the selectivity of this solvent with respect to the fluorine atom.