CN108359079A - 一种室温快速制备球形微孔有机网络材料的方法 - Google Patents

一种室温快速制备球形微孔有机网络材料的方法 Download PDF

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CN108359079A
CN108359079A CN201810313556.4A CN201810313556A CN108359079A CN 108359079 A CN108359079 A CN 108359079A CN 201810313556 A CN201810313556 A CN 201810313556A CN 108359079 A CN108359079 A CN 108359079A
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杨成雄
崔媛媛
严秀平
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Nankai University
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Abstract

一种室温快速制备球形微孔有机网络材料的方法，采用室温法制备，首先用双(三苯基膦)二氯化钯和碘化亚酮制备催化剂溶液，然后将四(4‑乙炔基苯)甲烷和卤代苯加入催化剂溶液中，通过室温搅拌法4小时制备球形微孔有机网络材料。本发明的优点是：1)采用室温搅拌法制备微孔有机网络材料，不仅避免了高温，并且大大缩短了反应时间，提供了一种合成微孔有机网络材料的新方法；2)该方法合成出的微孔有机网络材料具有形貌规则、尺寸均一、比表面积大、疏水性好等优良的性质，为一种新型的多功能多孔材料；该制备方法工艺简单、操作安全简便、环境友好、生产速度快，节约了合成周期与成本，有利于大规模推广应用。

Description

一种室温快速制备球形微孔有机网络材料的方法
【技术领域】
本发明涉及微孔有机网络材料的制备，特别是一种具有球形形貌、强疏水性的微孔有机网络材料的制备。
【背景技术】
微孔有机网络材料(microporous organic networks，MONs)近年来出现的一类新颖多功能多孔材料，它是以芳香炔和卤代苯或卤代联苯通过Sonogashira偶联反应形成的多孔网状物。作为一类新型的多功能多孔材料，MONs具有以下特点：(1)MONs合成单体和连接方式多样，可以形成性质各异的多孔材料以满足多种应用需求；(2)MONs具有良好的溶剂和热稳定性，可以满足实际应用过程中溶剂洗脱或加热的要求；(3)MONs骨架均由芳香性的单体偶联形成，使其具有很强的疏水性；(4)MONs规则有序的多孔性使其具有较大的比表面积和良好的尺寸选择性。从2013年开始，Seung Uk Son课题组分别报道了MONs用于催化、石英晶体微天平传感氨气、荧光传感硝基化合物、锂离子电池、吸附染料和芳香污染物的研究，揭示了MONs在诸多领域良好的应用潜力。
然而，目前合成MONs的方法仍以溶剂热法为主。该方法一般使用芳香炔和卤代苯为反应原料，以甲苯和三乙胺或甲醇为反应溶剂，以双(三苯基膦)二氯化钯和碘化亚酮为催化剂，在加热条件下(80-90℃)经过长时间(24小时)反应合成MONs。这种方法制备MONs的缺点是反应时间长、反应能耗高，不利于大规模合成和推广。
近年来，采用室温搅拌法合成多孔材料的研究引起了人们越来越多的关注。这种方法具有无需加热、反应温和、容易操作、易于推广等优点，是一种绿色的合成方法。然而，迄今为止，关于室温搅拌法用于合成MONs的研究未见报道。同时，用于快速合成MONs的研究也未见报道。因此，开展室温快速合成具有规则形貌、比表面积大、疏水性好的MONs方法具有重要意义。
【发明内容】
本发明的目的是针对现有MONs制备方法反应时间长、反应能耗高，不利于大规模合成和推广的问题，提供一种室温快速合成规则形貌、比表面积大、疏水性好的MONs方法。
本发明的技术方案：
一种室温快速制备球形微孔有机网络材料的方法，步骤如下：
1)制备催化剂溶液：将双(三苯基膦)二氯化钯和碘化亚酮固体粉末加入至甲苯和三乙胺的混合溶液中，在超声条件下超声至固体完全溶解，最终得到无色的催化剂溶液；
2)将四(4-乙炔基苯)甲烷和卤代苯加入至上述无色的催化剂溶液中，在室温条件下磁力搅拌4小时，样品悬浮于溶液中，离心分离，分别用二氯甲烷、丙酮和甲醇洗涤直至溶液无色，将样品室温真空干燥12小时，即可制得具有规则形貌、比表面积大、疏水性好的MONs。
所述双(三苯基膦)二氯化钯的浓度为12-96μmol/L，碘化亚酮的浓度为12-96μmol/L，双(三苯基膦)二氯化钯和碘化亚酮的摩尔比为1：1。
所述甲苯和三乙胺的混合溶液的总体积为60mL，其体积比为1：1。
所述四(4-乙炔基苯)甲烷的浓度为0.12-0.96mmol/L，卤代苯的浓度为0.24-1.92mmol/L，四(4-乙炔基苯)甲烷和卤代苯的摩尔比为1：2。四(4-乙炔基苯)甲烷、卤代苯、双(三苯基膦)二氯化钯和碘化亚酮的摩尔比为1：2：1：1。
所述卤代苯为对二碘苯、对二溴苯、对二氯苯、2-氨基对二溴苯或2-羟基对二溴苯。
本发明的优点及效果：
该方法采用室温搅拌法快速合成MONs，不仅避免了高温，并且大大缩短了反应时间，提供了一种合成MONs的新方法。该方法合成出的MONs具有形貌规则、尺寸均一、比表面积大、疏水性好等优良的性质，为一种新型的多功能多孔材料；该制备方法工艺简单、操作安全简便、环境友好、生产速度快，节约了合成周期与成本，有利于大规模推广应用，在多孔材料的合成、环境污染物吸附和去除、疏水材料的研究及应用等领域具有重大的实践意义。
【附图说明】
图1微孔有机网络材料的扫描电镜图。
图2微孔有机网络材料的接触角实验图。
【具体实施方式】
实施例1：
一种室温快速制备球形微孔有机网络材料的方法，步骤如下：
1)制备催化剂溶液：将33.6mg的双(三苯基膦)二氯化钯和8.8mg的碘化亚酮固体粉末加入至总体积为60mL体积比为1:1的甲苯和三乙胺的混合溶液中，在超声条件下超声至固体完全溶解，最终得到无色的催化剂溶液；
2)将200mg的四(4-乙炔基苯)甲烷和320mg的对二碘苯加入至上述无色的催化剂溶液中，在室温条件下磁力搅拌4小时，样品悬浮于溶液中，离心分离，分别用二氯甲烷、丙酮和甲醇洗涤直至溶液无色，将样品室温真空干燥12小时，即可制得具有规则形貌、比表面积大、疏水性好的MONs。
取1mg的MONs粉末作为扫描电镜和接触角实验试样。图1为MONs的扫描电镜图。图中显示：MONs呈规则球形、尺寸均一，大小为约600nm。图2为MONs的接触角实验，其接触角为140.7度，能明显观察到水滴悬浮于MONs表面，即MONs具有很强的疏水性。
实施例2：
一种室温快速制备球形微孔有机网络材料的方法，采用室温法制备，步骤和方法与实施例1基本相同，不同之处在于卤代苯为对二溴苯。
取1mg的MONs粉末作为扫描电镜和接触角实验试样，检测结果与实施例1相近。
实施例3:
一种室温快速制备球形微孔有机网络材料的方法，采用室温法制备，步骤和方法与实施例1基本相同，不同之处在于卤代苯为对二氯苯。
取1mg的MONs粉末作为扫描电镜和接触角实验试样，检测结果与实施例1相近。
实施例4:
一种室温快速制备球形微孔有机网络材料的方法，采用室温法制备，步骤和方法与实施例1基本相同，不同之处在于卤代苯为2-氨基对二溴苯。
取1mg的MONs粉末作为扫描电镜和接触角实验试样，检测结果与实施例1相近。
实施例5:
一种室温快速制备球形微孔有机网络材料的方法，采用室温法制备，步骤和方法与实施例1基本相同，不同之处在于卤代苯为2-羟基对二溴苯。
取1mg的MONs粉末作为扫描电镜和接触角实验试样，检测结果与实施例1相近。

Claims (5)

1.一种室温快速制备球形微孔有机网络材料的方法，其特征在于：采用室温法制备，步骤如下：
1)制备催化剂溶液：将双(三苯基膦)二氯化钯和碘化亚酮固体粉末加入至甲苯和三乙胺的混合溶液中，在超声条件下超声至固体完全溶解，最终得到无色的催化剂溶液；
2)将四(4-乙炔基苯)甲烷和卤代苯加入至上述无色的催化剂溶液中，在室温条件下磁力搅拌4小时，样品悬浮于溶液中，离心分离，分别用二氯甲烷、丙酮和甲醇洗涤直至溶液无色，将样品室温真空干燥12小时，即可制得具有规则形貌、比表面积大、疏水性好的MONs。
2.根据权利要求1所述室温快速制备球形微孔有机网络材料的方法，其特征在于：所述双(三苯基膦)二氯化钯的浓度为12-96μmol/L，碘化亚酮的浓度为12-96μmol/L，双(三苯基膦)二氯化钯和碘化亚酮的摩尔比为1：1。
3.根据权利要求1所述室温快速制备球形微孔有机网络材料的方法，其特征在于：所述甲苯和三乙胺的混合溶液的总体积为60mL，其体积比为1：1。
4.根据权利要求1所述室温快速制备球形微孔有机网络材料的方法，其特征在于：所述四(4-乙炔基苯)甲烷的浓度为0.12-0.96mmol/L，卤代苯的浓度为0.24-1.92mmol/L，四(4-乙炔基苯)甲烷和卤代苯的摩尔比为1：2；四(4-乙炔基苯)甲烷、卤代苯、双(三苯基膦)二氯化钯和碘化亚酮的摩尔比为1：2：1：1。
5.根据权利要求1所述室温快速制备球形微孔有机网络材料的方法，其特征在于：所述卤代苯为对二碘苯、对二溴苯、对二氯苯、2-氨基对二溴苯或2-羟基对二溴苯。
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