通过改变原料中丙烯腈(AN)与丙烯酰胺(AM)的配比,获得不同共聚组成的聚丙烯腈.结合凝胶渗透色谱(GPC),X射线衍射(XRD),核磁共振(NMR),失重差热联用(DSC-TG)等考察了AM对聚合反应的影响,剖析了聚合物的结构特征,评价了共聚产物在50 ℃～500 ℃氮气中的热性能.研究结果表明:反应物料中AN与AM的配比对产物分子量、转化率、共聚组成、共聚物的晶态结构和立体结构以及放热行为有着极大的影响.AM的加入对共聚产物分子量和聚合转化率的影响趋势相反.当AN与摩尔分数为0.75 %的AM反应时,转化率最高,分子量最低.在AM的摩尔分数为0 %～3.78 %的条件下,随着AM加入量的增多,共聚组成中AM量也增多,聚合物的规整度增高,结晶度变大,晶粒尺寸增加.AM的引入能够使PAN/AM环化提前,降低放热速率.并且,环化机理受共聚组成影响.AM的引入使得共聚物存在两种环化增长方式(离子增长和自由基增长).随着AM引入量的增多,氰基的自由基环化增长越来越少,离子环化增长越来越多,存在自由基机理向离子机理过渡的趋势.
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