Solution characterization of a hyperbranched polysaccharide carbamate derivative and specific phase separation behavior due to chain branching

Abstract

A hyperbranched polymer consisting of rigid helical part chains was prepared as highly branched cyclic dextrin tris(phenylcarbamate) (HTPC) with the weight-average molar masses of 880 and 590 kg mol⁻¹. Small-angle X-ray scattering (SAXS) measurement and viscometry were performed on the samples in good and poor solvents to determine the dimensional and hydrodynamic properties in solution. The HTPC molecule has a much more compact conformation than the linear chain with the same molar mass as expected for the hyperbranched architecture. While the corresponding linear polymer is soluble in methyl acetate (MEA) over a wide temperature range, HTPC is only soluble in the solvent at low temperatures. A typical LCST-type phase diagram was observed for the HTPC-MEA system, indicating that the interactions between the polymer segment of HTPC and the MEA molecules are substantially different from those of the linear chains. This is most likely due to the bending helical chains near the branching point of HTPC having different interactions with solvent molecules.