AbstractWork is reported on the effect of variation of molecular weight distribution on the properties of binder stocks. This work used three prepolymers (polypropylene glycol 1000, 2000, and 4000 and polypropylene glycol 400, 1000, and 2000) of different molecular weight and known molecular weight distribution. The prepolymer of the middle molecular weight was employed as standard, and stocks were prepared from it. To this prepolymer was added some of the high and low molecular weight prepolymers in proportions such that the crosslink density of stocks made from the mixture was the same as that of stocks made from the middle molecular weight prepolymer alone. Two series were prepared with different crosslinking agents. The proportions of high and low molecular weight prepolymer were successively increased until finally none of the middle molecular weight remained. Heterogeneity indexes of the glycols and their mixtures were measured by gel permeation chromatography. Elongation at break, modulus of elasticity, and extent of solvent swelling were determined on the crosslinked stocks. Properties which vary with crosslink density were found to show decreasing values with increasing heterogeneity index even though the stocks were formulated to a constant crosslink density. Narrow‐distribution stocks reach the maximum degree of cure faster than the broader‐distribution stocks. Infrared and thermal analysis confirm that monodisperse polymer has a greater extent of reaction than heterodisperse polymer. Results showed that the variation in elongation at break to be expected because of lot‐to‐lot variations in heterogeneity index is probably not greater than the experimental variation in the elongation test below a heterogeneity index of 1.5. Above 1.5, however, if the effects observed are entirely due to variation in heterogeneity index, lot‐to‐lot variations in molecular weight distribution cannot be ignored. An explanation is presented based on the varying ability of prepolymer molecules of different size to diffuse through uniform mesh openings resulting in lower final extents of reaction for broad distributi
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