CN109627437B - 三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用 - Google Patents

三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用 Download PDF

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CN109627437B
CN109627437B CN201811599920.4A CN201811599920A CN109627437B CN 109627437 B CN109627437 B CN 109627437B CN 201811599920 A CN201811599920 A CN 201811599920A CN 109627437 B CN109627437 B CN 109627437B
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triazine
arene
porous polymer
iodine
calix
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李亮
张志忠
李寒雪
安朵
张兴华
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Abstract

本发明公开了一种三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用。本发明利用均三嗪与4‑氨基杯芳烃上沿的氨基聚合形成C‑N键，从而构筑得到一类三嗪基杯[4]芳烃多孔聚合物。本发明利用富含氮原子的均三嗪对4‑氨基杯芳烃的修饰后，不仅增加聚合物的氮量和材料的比表面积，而且还提高了聚合物的热稳定性。本发明的三嗪基杯[4]芳烃多孔聚合物对湿度和水稳定，并在水溶液中对碘表现出相当高的负载能力，最高可以达到240％。

Description

三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用
技术领域
本发明属于有机多孔聚合物制备技术领域，具体涉及一种三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用。
背景技术
随着时代的迅速发展，能量消耗巨大，核能迅速开发，乏燃料后处理的问题也越来越受到关注。在核电事故中，不仅含有大量的131I，而且长寿命的129I的相对含量也很高，特别值得关注的是129I(半衰期为1570万年)。尽管放射性核素131I寿命短(8.02天的半衰期)，但它具有高度的挥发性，并且在穿透细胞中引起突变和死亡。因此在后处理厂需对其进行净化去除。
目前，放射性碘的捕集方法主要有液体吸收法、固体吸附法。固体吸附法因其可靠性高、操作简单、经济性好的优势被广泛采用。吸附材料主要集中在固体材料的开发，如活性炭，疏水沸石等，疏水沸石大多是含金属的固体材料，如银沸石是吸附效果较好的一类，然而此类材料由于其有限的比表面积，对于碘的吸附量并没有达到令人满意的程度。
由于杯芳烃有较强的吸附能力和比较大的比表面积，因此，发展了一种以杯[4]芳烃为主体的多孔有机聚合物，通过共价键连接后，具有良好的化学稳定性和热稳定性，材料均由轻质元素组成，密度低，比表面积大。基于上述优点，材料在吸附和存储方面表现出极大的优势和潜能，最近，Trabolsi等人制备了富含锂的富含炔烃杯[4]芳烃的持久性有机污染物，其对I2的吸附能力较高，其值为312wt％。[1]然而，这些材料都局限于吸附碘蒸汽中的I2，而其在水相中的吸附行为报道很少，此材料由于结构稳定，可以用来吸附水中的碘。本发明即是围绕该用途展开研究，并取得较好的结果。
[1]Shetty D,Raya J,Han D S,et al.Lithiated Polycalix[4]arenes forEfficient Adsorption of Iodine from Solution and Vapor Phases[J].Chemistry ofMaterials,2017,29(21).
发明内容
本发明的目的是提供一类三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用。
为了实现以上目的，本发明采用以下技术方案。
本发明提供一种三嗪基杯[4]芳烃多孔聚合物，其结构式如下所示：
Figure BDA0001922217290000011
其中：n为0,1,2,3或4。
本发明还提供一种三嗪基杯[4]芳烃多孔聚合物的制备方法，具体步骤如下：
将均三嗪、4-氨基杯[4]芳烃和碳酸钾溶于二氧六环中后，加热回流反应60～80h；待反应结束，冷却至室温，离心、洗涤、真空干燥，得到基于三嗪基功能性的杯[4]芳烃多孔聚合物。
本发明中，均三嗪、4-氨基杯[4]芳烃和碳酸钾的摩尔比为(2～4):(1～2):(8～16)。
本发明中，二氧六环的用量为：每摩尔4-氨基杯[4]芳烃用40～60mL二氧六环。
本发明中，先用水洗除去碳酸钾，然后依次用四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、氯仿和乙醇洗涤，以除去未反应的原料和形成的寡聚物小分子。表明生成了不溶性和共价交联的多孔有机材料。
本发明进一步提供一种上述的三嗪基杯[4]芳烃多孔聚合物作为碘吸附剂在吸附水中碘方面的应用。优选的，在含碘的水中投加三嗪基杯[4]芳烃多孔聚合物，在室温下吸附。
利用本发明的三嗪基杯[4]芳烃多孔聚合物测试碘吸附性能的评价方法如下：
1、将材料和配制碘的高浓度溶液(2ml)放到一个10ml的小瓶子里面，在室温条件下，每隔两个小时，过滤，称重，计算出材料的吸附量。并且，能测出材料的最大吸附量。
2、将吸碘后的材料进行TGA测试，得到材料中碘脱附行为发生的温度，用于评价材料吸碘后的稳定性。
和现有技术相比，本发明具有如下优点：
1、本发明的三嗪基杯[4]芳烃多孔聚合物作为水中碘吸附材料的用途前所未有。
2、本发明的三嗪基杯[4]芳烃多孔聚合物对于碘吸附的效率更高，单位时间内吸附量更大。
3、本发明单位质量的材料在常温下可以吸附更多的碘，负载量可以达到240％。
附图说明
图1为本发明两种材料的扫描电子显微镜。
图2为本发明两种材料的固体核磁图谱的标峰。
图3为本发明材料吸附量随时间的变化。
图4为本发明CalPOP-1和CalPOP-1_I2的热重曲线。
图5为本发明CalPOP-2和CalPOP-2_I2的热重曲线。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，以使本领域的技术人员能够更好的理解本发明的优点和特征，从而对本发明的保护范围做出更为清楚的界定。本发明所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。以上仅仅是本发明的较佳实施方式，根据本发明的上述构思，本领域的熟练人员还可对此作出各种修改和变换。然而，类似的这种变换和修改均属于本发明的实质。
实施例中，两种材料(CalPOP-1和CalPOP-2)合成的化学反应方程式如下式所示：
Figure BDA0001922217290000031
两种材料的SEM图如图1所示，固体核磁图谱的标峰如图2所示。
吸附实验：向含碘的碘化钾溶液水溶液中投加碘吸附剂，在室温下吸附两小时，然后过滤出固体，滤膜为微孔滤膜Ф50mm 0.45μm(PTFE(聚四氟乙烯))，称重。如此循环，直到材料的最大吸附量；
实施例1.CalPOP-1碘吸附实验
将25mg的CalPOP-1(记为m)和碘的碘化钾溶液(由600mg KI，300mg I2溶解在2mLH2O中进行配制)同时加入到5mL的玻璃瓶内，随后密封瓶口，将玻璃瓶放置于室温，压力为常压，反应2h、4h、6h、8h、10h、24h后过滤，称量吸附后CalPOP-2的质量记为ma，按照公式ma-m计算吸附量为54mg、59.7mg、59.8mg、60mg、60mg、60mg(图3)。
实施例2.CalPOP-2碘吸附实验
将25mg的CalPOP-2(记为m)和碘的碘化钾溶液(由600mg KI，300mg I2溶解在2mLH2O中进行配制)同时加入到5mL的玻璃瓶内，随后密封瓶口，将玻璃瓶放置于室温，压力为常压，反应2h、4h、6h、8h、10h、24h后过滤，称量吸附后CalPOP-1的质量记为ma，按照公式ma-m计算吸附量为2.6mg、9.1mg、10mg、10.3mg、10.3mg、10.3mg(图3)。CalPOP-2与CalPOP-1相比，杯芳烃下缘的取代基从乙基到丁基，空间位置增加，发生聚合后，比表面积会减小，从而使得其对碘的吸附量也减少。
实施例3.CalPOP-1碘脱附实验
称取10mg吸碘后的CalPOP-1置于Al2O3坩埚，从28℃开始，炉内采用高纯氮作为保护气体，环境气体也为高纯氮。仪器温度控制为28℃，预热20min，使样品温度平衡至28℃,升温程序为，起始温度为28℃，以每分钟5℃的升温速度升至700℃。根据得到的TGA曲线可以得出，碘的脱附行为发生在90-290℃。图4为本发明CalPOP-1和CalPOP-1＿I2的热重曲线。
实施例4.CalPOP-2碘脱附实验
称取10mg吸碘后的CalPOP-2置于Al2O3坩埚，从28℃开始，炉内采用高纯氮作为保护气体，环境气体也为高纯氮。仪器温度控制为28℃，预热20min，使样品温度平衡至28℃,升温程序为，起始温度为28℃，以每分钟5℃的升温速度升至700℃。根据得到的TGA曲线可以得出，碘的脱附行为发生在90-290℃。图5为本发明CalPOP-2和CalPOP-2＿I2的热重曲线。

Claims (7)

1.一种三嗪基杯[4]芳烃多孔聚合物，其特征在于，其结构式如下所示：
Figure FDA0002946814540000011
其中：n为0,1,2,3或4。
2.一种根据权利要求1所述的三嗪基杯[4]芳烃多孔聚合物的制备方法，其特征在于，具体步骤如下：
将均三嗪、4-氨基杯[4]芳烃和碳酸钾溶于二氧六环中后，加热回流反应60～80h；待反应结束，冷却至室温，离心、洗涤、真空干燥，得到基于三嗪基功能性的杯[4]芳烃多孔聚合物；其中，4-氨基杯[4]芳烃的结构式如下所示：
Figure FDA0002946814540000012
3.根据权利要求2所述的制备方法，其特征在于，均三嗪、4-氨基杯[4]芳烃和碳酸钾的摩尔比为(2～4):(1～2):(8～16)。
4.根据权利要求2所述的制备方法，其特征在于，二氧六环的用量为：每摩尔4-氨基杯[4]芳烃用40～60mL二氧六环。
5.根据权利要求2所述的制备方法，其特征在于，洗涤时，依次用水、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、氯仿和乙醇洗涤。
6.一种根据权利要求1所述的三嗪基杯[4]芳烃多孔聚合物作为碘吸附剂在吸附水中碘方面的应用。
7.根据权利要求6所述的应用，其特征在于，在含碘的水中投加三嗪基杯[4]芳烃多孔聚合物，在室温下吸附。
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EP0560567A1 (en) * 1992-03-09 1993-09-15 Texaco Development Corporation Calix-arene encapsulation of s-triazines and their use for reducing nitrogen oxides in Diesel fuel exhaust
DE19646537A1 (de) * 1996-10-30 1998-05-07 Inst Angewandte Chemie Berlin Polyazacalix[6]arene, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2004085442A2 (en) * 2003-03-24 2004-10-07 Centre National De La Recherche Scientifique New calix arene compounds, their process of preparation and their use, particularly as enzymatic mimes

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EP0560567A1 (en) * 1992-03-09 1993-09-15 Texaco Development Corporation Calix-arene encapsulation of s-triazines and their use for reducing nitrogen oxides in Diesel fuel exhaust
DE19646537A1 (de) * 1996-10-30 1998-05-07 Inst Angewandte Chemie Berlin Polyazacalix[6]arene, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2004085442A2 (en) * 2003-03-24 2004-10-07 Centre National De La Recherche Scientifique New calix arene compounds, their process of preparation and their use, particularly as enzymatic mimes

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