Synthesis of new degradable polymers containing azo-group in a polymer chain

氮杂化合物(氮杂丁二烯)不能被自由基引发剂或阳离子引发剂聚合，但容易被阴离子引发剂聚合。作为这一发现的延伸，在各种引发剂的作用下，α，ω-二烷基氮杂丁二烯的阴离子聚合反应表明，在某些阴离子引发剂的作用下，得到了具有1，4-反式单体单元的立体规则聚合物。在此基础上，研究了各种阴离子引发剂制备立体正则聚合物的最佳条件，结果表明烷基碘化镁是制备高分子量立体正则聚合物的最佳引发剂。用差示扫描量热法和热重分析法研究了聚合物的热降解性能。在150℃以上，立体正构体完全分解为相应的烯烃和氮气。立体正构体具有反式偶氮基团，在紫外光照射下可以从反式异构化为顺式异构化。随着反式异构化为顺式异构化，聚合物分子发生了膨胀和收缩。这项工作对实际应用进行了研究。

Azine compounds (azabutadienes) are not polymerized by radical initiators or cationic initiators, but easily polymerized by anionic initiators. In the extension of this finding, anionic polymerizations of α, ω-dialkylazabutadiene were performed with various kinds of initiator, indicating that stereoregular polymers with 1,4-trans monomer unit were obtained with some of anionic initiators. Accordingly, the optimum conditions for the preparation of the stereoregular polymers was investigated by various kinds of anionic initiators, which indicates that alkyl magnesium iodide was the best initiator for the stereoregular polymer with high molecular weight. The thermal degradability of the polymers was investigated by DSC and thermogravitomeric analysis. The stereoregular polymers were completely decomposed to the corresponding olefins and nitrogen above 150℃.The stereoregular have azo-group in trans-form, which can is allowed to isomerize reversibly from trans to cis under irradiation of UV light. The expansion and contraction of polymer molecule was found along with the isomerization from trans to cis. Practical application was investigated in this work.