CN112878053B - 一种基于微纳结构的超疏水织物及其制备方法 - Google Patents
一种基于微纳结构的超疏水织物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于微纳结构的超疏水织物及其制备方法。首次利用卡宾聚合共价接枝与固体表面自组装相结合的全新方法,以脂肪系重氮化合物与芳香系重氮化合物为单体经卡宾共聚合将具有单碳重复单元的含氟与含苯基的嵌段共聚物通过共价键接枝到织物表面,制得了具有超疏水和自清洁功能的改性织物。通过纤维表面诱导卡宾聚合物结晶驱动自组装在织物表面构筑了具有微纳复合的分级糙化结构,且二级结构为仿荷叶表面的纳米级乳突状结构。本发明在织物表面构建低表面能的糙化结构克服了目前浸渍涂层法牢度低且需要有机‑无机杂化处理的缺陷,并且通过对前体分子的合理设计能够得到多种尺度与形貌的低表面能糙化结构,具有好的疏水性与自清洁性能。
Description
技术领域
本发明涉及一种超疏水织物及其制备方法,具体涉及一种基于微纳结构的超疏水织物及其制备方法,属于特种功能性纺织品及其制备技术领域。
背景技术
随着近些年来仿生材料的发展,一些通过模拟大然界中奇特的现象而制备的功能材料不断问世。其中最为典型的是仿生学在超浸润材料制备领域的应用,特别是关于超疏水、自清洁功能表面制备的相关研究。这与我们息息相关,如生活中雨伞、工业用拒水布料以及高档抗油去污的衣用面料等。事实上一个真正意义上的超疏水表面不仅要有超过150°的静态接触角,还要有一定的滚动角,这个滚动角一般是小于10°,才能获得真正实用性的超疏水、自清洁功效。
有关超疏水表面的制备,主要有为“自上而下(Up-bottom)”和“自下而上(Bottom-up)”两种方法。前者主要包括模板法、刻蚀法和等离子处理法等,后者主要包括静电纺丝法、自组装法和层间沉积等,其中“自下而上”这种方法依赖于在特定反应条件下前驱体的化学反应,适用性更广,更具有普适性。随着近些年衍生的制备方法的增多,目前主要分为两种,一是在低表面能表面通过加入微纳米颗粒提供粗糙度,二是通过化学改性在已有纹理或说是糙化结构的表面上。所以超疏水织物的制备主要两种方式,一种是先在棉织物表面构造一定的糙化结构,然后再用低表面能物质去修饰糙化结构;另外一种方法是一步法在织物表面构建拥有低表面能的糙化结构。
目前关于超疏水织物表面构造的研究主要集中在第一种方法即在织物表面利用有无机微/纳米粒子构造一定的糙化结构,然后再用含氟/硅等低表面能物质去修饰糙化结构,主要是通过物理作用力将低表面能聚合物修饰后的无机微/纳米粒子附着在织物表面,主要有浸渍涂层法及其衍生的相关方法,这些方法步骤繁琐,非共价键作用力耐久性差,有时需要的高温高压会对纤维造成损伤。而一步法通过共价键将低表面能聚合物接枝到织物表面的报道很少,主要是由于传统的碳烯聚合物分子链刚性差易成膜而无法提供粗糙度,更别说微纳分级复合结构。
发明内容
本发明针对目前采用传统的化学接枝法制备超疏水织物存在的问题:通过化学作用将低表面能聚合物共价键接枝到织物上,或者是一些含低表面能元素的单体直接在纤维表面上的接枝位点处发生聚合反应生成低表面能聚合物,这两种主要的共价接枝方式由于传统的碳烯聚合的缺陷往往无法生成一定粗糙度的糙化结构,特别是生成制备超疏水功能表面所需要的微纳复合糙化结构。因此本发明公开了一种采用卡宾共聚合化学共价接枝制备超疏水织物的方法。利用纤维表面自身的官能团作为共价接枝位点,通过卡宾共聚合将具有单碳重复、立体规整特性的卡宾嵌段共聚物共价接枝到织物表面。化学共价接枝的卡宾嵌段共聚物在纤维表面的诱导下结晶进而驱动自组装最终在织物表面生成了具有微纳复合结构的低表面能糙化结构,并且二级结构为仿荷叶表面的乳突状形貌。
实现本发明目的的技术方案是:
基于微纳结构的超疏水织物,其制备方法为,在催化剂作用下,将脂肪系重氮化合物与活性织物在有机溶剂中反应;然后加入芳香系重氮化合物,进行卡宾共聚合共价接枝反应,得到基于微纳结构的超疏水织物。
本发明通过卡宾共聚合共价接枝反应在织物的纤维表面制得微纳复合结构的低表面能糙化结构,进而制备了一种超疏水织物,其化学结构式示意如下:
本发明中,以碳链氟烷基醇为起始剂,先后分别与溴乙酰溴和N, N`-二甲苯磺酰肼反应生成碳链氟烷基重氮乙酸酯,为脂肪系重氮化合物;碳链氟烷基醇中,碳原子数为3~10。优选的,碳链氟烷基醇为短碳链氟烷基醇,比如全氟己基乙醇或者全氟丁基乙醇。反应的温度为-5~5℃,最好为0~5℃;反应时间为3~5h。
本发明中,以含溴苯酯或苯酮为起始剂,与N, N`-二甲苯磺酰肼反应生成芳香系重氮苯酯化合物或者芳香系重氮苯酮类化合物,为芳香系重氮化合物。优选的,含溴苯酯为溴乙酸苯酯;含溴苯酮为2-溴-4`-(三氟甲基)苯乙酮。反应的温度为-5~5℃,最好为-5~0℃;反应的时间为3~5h。
本发明中,织物酰化后与N,N`-二甲苯磺酰肼反应制备活性织物。
本发明中,催化剂为氯化钯、氯化烯丙基钯(II)二聚物或双(乙腈)氯化钯(II);催化剂的用量为脂肪系重氮化合物摩尔量的0.3%~0.5%。
本发明中,有机溶剂为无水四氢呋喃和/或无水乙醇的混合液溶剂;所述卡宾聚合反应在震荡或者搅拌条件下进行;所述卡宾共聚合共价接枝反应的温度为25~35℃,最好为28~32℃;卡宾共聚合共价接枝反应的反应时间为12~24h。震荡指织物随着锥形瓶一起运动;搅拌指织物运动,锥形瓶不动。
本发明中,卡宾共聚合共价接枝反应在NaBPh4存在下进行,NaBPh4的用量为脂肪系重氮化合物摩尔量的1.5%~2%。
本发明中,脂肪系重氮化合物、芳香系重氮化合物与活性织物的用量比例为5mmol∶5mmol∶(0.7~0.9)g。
本发明公开了上述脂肪系重氮化合物与芳香系重氮化合物在制备上述基于微纳结构的超疏水织物中的应用以及上述基于微纳结构的超疏水织物作为自清洁疏水材料的应用。
与现有技术相比,本发明提供的技术方案其有益效果在于:
传统的制备超疏水织物方法如浸渍涂层法、化学气相沉积法以及溶胶凝胶法等物理改性方法均是利用织物表面与改性剂之间的范德华力、氢键力、静电吸附等分子间的相互作用,这些非共价键作用力使织物获得的超疏水效果很容易减弱或丧失,并且一些高温、高压等条件对纤维造成损伤。而卡宾共聚合共价接枝是在常温下进行的,对织物损伤很小,并且在化学作用力下使得获得的超疏水功能会更加持久。
由于传统的碳烯聚合的自身缺陷使得目前的化学接枝改性方法存在着一个很大的弊端,即在织物表面接枝的低表面能化合物往往成膜或成不均匀块状,无法生成均一形貌的粗糙结构。而本发明采用新颖的卡宾聚合使得共价接枝的低表面聚合物在基底诱导作用下结晶进而自组装形成了具有一定几何形貌的糙化结构。
利用不同前体的分子结构特征如脂肪系重氮化合物和芳香系重氮化合物在不同工艺下对织物进行均聚接枝能够形成不同几何形貌的糙化结构。并且通过短碳链氟烷基与含苯基的合理设计前体的分子结构能够获得微纳复合甚至是多级结构的低表面能糙化结构。
采用的低表面能化合物为短氟烷基链材料,规避了长氟碳链聚合物在自然环境中容易氧化降解生成环境污染物的问题,是一种相对环保的材料。超疏水织物的制备方法为“一浴法”,且在室温下反应,条件温和,副产物为氮气不需要尾气处理,易于工业化生产和推广。
附图说明
图1是实施例一制备的卡宾聚合接枝后的织物表面扫描电子显微镜(SEM)图,纤维表面分布着大小不一、均匀分散的立方体块状聚合物晶体,晶体表面平整光滑,六个面均为规则的四边形。对水接触角为125°;
图2是实施例二制备的卡宾聚合接枝后的织物表面扫描电子显微镜(SEM)图,纤维表面被一层致密涂层所覆盖,且涂层中嵌入了大量均匀分布的纳米级乳突状颗粒,其底部被牢牢包埋在涂层中。对水接触角为132°;
图3是实施例三制备的卡宾聚合接枝后的织物表面扫描电子显微镜(SEM)图,单根纤维被完整的片叶层状包裹且排列紧密。这些犹如花生叶般薄片构成了脊线分离网络,叶片表面光滑;
图4是实施例四制备的卡宾聚合接枝后的织物表面扫描电子显微镜(SEM)图,纤维表面分散着一层形貌均一的微米级球状颗粒,颗粒之间无聚集,且颗粒表面光滑;
图5是实施例五制备的卡宾聚合接枝后的织物表面扫描电子显微镜(SEM)图,聚合物在纤维表面更易形成堆积型颗粒,表面光滑;
图6是实施例六制备的卡宾共聚合接枝后的织物表面扫描电子显微镜(SEM)图,纤维表面覆盖着密集堆积的不规则微米级颗粒,颗粒表面又继续生长成纳米尺度的凸起。随着糙化结构不断生长,微米级颗粒表面富生的纳米级颗粒已经形成了规整的乳突,由此形成了非常完美的微-纳分级的二级糙化结构。对水接触角为155°;
图7是实施例七制备的卡宾共聚合接枝后的织物表面扫描电子显微镜(SEM)图,纤维表面覆盖着密集堆积的不规则微米级颗粒,颗粒表面又继续生长成纳米尺度的凸起。随着糙化结构不断生长,微米级颗粒表面富生的纳米级颗粒已经形成了规整的乳突,由此形成了非常完美的微-纳分级的二级糙化结构。对水接触角为158°;
图8为实施例七制备的超疏水织物自清洁测试效果图;
图9为实施例七制备的超疏水织物对不同液体的拒液性。
具体实施方式
本发明利用卡宾共聚合共价接枝含氟嵌段共聚合物,在纤维表面构筑基于微纳复合的二级糙化结构,且二级纳米结构呈现出理想的乳突结构;采用的低表面能化合物为短氟烷基链材料,规避了长氟碳链聚合物在自然环境中容易氧化降解生成环境污染物的问题,是一种相对环保的材料。超疏水织物的制备方法为“一浴法”,且在室温下反应,条件温和,副产物为氮气不需要尾气处理,易于工业化生产和推广。下面结合附图和实施例对本发明技术方案作进一步描述。
接触角测试
采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试,选取水作为测试液滴,液滴体积为5μL,分别测试五次取其平均值。
本发明所涉及的原料都是市售常规产品,织物为常规棉织物,经过常规碱化处理;具体操作方法以及测试方法为常规技术,搅拌、震荡为常规方法,所有例子操作参数一样,选择搅拌或者震荡后,具体的操作参数对本发明技术效果无影响。棉织物预处理:室温下,常规棉织物浸入质量分数为20%的氢氧化钠溶液处理25 min,蒸馏水洗涤三次,再在5%的冰醋酸中浸泡30 min,然后用去离子水水洗至中性,干燥得到碱化棉织物。本发明中,织物酰化后与N,N`-二甲苯磺酰肼反应制备活性织物,具体为,将0.815g碱化棉织物投入装有50mL无水四氢呋喃和1.68g碳酸氢钠的锥形瓶中,降温至0℃,氮气下滴加1.68g溴乙酰溴恒温反应30min,然后置于水浴震荡锅中自然升温至30℃恒温反应15小时,再分别用四氢呋喃和去离子水清洗干净,烘干,得到溴化织物。将溴化织物浸入在装有无水四氢呋喃的锥形瓶中,加入5.11g N, N'-双(对甲苯磺酰)肼后降温至0℃,氮气下滴加4.57g 1, 8-二氮杂二环十一碳-7-烯于0℃下反应30min,最后置于水浴震荡锅中自然升温至30℃,恒温振荡反应20小时,反应结束后,分别用四氢呋喃和去离子水清洗干净,烘干为活性织物,用于本发明实施例以及对比例。
合成例
(1)合成对三氟甲基重氮苯乙酮与重氮乙酸苯酯
三口烧瓶配有温度计,T型三通接氮气,瓶中加入60mL无水四氢呋喃,1.34g 2-溴-4’-(三氟甲基)苯乙酮和3.41g N, N'-双(对甲苯磺酰)肼并降温至0℃,将3.82g 1,8-二氮杂二环十一碳-7-烯滴加入混合液中(15分钟滴完)恒温反应3h。反应结束后用去离子水淬灭,二氯甲烷萃取3次,无水硫酸镁干燥,抽滤、旋蒸除去低沸点溶剂得0.77g产物对三氟甲基重氮苯乙酮。FT-IR (KBr, cm-1): 3108, 2937(C-H); 2111 (C=N2); 1621 (C=O); 1576(C-C); 1324 (C-F); 762 (C-F3); 708 (C-H). 1HNMR (400 MHz, CDCl3): 7.11-7.48(Ph-H); 7.60-7.96 (Ph-H); 4.78 (H-C=N2) ppm。
三口烧瓶配有温度计,T型三通接氮气,瓶中加入60mL无水四氢呋喃,1.08g 溴乙酸苯酯和3.41g N, N'-双(对甲苯磺酰)肼并降温至0℃,将3.82g 1,8-二氮杂二环十一碳-7-烯滴加入混合液中(15分钟滴完)恒温反应3h。反应结束后用去离子水淬灭并加入饱和碳酸氢钠溶液,二氯甲烷萃取3次,无水硫酸镁干燥,抽滤、旋蒸除去低沸点溶剂得0.55g产物重氮乙酸苯酯。FT-IR (KBr, cm-1): 3133 (C-H); 2117 (C=N2); 1705(C=O); 1594 (C-C); 1292 (CO-O); 728, 708 (C-H). 1H NMR (400 MHz, CDCl3): 7.11(Ph-H); 7.25(Ph-H); 7.37 (Ph-H); 4.79 (H-C=N2) ppm。
(2)合成十三氟辛基重氮乙酸酯
三口烧瓶配有温度计,T型三通接氮气,瓶中加入50mL无水四氢呋喃,1.82g全氟己基乙醇和1.26g碳酸氢钠并降温至0℃,滴加1.54g溴代乙酰溴,恒温反应3h制得中间体十三氟辛基溴乙酸酯2.09g。然后将制得的中间体投入装有60mL无水四氢呋喃的三口烧瓶中,再加入3.41g N, N'-双(对甲苯磺酰)肼并降温至0℃,逐滴将3.82g 1,8-二氮杂二环十一碳-7-烯加入混合液中反应3h。反应结束后用去离子水淬灭,二氯甲烷萃取3次,无水硫酸镁干燥,抽滤、旋蒸除去低沸点溶剂得1.64g产物十三氟辛基重氮乙酸酯。
实施例一 制备疏水织物
将5mmol合成的对三氟甲基重氮苯乙酮加入装有60mL无水四氢呋喃的圆底烧瓶中,将活性织物浸入瓶中,再加入9.15mg (0.025 mmol) (π-allylPdCl)2,然后置于-10℃并加入32.5mg(0.09 mmol) NaBPh4,在0℃下将锥形瓶移置水浴震荡锅中振荡反应1h,再升温至10℃反应1h、20℃反应1h,最后30℃下反应12h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为106°。
将5mmol合成的对三氟甲基重氮苯乙酮加入装有60mL无水四氢呋喃的圆底烧瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于-10℃并加入32.5mgNaBPh4,在0℃下将圆底烧瓶置于磁力搅拌器上,织物在搅拌动态(织物旋转,强度与震荡近似)下反应1h,升温至10℃反应1h,20℃反应1h,最后30℃下反应12h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为125°,表面结构参见图1。
实施例二 制备疏水织物
将5mmol合成的对三氟甲基重氮苯乙酮加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。在0℃下将锥形瓶移置水浴震荡锅中振荡反应1h,再升温至10℃反应1h、20℃反应1h,最后30℃下反应12h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为132°,表面结构参见图2。
实施例三 制备疏水织物
将5mmol合成的重氮乙酸苯酯加入装有60mL无水四氢呋喃的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。在0℃下将锥形瓶移置水浴震荡锅中振荡反应1h,然后再至10℃反应1h,20℃反应1h,最后30℃下反应12h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干,表面结构参见图3。
实施例四 制备疏水织物
将5mmol合成的重氮乙酸苯酯加入装有60mL无水四氢呋喃的圆底烧瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。在0℃下将圆底烧瓶置于磁力搅拌器上旋转动态(织物旋转,强度与震荡近似)下反应1h,升温至10℃反应1h,20℃反应1h,最后30℃下反应12h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干,表面结构参见图4。
实施例五 制备疏水织物
将5mmol合成的重氮乙酸苯酯加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。在0℃下将锥形瓶移置水浴震荡锅中振荡反应1h,升温至10℃反应1h,20℃反应1h,最后30℃下反应12h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干,表面结构参见图5。
实施例六 制备疏水织物
将5mmol合成的重氮乙酸苯酯加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。0℃下将锥形瓶移置水浴震荡锅中震荡1h,升温至10℃反应1h,20℃反应1h,25℃下反应3h,然后加入5mmol合成的十三氟辛基重氮乙酸酯反应1h,再升温至30℃反应12h。反应结束后,将接枝共聚物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为155°,表面结构参见图6,表面滚动角分别仅为7°。
实施例七 制备疏水织物
将5mmol合成的重氮乙酸苯酯加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。0℃下将锥形瓶移置水浴震荡锅中震荡1h,升温至10℃反应1h,20℃反应1h,25℃下反应3h,然后加入5mmol合成的十三氟辛基重氮乙酸酯反应1h,再升温至30℃反应24h。反应结束后,将接枝共聚物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为158°,表面结构参见图7,表面滚动角分别仅为5°。
参见图8,采用的污渍为粉笔末,水滴流经表面覆盖着粉末状污物的改性织物表面时能够自然滑落,同时将表面污物带走,表现出很好的自清洁能力;参见图9,拒液性测试选用了蒸馏水、乙二醇、正十四烷和食用豆油不同性质的液体,这些液体完整液滴形式停留在表面而不浸润。对照的,活性织物接触水滴时,水滴迅速铺展被织物吸收。
对比例
将5mmol合成的十三氟辛基重氮乙酸酯加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,置于低温反应釜中并降温至-10℃,加入32.5mg NaBPh4。在0℃下将锥形瓶移置水浴震荡锅中振荡1h,然后依次10℃反应1h,20℃反应1h,最后30℃下反应24h。反应结束后,将接枝聚合物的织物分别用乙醇和去离子水清洗干净,50℃下烘干,对水接触角为154°,但是不具备自清洁功能,进行上述同样的粉笔末测试,水滴流经表面覆盖着粉末状污物的改性织物表面时不能够将表面污物带走,织物表面有残留,因为表面结构与本发明不同;经过同样的测试,实施例二制备的疏水织物以及实施例五制备的疏水织物也不具备自清洁功能,织物表面有粉末残留。
实施例八 制备疏水织物
将5mmol合成的对三氟甲基重氮苯乙酮加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。0℃下将锥形瓶移置水浴震荡锅中震荡1h,升温至10℃反应1h,20℃反应1h,25℃下反应3h,然后加入5mmol合成的十三氟辛基重氮乙酸酯反应1h,再升温至30℃反应24h。反应结束后,将接枝共聚物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为142°。
实施例九 制备疏水织物
将5mmol合成的对三氟甲基重氮苯乙酮加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。在0℃下将圆底烧瓶置于磁力搅拌器上,织物在搅拌动态(织物旋转,强度与震荡近似)下反应1h,升温至10℃反应1h,20℃反应1h,25℃下反应3h,然后加入5mmol合成的十三氟辛基重氮乙酸酯反应1h,再升温至30℃反应24h。反应结束后,将接枝共聚物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为152°。
实施例十 制备疏水织物
将5mmol合成的重氮乙酸苯酯加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中,将活性织物浸入瓶中,再加入9.15mg (π-allylPdCl)2,然后置于低温反应釜中并降温至-10℃并加入32.5mg NaBPh4。在0℃下将圆底烧瓶置于磁力搅拌器上,织物在搅拌动态(织物旋转,强度与震荡近似)下反应1h,升温至10℃反应1h,20℃反应1h,25℃下反应3h,然后加入5mmol合成的十三氟辛基重氮乙酸酯反应1h,再升温至30℃反应24h。反应结束后,将接枝共聚物的织物分别用乙醇和去离子水清洗干净,50℃下烘干。对水接触角为146°。
本发明公开的超疏水织物,拓展了卡宾聚合在超浸润功能表面制备领域的应用研究。新颖的卡宾聚合有着单碳重复、立体规整的特性,再利用含不同功能侧基的共聚合可在纤维表面通过共价接枝构造具有一定粗糙度的糙化结构。通过纤维表面诱导卡宾共聚物结晶驱动自组装一步在织物表面构筑具有微纳复合结构的低表面能糙化结构,获得了具有超疏水、自清洁功效的改性织物。
Claims (6)
1.基于微纳结构的超疏水织物,其特征在于,所述基于微纳结构的超疏水织物的制备方法为,以碳链氟烷基醇为起始剂,先后分别与溴乙酰溴和N, N`-二甲苯磺酰肼反应制备脂肪系重氮化合物;以含溴苯酯或含溴苯酮为起始剂,分别与N, N`-二甲苯磺酰肼反应制备芳香系重氮化合物;织物酰化后与N,N`-二甲苯磺酰肼反应制备活性织物;在催化剂作用下,将脂肪系重氮化合物与活性织物在有机溶剂中反应;然后加入芳香系重氮化合物,进行卡宾共聚合共价接枝反应,得到基于微纳结构的超疏水织物;碳链氟烷基醇中,碳原子数为3~10。
2.根据权利要求1所述基于微纳结构的超疏水织物,其特征在于,制备脂肪系重氮化合物时,反应的温度为-5~5℃,时间为3~5h;制备芳香系重氮化合物时,反应的温度为-5~5℃,时间为3~5h。
3.根据权利要求1所述基于微纳结构的超疏水织物,其特征在于,碳链氟烷基醇为全氟己基乙醇或者全氟丁基乙醇;含溴苯酯为溴乙酸苯酯;含溴苯酮为2-溴-4`-(三氟甲基)苯乙酮。
4.根据权利要求1所述基于微纳结构的超疏水织物,其特征在于,催化剂为氯化钯、氯化烯丙基钯(II)二聚物或双(乙腈)氯化钯(II);有机溶剂为无水四氢呋喃和/或无水乙醇;卡宾共聚合共价接枝反应在NaBPh4存在下进行。
5.根据权利要求1所述基于微纳结构的超疏水织物,其特征在于,所述卡宾共 聚合反应在震荡或者搅拌下进行;所述卡宾共聚合共价接枝反应的温度为25~35℃;卡宾共聚合共价接枝反应的反应时间为12~24h。
6.权利要求1所述基于微纳结构的超疏水织物作为自清洁疏水材料的应用。
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