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玻璃化转变时的自由体积,对不同结构的聚合物不是常数,已由实验得到了说明。其原因是玻璃化转变时的体积膨胀系数部分地来自分子链构象变化的贡献。本文在文献[2]和[5]的基础上将Dimarzio定义的链倔硬能(?)与Lipotov关于玻璃化自由体积表达式联系起来,得到了T_g时的自由体积和孤立链的内旋转异构化能的关系式 上式的计算值和文献值较为一致,因此可以作为估算孤立链柔顺性参数的方法。
The glass transition of the free volume, for different structures of the polymer is not constant, has been experimentally illustrated. The reason for this is that the volumetric expansion coefficient at the glass transition comes in part from the contribution of the conformational changes in the molecular chains. Based on the literature [2] and [5], we link the chain stubborn energy (?) Defined by Dimarzio with Lipotov’s expression on the free glass volume and obtain the internal rotation of free volume and isolated chain at T_g The relationship between the constitutive energy The calculated value of the formula and the literature value is more consistent, and therefore can be used as a method to estimate the isolated chain compliance parameters.