交联卡拉胶纤维的制备
摘要
卡拉胶是从红藻中提取的天然高分子多糖,水溶性好,有很好的凝胶性能,本课题组利用卡拉胶优良的凝胶性能已成功制备出卡拉胶纤维。为进一步提高卡拉胶纤维的力学强度,本论文探讨了交联卡拉胶合成的工艺条件及交联卡拉胶纤维的湿法纺丝制备工艺。
首先,金属离子能与卡拉胶大分子形成络合物,在卡拉胶分子间形成离子交联结构。实验中分别用不同类型的卡拉胶溶液喷到不同的金属盐溶液中形成纤维,找出最适合纺丝的卡拉胶为1-型,最合适的金属盐溶液为7%的BaCl2溶液。其次,利用卡拉胶大分子上的羟基具有醇羟基的反应性能,分别用环氧氯丙烷、丁二酸酐、顺丁烯二酸酐、均苯四甲酸酐与卡拉胶进行反应,使卡拉胶大分子间生成醚键或酯键的交联。通过实验结果分析,最佳的交联剂为环氧氯丙烷,交联剂加入量为6.25%,反应温度90℃,反应时间2.0h,pH值为10.0,制得的交联卡拉胶纤维机械性能提升。在水相反应体系中,丁二酸酐与顺丁烯二酸酐与卡拉胶的酯化反应效率低,副反应占的比例较高,得到产品的效果差；均苯四甲酸酐与卡拉胶的酯化交联反应基本无法进行,并且在高温水溶液中对卡拉胶起到水解作用。在有机相反应体系中,丁二酸酐与顺丁烯二酸酐与卡拉胶的酯化反应制备出的卡拉胶溶液粘度增加,制备出的纤维强度略有增加,但效果不如环氧氯丙烷交联制备的卡拉胶纤维明显。
按照喷丝得出的最佳纺丝条件进行纺丝,制得的卡拉胶纤维强度为12.3cN/tex,断裂伸长率为13.46%,分别为未交联卡拉胶纤维的2.3倍和1.25倍,纤维机械性能得到明显提高。
Carrageenan is a natural polysaccharide extracted from red algae. It is water-soluble and has a gel characteristic. Carrageenan fibers have been successfully prepared in our research team. In order to increase the mechanical strength of carrageenan fibers, cross-linking carrageenan fibers were studied with the reaction between carrageenan macromolecule and cross-linking agents.
First of all, the cross-linked structure was formed between carrageenan macromolecules and metal ions as metal ions can form complexes with carrageenan. Carrageenan fibers were made with different types of carrageenan and different kinds of metal salt solution, the most appropriate type of carrageenan is iota-carrageenan and the most appropriate type of metal salt solution is BaCl2 solution.
Secondly, the hydroxyl groups in the carrageenan macromolecules can react with cross-linking agents such as epichlorohydrin, succinic anhydride, maleic anhydride, PMDA to form ether bond or ester bond. The result shows that the best cross-linking agent is epichlorohydrin. In order to obtain high quality crosslink ing carrageenan fiber, the optimal reaction condition is as follows:the epichlorohydrin added with the concentration of 6.25%, the reaction temperature is 90℃, the reaction time is 2.Oh, and the pH value is 10.0. In the water reaction system, the succinic anhydride or maleic anhydride can not reacted with carrageenan because of the hydrolysis of the anhydride and has no desired product. And so does PMDA. In the oil reaction system, the succinic anhydride or maleic anhydride can react with carrageenan to obtain cross-linked product.
Finally, the epichlorohydrin cross-linked carrageenan fiber was prepared via wet-spinning technology. The fiber strength is 12.3cN/tex which is 2.3 times of carrageenan fibers and the elongation is 13.46% which is 1.25 times of carrageenan fibers. The mechanical strength of cross-linked carrageenan fibers is significantly improved.
首先,金属离子能与卡拉胶大分子形成络合物,在卡拉胶分子间形成离子交联结构。实验中分别用不同类型的卡拉胶溶液喷到不同的金属盐溶液中形成纤维,找出最适合纺丝的卡拉胶为1-型,最合适的金属盐溶液为7%的BaCl2溶液。其次,利用卡拉胶大分子上的羟基具有醇羟基的反应性能,分别用环氧氯丙烷、丁二酸酐、顺丁烯二酸酐、均苯四甲酸酐与卡拉胶进行反应,使卡拉胶大分子间生成醚键或酯键的交联。通过实验结果分析,最佳的交联剂为环氧氯丙烷,交联剂加入量为6.25%,反应温度90℃,反应时间2.0h,pH值为10.0,制得的交联卡拉胶纤维机械性能提升。在水相反应体系中,丁二酸酐与顺丁烯二酸酐与卡拉胶的酯化反应效率低,副反应占的比例较高,得到产品的效果差；均苯四甲酸酐与卡拉胶的酯化交联反应基本无法进行,并且在高温水溶液中对卡拉胶起到水解作用。在有机相反应体系中,丁二酸酐与顺丁烯二酸酐与卡拉胶的酯化反应制备出的卡拉胶溶液粘度增加,制备出的纤维强度略有增加,但效果不如环氧氯丙烷交联制备的卡拉胶纤维明显。
按照喷丝得出的最佳纺丝条件进行纺丝,制得的卡拉胶纤维强度为12.3cN/tex,断裂伸长率为13.46%,分别为未交联卡拉胶纤维的2.3倍和1.25倍,纤维机械性能得到明显提高。
Carrageenan is a natural polysaccharide extracted from red algae. It is water-soluble and has a gel characteristic. Carrageenan fibers have been successfully prepared in our research team. In order to increase the mechanical strength of carrageenan fibers, cross-linking carrageenan fibers were studied with the reaction between carrageenan macromolecule and cross-linking agents.
First of all, the cross-linked structure was formed between carrageenan macromolecules and metal ions as metal ions can form complexes with carrageenan. Carrageenan fibers were made with different types of carrageenan and different kinds of metal salt solution, the most appropriate type of carrageenan is iota-carrageenan and the most appropriate type of metal salt solution is BaCl2 solution.
Secondly, the hydroxyl groups in the carrageenan macromolecules can react with cross-linking agents such as epichlorohydrin, succinic anhydride, maleic anhydride, PMDA to form ether bond or ester bond. The result shows that the best cross-linking agent is epichlorohydrin. In order to obtain high quality crosslink ing carrageenan fiber, the optimal reaction condition is as follows:the epichlorohydrin added with the concentration of 6.25%, the reaction temperature is 90℃, the reaction time is 2.Oh, and the pH value is 10.0. In the water reaction system, the succinic anhydride or maleic anhydride can not reacted with carrageenan because of the hydrolysis of the anhydride and has no desired product. And so does PMDA. In the oil reaction system, the succinic anhydride or maleic anhydride can react with carrageenan to obtain cross-linked product.
Finally, the epichlorohydrin cross-linked carrageenan fiber was prepared via wet-spinning technology. The fiber strength is 12.3cN/tex which is 2.3 times of carrageenan fibers and the elongation is 13.46% which is 1.25 times of carrageenan fibers. The mechanical strength of cross-linked carrageenan fibers is significantly improved.
引文
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