短链含氟丙烯酸酯拒水拒油剂的合成及应用
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摘要
以含氟丙烯酸酯(C_4F)、丙烯酸十八酯(SA)、甲基丙烯酸缩水甘油酯(GMA)、丙烯酸丁酯(BA)为共聚单体,采用细乳液聚合法制备短链含氟共聚物乳液。通过红外光谱测试表明各聚合单体参与了聚合反应,且反应完全;X射线电子能谱显示聚合物乳胶膜表面存在C、O、F元素;热重分析和粒径分布说明制备的乳液固含量高,稳定性良好。探讨了阳离子-非离子乳化剂的配比、含氟单体用量、聚合温度对乳液稳定性、棉织物拒水拒油效果影响。结果显示,当阳离子与非离子乳化剂的质量比为1:4时乳液具有最佳稳定性,C4F与SA摩尔比为2∶1时,织物达到最优拒水拒油性能,其θ_(water)=157°,θ_(olive oil)=148°,θ_(hexadecane)=128°。经30次洗涤后,织物仍有较好的拒水拒油效果,说明GMA的加入可提高其耐水洗性能。
A short chain fluoropolymer emulsion was synthesized with fluorinated acrylate(C_4F), octadecyl acrylate(SA), glycidyl methacrylate(GMA), butyl acrylate(BA) as comonomers, via miniemulsion polymerization.Infrared spectroscopy(FT-IR) test shows that each polymerized monomer participates in the polymerization and the reaction is complete.X-ray electron spectroscopy(XPS) proves the presence of C, O, F elements on the surface of the polymer latex film.Thermogravimetric analysis(TG) and the particle size distribution indicate that the prepared emulsion has a high solid content and good stability.The influence of ratio of cationic-nonionic emulsifier, the amount of fluorinated monomer and polymerization temperature on the stability of emulsion, water-repellency and oil-repellency of treated cotton fabric were studied.The results show that the emulsion has the best appearance stability when the mass ratio of cationic to nonionic emulsifier is 1∶4.Moreover, when the mole ratio of C_4F to SA is 2∶1, the treated fabric achieves the optimum water repellency and oil repellency, the θ_(water) is 157°, θ_(olive oil) is 148°,θ_(hexadecane) is 128°.After 30 times washing, the fabric still has a good water and oil repellency, which show that the washability of treated fabris is greatly improved with the addition of GMA.
A short chain fluoropolymer emulsion was synthesized with fluorinated acrylate(C_4F), octadecyl acrylate(SA), glycidyl methacrylate(GMA), butyl acrylate(BA) as comonomers, via miniemulsion polymerization.Infrared spectroscopy(FT-IR) test shows that each polymerized monomer participates in the polymerization and the reaction is complete.X-ray electron spectroscopy(XPS) proves the presence of C, O, F elements on the surface of the polymer latex film.Thermogravimetric analysis(TG) and the particle size distribution indicate that the prepared emulsion has a high solid content and good stability.The influence of ratio of cationic-nonionic emulsifier, the amount of fluorinated monomer and polymerization temperature on the stability of emulsion, water-repellency and oil-repellency of treated cotton fabric were studied.The results show that the emulsion has the best appearance stability when the mass ratio of cationic to nonionic emulsifier is 1∶4.Moreover, when the mole ratio of C_4F to SA is 2∶1, the treated fabric achieves the optimum water repellency and oil repellency, the θ_(water) is 157°, θ_(olive oil) is 148°,θ_(hexadecane) is 128°.After 30 times washing, the fabric still has a good water and oil repellency, which show that the washability of treated fabris is greatly improved with the addition of GMA.
引文
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[10] 王政, 倪士宝, 聂王焰, 等. 细乳液聚合制备含氟丙烯酸酯无皂乳液及其性能[J]. 高分子材料科学与工程, 2012, 28(12): 9-12.Wang Z, Ni S B, Nie W Y, et al. Synthesis and properties of soap-free fluorinated acrylate copolymer emulsion via miniemulsion polymerization[J]. Polymer Materials Science & Engineering, 2012, 28(12): 9-12.
[11] Zhang Q H, Wang Q Y, Zhan X L, 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: 4752-4760.
[12] 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, 41(11): 1-5.Yuan Y H, Zhang J P, Zhu Y Y, et al. Synthesis and application of water-and oil- repellent finishing agent with short-chain fluoroalkyl[J]. Dyeing and Finishing, 2016, 41(11): 1-5.
[2] 李俊, 陈庆民. 含氟丙烯酸酯聚合物研究进展[J]. 高分子材料科学与工程, 2005, 21(5): 14-18.Li J, Chen Q M. Research progress in fluorine-containing acrtlate polymer[J]. Polymer Materials Science & Engineering, 2005, 21(5): 14-18.
[3] Jiang G, Tuo X, Wang D, et al. Preparation, characterization, and properties of fluorinated polyurethanes[J]. J. Polym. Sci. Part A: Polym. Chem., 2009, 47: 3248-3256.
[4] 单良, 李战雄, 臧雄, 等. 核壳型含氟丙烯酸酯乳液的合成及其在棉织物整理中的应用[J]. 纺织学报, 2015, 36(1): 123-128.Shan L, Li Z X, Zhang X, et al. Synthesis of fluoro-acrylate emulsion with core-shell structure and its application on cotton fabric finishing[J]. Journal of Textile Research, 2015, 36(1): 123-128.
[5] Steenland K, Fletcher, T. Epidemiologic evidence on the health effects of perfluorooctanoic acid (PFOA)[J]. Environ. Health Persp., 2010, 118: 1100-1108.
[6] Liu J, Mejia A S. Microbial degradation of polyfluoroalkyl chemicals in the environment: a review[J]. Environ. Int., 2013, 61(4): 98-114.
[7] Darmanin T, Guittard F. Superoleophobic surfaces with short fluorinated chains[J]. Soft Matter, 2013, 9: 5982-5990.
[8] Darmanin T, Tarrade J, Celia E, et al. Superoleophobic meshes with high adhesion by electrodeposition of conducting polymer containing short perfluorobutyl chains[J]. J. Phys. Chem., C, 2014, 118: 2052-2057.
[9] Yan Z, Liu W, Wang H, et al. Synthesis and characterization of novel fluorinated siloxane star-like copolymer with short perfluoroalkyl chain and used for modification the epoxy resin[J]. J. Fluorine Chem., 2014, 157: 63-72.
[10] 王政, 倪士宝, 聂王焰, 等. 细乳液聚合制备含氟丙烯酸酯无皂乳液及其性能[J]. 高分子材料科学与工程, 2012, 28(12): 9-12.Wang Z, Ni S B, Nie W Y, et al. Synthesis and properties of soap-free fluorinated acrylate copolymer emulsion via miniemulsion polymerization[J]. Polymer Materials Science & Engineering, 2012, 28(12): 9-12.
[11] Zhang Q H, Wang Q Y, Zhan X L, 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: 4752-4760.
[12] 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, 41(11): 1-5.Yuan Y H, Zhang J P, Zhu Y Y, et al. Synthesis and application of water-and oil- repellent finishing agent with short-chain fluoroalkyl[J]. Dyeing and Finishing, 2016, 41(11): 1-5.