PVA微晶交联和SA/PAA双网络协效增强增韧SA纤维

doi:10.7503/cjcu20190473

摘要/Abstract

摘要：

为了提高海藻酸钠(SA)纤维的断裂强度和断裂伸长率, 以丙烯酸(AA)为化学交联组分, SA为离子交联组分, 聚乙烯醇(PVA)为微晶交联组分, 采用湿法纺丝和冻融循环方法制备含有PVA微晶交联点和海藻酸钠/聚丙烯酸(SA/PAA)双网络结构的海藻酸钠/聚丙烯酸/聚乙烯醇(SA/PAA/PVA)复合纤维. 通过流变性能、力学性能、红外光谱、 X射线衍射仪(XRD)和扫描电子显微镜(SEM)测试研究了交联剂N,N-亚甲基双丙烯酰胺(MBA)含量和PVA微晶交联对SA/PAA/PVA纺丝原液和复合纤维的结构与性能的影响. 结果表明, 当MBA质量分数为0.5%时, 纺丝原液的损耗模量(G″)最小, 可纺性最好, 复合纤维的断裂强度达到2.83 cN/dtex, 断裂伸长率达到9.38%, 比再生SA纤维分别提高了15.98%和38.96%; PVA冷冻之后形成微晶交联点并且PAA和PVA已经复合到体系中; PAA和PVA的加入提高了复合纤维的结晶度; 复合纤维的表面形貌趋于光滑和规整, 纤维断面更加致密.

关键词: 海藻酸钠, SA/PAA双网络, 微晶交联, 聚乙烯醇

Abstract:

In order to improve the breaking strength and elongation at break of sodium alginate(SA) fiber, acrylic acid(AA) was used as chemical crosslinking component, SA was used as ion crosslinking component, and polyvinyl alcohol(PVA) was used as microcrystalline crosslinking group. The sodium alginate/polyacrylic acid/polyvinyl alcohol(SA/PAA/PVA) composite fiber containing PVA microcrystalline cross-linking point and SA/PAA double network structure was prepared by wet spinning and freeze-thaw cycle method. The effects of cross-linking agent N,N-methylenebisacrylamide(MBA) content and PVA microcrystalline cross-linking on the structure and properties of SA/PAA/PVA spinning dope and composite fiber were studied by rheological properties, mechanical properties, infrared spectroscopy, X-ray diffractometer(XRD) and sweeping electron microscope(SEM) tests. The results showed that when the MBA content is 0.5%, the loss modulus(G″) of the spinning dope is the smallest and the spinnability is the best. The breaking strength of the composite fiber reached 2.83 cN/dtex, and the elongation at break reached 9.38%, which was 15.98% and 38.96% higher than that of the regenerated SA fiber. PVA formed a microcrystalline cross-linking point after freezing and PAA and PVA had been compounded into the system. The crystallinity of composite fibers increased after joining PAA and PVA. The surface morphology of the composite fiber tends to be smooth and regular, and the fiber cross section is more dense.

Key words: Sodium alginate, SA/PAA double network, Microcrystalline cross-linking, Polyvinyl alcohol

中图分类号:

O636

TrendMD:

闫铭,周炜东,张鸿,石军峰,赵云鹤,叶泳铭,郭静,于跃. PVA微晶交联和SA/PAA双网络协效增强增韧SA纤维. 高等学校化学学报, 2020, 41(2): 349.

YAN Ming,ZHOU Weidong,ZHANG Hong,SHI Junfeng,ZHAO Yunhe,YE Yongming,GUO Jing,YU Yue. PVA Microcrystalline Cross-linking and SA/PAA Double Network Synergistic Modification of SA Fiber ^†. Chem. J. Chinese Universities, 2020, 41(2): 349.

图/表 12

Scheme 1 Preparation of flow chart

Fig.1 Characterization of rheological properties of SA/PAA/PVA blend solution a—g. Loss modulus; a'—g' storage modulus. a, a'. Regenerated SA; b, b'. SA/PAA/PVA, not frozen; c, c'. SA/PAA/PVA, already frozen; d, d'. SA/PAA/PVA, 0.25%MBA; e, e'. SA/PAA/PVA, 0.5%MBA; f, f'. SA/PAA/PVA, 0.75%MBA; g, g'. SA/PAA/PVA, 1%MBA.

Scheme 2 Schematic diagram of SA/PAA composite fiber dual network structure

Fig.2 Breaking strength(a) and breaking elongation(b) of SA/PAA/PVA composite fibers at different MBA contents

Scheme 3 Roles of dynamic victim keys

Fig.3 Mechanical properties of regenerated SA fiber and SA/PAA/PVA composite fibers treated under different conditions a. Regenerated SA; b. not frozen, SA/PAA/PVA; c. 0.25% MB and already frozen, SA/PAA/PVA; d. 0.5% MBA and already frozen, SA/PAA/PVA.

Fig.4 Infrared spectra of regenerated SA fiber(a) and SA/PAA/PVA composite fiber(b)

Fig.5 Fitted IR curves of regenerated SA fiber(A) and SA/PAA/PVA composite fiber(B) (A) a—f. Fitted curves 1—6; g. originaL curve. (B) a—e. Fitted curves 1—5; f. original curve.

Table 1 Fractal peak fitting results of infrared spectrum of regenerated SA fiber and SA/PAA/PVA composite fiber

Sapmle	Type of hydrogen bond	Structural formula	$ν ˙$ /cm^-1	Peak area	Relative Strength(%)
Regenerated SA fiber	Free hydroxyl	—OH	3599	1.55	3.5
	Intramolecular hydrogen bond	OH…OH	3442	18.33	54.2
		Four association	3097	5.99
	Intermolecular hydrogen bond	OH…O(in ether)	3266	12.10	42.3
		OH…π	3543	6.25
		OH…N	3126	0.68
SA/PAA/PVAComposite fiber	Free hydroxyl	—OH	3582	5.21	8.9
	Intramolecular hydrogen bond	OH…OH	3403	14.85	37.1
		Four association	3165	6.95
	Intermolecular hydrogen bond	OH…O(in ether)	3287	12.80	54.0
		OH…π	3492	18.90

Table 1 Fractal peak fitting results of infrared spectrum of regenerated SA fiber and SA/PAA/PVA composite fiber

Sapmle	Type of hydrogen bond	Structural formula	$ν ˙$ /cm^-1	Peak area	Relative Strength(%)
Regenerated SA fiber	Free hydroxyl	—OH	3599	1.55	3.5
	Intramolecular hydrogen bond	OH…OH	3442	18.33	54.2
		Four association	3097	5.99
	Intermolecular hydrogen bond	OH…O(in ether)	3266	12.10	42.3
		OH…π	3543	6.25
		OH…N	3126	0.68
SA/PAA/PVAComposite fiber	Free hydroxyl	—OH	3582	5.21	8.9
	Intramolecular hydrogen bond	OH…OH	3403	14.85	37.1
		Four association	3165	6.95
	Intermolecular hydrogen bond	OH…O(in ether)	3287	12.80	54.0
		OH…π	3492	18.90

Fig.6 XRD patterns of regenerated SA fiber(a) and SA/PAA/PVA composite fiber(b)

Fig.7 TG(A) and DTG(B) curves of regenerated SA fiber(a) and SA/PAA/PVA composite fiber(b)

Fig.8 SEM images of surface(A, B) and cross-sectional(C, D) of regenerated SA fiber(A, C) and SA/PAA/PVA composite fiber(B, D)

参考文献 32

[1]	Sarikaya E., Çallioglu H., Demirel H., Composites Part B: Engineering, 2019,167, 461— 466 doi: 10.1016/j.compositesb.2019.03.020 URL
[2]	Sow L. C., Yu Toh N. Z., Wong C. W., Yang H., Food Hydrocolloids, 2019,94, 459— 467 doi: 10.1016/j.foodhyd.2019.03.041 URL
[3]	Bai Y. Y., Lei Y. H., Shen X. J., Luo J., Yao C. L., Sun R. C., Carbohydrate Polymers, 2017,174, 610— 616 doi: 10.1016/j.carbpol.2017.06.091 URL
[4]	Varaprasad K., Raghavendra G. M., Jayaramudu T., Seo J., Carbohydrate Polymers, 2016,135, 349— 355 doi: 10.1016/j.carbpol.2015.08.078 URL
[5]	Wu N. J., Niu F. K., Lang W. C., Xia M. F., Carbohydrate Polymers, 2019,221, 221— 230 doi: 10.1016/j.carbpol.2019.06.007 URL
[6]	Li X. L., Chen M. J., Chen H. B., Composites Part B: Engineering, 2019,164, 18— 25 doi: 10.1016/j.compositesb.2018.11.055 URL
[7]	Qin H. H., Fang X. X., Zhao X., Song F. J., You J. X., Industrial Textiles, 2018,36(4), 1— 6
	( 秦洪花, 房学祥, 赵霞, 宋福杰, 尤金秀 . 产业用纺织品, 2018,36(4), 1— 6)
[8]	Zhang K., Zhu P., Sui S. Y., Dong C. H., Zhang X. Y., Wuhan University Journal of Natural Sciences, 2017,22(3), 197— 200 doi: 10.1007/s11859-017-1235-4 URL
[9]	Helmiyati, Aprilliza M ., IOP Conference Series Materials Science and Engineering, 2017,188(1), 1— 5
[10]	You W. T., Dan W. H., Dan N. H., Liang Y. X., Liu B. W., Wen H. T., China Leather, 2017,4(8), 19— 24
	( 尤伟婷, 但卫华, 但年华, 梁永贤, 刘博文, 温会涛 . 中国皮革, 2017,4(8), 19— 24)
[11]	Ran Q., Liu X. P., Zhang C., Xiang X. L., Yunnan Chemical Technology, 2019,46(3), 127— 129
	( 冉青, 刘信平, 张驰, 向戌连 . 云南化工, 2019,46(3), 127— 129)
[12]	Summa M., Russo D., Penna I., Margaroli N., Bayer I. S., Bandiera T., Athanassiou A., Bertorelli R., European Journal of Pharmaceutics and Biopharmaceutics, 2018,122, 17— 24 doi: 10.1016/j.ejpb.2017.10.004 URL
[13]	Yuan N. N., Li S. J., Li G. Q., Journal of Drug Delivery Science and Technology, 2018,46, 348— 353 doi: 10.1016/j.jddst.2018.05.026 URL
[14]	Yang M. L., Wang L., Xia Y. Z., International Journal of Biological Macromolecules, 2019,124, 1238— 1245 doi: 10.1016/j.ijbiomac.2018.12.012 URL
[15]	Lacoste C., Hage R. E., Bergeret A., Corn S., Lacroix P., Carbohydrate Polymers, 2018,184, 1— 8 doi: 10.1016/j.carbpol.2017.12.019 URL
[16]	Zou X. Q., Zhang H., Chen T., Li H. T., Meng C. H., Xia Y., Guo J., Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019,567, 184— 192 doi: 10.1016/j.colsurfa.2018.12.019 URL
[17]	Megan S., Chris R., Julien B., Johan F. E., Journal of Applied Polymer Science, 2018,135(7), 45857— 45866 doi: 10.1002/app.45857 URL
[18]	Li X. F., Wang H., Li D. P., Long S. J., Zhang G. W., Wu Z. L., ACS Applied Materials & Interfaces, 2018,10(37), 31198— 31207 doi: 10.1021/acsami.8b13038 URL
[19]	Rao Z. L., Liu S. M., Wu R. Y., Wang G. L., Sun Z. X., Bai L. J., Wang W. X., Chen H., Yang H. W., Wei D. L., Niu Y. Z., International Journal of Biological Macromolecules, DOI: 10.1016/j.ijbiomac, 2019,129 916— 926
[20]	Gong J. P., Katsuyama Y., Kurokawa T., Osada Y., Advanced Materials, 2003,15(14), 1155— 1158 doi: 10.1002/adma.200304907 URL
[21]	Sun T. W., Yang R. H., Ma C. W., Liang Z., Acta Universitatis Medicinalis Anhui, 2018,53(7), 1139— 1142
	( 孙天文, 杨润怀, 马长望, 梁振 . 安徽医科大学学报, 2018,53(7), 1139— 1142)
[22]	Bahrami Z., Akbari A., Eftekhari-Sis B ., International Journal of Biological Macromolecules, 2019,129, 187— 197 doi: 10.1016/j.ijbiomac.2019.02.046 URL
[23]	Yang M. L., Shi Y. L., Yu Z. H., Liu J. W., Bai Y. X., Shi J. S., Food Science and Technology, 2019,44(4), 274— 280
	( 杨曼丽, 石云龙, 于志浩, 刘佳伟, 白映雪, 师进生 . 食品科技, 2019,44(4), 274— 280)
[24]	Zhu G. F., Zhang H., Li H. T., Chen T., Yu Y., Guo J., Acta Materiae Compositae Sinica, 2017,34(11), 2571— 2579
	( 祝国富, 张鸿, 李会涛, 陈涛, 于跃, 郭静 . 复合材料学报, 2017,34(11), 2571— 2579)
[25]	Zhang Y ., Study on Rheological Properties of Carbon Nanotubes/Sodium Alginate Solution and Preparation of Composite Fibers, Qingdao University, Qingdao, 2013
	( 张杨 . 碳纳米管/海藻酸钠溶液流变性能的研究及复合纤维的制备, 青岛: 青岛大学, 2013)
[26]	Tuo C., Morden Salt Science & Technology, 2017,44(3), 1— 2)
	( 庹超 . 现代盐化工, 2017,44(3), 1— 2)
[27]	Lei Z. Y., Wang Q. K., Sun S. T., Zhu W. C., Wu P. Y., Advanced Materials, 2017,29, 1700321— 1700326 doi: 10.1002/adma.v29.22 URL
[28]	Jiang Y. P., Yang T., Fei G. X., Xia H. S., Polymer Materials Science & Engineering, 2018,34(7), 150— 155
	( 蒋瑶珮, 杨涛, 费国霞, 夏和生 . 高分子材料科学与工程, 2018,34(7), 150— 155)
[29]	Guo Y., Wang X. H., Xie H. Y., Journal of Xinjiang Agricultural University, 2017,40(3), 198— 203
	( 郭渊, 王晓焕, 谢海燕 . 新疆农业大学学报, 2017,40(3), 198— 203)
[30]	Gao D. G., Zang Y. H., Lv B., Ma J. Z., Fine Chemicals, 2018,35(2), 298— 302
	( 高党鸽, 张亚红, 吕斌, 马建中 . 精细化工, 2018,35(2), 298— 302)
[31]	Wang Z., Wang Y., Liu G., Dong W. F., Plastic, 2017,46(6), 17— 19
	( 王竹, 汪洋, 刘耘, 东为富 . 塑料, 2017,46(6), 17— 19)
[32]	Wang Z. L., Xing S. L., Yin C. P., Yang J. S., Engineering Plastics Application, 2018,46(8), 131— 137
	( 王子龙, 邢素丽, 尹昌平, 杨金水 . 工程塑料应用, 2018,46(8), 131— 137)