CN110528273A - 一种纺织材料的高介电疏水整理方法 - Google Patents

一种纺织材料的高介电疏水整理方法 Download PDF

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CN110528273A
CN110528273A CN201910811837.7A CN201910811837A CN110528273A CN 110528273 A CN110528273 A CN 110528273A CN 201910811837 A CN201910811837 A CN 201910811837A CN 110528273 A CN110528273 A CN 110528273A
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赵春升
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Jishou Wanchang New Material Technology Co Ltd
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Abstract

本发明公开了一种纺织材料的高介电疏水整理方法，向包覆改性的纳米钛酸钡、纳米银中加分散剂、去离子水，超声分散处理后，边搅拌边加丙烯酸酯粘合剂，调节pH为碱性，滴加增稠剂混匀得复合涂层浆料；将化学刻蚀处理的纺织材料固定在涂层架上，将复合涂层浆料在其表面进行均匀刮涂，再将涂覆的纺织材料加热升温热处理得高介电涂层纺织材料；将十三氟辛基三乙氧基硅烷、氨丙基三乙氧基硅烷溶解于乙醇和水的混合液中，加冰醋酸调节pH，磁力搅拌，滴加到二氧化硅水溶胶中搅拌反应，再与水、氨基硅油混合超声均匀，调节pH，加入多巴胺搅拌均匀，将高介电涂层纺织材料浸没其中反应后，取出、用清水冲洗，烘干、焙烘得高介电疏水整理的纺织材料。

Description

一种纺织材料的高介电疏水整理方法
技术领域
本发明属于纺织材料领域，具体涉及一种纺织材料的高介电疏水整理方法。
背景技术
高介电常数材料已在电子电气和介电储能方面得到极大应用。随着科技日益发展，近年来人们对智能电子设备要求越来越高，开发柔性储能材料、柔性可穿戴电子设备引发研究人员的广泛兴趣。介电常数是描述材料在电场或电磁场下储存能量和吸波性能的重要参数，所以研究纤维基材介电常数对开发柔性储能材料意义重大。
材料表面的浸润性能是其自身的重要性质之一。随着人们需求的增加，具有
特殊浸润性功能的材料在实际的生产生活中有着广泛的应用前景。其中，自清洁
表面、液体减阻传输，以及作业于液体环境中的机器人和传感器，因其独特的性
质引起了研究者的广泛关注。然而，目前已有的疏液材料表面普遍存在适用范围
受限、机械耐久性较差等缺点，疏液涂层的应用稳定性受到极大挑战。此外，受
自然界中一些生物的启发，非对称浸润性材料的制备及应用在膜分离、生物医疗、
工业生产等领域取得了巨大进展。而非对称浸润性材料的功能化及其表界面性质
却未得到深入研究，这将不利于它们在将来的发展。
因此，按照本发明提供的技术方案制备了一种高介电疏水的纺织材料，是一种具有特殊功能性的纺织材料，应用前景广阔。
发明内容
本发明的目的是针对现有的问题，提供了一种纺织材料的高介电疏水整理方法，依照该方法制备的纺织材料具有优异的高介电性能和疏水性能。
本发明是通过以下技术方案实现的：
一种纺织材料的高介电疏水整理方法，包括如下步骤，下述原料按重量份计：
（1）复合涂层浆料的制备：
向35-40份包覆改性的纳米钛酸钡、4-5份纳米银中加入3-4份分散剂，再加入80-90份去离子水，超声分散处理30-40min后，边搅拌边加入15-25份丙烯酸酯粘合剂，用氨水调节pH为8-10，滴加2-3份增稠剂混合均匀，得到复合涂层浆料；
先利用沉淀包覆法将氧化钬、氧化镁、氧化锰包覆在纳米钛酸钡表面，再通过烧结将Ho3+、Mg2+、Mn2+扩散到纳米钛酸钡中，调节其介电性能；包覆氧化钬有助于形成“芯-壳”结构晶粒，能显著改善纳米钛酸钡的介电温度稳定性；以包覆改性的纳米钛酸钡、银颗粒为功能体，丙烯酸酯为粘合剂制备了复合涂层浆料；
（2）纺织材料的涂层后整理：
将化学刻蚀处理的纺织材料固定在涂层架上，将（1）中所得复合涂层浆料在纺织材料表面进行均匀刮涂，再将涂覆的纺织材料置于70-80℃烘箱内热处理5-10min，再升温至120-130℃热处理3-6min，得到高介电涂层纺织材料；
采用改良的处理方法实现了纺织材料的碱减量化学刻蚀处理，以化学刻蚀处理的纺织材料为基布，以包覆改性的纳米钛酸钡、银颗粒为功能体，丙烯酸酯为粘合剂制备了复合涂层浆料，采用涂层后整理方式对化学刻蚀处理的纺织材料进行处理，制备高介电常数纺织材料；纳米钛酸钡与聚合物表面能差相差较大，随纳米钛酸钡填充比的增大逐渐出现粒子的团聚，进而产生缝隙孔洞，涂层纺织材料介电常数增大，纳米银粒子的引入使得涂层纺织材料介电常数提高，而且由于库伦阻塞效应涂层纺织材料介电损耗维持在较低水平；
（3）纺织材料的疏水整理：
将1-2份十三氟辛基三乙氧基硅烷、0.4-0.5份氨丙基三乙氧基硅烷溶解于6-7份乙醇和0.6-0.7份水的混合液中，加冰醋酸调节pH为5，磁力搅拌30-50min后，滴加到12-13份二氧化硅水溶胶中，搅拌反应2-4h后，再与16-19份水、1-2份氨基硅油混合超声均匀，调节pH为8-9，加入0.1-0.2份多巴胺搅拌均匀，将（2）中所得高介电涂层纺织材料浸没其中反应2-4h后，取出、用大量清水冲洗，经40-45℃烘干、在130-140℃焙烘20-30min，得到高介电疏水整理的纺织材料；
由于纳米粒子、聚多巴胺、聚硅氧烷弹性体三者之间以共价键相互连接，制备的改性纺织材料表面出较好的疏水性能，通过微纳复合粗糙结构的构筑，经过碱减量处理的纺织材料在疏水改性处理之后，其水接触角以及接枝率都出现了很大的提升；改性纺织材料还具有较高的耐腐蚀性能，当被98%的浓硫酸侵蚀时，
浓硫酸液体会迅速从表面滚落且未留下明显的痕迹；
进一步的，步骤（1）中纳米钛酸钡的包覆改性：将4-9份纳米钛酸钡1:10加入到溶剂异丙醇中滚磨1-2h得悬浮液，将2-4份硝酸钬、3-6份乙酸镁、0.5-1份乙酸锰溶于55-110份去离子水中，加入悬浮液中滚磨1-2h，滴加氨水至pH为10，磁力搅拌1-2h生成沉淀，陈化1-2h后，过滤、水洗、烘干，在600-610℃下预烧1-2h得包覆改性的纳米钛酸钡。
进一步的，步骤（2）中纺织材料的化学刻蚀处理方法：先将纺织材料用乙醇和水浸泡超声30-40min除杂，再浸泡于370-390g/L的氢氧化钠溶液中，5-10min后取出，用保鲜膜包裹放入105-110℃烘箱中加热3-5min后，用大量清水洗净，在80-85℃下烘干，得到化学刻蚀处理的纺织材料。
进一步的，步骤（2）中涂层厚度控制在0.5-1mm。
本发明相比现有技术具有以下优点：
（1）对纳米钛酸钡进行包覆改性：先利用沉淀包覆法将氧化钬、氧化镁、氧化锰包覆在纳米钛酸钡表面，再通过烧结将Ho3+、Mg2+、Mn2+扩散到纳米钛酸钡中，调节其介电性能；包覆氧化钬有助于形成“芯-壳”结构晶粒，能显著改善纳米钛酸钡的介电温度稳定性；以包覆改性的纳米钛酸钡、银颗粒为功能体，丙烯酸酯为粘合剂制备了复合涂层浆料。
（2）采用改良的处理方法实现了纺织材料的碱减量化学刻蚀处理，以化学刻蚀处理的纺织材料为基布，以包覆改性的纳米钛酸钡、银颗粒为功能体，丙烯酸酯为粘合剂制备了复合涂层浆料，采用涂层后整理方式对化学刻蚀处理的纺织材料进行处理，制备高介电常数纺织材料；纳米钛酸钡与聚合物表面能差相差较大，随纳米钛酸钡填充比的增大逐渐出现粒子的团聚，进而产生缝隙孔洞，涂层纺织材料介电常数增大，纳米银粒子的引入使得涂层纺织材料介电常数提高，而且由于库伦阻塞效应涂层纺织材料介电损耗维持在较低水平。
（3）由于纳米粒子、聚多巴胺、聚硅氧烷弹性体三者之间以共价键相互连接，制备的改性纺织材料表面出较好的疏水性能，通过微纳复合粗糙结构的构筑，经过碱减量处理的纺织材料在疏水改性处理之后，其水接触角以及接枝率都出现了很大的提升；改性纺织材料还具有较高的耐腐蚀性能，当被98%的浓硫酸侵蚀时，
浓硫酸液体会迅速从表面滚落且未留下明显的痕迹。
具体实施方式
实施例1
一种纺织材料的高介电疏水整理方法，其特征在于，包括如下步骤，下述原料按重量份计：
（1）复合涂层浆料的制备：
向35份包覆改性的纳米钛酸钡、4份纳米银中加入3份分散剂，再加入80份去离子水，超声分散处理30min后，边搅拌边加入15份丙烯酸酯粘合剂，用氨水调节pH为8，滴加2份增稠剂混合均匀，得到复合涂层浆料；
其中，纳米钛酸钡的包覆改性：将4份纳米钛酸钡1:10加入到溶剂异丙醇中滚磨1h得悬浮液，将2份硝酸钬、3份乙酸镁、0.5份乙酸锰溶于55份去离子水中，加入悬浮液中滚磨1h，滴加氨水至pH为10，磁力搅拌1h生成沉淀，陈化1h后，过滤、水洗、烘干，在600℃下预烧2h得包覆改性的纳米钛酸钡；
（2）纺织材料的涂层后整理：
将化学刻蚀处理的纺织材料固定在涂层架上，将（1）中所得复合涂层浆料在纺织材料表面进行均匀刮涂，再将涂覆的纺织材料置于70℃烘箱内热处理10min，再升温至120℃热处理6min，得到高介电涂层纺织材料；
其中，纺织材料的化学刻蚀处理方法：先将纺织材料用乙醇和水浸泡超声30min除杂，再浸泡于370g/L的氢氧化钠溶液中，5min后取出，用保鲜膜包裹放入105℃烘箱中加热5min后，用大量清水洗净，在80℃下烘干，得到化学刻蚀处理的纺织材料；
涂层厚度控制在0.5mm；
（3）纺织材料的疏水整理：
将1份十三氟辛基三乙氧基硅烷、0.4份氨丙基三乙氧基硅烷溶解于6份乙醇和0.6份水的混合液中，加冰醋酸调节pH为5，磁力搅拌30min后，滴加到12份二氧化硅水溶胶中，搅拌反应2h后，再与16份水、1份氨基硅油混合超声均匀，调节pH为8，加入0.1份多巴胺搅拌均匀，将（2）中所得高介电涂层纺织材料浸没其中反应2h后，取出、用大量清水冲洗，经40℃烘干、在130℃焙烘30min，得到高介电疏水整理的纺织材料。
实施例2
一种纺织材料的高介电疏水整理方法，其特征在于，包括如下步骤，下述原料按重量份计：
（1）复合涂层浆料的制备：
向40份包覆改性的纳米钛酸钡、5份纳米银中加入4份分散剂，再加入90份去离子水，超声分散处理40min后，边搅拌边加入25份丙烯酸酯粘合剂，用氨水调节pH为10，滴加3份增稠剂混合均匀，得到复合涂层浆料；
其中，纳米钛酸钡的包覆改性：将9份纳米钛酸钡1:10加入到溶剂异丙醇中滚磨2h得悬浮液，将4份硝酸钬、6份乙酸镁、1份乙酸锰溶于110份去离子水中，加入悬浮液中滚磨2h，滴加氨水至pH为10，磁力搅拌2h生成沉淀，陈化2h后，过滤、水洗、烘干，在610℃下预烧1h得包覆改性的纳米钛酸钡；
（2）纺织材料的涂层后整理：
将化学刻蚀处理的纺织材料固定在涂层架上，将（1）中所得复合涂层浆料在纺织材料表面进行均匀刮涂，再将涂覆的纺织材料置于80℃烘箱内热处理5min，再升温至130℃热处理3min，得到高介电涂层纺织材料；
其中，纺织材料的化学刻蚀处理方法：先将纺织材料用乙醇和水浸泡超声40min除杂，再浸泡于390g/L的氢氧化钠溶液中，10min后取出，用保鲜膜包裹放入110℃烘箱中加热3min后，用大量清水洗净，在85℃下烘干，得到化学刻蚀处理的纺织材料；
涂层厚度控制在1mm；
（3）纺织材料的疏水整理：
将2份十三氟辛基三乙氧基硅烷、0.5份氨丙基三乙氧基硅烷溶解于7份乙醇和0.7份水的混合液中，加冰醋酸调节pH为5，磁力搅拌50min后，滴加到13份二氧化硅水溶胶中，搅拌反应4h后，再与19份水、2份氨基硅油混合超声均匀，调节pH为9，加入0.2份多巴胺搅拌均匀，将（2）中所得高介电涂层纺织材料浸没其中反应4h后，取出、用大量清水冲洗，经45℃烘干、在140℃焙烘20min，得到高介电疏水整理的纺织材料。
对比实施例1
本对比实施例1与实施例1相比，在步骤（1）中未对纳米钛酸钡进行包覆改性，除此外的方法步骤均相同。
对比实施例2
本对比实施例2与实施例2相比，在步骤（2）中未对纺织材料进行化学刻蚀处理，除此外的方法步骤均相同。
对照组 未经任何改性处理的空白涤纶织物
为了对比本发明制备的改性纺织材料的性能，对上述实施例1、实施例2、对比实施例1、对比实施例2方法对应制得的纺织材料，以及对照组对应的未经任何改性处理的空白涤纶织物，按照行业标准进行性能检测，具体对比数据如下表1所示：其中，实施例1、实施例2、对比实施例1、对比实施例2所述纺织材料以涤纶织物为例；
采用介电谱仪，对改性纺织材料介电性能进行测试，测试在恒温恒湿环境下进行（温度22℃，湿度65%RH），测试频率为1KHz；
表1
项目 介电常数 介电损耗 水滴接触角
实施例1 11.6 0.01 142°
实施例2 11.7 0.02 143°
对比实施例1 5.9 0.08 141°
对比实施例2 11.5 0.03 98°
对照组 1.6 0.11 87°
按照本发明实施例方法制备的改性纺织材料具有优异的介电性能和疏水性，是一种特殊功能性的纺织材料；当给改性纺织材料表面一个小角度的倾斜时，水滴会迅速地从表面滚落，这对其在防污方面的应用具有很大帮助；当被98%的浓硫酸侵蚀时，浓硫酸液体会迅速从表面滚落且未留下明显的痕迹；
在对比实施例1中未对纳米钛酸钡进行包覆改性，导致涂层纺织材料的介电常数降低、介电损耗增大，但是仍然优于对照组空白涤纶织物的介电性能；在对比实施例2中未对纺织材料进行化学刻蚀处理，导致涂层纺织材料的水滴接触角降低，但是仍然优于对照组空白涤纶织物的疏水性能。

Claims (4)

1.一种纺织材料的高介电疏水整理方法，其特征在于，包括如下步骤，下述原料按重量份计：
复合涂层浆料的制备：
向35-40份包覆改性的纳米钛酸钡、4-5份纳米银中加入3-4份分散剂，再加入80-90份去离子水，超声分散处理30-40min后，边搅拌边加入15-25份丙烯酸酯粘合剂，用氨水调节pH为8-10，滴加2-3份增稠剂混合均匀，得到复合涂层浆料；
（2）纺织材料的涂层后整理：
将化学刻蚀处理的纺织材料固定在涂层架上，将（1）中所得复合涂层浆料在纺织材料表面进行均匀刮涂，再将涂覆的纺织材料置于70-80℃烘箱内热处理5-10min，再升温至120-130℃热处理3-6min，得到高介电涂层纺织材料；
（3）纺织材料的疏水整理：
将1-2份十三氟辛基三乙氧基硅烷、0.4-0.5份氨丙基三乙氧基硅烷溶解于6-7份乙醇和0.6-0.7份水的混合液中，加冰醋酸调节pH为5，磁力搅拌30-50min后，滴加到12-13份二氧化硅水溶胶中，搅拌反应2-4h后，再与16-19份水、1-2份氨基硅油混合超声均匀，调节pH为8-9，加入0.1-0.2份多巴胺搅拌均匀，将（2）中所得高介电涂层纺织材料浸没其中反应2-4h后，取出、用大量清水冲洗，经40-45℃烘干、在130-140℃焙烘20-30min，得到高介电疏水整理的纺织材料。
2.根据权利要求1所述的一种纺织材料的高介电疏水整理方法，其特征在于，步骤（1）中纳米钛酸钡的包覆改性：
将4-9份纳米钛酸钡1:10加入到溶剂异丙醇中滚磨1-2h得悬浮液，将2-4份硝酸钬、3-6份乙酸镁、0.5-1份乙酸锰溶于55-110份去离子水中，加入悬浮液中滚磨1-2h，滴加氨水至pH为10，磁力搅拌1-2h生成沉淀，陈化1-2h后，过滤、水洗、烘干，在600-610℃下预烧1-2h得包覆改性的纳米钛酸钡。
3.根据权利要求1所述的一种纺织材料的高介电疏水整理方法，其特征在于，步骤（2）中纺织材料的化学刻蚀处理方法：
先将纺织材料用乙醇和水浸泡超声30-40min除杂，再浸泡于370-390g/L的氢氧化钠溶液中，5-10min后取出，用保鲜膜包裹放入105-110℃烘箱中加热3-5min后，用大量清水洗净，在80-85℃下烘干，得到化学刻蚀处理的纺织材料。
4.根据权利要求1所述的一种纺织材料的高介电疏水整理方法，其特征在于，步骤（2）中涂层厚度控制在0.5-1mm。
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CN112813683A (zh) * 2021-02-05 2021-05-18 武汉理工大学 一种超双疏织物及其制备方法
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CN111100425A (zh) * 2020-01-03 2020-05-05 西安交通大学 一种高介电光敏树脂基复合材料及其制备方法和应用
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