CN111748909A - 一种生物基尼龙56纳米纤维膜的制备方法与应用 - Google Patents

一种生物基尼龙56纳米纤维膜的制备方法与应用 Download PDF

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CN111748909A
CN111748909A CN202010617369.2A CN202010617369A CN111748909A CN 111748909 A CN111748909 A CN 111748909A CN 202010617369 A CN202010617369 A CN 202010617369A CN 111748909 A CN111748909 A CN 111748909A
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nanofiber membrane
bio
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fiber
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郝新敏
郭亚飞
梁高勇
李茂辉
闫金龙
乔荣荣
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Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
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Abstract

本发明公开了一种生物基尼龙56纳米纤维膜的制备方法与应用。该方法是以生物基尼龙切片为原料，经过静电纺丝制备纤维直径小于150nm，拉伸强度7‑20MPa的生物基尼龙56纳米纤维膜，并通过物理与化学方法对该纳米纤维膜改性，得到纤维表面覆盖有牢固的且纤维直径小于350nm，拉伸强度7‑25MPa的多层次无机纳米晶体的有机‑无机复合纳米纤维膜。本发明制备的纳米纤维膜，具有高效的吸附能力，良好的力学性、稳定性和耐用性，并且易于回收再利用。本发明制备的纳米纤维膜可在防护服装、防护用品、过滤材料、组织工程、药物传输、传感器、催化剂等领域应用。

Description

一种生物基尼龙56纳米纤维膜的制备方法与应用
技术领域
本发明属于化工领域，具体涉及一种可作为过滤材料的生物基尼龙56纳米纤维膜的制备方法与应用。
背景技术
随着科技和社会的不断发展，人们对自然界的认识越来越深入，开始逐渐的从单一的宏观世界慢慢的转向微观世界。而纳米科技的风生水起便是这一转变的一个重要体现。于1900年在美国巴尔的摩召开的第一届关于纳米科技的国际性会议表明了纳米时代的到来，并预示着纳米科技进入了高速发展的时期。纳米级材料在光学、热学、电学、磁学、力学以及化学等很多方面的性质优于传统材料。
纳米纤维是指纤维直径大小处于纳米尺寸范围内的超细纤维。与常规纤维相比，纳米纤维具有的界面效应、小尺寸效应以及大的比表面积等特点，在防护服、过滤、催化、生物医用、隔热等领域具有广阔而深远的应用前景，目前生产制备纳米纤维的方法有：混合纺丝法、闪蒸法、喷丝法、复合纺丝法以及静电纺丝法等。
静电纺丝纳米纤维操作工艺简单、材料可选择范围广、可进行多种功能化设计，目前已成为国内外的研究热点。其基本原理是基于聚合物溶液或熔体在强电场中，针头处的液滴会由球形变为圆锥形(即“泰勒锥”)，并从圆锥尖端延展得到纳米级直径的聚合物纤维。
静电纺纳米纤维的主要特性是直径小、比表面积大、负载能力强、膜孔隙率高、纤维均一性好，因此纳米纤维可制作吸附材料和过滤材料，应用于亚微米微粒的过滤等方面，能有效地用于原子工业、无菌室、精密工业、涂饰行业等。其过滤效率较之常规过滤材料效率大大提高。无机纳米纤维由于其独特性能，它可用于制作纳米尺度电子元件，也可用作储氢材料。在服装方面，纳米纤维应用前景也是令人注目的，利用纳米纤维的低密度、高孔隙度和大的比表面积做成多功能防护服。这种微细纤维铺成的网带由很多微孔类似于膜的产品，能允许蒸气扩散，即所谓可呼吸性，又能挡风和过滤细粒子，对气溶胶的阻挡性提供了对生物或化学武器和生物化学有毒性的防护性；而可呼吸性又保证了穿着者的舒适性。
发明内容
针对现有技术存在的缺陷，本发明的目的是提供一种强度更大、比表面积更大的生物基尼龙56纳米纤维膜及其制备方法。
本发明所提供的生物基尼龙56纳米纤维膜的制备方法，是以生物基尼龙56的切片为原料，经过溶解得到溶液，将溶液通过物理手段制成生物基尼龙56纳米纤维膜，再采用化学处理方法对纳米纤维膜进行处理。
其中，所述原料为生物基尼龙56，由微生物发酵得到的1,5-戊二胺与1,6-己二酸聚合而成。
该纳米纤维膜的制备方法具体包括以下步骤：
1)原料预处理：将原料生物基尼龙56切片放入羧基酸中进行搅拌溶解，得到高聚物溶液；
2)静电纺丝处理：将步骤1)所得溶液进行静电纺丝处理，得到生物基尼龙56纳米纤维膜。
上述方法步骤1)中，所述羧基酸为甲酸、乙酸、丙酸等中的一种或混合使用；
所述溶解的温度为10-40℃，溶解的时间为3-24小时；
所述高聚物溶液中原料的质量含量为5-25wt％，优选为15％-20％，具体可为10.95％、14.08％、17.00％、19.74％、22.29％。
当以甲酸为溶剂时，所述溶解的温度为25℃，溶解时间为8小时，所得到的溶液中原料的质量含量为20％。
上述方法步骤2)中，所述静电纺丝在静电纺丝机中进行；所述静电纺丝的条件为：温度为30-80℃，电压为15-30kV，静电纺丝处理时间为3-12小时；具体的，所述静电纺丝的条件为：45℃电压为28kV下进行静电纺丝处理3小时。
本发明还可对上述制备的生物基尼龙56纳米纤维膜进行复合处理，制备得到有机-无机复合纳米纤维膜。
所述有机-无机复合纳米纤维膜的制备方法，包括下述步骤：将生物基尼龙56纳米纤维膜浸泡在镁盐水溶液中，并缓慢加入氨水，进行反应，反应结束后取出并烘干，得到有机-无机复合纳米纤维膜。
上述复合处理方法中，所述镁盐选自下述至少一种：硫酸镁、硝酸镁和氯化镁；所述镁盐水溶液中镁盐的质量浓度为1％～10％，具体可为2.5％；所述氨水即工业氨水，质量浓度为25-28％；所述氨水与镁盐溶液的体积比为1:10-1:50，优选为1:10-1:25，具体可为3:40；
上述复合处理方法中，所述反应在20-60℃下反应1-9小时，具体的，所述反应的条件为：25℃反应1h。
上述复合处理方法中，所述烘干的温度为50-100℃。
本发明所制备的生物基尼龙56纳米纤维膜、有机-无机复合纳米纤维膜均为多层次纳米结构；本发明制备的生物基尼龙56纳米纤维膜的纤维直径为60-150nm，其中直径为70-110nm的纤维大于80％；其厚度为5-30μm，纳米纤维模拉伸强度7-20MPa；有机-无机复合纳米纤维膜的纤维直径为80-350nm，其中直径为100-200nm的纤维大于80％；其厚度为10-50μm，纳米纤维模拉伸强度7-25MPa。
本发明还保护上述生物基尼龙56纳米纤维膜、有机-无机复合纳米纤维膜的应用。
所述生物基尼龙56纳米纤维膜及有机-无机纳米纤维复合膜可用于防护服装、防护用品、过滤材料、组织工程、药物传输、传感器、催化剂等诸多领域。
所述生物基尼龙56纳米纤维膜可用于吸附阻隔空气中细菌、病毒、颗粒物(悬浮在空气中的固态、液态或固态与液态的颗粒状物质，如粉尘、烟、雾、微生物)等，本发明制备的生物基尼龙56纳米纤维膜对细菌的过滤效率在95％以上，对颗粒物过滤效率达98％以上。
所述生物基尼龙56有机-无机复合纳米纤维膜均可用于吸附水中Cr(VI)。
或该有机-无机复合纳米纤维膜可用于制备水过滤器的分离器件。
本发明与已有技术相比，具有如下的优点：
1、本发明生物基尼龙56纳米纤维膜制备过程中，采用了生物基高聚物作为基体，更加的节能环保且可持续性好。
2、本发明制备得到的生物基尼龙56纳米纤维膜，纤维直径为60-150nm，其中直径为70-110nm的纤维大于80％；其厚度为5-30μm，纳米纤维模拉伸强度7-20MPa；有机-无机复合纳米膜的纤维直径为80-350nm，其中直径为100-200nm的纤维大于80％；其厚度为10-50μm，纳米纤维模拉伸强度7-25MPa。
3、本发明制备得到的生物基尼龙56纳米纤维膜有机-无机复合纳米膜具有优良的抗拉强度、穿刺强度、抗撕裂性、耐用性和高柔性。
4、使用本发明生物基尼龙56纳米纤维膜吸附阻隔空气中细菌、病毒、颗粒物(悬浮在空气中的固态、液态或固态与液态的颗粒状物质，如粉尘、烟、雾、微生物)及有机-无机复合纳米膜进行重金属处理时，具有吸附量高、耐用性好且可使用多次等优点。
附图说明
图1为本发明制备过程中质量浓度为19.74wt％的生物基尼龙56纳米纤维膜放大不同倍数的扫描电镜图，图1-1为放大10000倍的照片，图1-2为放大20000倍的照片，图1-3为图1-2同一位置放大50000倍的照片。
图2为有机-无机复合纳米膜放大1000倍的照片。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明并不局限于此，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
下述实施例中的定量试验，均设置三次重复实验，结果取平均值。
下述实施例中高聚物溶液的质量浓度的计算方法：取甲酸密度值ρ＝1.22g/cm3,根据公式wt％＝m1/(m1+m2)，其中m1为切片质量；m2为甲酸质量，m2＝ρv。
下述实施例中纤维膜过滤性能按照标准YY 0469-2011方法测试。
下述实施例中过滤效率：在规定检测条件下，过滤元件滤除颗粒物的百分数。
下述实施例中细菌过滤效率：在规定流量，口罩材料对含菌悬浮粒子滤除的百分数。
实施例1、制备生物基尼龙56纳米纤维膜
1)原料预处理：在25℃条件下分别将原料(1.5g、2.0g、2.5g、3.0g、3.5g)生物基尼龙56切片放入10mL甲酸中搅拌溶解8小时，得到生物基尼龙56高聚物溶液，编号为1、2、3、4、5；
2)静电纺丝处理：将步骤1)所得5个高聚物溶液放入静电纺丝机中，将其注入针管中进行静电纺丝，以铝箔为基底便于从纺丝机中取下，单个针管纺丝推进速度为0.3mL/h，在45℃电压为28kV下进行静电纺丝处理3小时，得到生物基尼龙56纳米纤维膜，编号为1#、2#、3#、4#、5#。使用扫描电镜观察生物基尼龙56纳米纤维膜的微观形态，如图1所示。随机选取120根样品，测试直径及厚度结果如下表1所示，纳米纤维膜机械性能测试如下表2所示。
表1纤维膜直径及厚度测试结果
Figure BDA0002561843030000041
“蛛网状”结构是聚酰胺系列高聚物特有的一种结构，可以通过在溶液中加入微量的PVA或者引入盐离子来增大材料极性，使得其纤维直径更细有利于蛛网结构的生成。“蛛网状”结构具有孔隙率该、比表面积大、吸附性能好和力学性能稳定等优点。
将纤维薄膜在扫描电镜下放大一定倍数，观察纤维薄膜状态：
1#样品放大10000倍，没有发现“蛛网状”粘连的结构；
2#样品放大10000倍，可以看出非常明显的“蛛网状”结构变得非常明显，且纤维直径较1#样品较为均匀，继续放大样品到20000倍和50000倍，发现此时“蛛网状”结构尚不完整；
3#样品放大10000倍，可以观察到非常明显的“蛛网状”黏连结构，但是表层大多是破损的蛛网结构，而里面是比较完整的结构，推测是由于实验操作过程造成样品完整性损坏。该组样品较2#样品平均直径有所增加且纤维直径分布更不均匀。但是单从表观上观察纤维分布差别不大。
4#样品放大10000倍，可以看出非常明显的“蛛网状”黏连结构，继续放大20000倍、50000倍，可以清晰的看到一个非常完好的“蛛网状”结构，但是与3#样品对比4#样品平均直径有所增加且纤维直径分布非常不均匀。
5#样品放大10000倍，可以看出非常明显的“蛛网状”黏连结构，继续放大20000倍、50000倍，发现该样品与4#样品对比纤维直径分布明显不均匀。
表2生物基尼龙56纳米纤维膜机械性能测试结果
样品 弹性模量/MPa 断裂伸长率/％ 拉伸断裂应力/MPa 拉伸强度/MPa 最大力/N
1# 192.41 14.37 13.33 13.49 0.66
2# 142.43 19.59 15.02 15 0.83
3# 132.73 13.33 9.6 9.63 0.6
4# 103.87 12.15 6.45 7.2 0.48
5# 74.56 27.11 3.59 3.61 0.48
由表2可以看出，纳米纤维膜拉力性能呈现先增后减的结果。结合表1实验结果可以看出纤维直径越是均匀，分布越为集中的纤维膜在力学性能上表现得越好。
对上述1#-5#生物基尼龙56纳米纤维膜样品进行过滤性能测试，测试结果如下表2所示。生物基尼龙56纳米纤维膜对细菌的过滤效率在98％以上，对颗粒物过滤效率达90％以上。
表3生物基尼龙56纳米纤维膜过滤性能测试
样品 细菌过滤效率/％ 过滤效率/％
1# 98.3 99.1
2# 98.4 99.4
3# 98.4 99.5
4# 98.5 99.6
5# 98.6 99.8
实施例2、制备有机-无机复合纳米纤维膜
1)原料预处理：在25℃条件下将原料3.0g生物基尼龙56切片放入10mL甲酸中搅拌溶解8小时，得到高聚物溶液；
2)静电纺丝处理：将1)步骤所得溶液放入静电纺丝机中，将其注入针管中进行静电纺丝，以铝箔为基底便于从纺丝机中取下，单个针管纺丝推进速度为0.3mL/h，在，45℃电压为28kV下进行静电纺丝处理3小时，得到生物基尼龙56纳米纤维膜。
3)复合处理：剪取6×6cm的步骤2)得到的纳米纤维膜，在镁盐水溶液(1gMgSO4溶解于40mL去离子水)中，浸泡30min后，再缓慢滴加3mL氨水，25℃反应1h后，在60℃下烘干，得到有机-无机复合纳米纤维膜。有机-无机复合纳米纤维膜的性能检测：
1)纤维膜结构观测：使用扫描电镜观察有机-无机复合纳米纤维膜的微观形态，如图2所示。照片结构显示，在本发明处理过程中纤维结构保持完整，且纤维直径分布均匀，测纤维膜直径及厚度结果如下表4所示，可得纤维平均直径约为160nm左右，为其反应性提供了保证。
表4纤维膜直径及厚度测试结果
Figure BDA0002561843030000061
2)拉力测定：取一块上述方法得到的纳米纤维膜剪成8mm×30mm的样条放入拉力测试机中进行拉力测试，执行标准GB 13022-91。其断裂强度大于15MPa。
表5纳米纤维膜拉力测试结果
项目 弹性模量/MPa 断裂伸长率/％ 拉伸断裂应力/MPa 拉伸强度/MPa 最大力/N
样品 142.43 19.59 15.02 15 0.83
3)反应性测定：将一块通过上述步骤得到的纳米纤维膜放入配制好的K2Cr2O7的溶液中以验证其对Cr(VI)的去除效果，其中pH＝2时其去除效果最佳，吸附量可达114mg/g。

Claims (10)

1.一种生物基尼龙56纳米纤维膜的制备方法，包括下述步骤：
1)原料预处理：将原料生物基尼龙56切片放入羧基酸中进行搅拌溶解，得到高聚物溶液；
2)静电纺丝处理：将步骤1)所得溶液进行静电纺丝处理，得到所述生物基尼龙56纳米纤维膜。
2.根据权利要求1所述方法，其特征在于：所述步骤1)中，所述羧基酸为甲酸、乙酸、丙酸中的一种或混合使用；
所述溶解的温度为10-40℃，溶解的时间为3-24小时；
所述高聚物溶液中原料的质量含量为5-25wt％；
所述步骤2)中，所述静电纺丝在静电纺丝机中进行；所述静电纺丝的条件为：温度为30-80℃，电压为15-30kV，静电纺丝处理时间为3-12小时。
3.权利要求1或2所述方法制备得到的生物基尼龙56纳米纤维膜。
4.根据权利要求3所述的生物基尼龙56纳米纤维膜，其特征在于：所述纳米纤维膜为多层纳米结构；其纤维直径为60-150nm，其中直径为70-110nm的纤维大于80％；其厚度为5-30μm，纳米纤维模拉伸强度7-20MPa。
5.一种以权利要求3或4所述的生物基尼龙56纳米纤维膜为基础制备有机-无机复合纳米纤维膜的方法，包括下述步骤：将所述生物基尼龙56纳米纤维膜浸泡在镁盐水溶液中，并加入氨水进行反应，反应结束后取出并烘干，得到所述有机-无机复合纳米纤维膜。
6.根据权利要求5所述方法，其特征在于：所述镁盐选自下述至少一种：硫酸镁、硝酸镁和氯化镁；所述镁盐水溶液中镁盐的质量浓度为1％～10％；所述氨水的质量浓度为25-28％；
所述氨水与镁盐溶液的体积比为1:10-1:50；
所述反应的条件为：在20-60℃下反应1-9小时；
所述烘干的温度为50-100℃。
7.权利要求5或6所述方法制备得到有机-无机复合纳米纤维膜。
8.根据权利要求7所述的有机-无机复合纳米纤维膜，其特征在于：所述有机-无机复合纳米纤维膜为多层纳米结构；其纤维直径为80-350nm，其中直径为100-200nm的纤维大于80％；其厚度为10-50μm，纳米纤维模拉伸强度7-25MPa。
9.权利要求3或4所述生物基尼龙56纳米纤维膜或权利要求7或8所述有机-无机复合纳米纤维在下述至少一个领域中的应用：防护服装、防护用品、过滤材料、组织工程、药物传输、传感器、催化剂。
10.权利要求7或8所述有机-无机复合纳米纤维膜在下述1)或2)中的应用：
1)吸附水中Cr(VI)中的应用；
2)在制备水过滤器的分离器件中的应用。
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