Abstract
The well-fractionated poly(ethylene terephthalate) (PET) samples ranging in weight average molecular weight Mw from 0.9 to 16×104 have been studied by sedimentation velocity and equilibrium, and viscometry in hexafluoroisopropanol (HFIP) and m-cresol at 30°C. The second virial coefficient A2 determined in HFIP by the sedimentation equilibrium method is found to have high dependence on Mw expected for the helical wormlike chains in very good solvents. The constant Φ1/3P−1 in the Mandelkern-Flory equation is 2.54×106 for PET in HFIP and 2.57×106 in m-cresol, being in excellent agreement with that reported for several polymer-solvent systems. The dependences of sedimentation coefficient s0 on Mw agree with also those expected for good solvents. The Mark-Houwink-Sakurada relations established with HFIP and m-cresol as the solvents are [η]=2.95×10−4Mw0.72 in HFIP at 30°C (3.1×104<Mw) [η]=4.97×10−3Mw0.48 in HFIP at 30°C (3.1×104>Mw) [η]=4.04×10−4Mw0.68 in m-cresol at 30°C (2.4×104<Mw)The values of steric factor σ estimated from the unperturbed chain dimensions range from 1.3 to 1.5, irrespective of the solvent nature, and such small σ values suggest that the extent of steric hindrance to the internal rotation of PET chain is significantly low.
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Ohoya, S., Hasegawa, T., Tsubakiyama, K. et al. Ultracentrifugal Characterization of Poly(ethylene terephthalate) in Dilute Solutions. Polym J 33, 113–120 (2001). https://doi.org/10.1295/polymj.33.113
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DOI: https://doi.org/10.1295/polymj.33.113