LIGHT-SCATTERING STUDIES OF COPOLYMERS: I. EFFECT OF HETEROGENEITY OF CHAIN COMPOSITION ON THE MOLECULAR WEIGHT

Abstract

The classical light-scattering theory for polymer solutions is extended to solutions of copolymers which may be polydisperse in chain composition as well as in molecular weight. It is shown that much too high molecular weights will result from light-scattering data for copolymers owing to fluctuations in chain composition; the magnitude of this effect increases rapidly as the absolute value of the refractive index increment approaches zero. The methods for determining the usual weight-average molecular weight and polydispersity of composition are described.The theory was tested with experimental results on: (1) a mixture of polystyrene and poly(methylmethacrylate), considered as a copolymer with the highest possible polydispersity of composition; (2) a high conversion, statistical copolymer of styrene and methylmethacrylate (copolymer I); and (3) a block copolymer of the same monomers (copolymer II). The apparent molecular weight for copolymer I (M_w = 1.83 × 10⁵) varied markedly with refractive index increment in much the same way as the total molecular weight for the mixture. The molecular weight of copolymer II (M_w = 1.20 × 10⁶) remained essentially constant in the same series of solvents. The polydispersities of composition obtained were 0.72 and 0.05 for copolymer I and II respectively compared with the maximum possible value equal to 1.0.