尼龙1010扩链反应的动力学模型和分析

KINETIC MODEL OF CHAIN EXTENSION REACTION OF NYLON 1010 AND ANALYSIS OF EXPERIMENTAL RESULTS

双唑啉类化合物通过唑啉环与尼龙端羧基的开环加成反应使尼龙 10 10的分子量大幅提高 .以线性扩链反应的理想动力学模型为基础 ,通过对关键因素的修正使其更好地符合聚合物高粘度熔体扩链反应的实际过程 .通过数值积分方法 ,可以方便地模拟关键因素对扩链反应的影响 .理想线性模型与熔融扩链反应的前期规律相符合 ,但是其未考虑后期扩链产物的降解对偶联效果造成的影响 .通过基于降解的修正 ,该模型更好地符合了实际情况 .在扩链过程中 ,反应速率k和唑啉环与端羧基的比r是控制偶联效果的关键因素 ,温度和扩链剂加入量可以通过改变k和r进行方便的分析 .由于PA熔体反应体系的高粘性 ,2 ,2′ 双 (2 唑啉 ) (BOZ)和 1,4 双 (2 唑啉基 )苯 (PBO)

The kinetic model of chain extension reaction between bisoxazoline and carboxyl group was founded and modified to fit the real experimental results. By the Runge-Kutta numerical method, not only has the change of reaction conversion with time been clearly revealed, but also the key factors that mainly influence the chain extension have been easily tested. The ideal linear model of chain extension accords to a large extent with the former period of the reaction. However, it cannot illustrate the 'degradation' in the latter period due to the thermal unstability of products. Modified linear model gives more congruent results. During the whole period of the reaction, the reaction rate constant k and ratio of both reactants r are the key factors. The changes of reaction conditions, such as temperature and chain extender dosage, are simulated easily by varying the value of k and r. Considering the diffusibility in the polymer melt with high viscosity, the distinction of coupling effect of BOZ and PBO can be explained. No other than the same reason, the analysis could only be kept in the qualitative stage at present.