基于纳米粒子改性短链含氟整理剂的棉织物拒水拒油整理

doi:10.19398/j.att.202105018

摘要/Abstract

摘要：

针对长氟碳链聚合物带来的环境污染问题,利用细乳液聚合合成了六碳短链含氟丙烯酸酯乳液,并在聚合物体系中引入改性后的SiO₂来改善织物的整理效果。利用FTIR和DLS表征了聚合物乳液的结构和粒径分布,考察了不同条件下水、油接触角的变化趋势,表征了整理前后棉织物的结构组成、表面元素以及形貌变化,研究了棉织物的拒污性、耐水洗牢度以及物理力学性能在整理前后的变化。结果表明:当使用的氟单体质量分数为50%、烘焙温度为150℃、烘焙时间为150 s时,整理后织物表面的水接触角为147.9°、油接触角为141.2°,拒油等级能够达到3级,且整理后的棉织物具有一定的防污性,对多种液体具有良好的拒液性;织物在经过20次水洗后仍能保持较好的拒水拒油效果;织物的物理力学性能在整理前后变化不大,几乎不影响其服用性能。

关键词: 含氟丙烯酸酯, 细乳液聚合, 纳米SiO₂粒子, 拒水拒油, 棉织物

Abstract:

In view of environmental pollution caused by long fluorocarbon chain polymers, we prepared a six-carbon short-chain fluorinated acrylate emulsion by miniemulsion polymerization and introduced modified SiO₂ nanoparticles into the polymer system to promote the finishing effect of fabrics. The structure and particle size distribution of polymer emulsion were characterized by means of FTIR and DLS. The variation trend of water and oil contact angles under different conditions were investigated, and the changes in structural composition, surface elements and morphology of untreated and treated fabrics were characterized. The anti-fouling properties, water resistance, physical and mechanical properties of the cotton fabrics before and after finishing were discussed. The results indicated that when the mass fraction of fluorinated monomer used was 50%, the baking temperature was 150℃, the baking time was 150 s, the water contact angle on the surface of finished fabric was 147.9° and the oil contact angle was 141.2° and the oil repellency can reach level 3. In addition, the finished cotton fabric had certain anti-fouling property and good liquid repellency for a variety of liquids. The fabric can maintain good water and oil repellency even after 20 times of washing. The physical and mechanical properties of the treated fabric changed little before and after finishing, and the wearability was almost unaffected.

Key words: fluorinated acrylate, miniemulsion polymerization, nano SiO₂ particle, water and oil repellency, cotton fabric

中图分类号:

TS195.2

盛婷, 张佳文, 徐天祺, 胡叶蕾, 易玲敏. 基于纳米粒子改性短链含氟整理剂的棉织物拒水拒油整理[J]. 现代纺织技术, 2022, 30(2): 169-177.

SHENG Ting, ZHANG Jiawen, XU Tianqi, HU Yelei, YI Lingmin. Water and oil repellent finishing of cotton fabric based on short-chainfluorinated finishing agent modified with nanoparticles[J]. Advanced Textile Technology, 2022, 30(2): 169-177.

图/表 11

图1 聚合物乳胶膜的红外光谱图

Fig.1 FTIR spectrum of polymer emulsion film

图2 共聚物乳液粒径分布

Fig.2 Particle size distribution of copolymer emulsion

图3 氟单体质量分数对棉织物接触角的影响

Fig.3 The effect of fluorine monomer mass fraction on the contact angle of cotton fabric

表1 不同氟单体质量分数对乳胶膜表面自由能的影响

Tab.1 The effect of different fluorine monomer mass fractions on the surface free energy of latex film

编号	氟单体质量分数/%	接触角/(°)			表面自由能 /(mN·m^-1)
编号	氟单体质量分数/%	H₂O	CH₂I₂	Farmamide	表面自由能 /(mN·m^-1)
1	10	99.5	78.2	94.0	21.68
2	20	104.8	89.3	96.2	13.24
3	30	106.8	95.3	96.5	12.05
4	40	109	97.1	102.0	10.14
5	50	110.9	98.0	103.6	9.63
6	60	113.5	100.2	104.5	9.18

图4 烘焙温度和烘焙时间对棉织物接触角的影响

Fig.4 The effect of baking temperature and baking time on the contact angle of cotton fabric

图5 原棉和整理后棉织物的FTIR光谱图和XPS能谱图

Fig.5 FTIR and XPS spectra of pristine cotton and finished cotton fabric

图6 原样和整理后棉织物的SEM图

Fig.6 SEM image of pristine cotton and finished cotton fabric

图7 整理后棉织物的拒水拒油性能

Fig.7 Water and oil repellency of finished cotton fabric

图8 整理前后棉织物的拒液性照片

Fig.8 Liquid repellency photos of pristine cotton and finished cotton fabric

图9 水洗次数对织物接触角的影响

Fig.9 The effect of washing times on the contact angle of cotton fabric

表2 原棉和整理后棉织物的物理力学性能变化

Tab.2 Changes in physical and mechanical properties of pristine cotton and finished cotton fabrics

织物	透气率/(mm·s^-1)	透湿量/(g/m²·h)	断裂强力/N		折皱回复角/(°)
织物	透气率/(mm·s^-1)	透湿量/(g/m²·h)	经向	纬向	急弹	缓弹
原样	94.33	115.79	497	309	122.2	149.7
整理后棉织物	81.28	109.28	511	249	133.6	182.1

参考文献 23

[1]	LIU L M, PAN Y L, BHUSHAN B, et al. Mechanochemical robust, magnetic-driven, superhydro-phobic 3D porous materials for contaminated oil recovery[J]. Journal of Colloid and Interface Science, 2019, 538:25-33. DOI URL
[2]	YU F Y, GAO J, LIU C P, et al. Preparation and UV aging of nano-SiO₂/fluorinated polyacrylate polyurethane hydrophobic composite coating[J]. Progress in Organic Coatings, 2020, 141:105556. DOI URL
[3]	BAI S J, ZHENG W Y, YANG G F, et al. Synjournal of core-shell fluorinated acrylate copolymers and its application as finishing agent for textile[J]. Fibers and Polymers, 2017, 18(10):1848-1857. DOI URL
[4]	WAN S, CONG Y, JIANG D, et al. Weathering barrier enhancement of printed circuit board by fluorinated silica based superhydrophobic coating[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 538:628-638. DOI URL
[5]	JIANG J X, ZHANG G F, WANG Q Y, et al. Novel fluorinated polymers containing short perfluorobutyl side chains and their super wetting performance on diverse substrates[J]. ACS Applied Materials & Interfaces, 2016, 8(16):10513-10523.
[6]	XU W, AN Q F, HAO L F, et al. Synjournal of cationic core-shell fluorine-containing polyacrylate soap-free latex and its application on cotton substrate[J]. Fibers and Polymers, 2013, 14(6):895-903. DOI URL
[7]	LIN J, ZHENG C, ZHU M N, et al. Comparison of copolymer emulsions of fluorine and siloxane-containing acrylates with core-shell structure for water-repellent cotton fabrics coatings[J]. Polymers for Advanced Technologies, 2015, 26(1):68-76. DOI URL
[8]	KRAFFT M P, RIESS J G. Selected physicochemical aspects of poly-and perfluoroalkylated substances relevant to performance, environment and sustainability-Part one[J]. Chemosphere, 2015, 129:4-19. DOI URL
[9]	WANG Z Y, COUSINS I T, SCHERINGER M, et al. Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors[J]. Environment International, 2013, 60:242-248. DOI URL
[10]	ZHANG Q H, WANG Q Y, JIANG J X, et al. Microphase structure, crystallization behavior, and wettability properties of novel fluorinated copolymers poly(perfluoroalkyl acrylate-co-stearyl acrylate) containing short perfluorohexyl chains[J]. Langmuir, 2015, 31(16):4752-4760. DOI URL
[11]	ZHAO M, YU Y H, HAN Z W, et al. Preparation of a fluorocarbon polymerizable surfactant and its application in emulsion polymerization of fluorine-containing acrylate[J]. Polymers, 2017, 9(11):606. DOI URL
[12]	ZHAO J, LI Y, SHENG J L, et al. Environmentally friendly and breathable fluorinated polyurethane fibrous membranes exhibiting robust waterproof performance[J]. ACS Applied Materials & Interfaces, 2017, 9(34):29302-29310.
[13]	YANG Y, SHEN J, ZHANG L, et al. Preparation of a novel water and oil-repellent fabric finishing agent containing a short perfluoroalkyl chain and its application in textiles[J]. Materials Research Innovations, 2015, 19(S8):400-404.
[14]	袁艳华, 张锦盼, 朱玉赢, 等. 短氟碳链拒水拒油整理剂的合成及其应用[J]. 印染, 2016, 42(11):1-5, 18.
	YUAN Yanhua, ZHANG Jinpan, ZHU Yuying, et al. Synjournal and application of water- and oil- repellent finishing agent with short-chain fluoroalkyl[J]. China Dyeing & Finishing, 2016, 42(11):1-5, 18.
[15]	HONDA K, MORITA M, OTSUKA H, et al. Molecular aggregation structure and surface properties of poly(fluoroalkyl acrylate) thin films[J]. Macromolecules, 2005, 38(13):5699-5705. DOI URL
[16]	VAN OSS C J. Use of the combined Lifshitz-van der Waals and Lewis acid-base approaches in determining the apolar and polar contributions to surface and interfacial tensions and free energies[J]. Journal of Adhesion Science and Technology, 2002, 16(6):669-677. DOI URL
[17]	高秀云, 任小翠, 邹祥龙, 等. 细乳液聚合制备含氟丙烯酸酯三元共聚物及性能表征[J]. 皮革与化工, 2013, 30(1):7-12, 29.
	GAO Xiuyun, REN Xiaocui, ZOU Xianglong, et al. Synjournal of fluorinated acrylate ternary copolymer latex by miniemulsion polymerization and characterization[J]. Leather and Chemicals, 2013, 30(1):7-12,29.
[18]	ZHOU J H, CHEN X, DUAN H, et al. Synjournal and Characterization of nano-SiO₂ modified fluorine-containing polyacrylate emulsifier-free emulsion[J]. Applied Surface Science, 2015, 331:504-511. DOI URL
[19]	李晓伟, 杨勇, 张丽媛, 等. 全氟短碳链拒水拒油剂的合成及其应用[J]. 印染, 2014, 40(2):34-36,56.
	LI Xiaowei, YANG Yong, ZHANG Liyuan, et al. Synjournal and application of perfluorinated water- and oil-repellent with short carbon chain[J]. China Dyeing & Finishing, 2014, 40(2):34-36,56.
[20]	刘金庭, 徐祖顺, 高庆. 全氟丁基丙烯酸酯拒水剂的合成及应用[J]. 精细化工, 2017, 34(11):1294-1300.
	LIU Jinting, XU Zushun, GAO Qing. Synjournal and application of perfluorobutyl acrylate water repellent[J]. Fine Chemicals, 2017, 34(11):1294-1300.
[21]	XU W, AN Q F, HAO L F, et al. Synjournal of self-crosslinking fluorinated polyacrylate soap-free latex and its waterproofing application on cotton fabrics[J]. Fibers and Polymers, 2014, 15(3):457-464. DOI URL
[22]	ANJUM A S, SUNK C, ALI M, et al. Fabrication of coral-reef structured nano silica for self-cleaning and super-hydrophobic textile applications[J]. Chemical Engineering Journal, 2020, 401:125859. DOI URL
[23]	钱海洪, 王鸿博, 傅佳佳, 等. 电子束辐照接枝对棉织物抗皱/拒水拒油性能的影响[J]. 辐射研究与辐射工艺学报, 2017, 35(2):36-45.
	QIAN Haihong, WANG Hongbo, FU Jiajia, et al. Effects of electron beam irradiation grafting on anti-wrinkle / water and oil repellency of cotton fabric[J]. Journal of Radiation Research and Radiation Processing, 2017, 35(2):36-45.