SYNTHESIS OF BIPYRIDYL-BRANCHED POLYOXAZOLINE AND ITS GELATION BY MEANS OF METAL COORDINATION
SYNTHESIS OF BIPYRIDYL-BRANCHED POLYOXAZOLINE AND ITS GELATION BY MEANS OF METAL COORDINATION
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DOI：
10.1295/polymj.25.599
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发表时间：
1993-01-01
期刊：
影响因子：
2.8
通讯作者：
SAEGUSA, T
中科院分区：
文献类型：
--
作者：
CHUJO, Y;SADA, K;SAEGUSA, T
通过金属离子与2,2'-联吡啶支化聚(N-乙酰基乙烯亚胺)(PAEI)的配位制备聚恶唑啉水凝胶，PAEI是部分水解的PAEI在二环己基碳二亚胺存在下与3-{4-(4'-甲基-2,2'-联吡啶基)}丙酸反应合成的。通过用金属盐如硫酸铁(II)或三氯化钌(III)处理，2,2'-联吡啶支化PAEI的浓溶液以良好的收率得到聚恶唑啉凝胶。所得的有色凝胶在水中高度溶胀并且在环境温度下稳定以便处理。在镍(II)或钴(II)离子的情况下，由于从分子间到分子内方式的交联的快速配体交换反应，通过配位（凝胶状态）形成的分子间交联点是不稳定的。镍（II）和钴（II）凝胶在几个小时内就溶解在大量水中。制备了一系列具有不同数量官能团的PAEI，并通过与铁(II)配位进行交联反应。凝胶在水中的溶胀度和稳定性取决于预聚物中官能团的含量。干燥状态下吸水量可达自身重量的56倍。
Polyoxazoline hydrogel was prepared through the coordination of the metal ions to 2,2'-bipyridyl-branched poly(N-acetylethylenimine) (PAEI), which was synthesized from the partially hydrolyzed PAEI by the reaction with 3-{4-(4'-methyl-2,2'-bipyridyl)}propanoic acid in the presence of dicyclohexylcarbodiimide. Concentrated solution of 2,2'-bipyridyl-branched PAEI gave polyoxazoline gel in a good yield by the treatment with metal salts such as iron(II) sulfate, or ruthenium(III) trichloride. The resulting colored gel was highly swollen in water and stable at ambient temperature for handling. In the case of nickel(II) or cobalt(II) ions, the formed intermolecular cross-linking points via the coordination (gel state) were labile due to the rapid ligand exchange reaction of the cross-linking from intermolecular to intramolecular manner. The nickel(II) and cobalt(II) gels became soluble in a large amount of water within a few hours. A series of PAEIs having varying amounts of the functional groups were prepared and subjected to the cross-linking reaction by the coordination with iron(II). The swelling degree and the stability of the gel in water depended on the content of the functional groups in the prepolymers. Water uptake was up to 56 multiples of its own weight in dry state.