CN106380604B - 一种聚环膦腈多孔材料的制备方法及其用途 - Google Patents
一种聚环膦腈多孔材料的制备方法及其用途 Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
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Abstract
本发明公开了一种聚环膦腈多孔材料的制备方法及其用途，属于功能高分子孔材料领域。聚环膦腈多孔材料的制备方法是，在缚酸剂作用下，六氯环三磷腈单体与哌嗪类、吡嗪类或吡唑类化合物发生缩聚交联反应，进一步将其活化后即得多孔材料。该聚环膦腈多孔材料具有低成本、高比表面积、可在较大范围内任意调控孔径、优异稳定性等优点，在催化剂载体、气体捕获与储存、金属离子深度处理以及放射性污染物分离等诸多领域，特别是对CO2、碘蒸气及溶液中碘和甲基碘等小分子具有良好的捕获能力；该聚环膦腈多孔材料制备过程简单易行，原料来源丰富，特别适合于实现工业化应用。
Description
技术领域
本发明涉及一种聚环膦腈多孔材料的制备方法和应用，属于功能高分子孔材料领域。
背景技术
放射性碘是核工业产生的重要有害核素，又是医学上用于诊断和治疗的主要同位素。近年来，核工业和诊疗产业的飞速发展，特别是在事故工矿下，不可避免地会产生放射性碘废料，包括放射性固体和放射性气体。吸附过滤法是核工业常用的捕集碘方法之一，具有效率高、成本低廉、设备简单等优点。多孔材料等物理吸附碘，因设备操作简单、能耗低、传质速度快和可循环使用等特点相对更具发展前景。目前，有机胺(主要是三乙基二胺)浸渍的活性炭是应用最为广泛的吸附材料，但它存在如下缺点：1、由于有机胺易升华，导致吸附效率显著降低；2、碘吸附是放热过程，而有机胺降低了浸渍活性炭的着火点，加剧了安全隐患；3、浸渍碳易老化和风化，再生能力差，难重复使用，易导致捕获的碘解吸，造成二次污染。
针对上述问题以及核工业和诊疗产业的快速发展，设计开发对碘结合力强、吸附效率高和热稳定性优异的新型吸附材料具有重要的学术意义和应用价值。为此，本发明通过对孔表面进行修饰，将许多富含N原子的基团，如环膦腈、吡唑、哌嗪、吡嗪等引入到多孔有机聚合物骨架中，可以增强对小分子如碘、CO2的吸附力以及CO2/N2分离选择性，提高碘蒸气和溶液中碘及甲基碘的吸附量。
发明内容
本发明针对当前多孔聚合物与碘蒸气和溶液中碘及甲基碘分子间作用力弱、吸附量低，难以满足工业化应用要求等缺陷，目的之一在于提供一种具有新型结构、且结构稳定性良好的环膦腈聚合物。
本发明的第二个目的在于提供一种孔隙发达、孔径可在较大范围内任意调控，比表面 积大，对CO2和/或碘具有较好选择性吸附能力的环膦腈聚合物孔材料。
本发明的第三个目的在于提供一种反应条件温和、操作便捷的所述环膦腈聚合物的制备方法。
本发明的第四个目的在于提供一种活化过程简便的制备所述环膦腈聚合物孔材料的方法。
本发明的第五个目的在于提供所述环膦腈聚合物孔材料在吸附、储存CO2和/或碘蒸气和溶液中碘及甲基碘等小分子方面的应用，所述孔材料吸附量大、吸附可逆性好，可重复使用，具有广泛的市场应用前景。
本发明提供的一种聚环膦腈多孔材料，其结构如下所示：
其中，
代表重复结构单元：
-R-为下述结构中的任意一种或多种：
所述聚环膦腈多孔材料，制备方法在于，将六氯环三磷腈单体与哌嗪类、吡嗪类或吡唑类化合物溶于有机极性溶剂中，在缚酸剂作用下，40-80℃下反应12-48hr后水洗干燥，进一步将其活化后制得。
所述缚酸剂为三甲胺、三乙胺、三丙胺、吡啶、碳酸钾、氢氧化钠、碳酸钠、碳酸氢钠中的一种或多种。
所述有机极性溶剂为丙酮、四氢呋喃、乙腈、甲苯、N，N-二甲基酰胺、二甲基亚砜、二氧六环中的一种或多种。
所述哌嗪类、吡嗪类或吡唑类化合物为下述结构中的任意一种或多种：
所述活化条件为惰性气氛保护下，于150-250℃高温下活化2-48hr。
所述聚环膦腈多孔材料为多孔状粉末或颗粒的环膦腈聚合物，比表面积为200-1800m2/g，粉末或颗粒中的孔孔径为0.5-50nm。
本发明还提供了一种聚环膦腈多孔材料的实际用途，即应用于CO2和/或碘蒸气和溶液中碘及甲基碘等小分子的吸附或储存。
相对现有技术，本发明的有益效果在于：
1、获得了一种由具有平面三节点的环膦腈单元通过P-N键偶联构成的聚环膦腈，该聚环膦腈合成工艺简单，反应条件温和，经进一步活化后具有多孔结构，分子热稳定性好，孔容及比表面积可在一定范围内任意调控。
2、本发明提供的聚环膦腈多孔材料能够赋予其网络骨架较高的路易斯碱性，从而基于酸碱作用使得主体对路易斯酸性的客体分子，如CO2、碘蒸气和溶液中碘及甲基碘等小分子具备很强的吸附能力。
3、本发明提供的聚环膦腈多孔材料通过物理吸附CO2和/或碘，再生消耗能量小，可重复多次使用。
基于这些特性，此类材料在催化剂载体、金属离子深度处理、放射性污染物分离以及 气体捕获与储存等诸多领域有着广阔的应用前景。
附图说明
【图1】为实施例1中环膦腈聚合物在N2环境下的热失重曲线。
【图2】为实施例1中环膦腈聚合物孔材料N2吸附曲线。
具体实施方式
以下结合实施例对本发明作进一步解释说明，但本发明的保护范围不限于下述实施例。
本发明具体实施方式中反应中间产物的结构测试利用下列仪器进行：在Nicolet-20DXB型红外光谱仪上进行FT-IR测试，KBr压片制样；元素分析(Elemental analysis)在Vario EL III CHNOS Elementaranalysator上进行；比表面积和孔径分布在Micromeritics公司的ASAP 2020仪器上进行，样品测试前在真空条件下于180℃用分子泵脱气活化4hr；碘蒸气吸附量在自制的石英微天平上测试，溶液中碘或甲基碘吸附量利用紫外光谱进行测定。
实施例1
于装配有机械搅拌、回流冷凝器和恒压滴液漏斗、温度计、N2导入管的500mL五口圆底烧瓶中，依次加入乙腈300mL、六氯环三磷腈3.47g(0.01mol)、哌嗪5.16g(0.06mol)，搅拌均匀后，缓慢滴加入三乙胺30mL，N2保护下50℃反应24hr后，经过滤除去滤液，水洗涤3次后干燥即得到环膦腈聚合物，最后在真空条件(0.1mmHg)下，加热至200℃进行活化12hr，即得聚环膦腈多孔材料。经检测，该多孔材料比表面积为1067m2/g，平均孔径为2.1nm，CO2吸附量为15.1wt％(298K，1bar)，碘蒸汽吸附量为90.5wt％(333K)。
实施例2
于装配有机械搅拌、回流冷凝器和恒压滴液漏斗、温度计、N2导入管的500mL五口圆底烧瓶中，依次加入四氢呋喃250mL、六氯环三磷腈3.47g(0.01mol)、4，4-二哌啶13.44g(0.08mol)，搅拌均匀后，缓慢滴加入吡啶50mL，N2保护下45℃反应48hr后，过滤除 去滤液，水洗涤3次后干燥即得到环膦腈聚合物，最后在真空条件(0.1mmHg)下，加热至180℃进行活化24hr，即得聚环膦腈多孔材料。经检测，该多孔材料比表面积为1244m2/g，平均孔径为1.8nm，CO2吸附量为17.3wt％(298K，1bar)，碘蒸汽吸附量为102.1wt％(333K)，正己烷溶液中碘吸附量为84mg/g(295K，4hr)
实施例3
于装配有机械搅拌、回流冷凝器和恒压滴液漏斗、温度计、N2导入管的500mL五口圆底烧瓶中，依次加入丙酮400mL、六氯环三磷腈3.47g(0.01mol)、1H，1′H-7，7′-联嘧啶[4，5-b]吡啶2.36g(0.1mol)，搅拌均匀后，缓慢滴加入碳酸锂5g，N2保护下60℃反应12hr后，过滤除去滤液，水洗涤3次后干燥即得到环膦腈聚合物，最后在真空条件(0.1mmHg)下，加热至150℃进行活化48hr，即得聚环膦腈多孔材料。经检测，该多孔材料比表面积为1419m2/g，平均孔径为1.6nm，CO2吸附量为18.9wt％(273K，1bar)，CO2吸附量为12.8wt％(298K，1bar)。
Claims (7)
1.一种聚环膦腈多孔材料，其特征在于，具有如下所示结构：
其中，
代表重复结构单元：
-R-为下述结构中的任意一种或多种：
2.如权利要求1所述的聚环膦腈多孔材料，其特征在于，为多孔状粉末或颗粒的环膦腈聚合物，比表面积为200-1800m2/g，粉末或颗粒中的孔径为0.5-50nm。
3.如权利要求1所述的聚环膦腈多孔材料的制备方法，其特征在于，将六氯环三磷腈单体与哌嗪类、吡嗪类或吡唑类化合物溶于有机极性溶剂中，在缚酸剂作用下，40-80℃下反应12-48小时后水洗干燥，进一步将其活化后制得。
4.如权利要求3所述的聚环膦腈多孔材料的制备方法，其特征在于，所述哌嗪类、吡嗪类或吡唑类化合物为下述结构中的任意一种或多种：
5.如权利要求3所述的聚环膦腈多孔材料的制备方法，其特征在于，所述缚酸剂为三甲胺、三乙胺、三丙胺、吡啶、碳酸钾、氢氧化钠、碳酸钠、碳酸氢钠中的一种或多种。
6.如权利要求3所述的聚环膦腈多孔材料的制备方法，其特征在于，所述有机溶剂为丙酮、四氢呋喃、乙腈、甲苯、N，N-二甲基酰胺、二甲基亚砜、二氧六环中的一种或多种。
7.如权利要求1所述的聚环膦腈多孔材料的用途，其特征在于，应用于CO2和/或碘蒸气和溶液中碘和甲基碘的吸附或储存。
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| US4258170A (en) * | 1979-08-20 | 1981-03-24 | The Firestone Tire & Rubber Company | Polyphosphazene polymers containing pyrazole or imidazole substituents |
| CN101070389A (zh) * | 2007-06-21 | 2007-11-14 | 上海交通大学 | 一种含膦腈空心微球及其制备方法 |
| CN103992481A (zh) * | 2014-05-09 | 2014-08-20 | 苏州安鸿泰新材料有限公司 | 一种超支化聚磷腈阻燃成炭剂及其制备方法 |
| CN104497316A (zh) * | 2014-12-10 | 2015-04-08 | 上海交通大学 | 一类高含氮聚合物微球及其制备方法 |
| CN104607120A (zh) * | 2014-10-16 | 2015-05-13 | 江南大学 | 一种基于环交联型聚膦腈微球的颗粒乳化剂及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4258170A (en) * | 1979-08-20 | 1981-03-24 | The Firestone Tire & Rubber Company | Polyphosphazene polymers containing pyrazole or imidazole substituents |
| CN101070389A (zh) * | 2007-06-21 | 2007-11-14 | 上海交通大学 | 一种含膦腈空心微球及其制备方法 |
| CN103992481A (zh) * | 2014-05-09 | 2014-08-20 | 苏州安鸿泰新材料有限公司 | 一种超支化聚磷腈阻燃成炭剂及其制备方法 |
| CN104607120A (zh) * | 2014-10-16 | 2015-05-13 | 江南大学 | 一种基于环交联型聚膦腈微球的颗粒乳化剂及其制备方法 |
| CN104497316A (zh) * | 2014-12-10 | 2015-04-08 | 上海交通大学 | 一类高含氮聚合物微球及其制备方法 |
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