CN110256706A - 一种金属有机骨架材料高分子聚合物薄膜的合成方法 - Google Patents
一种金属有机骨架材料高分子聚合物薄膜的合成方法 Download PDFInfo
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Abstract
本发明公开了一种金属有机骨架材料高分子聚合物薄膜的合成方法，包括以下步骤：在高分子聚合物的溶液中依次加入金属盐溶液和有机配体溶液，混合均匀后刮涂在基底上，然后加热，自然冷却后剥离薄膜，浸泡，干燥，即得所述金属有机骨架材料高分子聚合物薄膜。与传统的制备方法相比，本发明本发明采用了简单的原位反应方法，通过刮涂方法即可得到负载不同金属有机骨架材料的聚合物薄膜材料，具有工艺简单、操作方便和适合批量生产等优点。
Description
技术领域
本发明涉及一种金属有机骨架材料高分子聚合物薄膜的合成方法，属于金属有机骨架材料制备技术领域。
背景技术
金属有机骨架材料(Metal-Organic Frameworks，简称MOFs)作为一种由金属或金属簇与有机配体得到的一类多孔性材料，有着较高的比表面积、规整的孔道和良好的结构可调性等优点。近些年在气体贮存/分离、催化、传感和污染物处理等方面展示出了非常好的应用前景。然而，作为一类多孔性的晶体材料，MOFs在使用过程中容易碎裂成更小的颗粒或者粉末。而这在实际应用中会是重大的问题，比如在催化、分离等工业过程中，这些因为MOFs晶体碎裂而产生的小颗粒或极细的粉尘，容易堵塞管道甚至引起爆炸等问题。这极大的限制MOFs材料的实际应用。探索新型的MOFs加工成型方法就显得尤为重要。
一般来说，工业上常见的方法是将MOFs粉体进行造粒。通常的造粒方法是直接在高压下将MOFs材料进行高压成型或者添加胶粘剂进行塑型。但是高压造粒法会在一定程度上影响MOFs自身的性质使得成型后器件的使用效率大打折扣。而添加胶粘剂进行塑型法中胶粘剂的加入，一定程度上会减少MOFs材料自身活性成分的比例，对最终器件中所能发挥的MOFs材料的性能造成一定的影响。
为了解决以上的问题，已报道的工作中进行了一系列的尝试。已知的主要加工成型方法主要可以分为两大类：在各类基底上原位生长MOFs和将MOFs与高分子进行复合加工成型。这两种方法主要通过：(1)诸如溶剂热，接种生长、电沉积等方法在各类基底(例如多孔二氧化钛和硅片等)上原位生长MOFs；(2)MOFs与各种类型的高分子结合，然后进行特殊后处理(如刮涂或者冷冻干燥等)。但是已报道的原位生长方法得到的MOFs膜通常存在着稳定性较差、易脆，而且常常需要较为耗能的生产制作过程等缺点。
另一种新型的方法将MOFs与各种类型的高分子复合能够同时结合MOFs材料和高分子材料的优良性质，在气体分离、离子导电和污染物滤除等许多方面都有着潜在的应用。然而，通过该方法得到的材料中MOFs与高分子的相容性、MOFs颗粒的分散均匀度等都是需要解决的问题
发明内容
发明目的：为了解决上述技术问题，本发明目的在于提供一种金属有机骨架材料高分子聚合物薄膜的合成方法，该方法采用原位烘干法，先刮涂聚合物和MOF前驱体溶液形成液体薄膜，再通过加热烘干同时实现MOFs的原位制备和快速大面积成膜。
技术方案：为达到上述发明目的，本发明采用如下技术方案：
一种金属有机骨架材料高分子聚合物薄膜的合成方法，包括以下步骤：
在高分子聚合物的溶液中依次加入金属盐溶液和有机配体溶液，混合均匀后刮涂在基底上，然后加热，自然冷却后剥离薄膜，浸泡，干燥，即得所述金属有机骨架材料高分子聚合物薄膜。
作为优选：
所述高分子聚合物选自可溶性的高聚物，优选PVC、PVDF、PMMA或PS。
所述金属盐选自Cu盐或Zr盐，，优选Cu(NO3)2·3H2O或ZrCl4。
所述有机配体选自均苯三甲酸、对苯二甲酸或2-氨基对苯二甲酸。
其中各原料的质量比为，高分子聚合物：金属盐和有机配体＝1:0.1-1:1。
所述高分子聚合物的溶液、金属盐溶液和有机配体溶液中的溶剂均选自DMF。
所述基底选自玻璃、铝箔或铜箔。
所述加热的条件为60-150℃保持25-35min，优选120℃保持30min。
所述浸泡是采用乙醇多次浸泡。
本发明将MOFs与高分子结合，通过调控高分子种类、配比、溶剂和反应温度等条件来进行大面积MOFs膜的原位合成。将对多种MOFs和高分子种类进行制备研究，结合工业上成熟的刮涂烘干成膜工艺，实现MOFs纳米晶体在高分子中的原位合成并能够得到纳米颗粒均匀分散的MOFs膜。通过原位合成能够增强MOFs纳米颗粒和高分子之间的相互作用，并且通过温度控制从而在膜中得到形貌规整且均匀分散的MOFs纳米颗粒，能够较好的解决普遍存在的MOFs纳米颗粒与高分子之间的分散性的问题。本发明方法与后合成方法相比，反应时间短，只需半小时左右即可成膜，性能优异。
技术效果：与传统的制备方法相比，本发明本发明采用了简单的原位反应方法，通过刮涂方法即可得到负载不同金属有机骨架材料的聚合物薄膜材料，具有工艺简单、操作方便和适合批量生产等优点。
附图说明
图1本发明所得HKUST-1@PVDF薄膜材料的PXRD及SEM图；
图2本发明所得HKUST-1@PVC薄膜材料的PXRD及SEM图；
图3本发明所得HKUST-1@PMMA薄膜材料的PXRD及SEM图；
图4本发明所得HKUST-1@PS薄膜材料的PXRD及SEM图；
图5本发明所得UiO-66@PVC薄膜材料的PXRD及SEM图；
图6本发明所得NH2-UiO-66@PVC薄膜材料的PXRD及SEM图。
具体实施方式
以下通过具体实施例进一步说明本发明。
实施例1：
室温下，在一个烧杯中依次加入1.4g PVDF粉末，10mL DMF溶液、0.1mmol/mL三水硝酸铜的DMF溶液2ml、0.025mmol/mL均苯三甲酸的DMF溶液8ml，将混合溶液在室温下搅拌均匀，然后刮涂在玻璃基板上之后转移至烘箱中，在120℃保持30min，待其自然冷却至室温后剥下用乙醇浸泡多次，再在60℃真空烘干后得到薄膜HKUST-1@PVDF。
用X-Ray粉末衍射(PXRD)分析所得HKUST-1@PVDF薄膜材料的结构(图1)；用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)分析所得薄膜HKUST-1@PVDF材料的尺寸、形貌和微结构，利用SEM通过计算得出HKUST-1直径约64nm。
实施例2：
本实例中的制备过程和步骤与上述实施例1基本相同，不同的是：本实例所用的聚合物是PVC，表征见图2。
实施例3：
本实例中的制备过程和步骤与上述实施例1基本相同，不同的是：本实例所用的聚合物是PMMA，表征见图3。
实施例4：
本实例中的制备过程和步骤与上述实施例1基本相同，不同的是：本实例所用的聚合物是PS，表征见图4。
实施例5：
本实例中的制备过程和步骤与上述实施例1基本相同，不同的是：本实例所用的金属盐溶液是0.12mmol/mL ZrCl4的DMF溶液、配体溶液是0.03mmol/mL对苯二甲酸的DMF溶液、聚合物是PVC，表征见图5。
实施例6：
本实例中的制备过程和步骤与上述实施例5基本相同，不同的是：本实例所用的配体是0.03mmol/mL 2-氨基对苯二甲酸的DMF溶液，表征见图6。
Claims (9)
1.一种金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，包括以下步骤：
在高分子聚合物的溶液中依次加入金属盐溶液和有机配体溶液，混合均匀后刮涂在基底上，然后加热，自然冷却后剥离薄膜，浸泡，干燥，即得所述金属有机骨架材料高分子聚合物薄膜。
2.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述高分子聚合物选自可溶性的高聚物，优选PVC、PVDF、PMMA或PS。
3.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述金属盐选自Cu盐或Zr盐，，优选Cu(NO3)2·3H2O或ZrCl4。
4.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述有机配体选自均苯三甲酸、对苯二甲酸或2-氨基对苯二甲酸。
5.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，其中各原料的质量比为，高分子聚合物：金属盐+有机配体＝1:0.1-1:1。
6.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述高分子聚合物的溶液、金属盐溶液和有机配体溶液中的溶剂均选自DMF。
7.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述基底选自玻璃、铝箔或铜箔。
8.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述加热的条件为60-150℃保持25-35min。
9.根据权利要求1所述的金属有机骨架材料高分子聚合物薄膜的合成方法，其特征在于，所述浸泡是采用乙醇多次浸泡。
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