Abstract
A large-scale precise fractionation of GR-S (X-55) was carried out at 25° C, using a fractional precipitation technique. Nine fractions, each weighing approximately 150 grams and comprising about 11 per cent by weight of the original unfractionated sample, were obtained, with number-average molecular weights varying from 4000 to 1,650,000. High molecular fractions undergo gelation rapidly, even when dried in the absence of light at reduced pressure, and the higher the molecular weight of the fraction, the greater the amount of gel formed. Compared to unfractionated butadiene-styrene copolymers of similar gel contents, the gel portions of the higher molecular fractions had unusually high swelling indices, indicating qualitatively that the average molecular weights between points of effective cross-linking in the three-dimensional gel structure were higher than those found in the past in unfractionated samples of similar gel contents. Through the concentration range studied, the intrinsic viscosity values varied as a straight-line function of the concentration terms for all the fractions. However, the negative slopes of these lines increased as the molecular weight of the fraction increased, demonstrating the greater dependence of the intrinsic viscosity values of the higher molecular fractions on the concentration variable. The relationship between number-average molecular weight, as determined by osmometric measurements, and limiting intrinsic viscosity of the GR-S fractions is given by the equation: [η]0=5.4×10−4 M0.66, which is similar to that obtained by French and Ewart. The μi values calculated from the equation of Huggins were essentially the same (0.35) through the molecular range 12,400 to 723,000.