CN110511376B - 一种多孔聚合物及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种多孔聚合物及其制备方法与应用。该多孔聚合物包括如下通式
。上述多孔聚合物是四氨基苯与对氰基苯甲醛进行缩合反应，生成具有苯并咪唑结构的氰基化合物，然后与ZnCl2混合，在惰性气氛中于300‑600℃进行聚合，反应结束后得到多孔共价有机框架（COF）聚合物材料。所述的多孔聚合物可通过负载BiOBr获得更多的应用。本发明的多孔共价有机框架（COF）聚合物及其催化剂，具有很好的气体甲醛吸附性和去除效果，且室温下可循环利用，回收操作简便。
Description
技术领域
本发明涉及甲醛吸附剂制备技术领域，具体涉及一种多孔聚合物及其制备方法与应用，属于共价有机骨架材料技术领域。
背景技术
室内空气质量对人的身体健康有至关重要的影响。甲醛是最普遍存在的室内空气污染物，对人体健康有不良影响。根据国际癌症研究机构(IARC)报道，甲醛被归类为致癌物质，属于危险物质组。室内甲醛的主要来源是建筑/装修材料、地板、油漆和家具等。在过去的几十年中，人们致力于避免在建筑材料和家用电器中使用甲醛衍生的热固性塑料，但是室内甲醛含量超标仍然相当严重。因此，解决室内气体甲醛污染成为人们普遍关注的焦点，越来越多的方法用于去除室内气体甲醛。
在可用的甲醛去除方法中，吸附法简单、高效、经济，是目前最适合的甲醛去除方法。早期研究比较多的甲醛吸附材料为活性炭等物理吸附材料。然而，甲醛的沸点较低(-20℃)且分子具有较强的极性，所以在室温下气态甲醛在表面为非极性或者弱极性活性炭等材料上的吸附一般较弱。因此，在空气低甲醛浓度条件下，单靠物理吸附去除甲醛是很困难的。为了提高材料的甲醛去除效果，一类胺基改性吸附材料引起关注。该类吸附材料在孔道表面负载含有胺基的分子，依靠胺基与甲醛的化学反应来增强对甲醛的吸附效果，避免物理吸附的甲醛脱附问题。活性炭、多孔硅、树脂等具有发达孔结构的材料被负载胺基，用于甲醛去除，表现出良好的甲醛去除效果。然而，一般此类材料采用后浸渍或者化学接枝的方法制备，材料制备过程复杂、成本较高，吸附性能不稳定。
发明内容
针对现有技术的不足，本发明提供了一种多孔聚合物及其制备方法与应用，该制备方法简单，成本低廉，且催化性能稳定。
一种多孔聚合物，具有如下结构通式
上述多孔聚合物的制备方法，包括以下步骤：
步骤1，将1,2,4,5-四氨基苯和4-氰基苯甲醛按摩尔比为1:2混合，溶于有机溶剂中，加入催化剂，调节反应液的pH至4-6，在50-120℃下下搅拌反应30-300分钟，反应完全后冷却至室温，倒入去离子水中沉淀、过滤，去离子水洗涤,在80℃下真空干燥24h，得到具有苯并咪唑结构的化合物；
步骤2，将具有苯并咪唑结构的化合物与催化剂ZnCl2混合装入石英管中，抽空密封，放入高温炉中加热至300-600℃，并保持高温30-50小时后，自然冷却至室温，用去离子水洗涤，真空干燥后得多孔聚合物。
作为改进的是，步骤1中溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺或二甲基亚砜。
作为改进的是，步骤1中的催化剂为亚硫酸氢钠NaHSO3、连二亚硫酸钠Na2S2O4或焦亚硫酸钠Na2S2O5中的一种。
作为改进的是，步骤2中的苯并咪唑化合物与ZnCl2的摩尔比为1:2-10。
上述多孔聚合物在甲醛去除上的应用。
上述应用，制备甲醛催化剂，所述甲醛催化剂为在多孔聚合物上负载BiOBr。
作为改进的是，所述甲醛催化剂中BiOBr的负载量为多孔聚合物质量的5％～20％。
上述甲醛催化剂的制备方法，包括以下步骤：将多孔聚合物分散于乙二醇溶液中搅拌10min，加入Bi(NO3)3·5H2O和KBr，继续搅拌30min，加热至120-180℃保持10h，过滤得沉淀，并将沉淀水洗后，60℃下真空干燥24h，即得甲醛催化剂。
作为改进的是，多孔聚合物的质量浓度1-10％，Bi(NO3)3·5H2O与KBr摩尔比为1:1。
有益效果：
与现有技术相比，本发明多孔聚合物及其制备方法与应用，具有如下优势：
1、本发明提供了一种在室温下高效去除空气中低浓度甲醛的多孔聚合物材料，通过高温缩聚的方法，将有机胺引入多孔聚合物材料孔道表面；
2、本发明材料的制备过程简单，无废液废渣产生，成本低；成品结构可控，后处理简单，可做成粉末状、颗粒状、块状，或者板状，也可负载于其他载体上做成整体器件；材料具有规则的微孔结构，孔结构可控，有利于气体扩散；胺含量稳定，甲醛去除效果优良，在室温下即可有效去除空气中低浓度的气体甲醛；
3、本发明提供的甲醛催化剂适用于去除人造板生产车间、居室、建材家具市场等封闭、半封闭空间的低浓度(空气中的甲醛含量≤1mg/m3)甲醛污染物。
附图说明
图1为实施例1制备的多孔聚合物的表面形貌，(a)为SEM图，(b)为TEM图；
图2为实施例2所得的多孔聚合物的N2吸附-脱附曲线；
图3为实施例3所得的多孔二氧化碳捕集剂的孔径分布曲线；
图4为实施例3所得的多孔聚合物在不同温度下的CO2和N2气吸附情况，其中，(a)为温度T＝273K，(b)为温度T＝298K；
图5为实施例4和实施例5所得的催化剂的甲醛去除效率曲线。
具体实施方式
下面结合附图和具体实施例对本发明作进一步描述。
一种多孔聚合物，具有如下结构通式
实施例1
上述多孔聚合物的制备方法，包括以下步骤：
步骤1，将1,2,4,5-四氨基苯(1.38g,10mmol),4-氰基苯甲醛(2.62g,20mmol),和亚硫酸氢钠(1.05g,10mmol)溶于N,N-二甲基甲酰胺(150mL)中，调节反应液的pH＝4，反应温度为50℃，搅拌反应30min，然后冷却至室温，加入300mL去离子水，沉淀、过滤，用去离子水洗涤,在80℃下真空干燥24h,得到含有苯并咪唑结构的氰基化合物。
步骤2，将含有苯并咪唑结构的氰基化合物与催化剂ZnCl2按摩尔比1:2装入石英管中，抽空密封，放入高温炉中加热300℃，反应30小时后，慢慢冷却至室温，用去离子水洗涤，真空干燥24小时，得到一种多孔聚合物。
实施例1产物的检测结果：比表面积达到1900m2/g，孔体积达到1.16cm3/g，最可几孔径为3.0nm，孔多分布于微孔和介孔之间。
实施例2
一种多孔聚合物的制备方法，包括以下步骤：
步骤1，将1,2,4,5-四氨基苯(0.138g,1mmol),4-氰基苯甲醛(1.31g,10mmol),和连二亚硫酸钠Na2S2O4(1mmol)溶于N,N-二甲基乙酰胺(150mL)中，调节反应液的pH＝6，反应温度为120℃，搅拌反应300分钟.然后冷却至室温，加入300mL去离子水,沉淀、过滤，用去离子水洗涤,在80℃下真空干燥24h,得到含有苯并咪唑结构的氰基化合物。
步骤2，将含有苯并咪唑结构的氰基化合物与催化剂ZnCl2按摩尔比1:10装入石英管中，抽空密封，放入高温炉中加热600℃，反应50小时后，慢慢冷却至室温，用去离子水洗涤，真空干燥24小时，得到一种多孔聚合物。
该实施例2产物检测结果：其比表面积达到2080m2/g，孔体积达到1.21cm3/g，最可几孔径为1.6nm，孔多分布于微孔和介孔之间。
实施例3
一种多孔聚合物的制备方法，包括以下步骤：
步骤1，将1，2，4，5-四氨基苯(0.138g，1mmol)，4-氰基苯甲醛(0.66g，5mmol)，和亚硫酸氢钠(0.105g，1mmol)溶于二甲基亚砜(150mL)中，调节反应液的pH＝5，反应温度为80℃，搅拌反应100分钟.然后冷却至室温，加入300mL去离子水，沉淀、过滤，用去离子水洗涤，在80℃下真空干燥24h，得到含有苯并咪唑结构的氰基化合物。
步骤2，将含有苯并咪唑结构的氰基化合物与催化剂ZnCl2按摩尔比1∶5装入石英管中，抽空密封，放入高温炉中加热400℃，反应40小时后，慢慢冷却至室温，用去离子水洗涤，真空干燥24小时，得到一种多孔聚合物。
该实施例3产物检测结果：其比表面积达到2107m2/g，孔体积达到1.31cm3/g，最可几孔径为2.1nm，孔多分布于微孔和介孔之间。
对于上述实施例1-3的多孔聚合物，置于甲醛初始浓度为1mg/m3的200L有机玻璃反应仓中，测试材料对低浓度甲醛的吸附效果。最后，在60℃真空保持24小时进行吸附材料回收，回收率为100％。
本发明各实施例所用材料的用量均为1.5g，测试结果如表1所示。
表1实施例和活性炭(商品)的甲醛去除效果
| 实例 | 2小时后甲醛浓度(mg/m<sup>3</sup>) |
| 实施例1 | 0.11 |
| 实施例2 | 0.06 |
| 实施例3 | 0.09 |
| 活性炭(商品) | 0.19 |
与商品活性炭(此商品活性炭为江苏瑞晨炭业科技有限公司JL-1.5型号)相比，实施例1～3均表现出较高的甲醛吸附率，吸附率最高达94％。由此可知，本发明制备的多孔聚合物对低浓度甲醛具有良好的吸附效果。
实施例4
一种甲醛催化剂，包括以下步骤：取实施例1制备的多孔聚合物1g分散于100mL乙二醇溶液中搅拌10min，加20mmol Bi(NO3)3·5H2O和20mmol KBr.继续搅拌30min，然后加热到120℃保持10h，将沉淀过滤、水洗，60℃真空干燥24h。
实施例5
一种甲醛催化剂，包括以下步骤：取实施例2制备的多孔聚合物10g分散于100mL乙二醇溶液中搅拌10min，加50mmol Bi(NO3)3·5H2O和50mmol KBr.继续搅拌30min，然后加热到180℃保持10h，将沉淀过滤、水洗，60℃真空干燥24h。
实施例6
一种甲醛催化剂，包括以下步骤：取实施例3制备的多孔聚合物5g分散于100mL乙二醇溶液中搅拌10min，加20mmol Bi(NO3)3·5H2O和20mmol KBr，继续搅拌30min，然后加热到150℃保持10h，将沉淀过滤、水洗，60℃真空干燥24h。
将实施例4-实施例6制备的催化剂在玻璃反应器中进行性能测试。将催化剂材料研碎，过80目和40目的筛，取50mg填充于直径5mm的玻璃管中，催化剂上下用适量的石英棉填充固定。在12W日光灯照射下(距离反应管25cm)，通入含1mg/m3甲醛的空气(模拟空气中的甲醛浓度)，体积空速为15000h-1。通过测量进出口的甲醛浓度，计算催化剂的甲醛去除率。
从图5可见，负载有BiOBr的实施例对甲醛有持续的去除效果，表现出较高的甲醛催化去除率(90％以上)。由此可知，本发明BiOBr负载型催化剂在可见光照射条件下对低浓度甲醛具有良好的催化去除效果。
Claims (3)
1.一种多孔聚合物在甲醛去除上的应用，其特征在于，制备甲醛催化剂，所述甲醛催化剂为在多孔聚合物上负载BiOBr，其中，多孔聚合物的结构通式如下所示：
2.根据权利要求1所述的多孔聚合物在甲醛去除上的应用，其特征在于，步骤1中溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺或二甲基亚砜。
3.根据权利要求1所述的多孔聚合物在甲醛去除上的应用，其特征在于，步骤1中的催化剂为亚硫酸氢钠 NaHSO3、连二亚硫酸钠 Na2S2O4 或焦亚硫酸钠 Na2S2O5 中的一种。
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