以玻璃化转变的热力学理论为基础,假定化学键的刚性能具有加和性,提出了新的三元共聚物的Tg-组成关系方程,方程中包含三元组的物质的量含量以及均聚物、周期共聚物的Tg。方程中周期共聚物poly[ij]和poly[iij]的Tg可以由二元共聚物数据回归求取,新方程中仅剩三个未知参数,即poly[ijik]的Tg,可以通过对三元共聚物Tg数据拟合得到,因此新方程可以方便地应用于三元共聚物Tg-组成-序列关系研究。将新方程用于MMA-St-AN三元共聚物的Tg-组成关系,理论值与实验值十分接近,说明新方程具有很好的适用性。由拟合结果同时预测了目前尚未合成的周期共聚物的Tg,poly[MSMA]、poly[SMSA]和poly[AMAS]的Tg分别为478.5K、353.5K和357.8K。
In view of bond rotation flexibility and under the assumption of the additivity of bond stiff energy, the relation of ternary copolymer Tg with its composition and ~quence was investigated in this paper. When C3 substituent was taken into consideration, an equation including mole fractions of triad, Tg＇s of corresponding periodic copolymers and homopolymers was proposed. Tg＇s of periodic copolymers of poly [ ij ] and poly [ iij ] could be determined by regressing a binary equation proposed earlier to binary copolymer Tg＇s. The new equation has only 3 fitting parameters of Tg＇s of poly[ijik] and could be applied conveniently in the study of ternary copolymer Tg. It was applied to interpret the relation of Tg＇s of methyl methacrylate-styrene-acrylonitrile （MMA-St-AN） terpolymers with their compositions. Excellent agreement between the theory and experiment was obtained. Meanwhile, Tg values of the assumed periodic copolymers that hasn＇t acquired yet were predicted.
参考文献
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