一种带疏水长链的水溶性偶氮引发剂的合成及端基疏水聚合物疏水缔合效应研究  

Synthesis of Water-soluble Azo Initiator with Hydrophobic Long Chain and Study on Associative Effect of Hydrophobically End-capped Polymer

作　　者：岳瑞丽[1] 刘朋飞[1] 范雅君[1] 梁兵[1] 

机构地区：[1]高分子材料工程国家重点实验室四川大学高分子研究所,成都610065

出　　处：《高分子学报》2016年第8期1128-1135,共8页Acta Polymerica Sinica

摘　　要：以偶氮二异丁腈、十二胺为主要原料,通过Pinner反应制备了一种两端各带有12个碳烷基链的水溶性偶氮引发剂——2,2'-偶氮二异丁基十二脒盐酸盐AIBL.采用核磁氢谱、元素分析及液相色谱对AIBL进行了结构及纯度表征,采用TGA、DSC和紫外分光光度计研究了其热分解现象和热分解动力学,采用表面张力仪对其表面活性进行了测定.结果表明,所合成的引发剂AIBL具有预想的结构和较高的纯度,其热分解反应属于一级反应,热分解活化能为134.80 k J/mol,70℃下水中的半衰期约为4 h;AIBL在水溶液中具有表面活性,其临界胶束浓度为0.13 g/L,对应的表面张力为33.57 m N/m.以丙烯酰胺为单体、AIBL为引发剂制备了水溶性端基疏水聚合物SPAM.采用溴化法研究其转化率,应用乌氏黏度法、零切黏度法以及荧光探针对其缔合作用进行了研究.结果表明,AIBL具有良好的引发丙烯酰胺聚合的能力;相对于不带疏水长链的引发剂所合成的聚合物PAM,SPAM具有明显的疏水缔合效应,这说明AIBL成功地将疏水长链引入到聚合物的端基中,从而形成端基疏水聚合物.The water-soluble azo initiator,2,2＇-azobis （2-methylpropiondodecylamidine） dihydrochloride （AIBL） ,with twelve alkyl carbon chain at the both ends, was prepared through Pinner reaction, using AIBN and n-Dodecylamine as main reactants. The structure and purity of AIBL were characterized by 1H-NMR, elemental analysis （EA） and HPLC. The thermal decomposition and thermal decomposition kinetics were studied with DSC, TGA and UV spectrophotometer. The surface activity was determined by surface tensionmeter. These results show that the synthesized initiator AIBL has a desirable structure and a high purity. Its thermal decomposition belongs to the first order reaction with the activation energy of thermal decomposition is 134.80 kJ/mol,and the half-life period of it at 70 ℃ in water is about 4 h. Its aqueous solution shows that the surficial activity with the CMC is 0. 13 g/L and the corresponding surface tension is 33.57 mN/m. The hydrophobically end-capped aqueous polymers SPAM were prepared using acrylamide as monomer and AIBL as initiator agent. The conversion rate of AM was studied by using the bromide method. The association effect of SPAM was studied with Ubbelohde viscosity, zero shear viscosity and fluorescence probe. The results show that AIBL has favourable ability to initiate polymerization of acrylamide. SPAM, compared with PAM which was synthesized by Initiator without hydrophobically long chain, has obviously hydrophobically associative effect, which indicated that AIBL has successfully introduced the hydrophobically long chain into the polymer end, forming hydrophobically end-capped polymer.

关 键 词：引发剂 偶氮二异丁基十二脒盐酸盐 热分解 水溶性 端基疏水聚合物 疏水缔合 

分 类 号：TQ317[化学工程—高聚物工业]