四硼酸钠/单宁酸交联对海藻酸钙纤维结构与性能的影响

doi:10.13475/j.fzxb.20240805401

摘要/Abstract

摘要：

为改善海藻酸钙(CA)纤维的耐盐性、耐洗涤性和力学性能,以单宁酸(TA)、四硼酸钠(STB)及其组合物为交联剂,通过浸渍法制备了不同种类交联剂的海藻酸钙纤维,借助红外光谱仪、X射线衍射仪、热重分析仪、扫描电子显微镜,并通过吸湿保湿性测试、耐盐耐洗涤性测试、力学性能测试等对纤维的结构和性能进行表征。结果表明:TA和STB均能够抑制纤维在含金属离子溶液中的钙钠离子交换,TA能够提高CA纤维的结晶度、增强分子间氢键作用,提高CA纤维的强度,STB能够提高CA纤维的断裂伸长和耐洗稳定性,通过TA和STB组合交联CA成功构建了硼酸盐共价键-单宁酸螯合作用-氢键协同交联网络,使得海藻酸钙纤维的断裂强度提升27.18%、断裂伸长率提升7.48%,经生理盐水和洗涤溶液处理后纤维的形貌和尺寸变化不大,其耐盐性和耐洗涤性能显著提高。

关键词: 生物基纤维, 海藻酸钙纤维, 四硼酸钠, 单宁酸, 交联网络, 耐盐耐洗涤性, 力学性能

Abstract:

Objective Calcium alginate fiber has poor mechanical properties and saline stability, which seriously limits its application in textile and garment fields. Most of the studies achieved the performance enhancement of calcium alginate fibers by chemical treatment of sodium alginate spinning stock solution and coagulation bath, and fewer studies related to direct cross-linking treatment of calcium alginate fibers. This paper introduces an effort to overcome the performance defects of calcium alginate fibers by impregnating them with cross-linking agents.

Method Calcium alginate (CA) fibers with different cross-linking types were prepared by impregnation method, and the structure and properties of the fibers were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and optical microscopy (POM) moisture absorption and retention test, salt resistance and washing resistance test, and mechanical properties test.

Results Sodium tetraborate (STB) is bonded to calcium alginate (CA) macromolecules through B—O covalent bonds, effectively improving the saline and washing stability of CA fibers. Tannic acid (TA) was employed to regulate the calcium ion cross-linking between CA macromolecules through its chelating action with calcium ions in CA, indirectly enhancing the coordinated action of CA macromolecules through the strong hydrogen bond between phenolic hydroxyl groups and CA. These two actions, while improving the stability of CA fibers, also more effectively improved the mechanical properties of CA fibers. By combining STB and TA to cross-link CA successfully, a synergistic cross-linking network of ″borate covalent bond-tannic acid chelation-hydrogen bond″ was formed. On the one hand, it dispersed STB and promoted the cross-linking effect of STB on CA more effectively. On the other hand, it positioned TA and promoted the enhancement of strong hydrogen bond coordination between CA macromolecules more effectively, achieving a significant improvement in the tensile strength and elongation at break of CA fibers. As a result, the breaking strength of calcium alginate fibers was increased by 27.18% and the elongation at break by 7.48%, thereby achieving a significant improvement in the saline and washing stability and mechanical properties of CA fibers.

Conclusion Both TA and STB inhibit the calcium-sodium ion exchange of the fibers in metal ion-containing solution. TA improves the crystallinity of CA fibers, enhances the intermolecular hydrogen bonding, and increases the strength of CA fibers, while STB improves the elongation at break and the washing stability of CA fibers. Through the combination of TA and STB crosslinking CA, a synergistic crosslinking network of “borate covalent bonding-tannic acid-hydrogen bonding” was successfully constructed, which increased the breaking strength of calcium alginate fibers by 27.18% and the elongation at break by 7.48%, and the morphology and size of the fibers did not change much after being treated with saline and washing solution, and the saline resistance and washing resistance were significantly improved.

Key words: bio-based fiber, calcium alginate fiber, sodium tetraborate, tannic acid, cross-linking network, salt and washing resistance, mechanical property

中图分类号:

TQ341.5

朱雷, 李晓俊, 程春祖, 徐纪刚, 杜心宇. 四硼酸钠/单宁酸交联对海藻酸钙纤维结构与性能的影响[J]. 纺织学报, 2025, 46(07): 28-36.

ZHU Lei, LI Xiaojun, CHENG Chunzu, XU Jigang, DU Xinyu. Influences of sodium tetraborate/tannic acid cross-linking on structure and properties of calcium alginate fibers[J]. Journal of Textile Research, 2025, 46(07): 28-36.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20240805401

http://www.fzxb.org.cn/CN/Y2025/V46/I07/28

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纤维种类	m₇₅/%	m₁₉₀/%	T_m/℃	m₃₅₀/%	m₆₀₀/%
CA	5.83	16.62	258	50.85	63.67
STB/CA	6.11	16.97	268	49.25	63.77
TA/CA	5.81	15.59	259	49.93	62.23
STB/TA/CA	5.56	16.12	262	49.50	62.36