CN117306257A - 一种超亲油疏水纳米纤维膜的制备方法及其应用 - Google Patents
一种超亲油疏水纳米纤维膜的制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及一种超亲油疏水纳米分离膜及其制备方法,制备所述纳米纤维膜的纺丝液中添加了氯化锂,提高了纺丝液的导电性,在射流模式下,将其静电纺丝在聚丙烯防粘无纺布上,所得纤维束的粒径较小,能够精确控制膜层间的堆积结构,提高了所述纳米分离膜的孔隙率;通过单体在PVDF纳米膜纤维上发生原位聚合,加强了纤维间的粘结,提高了膜孔道的连通性及稳定性,所得纳米分离膜的渗油通量具有较大的提升。
Description
技术领域
本发明属于功能性纳米膜制备领域,尤其涉及一种超亲油疏水纳米纤维膜的制备方法及其应用。
背景技术
频繁的石油泄漏事故、不断增加的工业含油废水以及大量排放的生活含油污水使水资源污染问题变得日益严重。泄露事故后,漂浮海面上的石油容易扩散形成一层不透气的油膜,阻碍水体的复氧作用,使海洋水体缺氧,影响海洋浮游生物生长,破坏海洋生态平衡。油是水资源系统中较为普遍的一种污染物,同时,水也是油液系统中的一种污染物。油中含水会使油液容易变质,而燃料油含水则会大大缩短内燃机车、船舶等动力装置的使用寿命并降低其安全性能。如何高效地对含油废水和含水废油进行油水分离,获得可重新利用的纯水和高纯度油品是我国乃至世界范围的科学难题之一。
实现油水混合物的高效快速分离,对于保护水环境、节约能源具有重要的意义。含油污水中油水乳化液是最难分离的一类,如何有效处理油水乳化液成为目前亟待解决的问题之一。常规的分离方法能耗较大或不能有效地将其处理以达到环保排放要求,故在应用时受到限制。膜破乳技术相对于传统的破乳技术具有分离效率较高、不需要添加化学试剂、无相变、经济性较高等优点使其具有良好的前景,但也存在膜污染严重和膜制备成本偏高等问题。同时,由于目前微滤技术制备工艺、应用通过量、膜操作的复杂性,使用成本方面均无法满足工业化应用的需求,开发一种高效、高通量、低能耗、低成本的油水乳液分离膜具有重要社会和经济意义。
静电纺丝聚偏氟乙烯(PVDF)纳米纤维多孔膜因其具有孔隙率高、结构可调性好等优点,在解决环境问题和水质过滤方面有着广泛的应用。虽然在理论上静电纺丝法制得的纤维纳米膜具有孔径小、孔道连通性好等优点,然而在实际操作中却往往难以控制,网状结构是随机分布的,分布很不均匀,也不连续,且网状的覆盖性比较差,很难实现油水高效分离、空气过滤、防尘防霾等的需求,因此如何开发一种连续性、孔结构稳定、连通性好、油水分离效率高的聚偏氟乙烯纳米膜已成为聚偏氟乙烯膜的研究热点。
发明内容
为了解决现有技术中的问题,本发明提供了一种超亲油疏水纳米纤维膜的制备方法和应用。
本发明提供的一种超亲油疏水纳米纤维膜的制备方法,包含如下步骤:
S1:将聚偏氟乙烯、氯化锂溶于N,N-二甲基甲酰胺中,加热搅拌1-2 h,获得纺丝溶液,通过静电纺丝制备成PVDF纳米纤维膜,纤维直径不超过100nm;
S2:将苯并恶嗪衍生物溶于有机溶剂中,用于浸泡S1中所得PVDF纳米纤维膜,浸泡10-15min后,将其放入常温真空条件下静置0.5-1h至溶剂完全挥发;
S3:将S2中吸附有苯并恶嗪及其衍生物的PVDF纳米纤维膜置于干燥箱中1-2h进行原位聚合反应后,将膜取出冷却至室温,放入去离子水中洗涤,然后于40-50℃烘箱中干燥,即得所述超亲油疏水纳米纤维膜。
在本发明的一些实施方式中,所述S1中,纺丝溶液中PVDF的浓度为20-22wt%,氯化锂的浓度为0.02 -0.1wt%。
由于静电纺丝纳米纤维形成的原理在于:通过高压静电把带电荷的高分子混合液体在电场力作用下拉伸、劈裂,溶剂经挥发干燥,最后使聚合物在接收基质上形成纤维,因此,纺丝液的导电性对于最终所得纳米纤维的粒径及其排列具有重要影响。在本发明中,发明人通过在PVDF纺丝液中添加少量氯化锂,有效提高了纺丝液的导电率,纳米纤维的直径更细、孔径更小。但氯化锂的添加量需适量,过少则无明显改善,过多则影响纺丝效果,射流丝束的稳定性变差。
在本发明的一些实施方式中,S1中的静电纺丝的操作条件为:纺丝电压25-30kV,灌注速度为2.0-2.5ml/h,纺丝尖端距离接收基材20-22cm,接收基材的滚动转速为50-60rpm,纺丝环境温度为21-25℃,环境湿度为50±3%RH。
在本发明的一些实施方式中,所述接收基材为聚丙烯无纺布、聚酯纤维无纺布和粘胶纤维无纺布中的至少一种,纺丝喷覆时间为9-10h。
在本发明的一些实施方式中,S2中所述苯并恶嗪衍生物的结构如式I,其中,R1为C1-3的烷基或取代有含氟甲基的苯基, R2为氢原子或C1-3的烷基。
虽然经过所述步骤S1所得PVDF纳米纤维膜的孔隙率较高,但其孔道之间的连通性不佳。发明人经过几次过滤实验后,所得PVDF纳米纤维膜的油过滤性能大大降低,这可能是由于油分滞留于孔道,无法顺利排出。因此,发明人在纺丝所得PVDF纳米纤维膜上经过浸润的方式在其中负载苯并恶嗪衍生物,苯并恶嗪衍生物在氯化锂的催化作用及加热条件下,在纤维内部发生了开环自聚合,其聚合反应过程如式II所示,所得聚合物在孔隙间形成网络,可引导油分通过,提高了孔隙间的连通性,最终制得了油通量较大的超亲油疏水纳米纤维膜。在试验过程中,发明人发现,苯并恶嗪衍生物上携带的基团影响到其在纤维上的附着率。由于PVDF表面具有大量的氟原子,表面张力极大,若苯并恶嗪衍生物所带基团的空间位阻较大,则无法与PVDF纳米纤维发生良好的共混附着,从而影响到后续苯并恶嗪衍生物在纤维内部的聚合。另外,其用量也不宜过多,否则会影响所述纤维膜的孔隙率及其稳定性。
在本发明的一些实施方式中,S2中所述有机溶剂为苯、甲苯、乙醇、乙醚、丙酮中的至少一种。
在本发明的一些实施方式中,所述苯并恶嗪衍生物在所述有机溶剂中的浓度为0.5-1.0wt%。
在本发明的一些实施方式中,S3中干燥箱的升温速率为5-10℃/min,并保持在200-220℃。
一种按照所述超亲油疏水纳米纤维膜的制备方法制备所得PVDF纳米纤维膜,该纳米纤维膜与油组分的接触角为0-5°,与油下水组分的接触角为162-170°,并将其应用于油水分离领域。
有益效果:与现有技术相比,本发明所提供的超亲油疏水纳米纤维膜具有以下优点:
1、在纺丝液中添加氯化锂,一方面提高了PVDF溶液的导电性,使得纤维直径更细、孔径更小,另一方面,可作为催化剂催化后续苯并恶嗪衍生物的自聚合;
2、使PVDF纳米纤维膜内部附着有苯并恶嗪衍生物,通过加热使其原位聚合,所得聚合物中具有的苯醚结构提高了纳米纤维膜内部孔道间的连通性,聚合物形成的交联网络结构提供了可靠的稳定性及膜孔道的油通量,使得所述纳米纤维膜具有优秀的油水分离效率;同时,制备方法简单,其原位聚合过程无有害小分子产生,对工作环境无不良影响。
具体实施方式
下面结合实例对本发明作进一步详细描述。需要说明的是,下面的实施例及对比例为本发明的示例,仅用来说明本发明,而不用来限制本发明。在不偏离本发明主旨或范围的情况下,可进行本发明构思内的其他组合和各种改良。
实施例1
S1:将聚偏氟乙烯20g、氯化锂0.02g溶于100g N,N-二甲基甲酰胺中,加热搅拌1h,获得纺丝溶液,在纺丝电压25kV,灌注速度为2.0ml/h,纺丝尖端距离接收基材聚丙烯防粘无纺布20cm,接收基材的滚动转速为50rpm,纺丝环境温度为21℃,环境湿度为50±3%RH的条件下静电纺丝9h制备成PVDF纳米纤维膜,纤维直径为98nm;
S2:将0.5g具有式I-1结构的苯并恶嗪衍生物溶于100g甲苯中,用于浸泡S1中所得PVDF纳米纤维膜,浸泡10min后,将其放入常温真空条件下静置0.5h至溶剂完全挥发;
;
S3:将S2中吸附有苯并恶嗪衍生物的PVDF纳米纤维膜置于干燥箱中,于5℃/min的升温速度下升温至200℃,并保持1h进行原位聚合反应后,将膜取出冷却至室温,放入去离子水中再取出,然后于40℃烘箱中干燥,即得所述超亲油超疏水纳米纤维膜。
实施例2
S1:将聚偏氟乙烯21g、氯化锂0.05g溶于100g N,N-二甲基甲酰胺中,加热搅拌1.5h,获得纺丝溶液,在纺丝电压25kV,灌注速度为2.0ml/h,纺丝尖端距离接收基材聚丙烯防粘无纺布20cm,接收基材的滚动转速为50rpm,纺丝环境温度为21℃,环境湿度为50±3%RH的条件下静电纺丝9h制备成PVDF纳米纤维膜,纤维直径为95nm;
S2:将0.5g具有式I-2结构的苯并恶嗪衍生物溶于100g甲苯中,用于浸泡S1中所得PVDF纳米纤维膜,浸泡10min后,将其放入常温真空条件下静置0.5h至溶剂完全挥发;
;
S3:将S2中吸附有苯并恶嗪衍生物的PVDF纳米纤维膜置于干燥箱中,于5℃/min的升温速度下升温至210℃,并保持1.5h进行原位聚合反应后,将膜取出冷却至室温,放入去离子水中再取出,然后于40℃烘箱中干燥,即得所述超亲油超疏水纳米纤维膜。
实施例3
S1:将聚偏氟乙烯22g、氯化锂0.1g溶于100g N,N-二甲基甲酰胺中,加热搅拌2h,获得纺丝溶液,在纺丝电压30kV,灌注速度为2.5ml/h,纺丝尖端距离接收基材聚丙烯防粘无纺布22cm,接收基材的滚动转速为60rpm,纺丝环境温度为25℃,环境湿度为50±3%RH的条件下静电纺丝10h制备成PVDF纳米纤维膜,纤维直径为88nm;
S2:将0.8g具有式I-3结构的苯并恶嗪衍生物溶于100g甲苯中,用于浸泡S1中所得PVDF纳米纤维膜,浸泡15min后,将其放入常温真空条件下静置1h至溶剂完全挥发;
;
S3:将S2中吸附有苯并恶嗪衍生物的PVDF纳米纤维膜置于干燥箱中,于5℃/min的升温速度下升温至210℃,并保持1.5h进行原位聚合反应后,将膜取出冷却至室温,放入去离子水中再取出,然后于50℃烘箱中干燥,即得所述超亲油超疏水纳米纤维膜。
实施例4
S1:将聚偏氟乙烯22g、氯化锂0.1g溶于100g N,N-二甲基甲酰胺中,加热搅拌2h,获得纺丝溶液,在纺丝电压30kV,灌注速度为2.5ml/h,纺丝尖端距离接收基材聚丙烯防粘无纺布22cm,接收基材的滚动转速为60rpm,纺丝环境温度为25℃,环境湿度为50±3%RH的条件下静电纺丝10h制备成PVDF纳米纤维膜,纤维直径为89nm;
S2:将1.0g具有式I-4结构的苯并恶嗪衍生物溶于100g甲苯中,用于浸泡S1中所得PVDF纳米纤维膜,浸泡15min后,将其放入常温真空条件下静置1h至溶剂完全挥发;
;
S3:将S2中吸附有苯并恶嗪衍生物的PVDF纳米纤维膜置于干燥箱中,于5℃/min的升温速度下升温至220℃,并保持1.5h进行原位聚合反应后,将膜取出冷却至室温,放入去离子水中再取出,然后于50℃烘箱中干燥,即得所述超亲油超疏水纳米纤维膜。
实施例5
操作过程同实施例4,不同之处在于,所用苯并恶嗪衍生物的结构如式I-5所示:
。
实施例6
操作过程同实施例4,不同之处在于,所用苯并恶嗪衍生物的结构如式I-6示:
。
实施例7
操作过程同实施例4,不同之处在于,所用苯并恶嗪衍生物的用量为1.2wt%。
对比例1
操作过程同实施例4,不同之处在于,不添加苯并恶嗪衍生物。
对上述实施例1-7及对比例1中所得超亲油超疏水纳米纤维膜进行以下性能测试:
接触角:在所述超亲油超疏水纳米纤维膜表面滴0.2ml的去离子水和煤油,采用JY-82接触角测试仪测定液滴与膜表面之间的夹角;
分离效率及油通量:参考标准ISO16332:2018依次对葵花油油水乳液、煤油油水乳液、环己烷油水乳液、正十六烷油水乳液进行分离,将所测分离效率剂油通量取平均值即得测试结果。
结果如表1所示:
由上表数据可知,本发明提供的制备方法所得超亲油疏水纳米纤维膜,具有优异的亲油疏水性,与水的接触角不低于163°,与油的接触角不高于5;对不同的油水乳液体系有着较好的分离效率,均在97%及以上,油通量也保持在780L/m2·h以上。不过,其中添加的苯并恶嗪衍生物的用量及其所带基团的大小对所述超亲油疏水纳米纤维膜的性能具有较大的影响,这是由于基团的空间位阻,致使其无法在纤维内部的孔隙间形成理想的网络结构,从而导致最终的分离效率及油通量有所下降。
综上可知,本发明提供的一种超亲油疏水纳米纤维膜在工业中分离油包水乳液体系的领域具有广阔的应用前景。
Claims (10)
1.一种超亲油疏水纳米纤维膜的制备方法,其特征在于,包括如下步骤:
S1:将聚偏氟乙烯、氯化锂溶于N,N-二甲基甲酰胺中,加热搅拌1-2 h,获得纺丝溶液,通过静电纺丝制备成PVDF纳米纤维膜,纤维直径不超过100nm;
S2:将苯并恶嗪衍生物溶于有机溶剂中,用于浸泡S1中所得PVDF纳米纤维膜,浸泡10-15min后,将其放入常温真空条件下静置0.5-1h至溶剂完全挥发;
S3:将S2中吸附有苯并恶嗪衍生物的PVDF纳米纤维膜置于干燥箱中1-2h进行原位聚合反应后,将膜取出冷却至室温,放入去离子水中洗涤,然后于40-50℃烘箱中干燥,即得所述超亲油疏水纳米纤维膜。
2.根据权利要求1所述超亲油疏水纳米纤维膜的制备方法,其特征在于,所述S1中,纺丝溶液中PVDF的浓度为20-22wt%,氯化锂的浓度为0.02 -0.1wt%。
3.根据权利要求1所述超亲油疏水纳米纤维膜的制备方法,其特征在于,S1中的静电纺丝的操作条件为:纺丝电压25-30kV,灌注速度为2.0-2.5ml/h,纺丝尖端距离接收基材20-22cm,接收基材的滚动转速为50-60rpm,纺丝环境温度为21-25℃,环境湿度为50±3%RH。
4.根据权利要求3所述超亲油疏水纳米纤维膜的制备方法,其特征在于,所述接收基材为聚丙烯无纺布、聚酯纤维无纺布和粘胶纤维无纺布中的至少一种,纺丝喷覆时间为9-10h。
5.根据权利要求1所述超亲油疏水纳米纤维膜的制备方法,其特征在于,S2中所述苯并恶嗪衍生物的结构如式I,其中,R1为C1-3的烷基或取代有含氟甲基的苯基,R2为氢原子或C1-3的烷基。
6.根据权利要求1所述超亲油疏水纳米纤维膜的制备方法,其特征在于,S2中所述有机溶剂为苯、甲苯、乙醇、乙醚、丙酮中的至少一种。
7.根据权利要求1或5所述超亲油疏水纳米纤维膜的制备方法,其特征在于,所述苯并恶嗪衍生物在所述有机溶剂中的浓度为0.5-1.0wt%。
8.根据权利要求1所述超亲油疏水纳米纤维膜的制备方法,其特征在于,S3中干燥箱的升温速率为5-10℃/min,并保持在200-220℃。
9.权利要求1-8任一项所述制备方法制备所得的超亲油疏水纳米纤维膜,其特征在于,该纳米纤维膜与油组分的接触角为0-5°,与油下水组分的接触角为162-170°。
10.权利要求9所述超亲油疏水纳米纤维膜的应用,其特征在于,应用于油水分离领域。
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