Intrinsic Viscosity of Cyclic Polystyrene

The intrinsic viscosity of cyclic polystyrenes (C-PS) and linear polystyrenes (L-PS) with molecular weight (MW) ranging from 16K to 370K was measured in THF using size exclusion chromatography coupled with a triple detection system. The C-PS samples were prepared by a ring-closure reaction of telechelic linear precursor synthesized by anionic polymerization. As-synthesized C-PS samples after the ring-closure reaction contain various byproducts, and they were fractionated by liquid chromatography at the critical condition to obtain highly pure C-PS. While the intrinsic viscosity of L-PS agrees well with the literature data, C-PS shows significantly lower value than the literature values. The Mark–Houwink exponent of C-PS is 0.67, somewhat lower than 0.70 for L-PS in the good solvent over the MW range examined. Therefore, the ratio of the intrinsic viscosity of C-PS to L-PS ( g ′ = [η] C /[η] L ) in THF is not MW independent but decreases as MW increases (0.63 ≥ [η] C /[η] L ≥ 0.57). The trend of intrinsic viscosity agrees well with the computer simulation result. The discrepancy in [η] C from the literature values can largely be attributed to the contamination of linear byproducts in the earlier studies.