CN115416382A - 一种层合结构中空微纳米纤维非织造材料及其制备方法与应用 - Google Patents
一种层合结构中空微纳米纤维非织造材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及功能纺织材料技术领域，具体涉及一种层合结构中空微纳米纤维非织造材料及其制备方法与应用，包括以下步骤：(1)将聚丙烯腈粉末完全溶解于溶剂中，随后加入远红外纳米颗粒并分散均匀；(2)以聚丙烯腈/远红外纳米颗粒混合溶液为壳层，以温度可控的湿空气为核层，利用同轴静电纺丝方法进行纺丝，利用液体凝固池接收纺制的纤维，通过梯度调控纺丝溶液性质及纺丝工艺参数，制得具有不同纤维直径与中空度的层合结构微纳米纤维集合体；(3)通过水刺方法对微纳米纤维集合体进行加固，制备得到具有层合结构的中空微纳米纤维非织造材料。本发明的层合结构中空微纳米纤维非织造材料可用于高性能防寒保暖纺织制品及安全防护服装的设计开发。
Description
技术领域
本发明涉及功能纺织材料技术领域，具体涉及一种层合结构中空微纳米纤维非织造材料及其制备方法与应用。
背景技术
低温严寒环境容易引起人体冻伤，造成机体免疫能力下降，并引发心血管及呼吸***疾病，严重影响人们的身体健康和生命安全。因此，需要穿着具有保暖功能的防寒服装来抵御严寒环境对人体的危害。当前，防寒保暖服装常用的保暖填充材料主要为羽绒纤维，其虽具有良好的保暖性能，但面临产量低、成本高、加工处理工艺复杂等不足，极大的限制了其实际应用。
中空纤维内部含有大量的静止空气，可有效提高纤维材料的保暖性能，有望成为羽绒纤维的良好替代品。目前，多数研究者将中空纤维引入到纱线制备过程中，通过向普通实心纤维原料中添加中空短纤维，并进一步经过梳理、并条、粗纱、细纱等工序纺制含中空纤维的混纺纱线，随后采用机织或针织技术将中空纤维混纺纱线织制成含有中空纤维的保暖面料。然而，纺纱加捻作用使得中空纤维在纱线中紧密排列，限制了中空纤维的结构优势，导致材料的保暖性能未能得到大幅提升。此外，有研究者通过将中空微米短纤维与实心微米短纤维混合，并掺入纳米短纤维，进一步通过梳理、成网、纤网层叠及热粘合的方法来制备三维体型中空纤维保暖絮片(CN111648025B)，但纳米短纤维的纳米效应导致其在梳理过程中容易静电吸附在梳理成网设备内的机构上，造成纳米纤维分布均匀性难以控制，且梳理过程容易造成纳米纤维的结构发生破坏，不利于絮片材料的结构成型及保暖性能的大幅提升。近期，中国专利CN114714693A报道了一种纳米纤维保暖材料及其制备方法，该轻薄纳米纤维保暖透湿面料包含外层支撑面料、纳米纤维远红外防水透湿层、纳米纤维保暖层和发热面料，但其采用石蜡油为内核制备聚氨酯中空纳米纤维保暖层，后续需要通过使用有机溶剂浸泡的方法来去除聚氨酯纳米纤维的石蜡内核层，然而纳米纤维连续性好的结构导致其内部石蜡内核层难以完全去除，且制备流程复杂，生产成本较高。
因此，本申请有必要提出一种层合结构中空微纳米纤维非织造材料及其制备方法与应用，以解决上述相关技术问题。
发明内容
针对以上问题，本发明提供了一种层合结构中空微纳米纤维非织造材料及其制备方法与应用，采用中空纤维的管壁内部掺杂的远红外颗粒能够有效吸收并放射远红外线，因而能够进一步提升非织造材料的保暖性能，所制备的材料有望应用于新型高效防寒保暖纺织品及安全防护服装的设计开发。
为了实现上述目的，本发明采用的技术方案如下：
一种层合结构中空微纳米纤维非织造材料，包括上表层、下表层、以及设于上表层和下表层之间的中间层，所述上表层和下表层均为纤维堆积紧密的中空纳米纤维层，所述中间层为纤维堆积蓬松的中空微米纤维层，且中间层的厚度大于上表层和下表层的厚度。
优选地，所述上表层和下表层中，纤维直径为0.2～1μm，中空度为20～40％，纤维层厚度为0.5～2mm，纤维堆积密度为10～15mg/cm3；所述中间层中，纤维直径为1～3μm，中空度为50～80％，纤维层厚度为10～25mm，纤维堆积密度为3～8mg/cm3。
优选地，所述层合结构中空微纳米纤维非织造材料的导热系数为0.025～0.029W/(m·K)。
本发明还提供了一种层合结构中空微纳米纤维非织造材料的制备方法，包括以下步骤：
步骤1、将聚丙烯腈粉末溶解于溶剂中，随后加入远红外纳米颗粒并分散均匀，得聚丙烯腈/远红外纳米颗粒混合溶液；
步骤2、以聚丙烯腈/远红外纳米颗粒混合溶液为壳层，以温度可控的湿空气为核层，利用同轴静电纺丝方法进行纺丝，并利用液体凝固池接收纺制的纤维，通过梯度调控纺丝溶液性质及纺丝工艺参数，制得具有不同纤维直径与中空度的层合结构微纳米纤维集合体；
步骤3、对步骤2得到的层合结构微纳米纤维集合体进行水刺加固，然后鼓风烘干，制备得到层合结构中空微纳米纤维非织造材料。
优选地，在步骤1中，溶剂为N,N-二甲基甲酰胺、二甲基亚砜、环丁砜中的一种或多种的混合；远红外纳米颗粒为碳纳米管、石墨烯、电气石粉、陶瓷纳米颗粒中的一种或多种；
其中，聚丙烯腈/远红外纳米颗粒混合溶液中，聚丙烯腈的质量浓度为5～35wt％，远红外纳米颗粒的质量浓度为0.1～5wt％。
优选地，在步骤2中，同轴静电纺丝的同轴喷丝口呈阵列式排布，同轴喷丝口壳层灌注步骤1所得的聚丙烯腈/远红外纳米颗粒混合溶液，同轴喷丝口核层灌注的介质为可控温的湿空气；
其中，可控温的湿空气的温度为30～40℃、湿度为80～95％；
其中，凝固池中盛放的液体为去离子水；
其中，纤维集合体内部中空微纳米纤维具有连续性。
优选地，在步骤2中，同轴喷丝口壳层聚合物溶液灌注速度为1～10mL/h，核层湿空气的流速为1～20m/s，电压为10～50kV，喷丝口与液体凝固池液面间的间距为10～50cm，环境温度为15～30℃，环境湿度为30～70％。
本发明还提供了一种层合结构中空微纳米纤维非织造材料在防寒保暖领域中的应用。
采用上述技术方案：本发明的层合结构主要是指在非织造材料的纵截面上，上、下表面层为厚度较小的中空纳米纤维层，且中空纳米纤维堆积紧密，可有效减少非织造材料内部的空气对流；中间层为中空微米纤维层，其较粗的直径使其具有较大的弯曲刚度，可以有效支撑上、下中空纳米纤维层的纵向结构，且中空微米纤维堆积较为蓬松，微纳米纤维的中空结构与多层层合堆积结构可以有效提升非织造材料的静止空气含量；此外，中空纤维管壁内部所含的远红外纳米颗粒能够有效吸收并放射远红外线，因而具有高效防寒保暖性能。
本发明有益效果：
1、本发明采用同轴静电纺丝方法制备中空微纳米纤维，不同于传统的核壳静电纺丝方法，本发明在核层加载温度可控的湿空气，具有一定温度的湿空气可以促使聚丙烯腈/远红外纳米颗粒混合纺丝溶液发生快速相分离，形成稳定的中空核层，从而可以有效避免中空结构的塌陷；此外，由于核层使用的是空气介质，后续过程中不需要采用有机溶剂浸泡的方法去除核层中空结构模板介质，可有效提升中空纤维的纺丝速率，减少有机溶剂的使用，降低生产成本。
2、本发明采用凝固浴池接收静电纺中空微纳米纤维，通过梯度调控纺丝溶液中聚丙烯腈与远红外纳米颗粒的质量浓度及纺丝工艺参数，制得不同纤维直径与中空度的层合结构微纳米纤维集合体，并通过水刺工艺对纤维集合体进行加固，制备得到的非织造保暖材料上、下中空纳米纤维层具有较高的堆积密度，能够减少材料内部空气对流，蓬松堆积的中空微米纤维中间层具有较高的孔隙率，与中空纤维的耦合作用可有效提升非织造材料对静止空气的储存能力，从而提升材料的保暖性能。
3、本发明所制备的层合结构中空微纳米纤维非织造材料内部，中空纤维的管壁内部掺杂的远红外颗粒能够有效吸收并放射远红外线，因而能够进一步提升非织造材料的保暖性能，所制备的材料有望应用于新型高效防寒保暖纺织品及安全防护服装的设计开发。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述，但本发明的实施方式不限于此。
实施例1：一种层合结构中空微纳米纤维非织造材料的制备方法，包括如下步骤：
步骤1、称取聚丙烯腈粉末分散于N,N-二甲基甲酰胺中，在室温环境下搅拌至完全溶解，随后向溶液中加入碳纳米管并超声分散均匀，从而得到上、下表层纤维的纺丝溶液，纺丝溶液中聚丙烯腈的质量浓度为8wt％，碳纳米管的质量浓度为0.5wt％；以同样的方法配制中间层纤维的纺丝溶液，纺丝溶液中聚丙烯腈的质量浓度为33wt％，碳纳米管的质量浓度为1wt％；
步骤2、采用同轴静电纺丝技术对步骤1得到的纺丝溶液进行纺丝，纺制的纤维接收于正方形去离子水凝固浴池中，上、下表层纤维纺制时，同轴喷丝口壳层聚合物溶液灌注速度为1mL/h、电压为35kV、喷丝口与接收液面间距为15cm、环境温度为25℃、环境湿度为35％，同轴喷丝口核层空气的流速为2m/s；中间层纤维纺制时，同轴喷丝口壳层聚合物溶液灌注速度为3mL/h、电压为20kV、喷丝口与接收液面间距为25cm、环境温度为25℃、环境湿度为70％，同轴喷丝口核层空气的流速为18m/s；核层湿空气的温度均为35℃、湿度为90％；
步骤3、对步骤2得到的层合结构中空微纳米纤维集合体进行水刺处理，随后在鼓风烘箱中烘干，制备得到层合结构中空微纳米纤维非织造材料。层合非织造材料上、下表层中空纳米纤维平均直径约为0.3μm，中空度约为23％，纤维层厚度为2mm，堆积密度为14.5mg/cm3；中间层中空微米纤维平均直径约为2.5μm，中空度约为68％，纤维层厚度为23mm，堆积密度为4mg/cm3；制备得到的层合结构中空微纳米纤维非织造材料的导热系数为0.0253W/(m·K)。
实施例2：一种层合结构中空微纳米纤维非织造材料的制备方法，包括如下步骤：
步骤1、称取聚丙烯腈粉末分散于N,N-二甲基甲酰胺中，在室温环境下搅拌至完全溶解，随后向溶液中加入石墨烯并超声分散均匀，从而得到上、下表层纤维的纺丝溶液，纺丝溶液中聚丙烯腈的质量浓度为10wt％，石墨烯的质量浓度为1wt％；以同样的方法配制中间层纤维的纺丝溶液，纺丝溶液中聚丙烯腈的质量浓度为30wt％，石墨烯的质量浓度为1.5wt％；
步骤2、采用同轴静电纺丝技术对步骤1得到的纺丝溶液进行纺丝，纺制的纤维接收于正方形去离子水凝固浴池中，上、下表层纤维纺制时，同轴喷丝口壳层聚合物溶液灌注速度为2mL/h、电压为35kV、喷丝口与接收液面间距为15cm、环境温度为25℃、环境湿度为40％，同轴喷丝口核层空气的流速为5m/s；中间层纤维纺制时，同轴喷丝口壳层聚合物溶液灌注速度为3mL/h、电压为20kV、喷丝口与接收液面间距为27cm、环境温度为25℃、环境湿度为65％，同轴喷丝口核层空气的流速为15m/s；核层湿空气的温度均为35℃、湿度为85％；
步骤3、对步骤2得到的层合结构中空微纳米纤维集合体进行水刺处理，随后在鼓风烘箱中烘干，制备得到层合结构中空微纳米纤维非织造材料。层合非织造材料下、下表层中空纳米纤维平均直径约为390nm，中空度约为26％，纤维层厚度为1.5mm，堆积密度为14mg/cm3；中间层中空微米纤维直径约为1.9μm，中空度约为59％，纤维层厚度为20mm，堆积密度为5.3mg/cm3；制备得到的层合结构中空微纳米纤维非织造材料的导热系数为0.0261W/(m·K)。
实施例3：一种层合结构中空微纳米纤维非织造材料的制备方法，包括如下步骤：
步骤1、称取聚丙烯腈粉末分散于N,N-二甲基甲酰胺中，在室温环境下搅拌至完全溶解，随后向溶液中加入碳纳米管并超声分散均匀，从而得到上、下表层纤维的纺丝溶液，纺丝溶液中聚丙烯腈的质量浓度为13wt％，电气石粉的质量浓度为1wt％；以同样的方法配制中间层纤维的纺丝溶液，纺丝溶液中聚丙烯腈的质量浓度为25wt％，电气石粉的质量浓度为2wt％；
步骤2、采用同轴静电纺丝技术对步骤1得到的纺丝溶液进行纺丝，纺制的纤维接收于正方形去离子水凝固浴池中，上、下表层纤维纺制时，同轴喷丝口壳层聚合物溶液灌注速度为2mL/h、电压为35kV、喷丝口与接收液面间距为17cm、环境温度为25℃、环境湿度为40％，同轴喷丝口核层空气的流速为4m/s；中间层纤维纺制时，同轴喷丝口壳层聚合物溶液灌注速度为3mL/h、电压为25kV、喷丝口与接收液面间距为25cm、环境温度为25℃、环境湿度为65％，同轴喷丝口核层气空气的流速为16m/s；核层湿空气的温度均为30℃、湿度为80％；
步骤3、对步骤2得到的层合结构中空微纳米纤维集合体进行水刺处理，随后在鼓风烘箱中烘干，制备得到层合结构中空微纳米纤维非织造材料。层合非织造材料上、下表层纤维平均直径约为700nm，中空度约为32％，纤维层厚度为1mm，堆积密度为10.5mg/cm3；中间层中空微米纤维直径约为2.3μm，中空度约为53％，纤维层厚度为15mm，堆积密度为7.5mg/cm3；制备得到的层合结构中空微纳米纤维非织造材料的导热系数为0.0281W/(m·K)。
上述实施例仅用来进一步说明本发明的具体实施方式，但本发明并不局限于上述实施例，凡是根据本发明的技术实质，对以上实施例所作的等同变化与修饰皆包括在本发明技术方案的保护范围内。
Claims (8)
1.一种层合结构中空微纳米纤维非织造材料，其特征在于，包括上表层、下表层、以及设于上表层和下表层之间的中间层，所述上表层和下表层均为纤维堆积紧密的中空纳米纤维层，所述中间层为纤维堆积蓬松的中空微米纤维层，且中间层的厚度大于上表层和下表层的厚度。
2.根据权利要求1所述的一种层合结构中空微纳米纤维非织造材料，其特征在于，所述上表层和下表层中，纤维直径为0.2～1μm，中空度为20～40％，纤维层厚度为0.5～2mm，纤维堆积密度为10～15mg/cm3；所述中间层中，纤维直径为1～3μm，中空度为50～80％，纤维层厚度为10～25mm，纤维堆积密度为3～8mg/cm3。
3.根据权利要求2所述的一种层合结构中空微纳米纤维非织造材料，其特征在于，所述层合结构中空微纳米纤维非织造材料的导热系数为0.025～0.029W/(m·K)。
4.根据权利要求1所述的一种层合结构中空微纳米纤维非织造材料的制备方法，其特征在于，包括以下步骤：
步骤1、将聚丙烯腈粉末溶解于溶剂中，随后加入远红外纳米颗粒并分散均匀，得聚丙烯腈/远红外纳米颗粒混合溶液；
步骤2、以聚丙烯腈/远红外纳米颗粒混合溶液为壳层，以温度可控的湿空气为核层，利用同轴静电纺丝方法进行纺丝，并利用液体凝固池接收纺制的纤维，通过梯度调控纺丝溶液性质及纺丝工艺参数，制得具有不同纤维直径与中空度的层合结构微纳米纤维集合体；
步骤3、对步骤2得到的层合结构微纳米纤维集合体进行水刺加固，然后鼓风烘干，制备得到层合结构中空微纳米纤维非织造材料。
5.根据权利要求4所述的一种层合结构中空微纳米纤维非织造材料的制备方法，其特征在于，在步骤1中，溶剂为N,N-二甲基甲酰胺、二甲基亚砜、环丁砜中的一种或多种的混合；远红外纳米颗粒为碳纳米管、石墨烯、电气石粉、陶瓷纳米颗粒中的一种或多种；
聚丙烯腈/远红外纳米颗粒混合溶液中，聚丙烯腈的质量浓度为5～35wt％，远红外纳米颗粒的质量浓度为0.1～5wt％。
6.根据权利要求4所述的一种层合结构中空微纳米纤维非织造材料的制备方法，其特征在于，在步骤2中，同轴静电纺丝的同轴喷丝口呈阵列式排布，同轴喷丝口壳层灌注步骤1所得的聚丙烯腈/远红外纳米颗粒混合溶液，同轴喷丝口核层灌注的介质为可控温的湿空气；
可控温的湿空气的温度为30～40℃、湿度为80～95％；
凝固池中盛放的液体为去离子水；
纤维集合体内部中空微纳米纤维具有连续性。
7.根据权利要求4所述的一种层合结构中空微纳米纤维非织造材料的制备方法，其特征在于，在步骤2中，同轴喷丝口壳层聚合物溶液灌注速度为1～10mL/h，核层湿空气的流速为1～20m/s，电压为10～50kV，喷丝口与液体凝固池液面间的间距为10～50cm，环境温度为15～30℃，环境湿度为30～70％。
8.根据权利要求1所述的层合结构中空微纳米纤维非织造材料在防寒保暖领域中的应用。
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| CN117051538A (zh) * | 2023-08-21 | 2023-11-14 | 波司登羽绒服装有限公司 | 一种纳米纤维膜保暖材料及其制备方法和羽绒服 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088442A (zh) * | 2013-01-23 | 2013-05-08 | 上海交通大学 | 一种同轴静电纺丝制备中空纤维的方法 |
| CN107139553A (zh) * | 2017-04-13 | 2017-09-08 | 深圳市和煦健康科技有限公司 | 一种保暖抗寒面料结构 |
| CN111455474A (zh) * | 2020-03-23 | 2020-07-28 | 东华大学 | 一种仿羊毛卷曲静电纺纳米纤维及其制备方法 |
| CN111485329A (zh) * | 2020-03-23 | 2020-08-04 | 东华大学 | 一种具有三明治结构的纳米纤维絮片及其制备方法 |
| WO2020221286A1 (zh) * | 2019-04-30 | 2020-11-05 | 西南石油大学 | 一种β-FeOOH/聚丙烯腈的复合纳米纤维膜及其制备方法与应用 |
| WO2020232931A1 (zh) * | 2019-05-21 | 2020-11-26 | 江西先材纳米纤维科技有限公司 | 电纺聚丙烯腈纳米纤维连续长线纱的制备方法和应用 |
| CN113529279A (zh) * | 2021-07-08 | 2021-10-22 | 吉祥三宝高科纺织有限公司 | 一种防水透湿纳米纤维膜湿度诱导致密成型工艺 |
| CN114714693A (zh) * | 2022-02-15 | 2022-07-08 | 昆承新材料科技(江苏)有限公司 | 一种纳米纤维保暖材料及其制备方法 |
| CN114892290A (zh) * | 2022-05-09 | 2022-08-12 | 苏州中色德源环保科技有限公司 | 一种无芯液干-湿法中空纤维膜纺丝工艺 |
-
2022
- 2022-09-02 CN CN202211073265.5A patent/CN115416382B/zh active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088442A (zh) * | 2013-01-23 | 2013-05-08 | 上海交通大学 | 一种同轴静电纺丝制备中空纤维的方法 |
| CN107139553A (zh) * | 2017-04-13 | 2017-09-08 | 深圳市和煦健康科技有限公司 | 一种保暖抗寒面料结构 |
| WO2020221286A1 (zh) * | 2019-04-30 | 2020-11-05 | 西南石油大学 | 一种β-FeOOH/聚丙烯腈的复合纳米纤维膜及其制备方法与应用 |
| WO2020232931A1 (zh) * | 2019-05-21 | 2020-11-26 | 江西先材纳米纤维科技有限公司 | 电纺聚丙烯腈纳米纤维连续长线纱的制备方法和应用 |
| CN111455474A (zh) * | 2020-03-23 | 2020-07-28 | 东华大学 | 一种仿羊毛卷曲静电纺纳米纤维及其制备方法 |
| CN111485329A (zh) * | 2020-03-23 | 2020-08-04 | 东华大学 | 一种具有三明治结构的纳米纤维絮片及其制备方法 |
| CN113529279A (zh) * | 2021-07-08 | 2021-10-22 | 吉祥三宝高科纺织有限公司 | 一种防水透湿纳米纤维膜湿度诱导致密成型工艺 |
| CN114714693A (zh) * | 2022-02-15 | 2022-07-08 | 昆承新材料科技(江苏)有限公司 | 一种纳米纤维保暖材料及其制备方法 |
| CN114892290A (zh) * | 2022-05-09 | 2022-08-12 | 苏州中色德源环保科技有限公司 | 一种无芯液干-湿法中空纤维膜纺丝工艺 |
Non-Patent Citations (2)
| Title |
|---|
| 顾其胜等: "《海藻酸盐基生物医用材料与临床医学》", 上海科学技术出版社, pages: 134 - 135 * |
| 高宁;彭应杰;张爱英;叶霖;冯增国: "溶液参数对静电纺丝PAN@PS复合纳米纤维形貌及结构的影响", 合成树脂及塑料, vol. 36, no. 03, pages 12 - 17 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117051538A (zh) * | 2023-08-21 | 2023-11-14 | 波司登羽绒服装有限公司 | 一种纳米纤维膜保暖材料及其制备方法和羽绒服 |
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