CN110130101B - 一种间位芳纶织物表面功能改性的方法 - Google Patents
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Abstract
本发明涉及一种间位芳纶织物表面功能改性的方法，属纺织技术领域。所述的方法是指利用由N,N‑二甲基乙酰胺、LiCl、无机功能纳米粒子混配组成的改性液在低温正压条件下处理间位芳纶织物，使其纤维表层大分子与N,N‑二甲基乙酰胺、LiCl发生反应，形成微溶解层，纤维表面的无机功能纳米粒子在正压的作用下被挤压进入微溶解层，后在高温负压条件下，微溶解层中的N,N‑二甲基乙酰胺挥发抽离，无机功能纳米粒子固化在间位芳纶纤维表层，增强了间位芳纶表层阻燃、抗静电、耐辐射等功能。本发明在保存纤维主体结构不受损，力学性能无明显下降的前提下，有效提高间位芳纶表层阻燃、抗静电、耐辐射等功能改性的效率及持久性，且该方法无污水产出，降低了生产成本。
Description
技术领域
本发明涉及一种间位芳纶织物表面功能改性的方法，属于纺织技术领域。
背景技术
间位芳纶是一种高强、高模的高科技特种纤维，优异的机械性能、阻燃耐热性能、耐化学性能、耐辐射性能等使其作为宇宙开发材料和重要战略物资而被研究使用，后作为高技术含量纤维材料被广泛应用于民用领域。随着应用范围越来越广，对其附加功能性要求也越来越高，但间位芳纶的结晶度和取向度均很高，玻璃化温度在270oC以上，故常规功能改性方法对其不太实用。目前应用较多的间位芳纶功能改性方法有表面涂层、表面接枝等。中国公开出版物《化工新型材料》公开时间2014年第42卷第8期，文章名称为芳纶表面氧化锌纳米棒的制备及表征，该文献介绍了以硝酸锌、六亚甲基四胺为原料，通过低温水浴方法在芳纶表面实现氧化锌纳米棒的修饰，结果表明氧化锌纳米棒修饰后的芳纶具有良好的抗紫外性和优异的热稳定性。其不足在于该方法中氧化锌纳米棒是生长在纤维表面，其牢度不佳，不满足实际应用需要。中国公开出版物《非织造布》公开时间2012年第20卷4期，文章名称为芳纶-有机硅涂层复合材料的研制及应用，该文献介绍了采用涂敷的方法制备芳纶-阻燃有机硅层复合材料，该技术制得的复合材料具有耐老化、高强、阻燃、耐腐蚀等优异性能。其不足在于该方法制得的复合材料存在界面牢度问题，且刚度较高，柔软性差。中国公开出版物《合成纤维》公开时间2016年第45卷3期，文章名为间位芳纶溶解及凝固性能研究，该文献介绍了间位芳纶在以N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMAc）、二甲基亚砜（DMSO）、1-甲基-2-吡咯烷酮（NMP）为溶剂，分别加入LiCl和CaCl2制备的几种溶解体系中的溶解性能及不同凝固浴对其凝固性能的影响。其不足在于间位芳纶溶解对其优良的力学性能造成不可逆转的损坏，限制了其应用范围。中国硕士学位论文公开时间2015年5月，文章名称为纳米粒子增强芳纶纸性能的研究，该文献采用纳米SiO2和纳米Al2O3对芳纶纸的力学性能和介电性能进行增强，并讨论了芳纶纸的最佳热压成型工艺条件。其不足是纳米粒子利用率低。
发明内容
针对上述存在的问题，本发明的目的在于提供一种间位芳纶表面功能改性的方法，为了实现上述目的，其技术解决方案为：
一种间位芳纶织物表面功能改性的方法，所述表面功能改性方法步骤如下：
a) 配制改性液
改性液的配制按质量比分别为：
N,N-二甲基乙酰胺 80~99.89 %
LiCl 0.1~10 %
无机功能纳米粒子 0.01~10 %
混配，超声分散30min，使无机功能纳米粒子和LiCl均匀分散在N,N-二甲基乙酰胺中，形成含无机功能纳米粒子的改性液；
b) 间位芳纶织物的表面改性
按浴比1:5将间位芳纶织物加入含无机功能纳米粒子的改性液中，经两浸两轧处理后在温度为40-100oC，压强为0.2MPa~10MPa的低温正压环境中对间位芳纶织物处理10-60min，在温度的作用下，包覆在间位芳纶织物表面改性液中的LiCl、N,N-二甲基乙酰胺与间位芳纶织物中纤维表层反应形成微溶解层，同时，在正压的作用下，改性液中的无机功能纳米粒子被挤压进入微溶解层，将低温正压环境处理后的间位芳纶织物置于温度为165-200oC，压强为-0.5MPa~-0.25MPa的高温负压环境中固化60-240min，微溶解层中的N,N-二甲基乙酰胺在高温负压环境中挥发抽离，微溶解层中的无机功能纳米粒子固化在间位芳纶织物中纤维表层。
所述的无机功能纳米粒子为碳纳米管或纳米Fe2O3或纳米Fe4[Fe(CN)6]3中的一种。
由于采用了以上技术方案，本发明是利用由N,N-二甲基乙酰胺、LiCl、无机功能纳米粒子混配组成的改性液在低温正压条件下处理间位芳纶织物，使其纤维表层与包覆在纤维表面改性液中的N,N-二甲基乙酰胺、LiCl发生反应，形成微溶解层，包覆在纤维表面的无机功能纳米粒子在正压的作用下被挤压进入微溶解层，后在高温负压条件下，微溶解层中的N,N-二甲基乙酰胺挥发抽离，微溶解层中的无机功能纳米粒子固化在间位芳纶织物中纤维表层，嵌入进纤维表层的无机功能纳米粒子增强了间位芳纶表层阻燃、抗静电、耐辐射等功能。间位芳纶织物经由N,N-二甲基乙酰胺、LiCl、无机功能纳米粒子组成的改性液两浸两轧后，改性液中的N,N-二甲基乙酰胺、LiCl、无机功能纳米粒子均匀包覆在间位芳纶织物中纤维表面，后在温度为40-100oC，压强为0.2MPa~10MPa的低温正压条件下对间位芳纶处理10-60min，在温度的作用下，间位芳纶纤维表面的LiCl与N,N-二甲基乙酰胺络合，释放出活性氯离子，活性氯离子在正压的作用下，更易进入纤维表层大分子间孔隙，破坏纤维表层大分子间氢键，使表层大分子间连接断裂或减弱，形成微溶解层，同时，在正压强作用下，包裹在间位芳纶纤维表面的无机功能纳米粒子被挤压进入微溶解层。将经低温正压处理过的微溶解层中含无机功能纳米粒子的芳纶织物置于温度为165-200oC，压强为-0.5MPa~-0.25MPa的高温负压环境中固化60-240min，微溶解层中的N,N-二甲基乙酰胺在高温负压环境中挥发抽离，间位芳纶表层大分子间重新建立氢键，无机功能纳米粒子固化在微溶解层中，成为间位芳纶表面改性层。因此，和现有技术相比，本技术方案在保存纤维主体结构不受损，力学性能无明显下降的前提下，有效提高间位芳纶表层阻燃、抗静电、耐辐射等功能改性的效率及持久性，且该方法无污水产出，降低了生产成本。
具体实施方式
下面结合具体实施例对本发明的一种间位芳纶表面功能改性的方法作进一步详细描述：
一种间位芳纶织物表面功能改性的方法，所述表面功能改性方法步骤如下：
a) 配制改性液
改性液的配制按质量比分别为：
N,N-二甲基乙酰胺 80~99.89 %
LiCl 0.1~10 %
无机功能纳米粒子 0.01~10 %
混配，超声分散30min，使无机功能纳米粒子和LiCl均匀分散在N,N-二甲基乙酰胺中，形成含无机功能纳米粒子的改性液；无机功能纳米粒子为碳纳米管或纳米Fe2O3或纳米Fe4[Fe(CN)6]3中的一种。
b) 间位芳纶织物的表面改性
按浴比1:5将间位芳纶织物加入含无机功能纳米粒子的改性液中，经两浸两轧处理后在温度为40-100oC，压强为0.2MPa~10MPa的低温正压环境中对间位芳纶织物处理10-60min，在温度的作用下，包覆在间位芳纶织物表面改性液中的LiCl、N,N-二甲基乙酰胺与间位芳纶织物中纤维表层反应形成微溶解层，同时，在正压的作用下，改性液中的无机功能纳米粒子被挤压进入微溶解层，将低温正压环境处理后的间位芳纶织物置于温度为165-200oC，压强为-0.5MPa~-0.25MPa的高温负压环境中固化60-240min，微溶解层中的N,N-二甲基乙酰胺在高温负压环境中挥发抽离，微溶解层中的无机功能纳米粒子固化在间位芳纶织物中纤维表层。
具体实施例
按上述方法。
实施例1
改性液由99.89 % N,N-二甲基乙酰胺、0.1 % LiCl、0.01 % 碳纳米管混配组成，超声分散30min，使碳纳米管和LiCl均匀分散在N,N-二甲基乙酰胺中，按浴比1:5将间位芳纶织物加入含碳纳米管的改性液中，经两浸两轧处理后在温度为40oC，压强为0.2MPa的低温正压环境中对间位芳纶织物处理10min，后将低温正压环境处理后的间位芳纶织物置于温度为165oC，压强为0.05MPa的高温负压环境中固化60min，微溶解层中的碳纳米管固化在间位芳纶织物中纤维表层，完成间位芳纶织物表面阻燃功能改性。以间位芳纶织物表面功能改性样品的K/S值来评价织物表层纳米粒子的固着量，结果见表1。
实施例2
改性液由90 % N,N-二甲基乙酰胺、5 % LiCl、5 % 纳米Fe2O3混配组成，超声分散30min，使纳米Fe2O3和LiCl均匀分散在N,N-二甲基乙酰胺中，按浴比1:5将间位芳纶织物加入含纳米Fe2O3的改性液中，经两浸两轧处理后在温度为70oC，压强为5MPa的低温正压环境中对间位芳纶织物处理35min，后将低温正压环境处理后的间位芳纶织物置于温度为180oC，压强为-0.25MPa的高温负压环境中固化150min，微溶解层中的纳米Fe2O3固化在间位芳纶织物中纤维表层，完成间位芳纶织物表面抗静电、耐辐射功能改性。以间位芳纶织物表面功能改性样品的K/S值来评价织物表层纳米粒子的固着量，结果见表1。
实施例3
改性液由80 % N,N-二甲基乙酰胺、10 % LiCl、10 % 纳米Fe4[Fe(CN)6]3混配组成，超声分散30min，使纳米Fe4[Fe(CN)6]3和LiCl均匀分散在N,N-二甲基乙酰胺中，按浴比1:5将间位芳纶织物加入含纳米Fe4[Fe(CN)6]3的改性液中，经两浸两轧处理后在温度为100oC，压强为10MPa的低温正压环境中对间位芳纶织物处理60min，后将低温正压环境处理后的间位芳纶织物置于温度为200oC，压强为-0.5MPa的高温负压环境中固化240min，微溶解层中的纳米Fe4[Fe(CN)6]3固化在间位芳纶织物中纤维表层，完成间位芳纶织物表面抗静电、耐辐射功能改性。以间位芳纶织物表面功能改性样品的K/S值来评价织物表层纳米粒子的固着量，结果见表1。
表1 间位芳纶织物表面功能改性样品的K/S值
| 样品 | K/S |
| 实施例1 | 2.5 |
| 实施例2 | 14.5 |
| 实施例3 | 13.0 |
Claims (2)
1.一种间位芳纶织物表面功能改性的方法，其特征在于，所述表面功能改性方法步骤如下：
a) 配制改性液
改性液的配制按质量比分别为：
N,N-二甲基乙酰胺 80~99.89 %
LiCl 0.1~10 %
无机功能纳米粒子 0.01~10 %
混配，超声分散30min，使无机功能纳米粒子和LiCl均匀分散在N,N-二甲基乙酰胺中，形成含无机功能纳米粒子的改性液；
b) 间位芳纶织物的表面改性
按浴比1:5将间位芳纶织物加入含无机功能纳米粒子的改性液中，经两浸两轧处理后在温度为40-100oC，压强为0.2MPa~10MPa的低温正压环境中对间位芳纶织物处理10-60min，在温度的作用下，包覆在间位芳纶织物表面改性液中的LiCl、N,N-二甲基乙酰胺与间位芳纶织物中纤维表层大分子发生反应形成微溶解层，同时，在正压的作用下，改性液中的无机功能纳米粒子被挤压进入微溶解层，将低温正压环境处理后的间位芳纶织物置于温度为165-200oC，压强为-0.5MPa~-0.25MPa的高温负压环境中固化60-240min，微溶解层中的N,N-二甲基乙酰胺在高温负压环境中挥发抽离，微溶解层中的无机功能纳米粒子固化在间位芳纶织物中纤维表层。
2.根据权利要求1所述的一种间位芳纶织物表面功能改性的方法，其特征在于，所述的无机功能纳米粒子为碳纳米管或纳米Fe2O3中的一种。
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