类海藻酸钠溶液性能的复合变性淀粉制备及性能研究
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摘要
本文依据羧甲基基团具有良好水溶性和短链烷基基团具有空间位阻和疏水缔合作用的特点,将烷基基团引入到羧甲基淀粉分子中,设计合成了一系列亲水／疏水复合变性淀粉,改进和完善了单一改性的羧甲基淀粉的热稳定性和水溶液性质。详细研究了烷基酯化的反应条件、复合变性淀粉的水溶液性质,总结得出了羧甲基淀粉烷基酸酯在溶液中的粘度性质规律；通过调节控制烷基碳链长度和羧甲基／乙酰基比例,得到了与海藻酸钠具有类似溶液性能的羧甲基淀粉乙酸酯,拓展了淀粉衍生物的应用领域。
论文首先以氯乙酸为醚化试剂,通过醚化反应合成了含有羧基阴离子的羧甲基淀粉(CMS),然后对羧甲基淀粉通过酯化反应进行了疏水改性,制备了羧甲基淀粉烷基酸酯。羧甲基淀粉乙酸酯和羧甲基淀粉丁酸酯在水中使用酸酐进行酯化反应的最佳条件下的反应效率最高为80%和73.1%；羧甲基淀粉已酸酯和羧甲基淀粉辛酸酯在DMSO中使用酰氯进行酯化的最佳条件下的反应效率最高为84%和75.6%。通过IR表征了羧甲基淀粉烷基酸酯的化学结构、TG研究了羧甲基淀粉烷基酸酯的热稳定性。
对于合成的一系列亲水／疏水复合变性淀粉衍生物,详细研究了其水溶液的性质(增稠性质、抗盐性质、温度敏感性质、剪切恢复性质等)及其影响因素(温度、剪切力、烷基取代度等)的影响,并总结了短链烷基的碳链长度对溶液粘度的影响规律。羧甲基淀粉乙酸酯主要依靠乙酰基的空间位阻作用使淀粉分子链更为伸展,提高溶液的粘度值；羧甲基淀粉丁酸酯、羧甲基淀粉已酸酯、羧甲基淀粉辛酸酯依靠疏水缔合作用形成的空间网络结构来提高溶液粘度值,当辛酰基取代度为0.41时,溶液粘度高达35800mPa.s；较弱的疏水缔合作用不能提高溶液粘度的抗剪切性质和剪切恢复性质,随着疏水碳链长度的增加(乙酰基、丁酰基、已酰基、辛酰基),溶液粘度的抗剪切性质和剪切恢复性质变差；但随着疏水碳链长度的增加,溶液粘度的抗温性质得到了改善,其Ea值由2.082kJ/mol下降至0.077kJ/mol;提高分子链刚性,降低疏水缔合网络结构对溶液粘度的贡献,有利于提高溶液的抗盐性和抗剪切性质。
选择粘度值与海藻酸钠相近,抗盐、抗剪切性好的羧甲基淀粉乙酸酯(DScm,=0.76,DSacetyl＝0.30),详细研究了羧甲基淀粉乙酸酯的溶液性质及其影响因素；并与海藻酸钠的溶液性质(抗剪切性质、抗盐性质、抗温性质和粘度稳定性质等)进行了比较。结果表明,对于具有合适亲水／疏水比例的羧甲基淀粉乙酸酯,其抗盐、抗剪切性质、抗温性质、粘度稳定性质与海藻酸钠类似,具有优异的溶液粘度性质,可替代海藻酸钠在食品、纺织等某些领域的应用。
In this study, based on the hydrophilicity of carboxymethyl group and steric hindrance and hydrophobicity of alkyl group, a series of composite-modified starch with different ratios of hydrophilic group to hydrophobic group were synthesized by introducing alkyl group in to carboxymethyl starch, the stability and solution properties of carboxymethyl starch were improved. The synthetic conditions of esterification and properties of aqueous solutions of composite-modified starch were studied in detail. Acetylated carboxymethyl starch, which has the similar aqueous solution properties with sodium alginate, was prepared by changing the molar ratio of carboxymethyl group to acetyl group. It provided the law of viscosity of the aqueous solutions and extended the application of starch and carboxymethyl starch.
Firstly, carboxymethyl starch (CMS), a cold-water-soluble starch derivative was prepared via etherification between starch and chloroacetic acid. Secondly, the alkyl group esterified carboxymethyl starch was prepared by the esterification of CMS. The maximum degree of the reaction efficiency (RE) of ACMS and BCMS was80%and73.1%. respectively using anhydride as esterification reagent in water. The maximum degree of reaction efficiency (RE) of HCMS and OCMS was84%and75.6%, respectively using fatty acid chlorides in DMSO. The chemical structure of alkylated CMS was characterized by IR and the thermal stability was analyzed by TG.
The aqueous solution properties of the series of hydrophilic/hydrophobic composite-modified starch, such as the thickening properties, salt-tolerance, temperature sensitivity and relative hysteresis area and its influence factors, such as temperature, shear rate, degree of substitution of alkyl group was discussed in detail and the regularity of the solution properties of alkyl was summarized. The increase of viscosity of the acetylated CMS mainly depends on the stretching of the molecular starch chain because of the steric hindrance of acetyl group. The thickening effect of the aqueous solution of butyl group, hexyl group and octyl group is relying on the hydrophobic interaction in the formation of the network structure. The viscosity of the octylated CMS reaches35800mPa.s when the DSoctyl is0.41.The weak hydrophobic aggregation can not improve the shear-resistance and relative hysteresis area. Therefore, the shear-resistance and relative hysteresis area were getting worse with the increase of the chain length of alkyl group. But the temperature sensitivity of CMS was improved as the chain length of alkyl group increased. The Eα value was decreased from2.082kJ/mol to0.077kJ/mol. Improving the rigidity of the molecular chain and reducing the network structure of the hydrophobic contribution to the viscosity of the solution are benefit for improving the salt-tolerance and shear-resistance of the aqueous solution.
Acetylated CMS (DScm=0.76. DSacetyl=0.30) with good salt-tolerance, shear-resistance and similar viscosity value with sodium alginate was chosen and the influences of the aqueous solution were studied. The aqueous solution properties of ACMS. such as shear-resistance, salt-tolerance, temperature sensitivity and viscosity stability were compared with that of sodium alginate. The results indicated that the shear-resistance, salt-tolerance, temperature sensitivity and viscosity stability of ACMS with optimal molar ratio of carboxymethyl grou to acetyl group is similar with that of sodium alginate. It may replace sodium alginate in some areas of the food, textile and other applications.
论文首先以氯乙酸为醚化试剂,通过醚化反应合成了含有羧基阴离子的羧甲基淀粉(CMS),然后对羧甲基淀粉通过酯化反应进行了疏水改性,制备了羧甲基淀粉烷基酸酯。羧甲基淀粉乙酸酯和羧甲基淀粉丁酸酯在水中使用酸酐进行酯化反应的最佳条件下的反应效率最高为80%和73.1%；羧甲基淀粉已酸酯和羧甲基淀粉辛酸酯在DMSO中使用酰氯进行酯化的最佳条件下的反应效率最高为84%和75.6%。通过IR表征了羧甲基淀粉烷基酸酯的化学结构、TG研究了羧甲基淀粉烷基酸酯的热稳定性。
对于合成的一系列亲水／疏水复合变性淀粉衍生物,详细研究了其水溶液的性质(增稠性质、抗盐性质、温度敏感性质、剪切恢复性质等)及其影响因素(温度、剪切力、烷基取代度等)的影响,并总结了短链烷基的碳链长度对溶液粘度的影响规律。羧甲基淀粉乙酸酯主要依靠乙酰基的空间位阻作用使淀粉分子链更为伸展,提高溶液的粘度值；羧甲基淀粉丁酸酯、羧甲基淀粉已酸酯、羧甲基淀粉辛酸酯依靠疏水缔合作用形成的空间网络结构来提高溶液粘度值,当辛酰基取代度为0.41时,溶液粘度高达35800mPa.s；较弱的疏水缔合作用不能提高溶液粘度的抗剪切性质和剪切恢复性质,随着疏水碳链长度的增加(乙酰基、丁酰基、已酰基、辛酰基),溶液粘度的抗剪切性质和剪切恢复性质变差；但随着疏水碳链长度的增加,溶液粘度的抗温性质得到了改善,其Ea值由2.082kJ/mol下降至0.077kJ/mol;提高分子链刚性,降低疏水缔合网络结构对溶液粘度的贡献,有利于提高溶液的抗盐性和抗剪切性质。
选择粘度值与海藻酸钠相近,抗盐、抗剪切性好的羧甲基淀粉乙酸酯(DScm,=0.76,DSacetyl＝0.30),详细研究了羧甲基淀粉乙酸酯的溶液性质及其影响因素；并与海藻酸钠的溶液性质(抗剪切性质、抗盐性质、抗温性质和粘度稳定性质等)进行了比较。结果表明,对于具有合适亲水／疏水比例的羧甲基淀粉乙酸酯,其抗盐、抗剪切性质、抗温性质、粘度稳定性质与海藻酸钠类似,具有优异的溶液粘度性质,可替代海藻酸钠在食品、纺织等某些领域的应用。
In this study, based on the hydrophilicity of carboxymethyl group and steric hindrance and hydrophobicity of alkyl group, a series of composite-modified starch with different ratios of hydrophilic group to hydrophobic group were synthesized by introducing alkyl group in to carboxymethyl starch, the stability and solution properties of carboxymethyl starch were improved. The synthetic conditions of esterification and properties of aqueous solutions of composite-modified starch were studied in detail. Acetylated carboxymethyl starch, which has the similar aqueous solution properties with sodium alginate, was prepared by changing the molar ratio of carboxymethyl group to acetyl group. It provided the law of viscosity of the aqueous solutions and extended the application of starch and carboxymethyl starch.
Firstly, carboxymethyl starch (CMS), a cold-water-soluble starch derivative was prepared via etherification between starch and chloroacetic acid. Secondly, the alkyl group esterified carboxymethyl starch was prepared by the esterification of CMS. The maximum degree of the reaction efficiency (RE) of ACMS and BCMS was80%and73.1%. respectively using anhydride as esterification reagent in water. The maximum degree of reaction efficiency (RE) of HCMS and OCMS was84%and75.6%, respectively using fatty acid chlorides in DMSO. The chemical structure of alkylated CMS was characterized by IR and the thermal stability was analyzed by TG.
The aqueous solution properties of the series of hydrophilic/hydrophobic composite-modified starch, such as the thickening properties, salt-tolerance, temperature sensitivity and relative hysteresis area and its influence factors, such as temperature, shear rate, degree of substitution of alkyl group was discussed in detail and the regularity of the solution properties of alkyl was summarized. The increase of viscosity of the acetylated CMS mainly depends on the stretching of the molecular starch chain because of the steric hindrance of acetyl group. The thickening effect of the aqueous solution of butyl group, hexyl group and octyl group is relying on the hydrophobic interaction in the formation of the network structure. The viscosity of the octylated CMS reaches35800mPa.s when the DSoctyl is0.41.The weak hydrophobic aggregation can not improve the shear-resistance and relative hysteresis area. Therefore, the shear-resistance and relative hysteresis area were getting worse with the increase of the chain length of alkyl group. But the temperature sensitivity of CMS was improved as the chain length of alkyl group increased. The Eα value was decreased from2.082kJ/mol to0.077kJ/mol. Improving the rigidity of the molecular chain and reducing the network structure of the hydrophobic contribution to the viscosity of the solution are benefit for improving the salt-tolerance and shear-resistance of the aqueous solution.
Acetylated CMS (DScm=0.76. DSacetyl=0.30) with good salt-tolerance, shear-resistance and similar viscosity value with sodium alginate was chosen and the influences of the aqueous solution were studied. The aqueous solution properties of ACMS. such as shear-resistance, salt-tolerance, temperature sensitivity and viscosity stability were compared with that of sodium alginate. The results indicated that the shear-resistance, salt-tolerance, temperature sensitivity and viscosity stability of ACMS with optimal molar ratio of carboxymethyl grou to acetyl group is similar with that of sodium alginate. It may replace sodium alginate in some areas of the food, textile and other applications.
引文
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