Excluded‐Volume Effects in Dilute Polymer Solutions. II. Limiting Viscosity Number

Measurements of [η] were made for seven fractions of polychloroprene (PCP) in methyl ethyl ketone, n‐butyl acetate, and carbon tetrachloride at 25°C and for three fractions of PCP in trans‐decalin at a number of temperatures ranging from 0.05° to 65°C. On a log–log graph paper, the values of αη3( = [η]/[η]θ) calculated from these data formed a composite curve when plotted against αs3( = 〈S2〉3/2/〈S2〉03/2) obtained from light‐scattering experiments under the same conditions. This curve is characterized by a relatively marked upward curvature in the vicinity of the origin, followed by a linear portion of unit slope. Its initial tangent has a slope of 0.65, which is much smaller than 0.81 predicted theoretically by Kurata and Yamakawa. Plots of αη3 vs the interaction parameter z were prepared by evaluating z for each αs by use of the Yamakawa equation. They were fitted by a single curve having a slight downward curvature, suggesting that no drainage effect manifests itself in the viscosity behavior of the sys...

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