4.1 引言 近年来,随着聚合热力学的迅速发展,发现了很多新的现象。例如,α-MeSt的聚合物不能在高于65℃(常压)下获得;在聚醛、聚酮的系列中没有聚丙酮;等等。研究认为,这是由于在较高的温度下,其聚合物在热力学上是不稳定的。决定热力学稳定性的最重要的热力学参数是聚合热,它影响反应器的设计和操作,因此,讨论聚合热是有实际意义的。由于对平衡现象的进一步讨论涉及许多理论问题,而这些理论又很难得到可靠的实验验证,但进行适当的讨论也还是有益的。 4.1 Introduction In recent years, with the rapid development of thermodynamics, many new phenomena have been found. For example, polymers of α-MeSt can not be obtained above 65 ° C (atmospheric pressure); there is no polyacetone in the series of polyaldehydes, polyketones and the like. It is believed that this is due to the thermodynamically unstable polymer at higher temperatures. The most important thermodynamic parameter that determines the thermodynamic stability is the heat of polymerization, which affects the design and operation of the reactor. Therefore, it is of practical significance to discuss the heat of polymerization. As further discussion of the equilibrium involves many theoretical issues that are difficult to obtain credible experimental proofs, it is also useful to have an appropriate discussion.