| Abstract: | A hyperbranched polyester was fractionated by precipitation to produce 10 fractions with molecular weights between 20 × 103 and 520 × 103 g mol?1. Each of these fractions was examined by size exclusion chromatography, dilute‐solution viscometry, intensity, and quasi‐elastic light scattering in chloroform solution at 298 K. High‐resolution solution‐state 13C NMR was used to determine the degree of branching; for all fractions this factor was 0.5 ± 0.1. Viscometric contraction factors, g′, decreased with increasing molecular weight, and the relation of this parameter to the configurational contraction factor, g, calculated from a theoretical relation suggested a very strong dependence on the universal viscosity constant, Φ, on the contraction factor. A modified Stockmayer–Fixman plot was used to determine the value of (〈r2〉o/Mw)1/2, which was much larger than the value for the analogous linear polymer. The scaling relations of the various characteristic radii (Rg, Rh, RT, and Rη) with molecular weight all had exponents less than 0.5 that agreed with the theoretical predictions for hyperbranched polymers. The exponent for Rg was interpreted as fractal dimension and had a value of 2.38 ± 0.25, a value that is of the same order as that anticipated by theory for branched polymers in theta conditions and certainly not approaching the value of 3 that would be associated with the spherical morphology and uniform segment density distribution of dendrimers. Second virial coefficients from light scattering are positive, but the variation of the interpenetration function, ψ, with molecular weight and the friction coefficient, ko, obtained from the concentration dependence of the diffusion coefficient suggests that chloroform is not a particularly good solvent for the hyperbranched polyester and that the molecules are soft and penetrable with little spherical nature. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1339–1351, 2003 |
