基于点击化学和可逆加成-断裂链转移自由基聚合合成极性链接枝聚丁二烯

Synthesis of polar link-branched polybutadiene based on click chemistry and reversible addition-fragmentation chain transfer radical polymerization

以1-硫代甘油作为改性剂、聚丁二烯为主链,通过热引发和光引发合成了侧基含有羟基的聚丁二烯,以S-1-十二烷基-S′(α-α′-二甲基-α′′乙酸)-三硫代碳酸酯作为可逆加成-断裂链转移自由基聚合试剂、偶氮二异丁腈为引发剂,合成了端羧基聚N,N-二甲基丙烯酰胺,然后将两种官能化的聚合物进行酯化反应制得聚N,N-二甲基丙烯酰胺接枝聚丁二烯。结果表明,采用光引发可以显著提高点击化学的反应效率。用核磁共振氢谱证实了产物含羟基聚丁二烯和端羧基聚N,N-二甲基丙烯酰胺以及接枝聚合物的结构,并显示通过这种方法所制备接枝聚合物的接枝链数目和长度均可控。

Polybutadiene containing hydroxyl group was synthesized by thermal initiation and photoinitiation using 1-thioglycerol as modifier and polybutadiene as main chain.Carboxyl-terminated poly(N,N-dimethyl acrylamide)was synthesized with S-1-dodecyl-S′(α-α′-dimethyl-α"acetic acid)-trithiocarbonate as reversible addition-fragmentation chain transfer radical polymerization reagent and azo-diisobutyronitrile as initiator.Then the two functiona-lized polymers were esterified to prepare polybuta-diene grafted with N,N-dimethylacrylamide.The results showed that the efficiency of click chemical reaction could be significantly improved by using photoinitiation.The structure of hydroxy-containing polybutadiene and carboxy-terminated poly(N,N-dimethylacrylamide)as well as grafted polymers were confirmed by hydrogen spectrum of nuclear magnetic resonance,and the number and length of grafted polymers prepared by this method were controllable.