thermal field-flow fractionation
thermal diffusion coefficient
molecular weight calibration
Polymer and Materials Science
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Copolymer characterization is accomplished with respect to measurement of thermal diffusion coefficient (DT) and molecular weight determination by thermal field-flow fractionation. The examined copolymers are the eight poly(ethylene-co-vinyl acetate)s [P(E-V)] having different compositions of vinyl acetate ranging from 25 to 70% and the molecular weight from 110,000 to 285,000, and three polyvinyl acetate standards as component homopolymer. The carrier solvents are tetrahydrofuran, toluene, and chlorobenzene which have different viscosities and thermal conductivities. Measured DT values vary from 1.36 × 10-8 to 5.97 × 10-8 cm2/(s . K) which are dependent on the composition of copolymers and types of carriers. These values increase linearly with the increase of weight percent of vinyl acetate. It is possible to estimate DT values of polyethylene from the extrapolated intercept in the plots of DT vs. vinyl acetate wt % of copolymer. Tetrahydrofuran is found to be the appropriate carrier solvent for the separation of P(E-V) copolymers since DT varies greatly with the increase of wt % in THF. Attempts are made to correlate the measured retention data with molecular sizes of copolymers for the construction of the molecular weight calibration curve. Good correlations (r2 ≥ 0.931) are found in which D/DT values of polymers vary inversely with the product of hydrodynamic volume by weight ratio of vinyl acetate. Based on this relationship, the unknown molecular weight of copolymer sample can be determined from component homopolymers for which standards are readily available. © 1995 John Wiley & Sons, Inc.
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