pH响应均三嗪淀粉醚的合成及性能研究
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摘要
本文依据叔胺基团和羧基基团分别具有酸性或碱性pH响应能力,分别将其引入到均三嗪结构中,设计合成出具有不同pH响应能力、可亲水／疏水转变的新型均三嗪叔胺型淀粉醚和两性淀粉醚,详细研究了合成条件、水溶液性质及应用性能,希望为设计合成具有pH响应能力的淀粉基功能材料提供新思路和新方法,同时开发出具有潜在应用前景的高性能和高附加值淀粉化学品。
论文首先设计以二甲胺为亲核试剂、三聚氯氰为底物,通过亲核取代反应合成了含有两个叔胺基团的阳离子醚化剂2,4-二(二甲氨基)-6-氯-[1,3,5]-三嗪(BDAT),详细研究了反应条件对BDAT产率的影响,在最优反应条件下,BDAT产率为94%；BDAT对淀粉进行醚化反应制备出新型叔胺阳离子淀粉2,4-二(二甲氨基)-[1,3,5]-三嗪-6-淀粉醚(BDATS),在最佳反应条件下,产物取代度可达1.01,反应效率最高为68.0%。通过IR、13C-NMR等证明得到的阳离子淀粉结构正确。BDATS水溶液性质研究表明：BDATS水溶液具有可逆的pH响应能力,其溶液透光率、Zeta电位、表面张力和粘度等随pH变化而变化；取代度增加,溶液pH突变点向低pH方向移动。
论文设计以氨基乙酸为亲核试剂、三聚氯氰为底物,通过亲核取代反应合成了两性醚化剂2,4-二(羧甲基氨基)-6-氯-[1,3,5]-三嗪(CDT),通过MS、IR、13C-NMR等证明得到的醚化剂结构正确。CDT与淀粉进行醚化反应制备出新型两性淀粉醚2,4-二(羧甲基氨基)-[1,3,5]-三嗪-6-淀粉醚(CDTS),在最佳反应条件下,产物取代度可达0.88,反应效率可达73.4%。IR证明淀粉与CDT发生了醚化反应。CDTS水溶液性质表明其透光率随pH变化呈U形分布。在等电点附近,CDTS水溶液出现相分离,Zeta电位、溶液透光率降低。调控CDTS取代度可以控制其水溶液的pH响应能力。
以BDATS作为絮凝剂对三种阴离子染料进行了絮凝研究,结果表明BDATS对阴离子染料絮凝是通过静电中和和高分子架桥共同作用。在pH为2,取代度为0.63的样品对RR141、AR1和AB324的色度去除率分别为99.5%、97.9%和98.4%,染料絮凝量分别为1158mg／g、873mg／g和2296mg／g。依靠絮凝剂的pH响应特性,絮凝饱和的絮凝剂可以在碱性条件下(pH=8)再生并循环使用。十次再生循环使用表明,絮凝剂对三种染料的平均色度去除率超过96%,絮凝剂平均回收率在75%以上。
In this study, based on acidic and alkaline responsiveness of tertiary amino and carboxyl groups, pH-responsive s-triazine tertiary amine starch ether and amphoteric starch were designed and synthesized by introduction of tertiary amino groups and carboxyl groups into starch using cyanuric chloride as an analyte. The synthetic conditions, properties of aqueous solutions and applications of the products were studied in detail. It provided a new idea to synthesize pH-responsive starch-based functional material, and developed high-performance and high value-added starch-based material with potential applications.
Firstly, etherifying agent2,4-bis(dimethylamino)-6-chloro-[1,3,5]-triazine (BDAT) containing two tertiary amine was synthesized by nucleophilic substitution reaction between dimethylamine and cyanuric chloride. The effect of reaction conditions on the yield of BDAT was thoroughly studied. The highest yield of the BDAT reached94%. The structure of the product was confirmed by IR,1H NMR,13C NMR and MS spectroscopy. Then, BDAT was grafted to starch to form a new tertiary amine starch ether2,4-bis(dimethylamino)-[1,3,5]-triazine-6-yl)-starch (BDATS) via etherification reaction. The maximum degree of substitution (DS) and reaction efficiency (RE) were1.01and68.0%, respectively. The structure of the starch derivatives was confirmed by IR and13C NMR spectroscopy. BDATS demonstrated reversible pH responsiveness in aqueous solution. Solution properties of the obtained BDATS, such as transmittance, Zeta-potential, surface tension and viscosity, were measured as a function of pH. The critical pH of the solution shifted to a low pH by increasing DS of the BDATS.
Amphoteric etherifying agent2,4-diglycino-6-chloro-[1,3,5]-triazine (CDT) was synthesized via nucleophilic substitution reaction between glycine and cyanuric chloride. Its structure was confirmed by IR,13C NMR and MS spectroscopy. A new amphoteric starch ether2,4-diglycino-[1,3,5]-triazine-6-yl)-starch (CDTS) was prepared via etherification between starch and2,4-diglycino-6-chloro-[1,3,5]-triazine. The maximum DS and RE were0.88and73.4%, respectively. The structure of the starch derivatives was confirmed by IR. The transmittance of CDTS solution showed the characteristic U-shaped distribution relative to the pH. Phase transition can occur at and around the isoelectric point (IEP) of the ampholytic polymers, leading to decrease of Zeta potential and solution transmittance. Furthermore. pH-responsive properties of the solution can be controlled by regulating DS of CDTS.
BDATS was used as flocculant for removal of three anionic dyes from water. It was found that coagulation mechanisms were electrostatic neutralization and bridge between the dyes and the flocculants. The maximum color removal ratios of99.5%,97.9%and98.4%were observed at pH2, and the maximum flocculation capacity was1158mg/g for RR141,873mg/g for AR1and2296mg/g for AB324for cationic starch with degree of substitution0.63. The spent flocculant can be regenerated efficiently using alkaline solution at pH8. Repeated flocculation/regeneration study showed that flocculant can be regenerated and reused over ten successive cycles. After ten cycles of flocculation/regeneration, the average color removal ratio for the three dyes exceeded96%, and the recovery ratio of the flocculant was above75%.
论文首先设计以二甲胺为亲核试剂、三聚氯氰为底物,通过亲核取代反应合成了含有两个叔胺基团的阳离子醚化剂2,4-二(二甲氨基)-6-氯-[1,3,5]-三嗪(BDAT),详细研究了反应条件对BDAT产率的影响,在最优反应条件下,BDAT产率为94%；BDAT对淀粉进行醚化反应制备出新型叔胺阳离子淀粉2,4-二(二甲氨基)-[1,3,5]-三嗪-6-淀粉醚(BDATS),在最佳反应条件下,产物取代度可达1.01,反应效率最高为68.0%。通过IR、13C-NMR等证明得到的阳离子淀粉结构正确。BDATS水溶液性质研究表明：BDATS水溶液具有可逆的pH响应能力,其溶液透光率、Zeta电位、表面张力和粘度等随pH变化而变化；取代度增加,溶液pH突变点向低pH方向移动。
论文设计以氨基乙酸为亲核试剂、三聚氯氰为底物,通过亲核取代反应合成了两性醚化剂2,4-二(羧甲基氨基)-6-氯-[1,3,5]-三嗪(CDT),通过MS、IR、13C-NMR等证明得到的醚化剂结构正确。CDT与淀粉进行醚化反应制备出新型两性淀粉醚2,4-二(羧甲基氨基)-[1,3,5]-三嗪-6-淀粉醚(CDTS),在最佳反应条件下,产物取代度可达0.88,反应效率可达73.4%。IR证明淀粉与CDT发生了醚化反应。CDTS水溶液性质表明其透光率随pH变化呈U形分布。在等电点附近,CDTS水溶液出现相分离,Zeta电位、溶液透光率降低。调控CDTS取代度可以控制其水溶液的pH响应能力。
以BDATS作为絮凝剂对三种阴离子染料进行了絮凝研究,结果表明BDATS对阴离子染料絮凝是通过静电中和和高分子架桥共同作用。在pH为2,取代度为0.63的样品对RR141、AR1和AB324的色度去除率分别为99.5%、97.9%和98.4%,染料絮凝量分别为1158mg／g、873mg／g和2296mg／g。依靠絮凝剂的pH响应特性,絮凝饱和的絮凝剂可以在碱性条件下(pH=8)再生并循环使用。十次再生循环使用表明,絮凝剂对三种染料的平均色度去除率超过96%,絮凝剂平均回收率在75%以上。
In this study, based on acidic and alkaline responsiveness of tertiary amino and carboxyl groups, pH-responsive s-triazine tertiary amine starch ether and amphoteric starch were designed and synthesized by introduction of tertiary amino groups and carboxyl groups into starch using cyanuric chloride as an analyte. The synthetic conditions, properties of aqueous solutions and applications of the products were studied in detail. It provided a new idea to synthesize pH-responsive starch-based functional material, and developed high-performance and high value-added starch-based material with potential applications.
Firstly, etherifying agent2,4-bis(dimethylamino)-6-chloro-[1,3,5]-triazine (BDAT) containing two tertiary amine was synthesized by nucleophilic substitution reaction between dimethylamine and cyanuric chloride. The effect of reaction conditions on the yield of BDAT was thoroughly studied. The highest yield of the BDAT reached94%. The structure of the product was confirmed by IR,1H NMR,13C NMR and MS spectroscopy. Then, BDAT was grafted to starch to form a new tertiary amine starch ether2,4-bis(dimethylamino)-[1,3,5]-triazine-6-yl)-starch (BDATS) via etherification reaction. The maximum degree of substitution (DS) and reaction efficiency (RE) were1.01and68.0%, respectively. The structure of the starch derivatives was confirmed by IR and13C NMR spectroscopy. BDATS demonstrated reversible pH responsiveness in aqueous solution. Solution properties of the obtained BDATS, such as transmittance, Zeta-potential, surface tension and viscosity, were measured as a function of pH. The critical pH of the solution shifted to a low pH by increasing DS of the BDATS.
Amphoteric etherifying agent2,4-diglycino-6-chloro-[1,3,5]-triazine (CDT) was synthesized via nucleophilic substitution reaction between glycine and cyanuric chloride. Its structure was confirmed by IR,13C NMR and MS spectroscopy. A new amphoteric starch ether2,4-diglycino-[1,3,5]-triazine-6-yl)-starch (CDTS) was prepared via etherification between starch and2,4-diglycino-6-chloro-[1,3,5]-triazine. The maximum DS and RE were0.88and73.4%, respectively. The structure of the starch derivatives was confirmed by IR. The transmittance of CDTS solution showed the characteristic U-shaped distribution relative to the pH. Phase transition can occur at and around the isoelectric point (IEP) of the ampholytic polymers, leading to decrease of Zeta potential and solution transmittance. Furthermore. pH-responsive properties of the solution can be controlled by regulating DS of CDTS.
BDATS was used as flocculant for removal of three anionic dyes from water. It was found that coagulation mechanisms were electrostatic neutralization and bridge between the dyes and the flocculants. The maximum color removal ratios of99.5%,97.9%and98.4%were observed at pH2, and the maximum flocculation capacity was1158mg/g for RR141,873mg/g for AR1and2296mg/g for AB324for cationic starch with degree of substitution0.63. The spent flocculant can be regenerated efficiently using alkaline solution at pH8. Repeated flocculation/regeneration study showed that flocculant can be regenerated and reused over ten successive cycles. After ten cycles of flocculation/regeneration, the average color removal ratio for the three dyes exceeded96%, and the recovery ratio of the flocculant was above75%.
引文
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