Vitrification of polymer solutions as a function of solvent quality, analyzed via vapor pressures

被引:14
|
作者
Bercea, M
Wolf, BA
机构
[1] Univ Mainz, Inst Chem Phys, D-55099 Mainz, Germany
[2] Univ Mainz, Mat Wissensch Forsch Zentrum, D-55099 Mainz, Germany
来源
JOURNAL OF CHEMICAL PHYSICS | 2006年 / 124卷 / 17期
关键词
D O I
10.1063/1.2193153
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Vapor pressures (headspace sampling in combination with gas chromatography) and glass transition temperatures [differential scanning calorimetry (DSC)] have been measured for solutions of polystyrene (PS) in either toluene (TL) (10-70 degrees C) or cyclohexane (CH) (32-60 degrees C) from moderately concentrated solutions up to the pure polymer. As long as the mixtures are liquid, the vapor pressure of TL (good solvent) is considerably lower than that of CH (theta solvent) under other identical conditions. These differences vanish upon the vitrification of the solutions. For TL the isothermal liquid-solid transition induced by an increase of polymer concentration takes place within a finite composition interval at constant vapor pressure; with CH this phenomenon is either absent or too insignificant to be detected. For PS solutions in TL the DSC traces look as usual, whereas these curves may become bimodal for solutions in CH. The implications of the vitrification of the polymer solutions for the determination of Flory-Huggins interaction parameters from vapor pressure data are discussed. A comparison of the results for TL/PS with recently published data on the same system demonstrates that the experimental method employed for the determination of vapor pressures plays an important role at high polymer concentrations and low temperatures.
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页数:7
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