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

吖嗪类化合物（氮杂丁二烯类）不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。在此基础上，用不同的引发剂进行了α，ω-二烷基氮杂丁二烯的阴离子聚合，结果表明，在某些阴离子引发剂存在下，可以得到含有1，4-反式单体单元的有规立构聚合物。在此基础上，研究了不同阴离子引发剂对制备高分子量立构规整聚合物的最佳条件，结果表明，烷基碘化镁是制备高分子量立构规整聚合物的最佳引发剂。用DSC和热重分析研究了聚合物的热降解性能。该聚合物在150℃以上完全分解为相应的烯烃和氮原子，其偶氮基团以反式存在，在紫外光照射下可发生反式到顺式的可逆异构化反应。聚合物分子的膨胀和收缩沿着由反式到顺式的异构化过程。在这项工作中的实际应用进行了调查。

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.