摘要
本文依据双醛淀粉(DAS)中醛基的高反应活性,通过C=N双键向双醛淀粉中引入一定量的芳香基团或烷基基团,同时破坏双醛淀粉中的缩醛/半缩醛结构,释放出羟基。淀粉的羟基与引入的疏水性芳基或烷基能使淀粉衍生物具有合适的亲水/疏水平衡,赋予双醛淀粉希夫碱表面活性。同时,高的芳基或烷基取代度使双醛淀粉希夫碱不溶于水,并且具有优良的金属离子吸附能力。详细研究了双醛淀粉希夫碱的合成条件,水溶性双醛淀粉希夫碱的表面活性,以及水不溶性双醛淀粉希夫碱对金属离子的吸附。
论文首先以苯胺(AN)为代表,研究了油溶性氨基化合物与双醛淀粉在DMSO均相体系和乙酸催化的条件下生成双醛淀粉希夫碱的最佳反应条件,在此基础上又合成了苄胺(BN)、苯乙胺(PEA)、正己胺(HA)和正辛胺(OA)双醛淀粉希夫碱。还研究了以水为溶剂合成双醛淀粉-间氨基苯酚(AP)希夫碱的最佳反应条件,反应效率最高为65%。通过FT-IR、NMR和XRD对双醛淀粉脂肪胺/芳香胺希夫碱的化学结构进行了研究。DAS-ANs、DAS-BNs、DAS-PEAs、DAS-HAs和DAS-OAs的取代度小于0.2时,其在水中的溶解度在1.80-2.00g·100g-1之间,取代度大于0.2时不溶于水；而双醛淀粉-间氨基酚希夫碱均不溶于水。
对于水溶性双醛淀粉脂肪胺/芳香胺希夫碱,研究了其水溶液的表面张力、发泡能力、硬水稳定性和乳化能力,以及疏水基团结构对表面活性的影响规律。当疏水基团的取代度小于0.2时,DAS-ANs、DAS-BNs、DAS-PEAs、DAS-HAs和DAS-OAs在临界聚集浓度(CAC)分别为1.66、0.62、0.31、0.33和0.23g·L-1时,表面张力(γCAC)分别为58.25、47.96、46.27、38.03和36.17mN·m-1。研究表明,双醛淀粉脂肪胺希夫碱的表面张力小于双醛淀粉芳香胺希夫碱；对于同系物(DAS-BNs和DAS-PEAs; DAS-HAs和DAS-OAs),碳链长度的增加对表面张力(γCAC)的影响不大,但随着疏水基团疏水性的增强,CAC减小。而DAS-ANs的表面张力与DAS-BNs和DAS-PEAs的差异较大。水溶性双醛淀粉脂肪胺/芳香胺希夫碱的发泡力随表面张力的下降而提高,而双醛淀粉脂肪胺希夫碱的泡沫稳定性高于双醛淀粉芳香胺希夫碱。产品的硬水稳定性均达到最高级。
水不溶性双醛淀粉脂肪胺/芳香胺希夫碱的金属离子吸附研究表明：双醛DAS-APs对Cu(Ⅱ)和Pb(Ⅱ)有很好的吸附能力；吸附在2h时达到平衡；随着间氨基苯酚取代度的增加,吸附能力增加；在pH为5.3的Cu(Ⅱ)溶液和pH为4.0的Pb(Ⅱ)溶液中,DAS-APs对Cu(Ⅱ)和Pb(Ⅱ)的最大吸附量分别为0.96mmol·g-1和2.34mmol·g-1。
In this study, aryl or alkyl groups were introduced to dialdehyde starch (DAS) by C=N based on the high reactive aldehyde groups of DAS, and the Schiff-bases of DAS were obtained. The formation of C=N partially destroyed the acetal or hemiacetal structure of DAS, and gave the starch derivatives proper hydrophilic/hydrophobic balance by released hydroxyl groups and aryl (or alkyl) groups, then the resulting water-soluble Schiff-bases of DAS could show surface activities, and the resulting water-insoluble ones with the degree of substitution (DS) of aryl (alkyl) groups could show metal ion adsorption capacity. Surface tension, foaming behavior, stability in hard water and emulsifying capacity of water-soluble Schiff-bases of DAS had also been measured, and the water-insoluble Schiff-bases of DAS had been used as sorbent to remove Cu(II) and Pb(II) ions in aqueous solution. The synthesis conditions of Schiff-bases of DAS were also studied.
The synthesis conditions of aniline Schiff-bases of DAS (DAS-ANs) were optimized to achieve the highest reaction efficiency with acetic acid as catalyst in dimethyl sulfoxide (DMSO) homogeneous system. These optimized synthesis conditions were applied to synthesize other Schiff-bases between DAS and oil-soluble amino reactants, such as benzylamine (BN), phenethylamine (PEA), n-hexylamine (HA) and n-octylamine (OA). The water solubility of Schiff-bases of DAS with oil-soluble amine were researched. It demonstrated that the water solubility was between1.80-2.00g·1OOg-1when the DS of oil-soluble amine was less than0.2, and they were insoluble in water when the DS of oil-soluble amine was greater than0.2. m-Aminophenol (AP) Schiff-bases of DAS were synthesized in water, and the highest reaction efficiency was65%. The synthesized DAS-APs were all insoluble in water. The structures of all Schiff-bases of DAS were characterized by FT-IR, NMR and XRD.
Surface tension, foaming behavior, stability in hard water and emulsifying capacity of water-soluble alipatic/aromatic amine Schiff-bases of DAS had been measured, and the effect of aryl and alkyl groups on surface tension had been studied. When the DS of hydrophobic groups was less than0.2, the surface tension at critical aggregation concentration (γCAC) of DAS-ANs, DAS-BNs, DAS-PEAs, DAS-HAs and DAS-OAs was58.25,47.96,46.27,38.03and36.17mN-m-1at1.66,0.62,0.31,0.33and0.23g·L-1, respectively. These data suggested that (1) the surface tension of alipatic amine Schiff-bases of DAS was less than that of aromatic amine Schiff-bases of DAS;(2) the increase of alkyl chain length among homologues, such as BN and PEA, or HA and OA, did not affected yCAC obviously, but the critical aggregation concentration (CAC) decreased as the hydrophobicity of alkyl or aryl groups increased. The γCAC and CAC of DAS-ANs were different from that of DAS-BNs and DAS-PEAs. The foaming behavior showed that the foaming power of water-soluble alipatic/aromatic amine Schiff-bases of DAS increased as the surface tension decreased, and the foam stability of alipatic amine Schiff-bases of DAS was better than that of aromatic amine Schiff-bases of DAS. The stability in hard water all reached the highest level.
The adsorption studies of water-insoluble alipatic/aromatic amine Schiff-bases of DAS showed that:(1) there is good adsorption capacity of DAS-APs for Cu(II) and Pb(II);(2)2h was needed for the equilibrium of adsorption;(3) adsorption capacity increased as the DS of AP increased;(4) the maximum adsorption capacity for Cu(II)(pH5.3) and Pb(II)(pH4.0) were0.96mmol·g-1and2.34mmol·g-1, respectively.
引文
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