壳聚糖和n -乙烯基咪唑接枝共聚物的合成及其水溶液性质

A. Sorokin, M. G. Kholyavka, M. Lavlinskaya
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摘要

本工作的目的是合成不同组成的壳聚糖和n -乙烯基咪唑接枝共聚物,并研究其水溶液的性质。在硝酸铈铵氧化还原引发剂的作用下,采用溶液聚合法制备了壳聚糖和n -乙烯基咪唑接枝共聚物。用红外光谱对合成的接枝共聚物进行了表征,确定了其组成;用凝胶渗透色谱对聚n -乙烯基咪唑的接枝侧链进行了表征,确定了其分子量和多分散指数。结果表明,所得产物具有收率高、接枝效率高、多分散性指数低的特点。结果表明,当n -乙烯基咪唑链的含量在57wt %以上时,所合成的接枝共聚物是水溶性的。所得共聚物的水溶液采用动态光散射、透射电子显微镜和激光多普勒微电泳进行表征。研究表明,在水溶液中,接枝共聚物的大分子对介质反应具有刺激敏感性,当浓度高于10-2 wt%时,其特征是倾向于自缔合形成核冠聚集体,其几何形状取决于接枝链的分子质量。溶液中大分子的伴生物的特征是电动势的正值,其值也取决于介质反应。因此,我们发现硝酸铈铵引发剂可以得到壳聚糖和n -乙烯酰咪唑接枝共聚物,它们在水溶液中具有刺激敏感性,并且在浓度大于10-2 wt%时易于自缔合。
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Synthesis of chitosan and N-vinylimidazole graft-copolymers and the properties of their aqueous solutions
The aim of this work is to synthesise chitosan and N-vinylimidazole graft-copolymers of various compositions and to study the properties of their aqueous solutions.Chitosan and N-vinylimidazole graft-copolymers were obtained by solution polymerisation in the presence of a ceric ammonium nitrate redox initiator. The synthesised graft copolymers were characterised by FTIR to determine their compositions and the grafted side chains of poly-N-vinylimidazole were characterised by gel permeation chromatography to determine their molecular wights and polydispersity indices. It was established that the obtained products are characterised by high values of yield and grafting efficiency and low values of the polydispersity index. It was found that when the content of the N-vinylimidazole links is above 57 wt%, the synthesised graft copolymers are water-soluble. Aqueous solutions of the obtained copolymers were characterised using dynamic light scattering, transmission electron microscopy, and laserDoppler microelectrophoresis. The study showed that macromolecules of graft copolymers in aqueous solutions have stimuli-sensitive properties with respect to the medium reaction and at a concentration above 10–2 wt% are characterised by a tendency to self-association forming core-crown aggregates, the geometry of which depends on the molecular masses of the grafted chains. Associates of macromolecules in solutions are characterised by positive values of the electrokinetic potential, the values of which also depend on the medium reaction. Thus, it was found that the ceric ammonium nitrate initiator allows obtaining chitosan and N-vinylimidazole graft-copolymers showing stimuli-sensitive properties in aqueous solutions and prone to self-association at concentrations above 10–2 wt%.
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