CN111593578A - 一种超疏水芳纶织物的制备方法 - Google Patents

一种超疏水芳纶织物的制备方法 Download PDF

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CN111593578A
CN111593578A CN201910126508.9A CN201910126508A CN111593578A CN 111593578 A CN111593578 A CN 111593578A CN 201910126508 A CN201910126508 A CN 201910126508A CN 111593578 A CN111593578 A CN 111593578A
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tio
polyvinylidene fluoride
fabric
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徐思峻
程德亮
李双燕
崔振华
程曼丽
黄晓梅
季涛
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Jiangsu Tangwear Industry Co ltd
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Abstract

本发明提供了一种超疏水芳纶织物的制备方法,包括如下步骤:(1)将一定质量的微米级TiO2与纳米级TiO2均匀混合投入到一定质量的乙醇溶液中,随后加入十三氟辛基三乙氧基硅烷并搅拌20‑150分钟,最后加入一定质量的去离子水进行水解氟化接枝反应,反应制得的氟化TiO2经乙醇、水洗多次后烘干备用;(2)步骤(1)所得到的氟化TiO2与聚偏四氟乙烯粉末混溶于DMF/丙酮中,制得纺丝原液,将纺丝原液利用静电纺丝方法在芳纶织物表面喷涂TiO2聚偏氟乙烯纳米纤维层,制得涂层织物;(3)随后将步骤(2)制得的涂层织物进行高温处理形成聚偏氟乙烯纳米纤维热粘层。使用该制备方法制得的织物牢固性能好、耐磨性能好且能在高温环境下使用。

Description

一种超疏水芳纶织物的制备方法
技术领域
本发明属于功能纺织品领域,尤其涉及一种超疏水芳纶织物的制备方法。
背景技术
芳纶全称为聚苯二甲酰苯二胺纤维,是一种新型高科技合成纤维,具有超高强、高模、耐高温、耐酸碱、重量轻等优良性能。对位芳纶强度是钢丝的5~6倍,模量为钢丝或玻璃纤维的2~3倍,韧性是钢丝的2倍,重量仅为钢丝的1/5左右。芳纶同时具有极为优异的耐热阻燃性能,300℃高温不分解,不熔融。其极限氧指数大于28,具有永久阻燃性。因此芳纶尤其是间位芳纶常用于高温火场用安全防护服如消防服、森林救火服等。但是在高温火场场合,芳纶也有其固有缺陷。第一、耐光性差,芳纶长时间暴露在紫外光下,力学性能损失较大。第二、芳纶疏水性一般,在超高温火场环境中一旦沾染水分子会迅速将其汽化变成高温水蒸气,通知织物空隙接触人体,造成灼伤。因此,高温环境中芳纶应解决抗紫外和防水问题。
鉴于芳纶特殊的纺丝原理,通过物理改性和化学改性的方法对芳纶进行抗紫外和防水改性较为困难且会影响芳纶力学和阻燃性能。较为有效的方式是芳纶织物后整理法。实际上利用仿生学原理采用TiO2、ZnO、SiO2等半导体微纳米颗粒在芳纶表面构建微纳米粗糙结构可以同时实现超疏水和防紫外功能。然而上述纳米材料与芳纶织物结合牢度不佳,利用传统的浸渍、喷涂等方法难以操控其微纳米形貌。因此如何构建可控的高度超疏水的微纳米构造并提高其与纤维的结合牢度是面料超疏水改性多年来面临的难题。
发明内容
(一)要解决的技术问题
本发明要解决的技术问题是,针对传统粘合度低的问题,提出一种超疏水芳纶织物的制备方法,使用该制备方法制得的织物牢固性能好、耐磨性高且能在高温环境下使用。
(二)技术方案
本申请提供了一种超疏水芳纶织物的制备方法,包括如下步骤:
(1)将一定质量的微米级TiO2与纳米级TiO2均匀混合投入到一定质量的乙醇溶液中,随后加入十三氟辛基三乙氧基硅烷并搅拌20-150分钟,最后加入一定质量的去离子水进行水解氟化接枝反应,反应制得的氟化TiO2经乙醇、水洗多次后烘干备用;
(2)步骤(1)所得到的氟化TiO2与聚偏四氟乙烯粉末混溶于DMF/丙酮中,制得纺丝原液,将纺丝原液利用静电纺丝方法在芳纶织物表面喷涂TiO2聚偏氟乙烯纳米纤维层,制得涂层织物;
(3)随后将步骤(2)制得的涂层织物进行高温处理形成聚偏氟乙烯纳米纤维热粘层。
在本申请的一些实施例中,所述微米级TiO2颗粒粒径为0.5-1.2微米,所述纳米级TiO2粒径为70-200纳米;其两者的质量比为3:1-1:2。
在本申请的一些实施例中,在步骤(1)中,TiO2与乙醇的质量比为1:30-1:100;投入的十三氟辛基三乙氧基硅烷质量为TiO2质量的0.8-3%;水与乙醇的质量比为1:1-1:1.5;反应温度10-25℃;反应时间0.5-1.5小时。
在本申请的一些实施例中,聚偏四氟乙烯/氟化TiO2纺丝原液中聚偏四氟乙烯浓度百分比为8%-15%;氟化TiO2质量为聚偏四氟乙烯干重的1.2-20%。
在本申请的一些实施例中,所述步骤(3)中高温处理温度为180-190℃,处理时间为0.5-1小时。
(三)有益效果
从上述技术方案可以看出,本申请至少具有以下有益效果其中之一:
1、本申请提供的一种超疏水芳纶织物的制备方法,通过静电纺丝在芳纶表面直接静电喷涂TiO2-聚偏四氟乙烯纳米纤维,并经热熔后粘附于芳纶表面。该步骤制得的织物耐久性能显著提高,其中耐洗性>30次,而普通涂层<10次;抗紫外线性能≥100+,而普通涂层≤50;24小时紫外线照射强力损失率<10%,未涂层芳纶织物>30%。耐洗性能和耐光性提升显著。
2、通过静电纺丝方法得到的TiO2-聚偏四氟乙烯纳米纤维涂层,纤维间含有大量纳米级空隙,具有良好的透气性和强烈的超疏水性,其织物透湿量>8000g·(m2·24h)-1,耐静水压>8700mmH20,接触角>150°。
3、TiO2-聚偏四氟乙烯纳米涂层耐酸、碱、盐,耐高温,阻燃性好,适用范围广,可广泛应用于防水,个体防护,消防等领域。
附图说明
图1是本发明实施例中超疏水芳纶面料熔融处理后纳米纤维涂层SEM图谱;
图2是本发明实施例中超疏水芳纶面料UPF值(实测值为100+);
图3是本发明实施例中超疏水芳纶面料自来水溶液在表面形成的接触角。
具体实施方式
本申请提供了一种超疏水芳纶织物的制备方法。为使本申请的目的、技术方案和优点更加清楚明白,以下结合具体实施例和附图,对本申请进一步说明。
在发明提供了超疏水芳纶织物的制备方法,以下分别对本实施例的各个组成部分进行详细描述:
具体实施例1:
如图1-3所示:一种超疏水芳纶织物的制备方法具体步骤如下:
(1)将0.6g平均粒径为0.5微米的TiO2与0.6g平均粒径为100纳米的TiO2均匀混合并投入到60g的乙醇溶液中,剧烈搅拌30分钟;随后加入0.12g的十三氟辛基三乙氧基硅烷并搅拌60分钟,最后加入30g去离子水,超声震荡60分钟进行水解氟化接枝反应即可得到氟化TiO2颗粒;反应制得的氟化TiO2经乙醇、水洗多次后烘干备用;投入的十三氟辛基三乙氧基硅烷质量为TiO2质量的0.8%;反应温度10℃;反应时间0.5小时。
(2)将1g的氟化TiO2与8g的聚偏四氟乙烯粉末混溶于100gDMF/丙酮中,DMF与丙酮体积质量比为1:1,将上述混合纺丝溶液置于喷丝头中,在芳纶表面进行原位纺丝,其纺丝距离为18cm,纺丝电压为20kV。制得纺丝原液,将纺丝原液利用静电纺丝方法在芳纶织物表面喷涂TiO2聚偏氟乙烯纳米纤维层,制得涂层织物;聚偏四氟乙烯/氟化TiO2纺丝原液中聚偏四氟乙烯浓度百分比为8%;氟化TiO2质量为聚偏四氟乙烯干重的1.2%。
(3)随后将步骤(2)制得的涂层织物进行高温处理形成聚偏氟乙烯纳米纤维热粘层,高温处理温度为180℃,处理时间为0.5小时,即可将纳米纤维热熔粘合在芳纶表面。
具体实施例2:
(1)将0.6g平均粒径为0.5微米的TiO2与0.6g平均粒径为100纳米的TiO2均匀混合并投入到50g的乙醇溶液中,剧烈搅拌30分钟;随后加入0.6g的十三氟辛基三乙氧基硅烷并搅拌60分钟,最后加入30g去离子水,超声震荡60分钟进行水解氟化接枝反应即可得到氟化TiO2颗粒;反应制得的氟化TiO2经乙醇、水洗多次后烘干备用;投入的十三氟辛基三乙氧基硅烷质量为TiO2质量的3%;反应温度25℃;反应时间1.5小时。
(2)将2g的氟化TiO2与10g聚偏四氟乙烯粉末混溶于100g的DMF/丙酮中,DMF与丙酮体积质量比为1:1,将上述混合纺丝溶液置于喷丝头中,在芳纶表面进行原位纺丝,其纺丝距离为18cm,纺丝电压为20kV。制得纺丝原液,将纺丝原液利用静电纺丝方法在芳纶织物表面喷涂TiO2聚偏氟乙烯纳米纤维层,制得涂层织物;聚偏四氟乙烯/氟化TiO2纺丝原液中聚偏四氟乙烯浓度百分比为15%;氟化TiO2质量为聚偏四氟乙烯干重的20%。
(3)随后将步骤(2)制得的涂层织物进行高温处理形成聚偏氟乙烯纳米纤维热粘层,高温处理温度为190℃,处理时间为0.5小时,即可将纳米纤维热熔粘合在芳纶表面。
具体实施例3:
(1)将0.6g平均粒径为0.5微米的TiO2与0.6g平均粒径为100纳米的TiO2均匀混合并投入到60g的乙醇溶液中,剧烈搅拌30分钟;随后加入0.12g的十三氟辛基三乙氧基硅烷并搅拌60分钟,最后加入30g去离子水,超声震荡60分钟进行水解氟化接枝反应接枝反应即可得到氟化TiO2颗粒;反应制得的氟化TiO2经乙醇、水洗多次后烘干备用;投入的十三氟辛基三乙氧基硅烷质量为TiO2质量的0.9%;反应温度15℃;反应时间1.2小时。
(2)将1g的氟化TiO2与9g的聚偏四氟乙烯粉末混溶于DMF/丙酮中,DMF与丙酮体积质量比为1:1,将上述混合纺丝溶液置于喷丝头中,在芳纶表面进行原位纺丝,其纺丝距离为18cm,纺丝电压为20kV。制得纺丝原液,将纺丝原液利用静电纺丝方法在芳纶织物表面喷涂TiO2聚偏氟乙烯纳米纤维层,制得涂层织物;聚偏四氟乙烯/氟化TiO2纺丝原液中聚偏四氟乙烯浓度百分比为12%;氟化TiO2质量为聚偏四氟乙烯干重的10%。
(3)随后将步骤(2)制得的涂层织物进行高温处理形成聚偏氟乙烯纳米纤维热粘层,高温处理温度为185℃,处理时间为0.8小时,即可将纳米纤维热熔粘合在芳纶表面。
至此,已经结合附图对本实施例进行了详细描述。依据以上描述,本领域技术人员应当对本申请有了清楚的认识。
需要说明的是,在附图或说明书正文中,未绘示或描述的实现方式,均为所属技术领域中普通技术人员所知的形式,并未进行详细说明。此外,上述对各元件和方法的定义并不仅限于实施例中提到的各种具体结构、形状或方式。
还需要说明的是,本文可提供包含特定值的参数的示范,但这些参数无需确切等于相应的值,而是可在可接受的误差容限或设计约束内近似于相应值。实施例中提到的方向用语,例如“上”、“下”、“前”、“后”、“左”、“右”等,仅是参考附图的方向,并非用来限制本申请的保护范围。此外,除非特别描述或必须依序发生的步骤,上述步骤的顺序并无限制于以上所列,且可根据所需设计而变化或重新安排。并且上述实施例可基于设计及可靠度的考虑,彼此混合搭配使用或与其他实施例混合搭配使用,即不同实施例中的技术特征可以自由组合形成更多的实施例。
以上所述的具体实施例,对本申请的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本申请的具体实施例而已,并不用于限制本申请,凡在本申请的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。

Claims (5)

1.一种超疏水芳纶织物的制备方法,其特征在于,包括如下步骤:
(1)将一定质量的微米级TiO2与纳米级TiO2均匀混合投入到一定质量的乙醇溶液中,随后加入十三氟辛基三乙氧基硅烷并搅拌20-150分钟,最后加入一定质量的去离子水进行水解氟化接枝反应,反应制得的氟化TiO2经乙醇、水洗多次后烘干备用;
(2)步骤(1)所得到的氟化TiO2与聚偏四氟乙烯粉末混溶于DMF/丙酮中,制得纺丝原液,将纺丝原液利用静电纺丝方法在芳纶织物表面喷涂TiO2聚偏氟乙烯纳米纤维层,制得涂层织物;
(3)随后将步骤(2)制得的涂层织物进行高温处理形成聚偏氟乙烯纳米纤维热粘层。
2.根据权利要求1所述的一种超疏水芳纶织物的制备方法,其特征在于,所述微米级TiO2颗粒粒径为0.5-1.2微米,所述纳米级TiO2粒径为70-200纳米;其两者的质量比为3:1-1:2。
3.根据权利要求1所述的一种超疏水芳纶织物的制备方法,其特征在于,在步骤(1)中,TiO2与乙醇的质量比为1:30-1:100;投入的十三氟辛基三乙氧基硅烷质量为TiO2质量的0.8-3%;水与乙醇的质量比为1:1-1:1.5;反应温度10-25℃;反应时间0.5-1.5小时。
4.根据权利要求1所述的一种超疏水芳纶织物的制备方法,其特征在于,聚偏四氟乙烯/氟化TiO2纺丝原液中聚偏四氟乙烯浓度百分比为8%-15%;氟化TiO2质量为聚偏四氟乙烯干重的1.2-20%。
5.根据权利要求1所述的一种超疏水芳纶织物的制备方法,其特征在于:所述步骤(3)中高温处理温度为180-190℃,处理时间为0.5-1小时。
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JP7448261B2 (ja) 2021-08-02 2024-03-12 中国科学院蘇州納米技術与納米▲ファン▼生研究所 原位置疎水性変性アラミドナノエアロゲル繊維、その製造方法及び使用

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* Cited by examiner, † Cited by third party
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