CN112593408A - 一种抗紫外无纺膜及其制备方法 - Google Patents
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Abstract
本发明涉及无纺布技术领域,提供了一种抗紫外无纺膜及其制备方法,包括以下步骤:首先利用静电纺丝法制备富含锌离子的聚丙烯腈无纺膜,再将其浸没在含有2‑甲基咪唑的甲醇溶液中,在无纺膜表面原位生成金属间框架化合物ZIF‑8,利用聚乙烯亚胺对该无纺膜进行表面改性后,再在其表面上负载苯并三唑类紫外吸收剂,即得到抗紫外无纺膜。本发明所得的无纺膜具有优良的抗紫外性能,紫外吸收剂在聚丙烯腈纤维上附着牢固,具有持久的抗紫外性能。
Description
技术领域
本发明涉及一种抗紫外无纺膜及其制备方法,属于无纺布制备技术领域。
背景技术
太阳光中波长在300-400nm的紫外线可以穿过臭氧层到达地面。适当的紫外线照射对人体发育有好处,但是过度的紫外线照射可晒伤皮肤,甚至诱发黑色素瘤皮肤癌,给人体带来严重伤害。纺织品是保护人体防辐射的第一道屏障,提高纺织品的抗紫线外性能,可以有效防止人体被紫外线损伤。提高纺织品抗紫外性能的途径通常是在织物中加入紫外吸收剂。例如,中国专利(CN108456947B)“一种抗紫外PET纤维及其制备方法”将PET切片与复合有机紫外吸收剂的中空多孔微球混合均匀后熔融纺丝制得PET纤维,由于最终制得的产品中均匀分散有复合有机紫外吸收剂的中空多孔微球而使得PET纤维具有较好的抗紫外性能。在该专利中,负载有紫外吸收剂的中空多孔微球通过熔融纺丝过程被复合到PET纤维内部,使得紫外吸收剂在纤维上可以稳定固着,不易脱落,但是抗紫外微球的加入对纺丝质量产生影响,紫外吸收剂存在于纤维内部的这种结构也影响紫外吸收剂的防紫外功能。中国专利(公开号CN107747173)“农用非织造布的防紫外整理方法”利用抗紫外整理剂溶液浸轧处理农用非织造布,制备得到抗紫外的非织造布,方法简单易行,但是紫外线屏蔽剂与纤维的结合力较弱,不耐洗涤,无纺布的防紫外性能持久性能较差。中国专利(申请号:201911407797.6)“一种耐洗防紫外无纺布复合面料”将抗紫外层通过胶黏剂粘在两层无纺布之间,制备了一种三明治型的抗紫外无纺布复合材料,该发明目的在于保护无纺布中携带的抗紫外屏蔽剂,使其在洗涤过程中不易脱落,从而延长了无纺布抗紫外时间。但是该复合材料结构较为复杂,制备流程长,增加了无纺布制备成本。
发明内容
为了克服现有技术中织物抗紫外性能差和抗紫外剂在织物上不能耐久的问题,本发明提供一种抗紫外无纺膜及其制备方法,利用外延生长法在无纺膜上负载金属间框架化合物ZIF-8,利用ZIF-8对紫外吸收剂强烈的吸附能力实现紫外吸收剂的稳定负载,使得负载在纤维表面的紫外吸收剂能够与无纺膜牢固结合,长期发挥其抗紫外的功能。
为实现上述目的,本发明的技术方案是采用以下步骤:
(1)将聚丙烯腈溶解于N,N-二甲基甲酰胺中,配置成质量分数8-20%的聚丙烯腈纺丝液。再向该纺丝液中添加一定量的六水合硝酸锌,室温搅拌12h,得到含有锌离子的纺丝液;
(2)调节静电纺丝机的纺丝电压为10-40kV,使纺丝液喷射到铝箔收集板上,得到富含锌离子的聚丙烯腈无纺膜;
(3)将步骤(2)中制得的无纺膜浸没在50mL含3.0克2-甲基咪唑的甲醇溶液中,室温下放置24h,使得ZIF-8纳米颗粒在无纺膜上生成。将所得无纺膜用50mL甲醇漂洗3次,60℃烘干,得到负载了ZIF-8纳米颗粒的无纺膜;
(4)将步骤(3)中所得到的的无纺膜放置于50mL含有0.5g的聚乙烯亚胺(PEI,分子量10000Da)的甲醇溶液中,室温下保持12h,将所得无纺膜用甲醇漂洗3次,得到改性的负载了ZIF-8纳米颗粒的无纺膜;
(5)将步骤(4)中得到的无纺膜放置于50mL质量分数为0.1~0.3Wt%的紫外线吸收剂的甲醇溶液中,室温下保持12h,用甲醇漂洗3次,60℃干燥,得到抗紫外无纺膜。
所述的聚丙烯腈和六水合硝酸锌的质量比为100:0.5~2.5。
所述的紫外吸收剂为苯并三唑类紫外吸收剂中的一种或多种。
与背景技术相比,本发明具有的有益效果是:
本发明在聚丙烯腈纺丝液中引入了锌离子,使得在后续的反应中,金属间框架化合物ZIF-8在纤维表面上原位形成,再通过ZIF-8的吸附作用将紫外吸收剂固定在无纺膜上。本发明中的方法一方面使得紫外吸收剂裸露在无纺膜的表面上,可以充分发挥其抗紫外功能,另一方面通过ZIF-8对紫外吸收剂强烈的吸附作用,使得紫外吸收剂牢固的负载在无纺膜上,不易脱落,可持久地发挥作用。
附图说明
图1是实施例1制备的抗紫外无纺膜的场发射扫描电镜照片。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1:
(1)取0.8克聚丙烯腈溶解于9.2克N,N-二甲基甲酰胺中,配置成质量分数8%的聚丙烯腈纺丝液。再向该纺丝液中添加0.004g六水合硝酸锌,室温搅拌12h,得到含有锌离子的纺丝液;
(2)调节静电纺丝机的纺丝电压为10kV,使纺丝液喷射到铝箔收集板上,得到富含锌离子的聚丙烯腈无纺膜;
(3)将步骤(2)中制得的无纺膜浸没在50mL含3.0克2-甲基咪唑的甲醇溶液中,室温下放置24h,使得ZIF-8纳米颗粒在无纺膜上生成。将所得无纺膜用50mL甲醇漂洗3次,60℃干燥,得到负载了ZIF-8纳米颗粒的无纺膜;
(4)将步骤(3)中所得到的的无纺膜放置于50mL含有0.5g的聚乙烯亚胺(PEI,分子量10000Da)的甲醇溶液中,室温下保持12h,将所得无纺膜用甲醇漂洗3次,得到改性的ZIF-8无纺膜;
(5)将步骤(4)中得到的无纺膜放置于50mL质量分数为0.1Wt%的紫外线吸收剂UV-327的甲醇溶液中,室温下保持12h后,用甲醇漂洗3次,60℃干燥,得到抗紫外无纺膜,该抗紫外无纺膜的纳米纤维直径约50nm。
实施例2:
(1)将1.2克聚丙烯腈溶解于7.8克N,N-二甲基甲酰胺中,配置成质量分数12%的聚丙烯腈纺丝液。再向该纺丝液中添加0.018克六水合硝酸锌,室温搅拌12h,得到含有锌离子的纺丝液;
(2)调节静电纺丝机的纺丝电压为25kV,使纺丝液喷射到铝箔收集板上,得到富含锌离子的聚丙烯腈无纺膜;
(3)将步骤(2)中制得的无纺膜浸没在50mL含3.0克2-甲基咪唑的甲醇溶液中,室温下放置24h,使得ZIF-8纳米颗粒在无纺膜上生成。将所得无纺膜用50mL甲醇漂洗3次,60℃干燥,得到负载了ZIF-8纳米颗粒的无纺膜;
(4)将步骤(3)中所得到的的无纺膜放置于50mL含有0.5g的聚乙烯亚胺(PEI,分子量10000Da)的甲醇溶液中,室温下保持12h,将所得无纺膜用甲醇漂洗3次,得到改性的负载了ZIF-8纳米颗粒的无纺膜;
(5)将步骤(4)中得到的无纺膜放置于50mL质量分数为0.2Wt%的紫外线吸收剂(包括UV-328、UV329、UV234、UV360四种紫外吸收剂,该四种紫外吸收剂的质量分数均为0.05Wt%)的甲醇溶液中,室温下保持12h,用甲醇漂洗3次,60℃干燥,得到抗紫外无纺膜,该无纺膜的纤维直径约为100nm。
实施例3:
(1)将2克聚丙烯腈溶解于8克N,N-二甲基甲酰胺中,配置成质量分数20%的聚丙烯腈纺丝液。再向该纺丝液中添加0.05克六水合硝酸锌,室温搅拌12h,得到含有锌离子的纺丝液;
(2)调节静电纺丝机的纺丝电压为40kV,使纺丝液喷射到铝箔收集板上,得到富含锌离子的聚丙烯腈无纺膜;
(3)将步骤(2)中制得的无纺膜浸没在50mL含3.0克2-甲基咪唑的甲醇溶液中,室温下放置24h,使得ZIF-8纳米颗粒在无纺膜上生成。将所得无纺膜用50mL甲醇漂洗3次,60℃干燥,得到负载了ZIF-8纳米颗粒的无纺膜;
(4)将步骤(3)中所得到的的无纺膜放置于50mL含有0.5g的聚乙烯亚胺(PEI,分子量10000Da)的甲醇溶液中,室温下保持12h,将所得无纺膜用甲醇漂洗3次,得到改性的负载了ZIF-8纳米颗粒的无纺膜;
(5)将步骤(4)中得到的无纺膜放置于50mL质量分数为0.3Wt%的紫外线吸收剂(包括UV-P、UV-320、UV-327三种紫外吸收剂,该三种紫外吸收剂的质量分数均为0.1Wt%)的甲醇溶液中,室温下保持12h,用甲醇漂洗3次,60℃干燥,得到抗紫外无纺膜C,该无纺膜的纤维直径约为500nm。
实施例4:无纺膜抗紫外性能测试
紫外线防护标准通常采用紫外线防护系数来加以评定,UPF值越高,则紫外线的防护效果越好。根据我国国家标准GB/T18830-2009(纺织品防紫外线性能的评定)中规定:只有当样品的UPF值大于40,并且UVA的透过率小于5%时,才能称之为“防紫外线产品”。利用UV-1000F型紫外线透射分析仪,根据该标准对所制得的无纺膜进行了紫外防护性能测试,测试结果见表1。
为了测定紫外吸收剂在无纺膜上固着牢度,将实施例1-3于室温下浸泡在水中漂洗3分钟,置于60℃烘箱中烘干,重复该漂洗步骤,分别检测漂洗后各实施例无纺膜的UPF值和UVA透过率。测试结果统计于表1中。
附表1各实施例经过不同洗涤次数后的紫外防护系数UPF统计表
由上表可知,实施例1-3样品均具有优秀的紫外防护性能,其UPF值随着无纺膜中六水合硝酸锌添加量的增加以及紫外吸收剂浓度的增加而升高。紫外吸收剂在无纺膜上附着牢度好,经过洗涤之后,其UPF值和UVA透过率没有太大改变,证明本发明中的无纺膜具有持久、耐洗涤的紫外防护性能。
以上列举的仅是本发明的具体实施例。本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (4)
1.一种抗紫外无纺膜,其特征在于,由聚丙烯腈纳米纤维、金属间框架化合物ZIF-8和紫外吸收剂组成。
2.根据权利要求1所述的抗紫外无纺膜的制备方法,其特征在于,包括以下步骤:
(1)将聚丙烯腈溶解于N,N-二甲基甲酰胺中,配置成质量分数8-20%的聚丙烯腈纺丝液。再向该纺丝液中添加一定量的六水合硝酸锌,室温搅拌12h,得到含有锌离子的纺丝液。
(2)调节静电纺丝机的纺丝电压为10-40kV,使纺丝液喷射到铝箔收集板上,得到富含锌离子的聚丙烯腈无纺膜。
(3)将步骤(2)中制得的无纺膜浸没在50mL含3.0克2-甲基咪唑的甲醇溶液中,室温下放置24h,使得ZIF-8纳米颗粒在无纺膜上生成。将所得无纺膜用50mL甲醇漂洗3次,60℃烘干,得到负载了ZIF-8纳米颗粒的无纺膜;
(4)将步骤(3)中所得到的的无纺膜放置于50mL含有0.5g的聚乙烯亚胺(PEI,分子量10000Da)的甲醇溶液中,室温下放置12h,将所得无纺膜用甲醇漂洗3次,得到改性的ZIF-8无纺膜;
(5)将步骤(4)中得到的无纺膜放置于50mL质量分数为0.1~0.3Wt%的紫外线吸收剂的甲醇溶液中,室温下保持12h,用甲醇漂洗3次,60℃烘干,得到抗紫外无纺膜。
3.根据权利要求2所述的一种抗紫外无纺膜的制备方法,其特征在于:聚丙烯腈和六水合硝酸锌的质量比为100:0.5~2.5.
4.根据权利要求1所述的一种抗紫外无纺膜,其特征在于:所述的紫外吸收剂为苯并三唑类紫外吸收剂中的一种或多种。
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