CN110452365A - 一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用 - Google Patents
一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用 Download PDFInfo
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Abstract
本发明公开了一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用。本发明合成的新型D‑π‑D型共轭多孔聚合物，具有大的比表面积和高化学稳定以及热稳定性。在可见光照射下温和地催化伯胺氧化制备亚胺，伯胺转化率达到90％以上，亚胺选择性达到95％以上。而且作为无金属催化的多相催化剂，易于分离和回收，具有重复使用的优势，产物亚胺易纯化，反应条件温和、催化效果好、底物适用范围宽、亚胺选择性高和催化剂可回收等优点。因此，本发明设计的D‑π‑D型共轭多孔聚合物对伯胺氧化偶联制备亚胺具有广泛的应用前景。
Description
技术领域
本发明涉及一种多相光催化材料的制备及其应用，具体地说，涉及一种D-π-D型共轭多孔聚合物的制备及其在光催化中的应用。
背景技术
亚胺俗称席夫碱，是一类具有药理学活性和生理学活性的化合物，在医药学和生物领域得到广泛应用。此外，作为一种非常重要的有机合成中间体，亚胺也广泛地被应用于氧化还原反应、加成反应、环加成反应和缩合反应等。传统亚胺由醛或酮与胺发生缩合反应而得，而该缩合反应通常需要路易斯酸催化，比如TiCl4、Al2O3或MgSO4等，此方法通常需要较高的温度和较长的反应时间，并且反应过程中会有羧酸生成，造成原料浪费，不符合绿色化学的发展。
近年来，伯胺氧化偶联制备亚胺凭借高效节能、绿色环保等优点收到更多的青睐，常见的催化剂主要有过渡金属催化剂、仿生催化剂和光催化剂等。其中，可见光催化伯胺氧化偶联制备亚胺凭借绿色温和的优势吸引到越来越多的关注，常见的光催化剂主要包括贵金属催化剂、共轭有机染料、燃料敏化半导体等，但这些催化剂仍存在一些不足，包括催化剂难回收、成本高昂、金属残留、催化剂稳定性差等缺陷。
共轭多孔聚合物(CPPs)作为一类新型的共轭多孔材料，以有机共轭小分子为构建单体通过交叉偶联聚合而成，具有高比表面积、永久孔道、高热稳定性以及宽可见光吸收等优秀的物理化学性质。并且，共轭多孔聚合物具有设计灵活的特性，可以从分子层面设计调控它的能级分布和可见光吸收等光电特性。此外，作为多相催化剂，共轭多孔聚合物具有易回收和可重复使用的优势，有利于催化剂成本的降低和产物亚胺的分离提纯。
发明内容
本发明的目的在于克服现有技术的不足，提供一种D-π-D型共轭多孔聚合物，其能够高效和高选择性地光催化伯胺氧化制备亚胺。
为了实现上述目的，本发明采用如下技术方案：
一种D-π-D型共轭多孔聚合物，其结构如式(I)：
其中，三苯胺是电子给体，蒽是π联结体。
上述共轭多孔聚合物的制备方法，包括如下步骤：由三(4-硼酸频哪醇酯苯基)胺和9,10-二溴蒽在Pd(PPh3)4催化下发生Suzuki偶联反应得到，如下所示：
作为优选的，在上述的制备方法中，所述Suzuki反应中，三(4-硼酸频哪醇酯苯基)胺和9,10-二溴蒽的摩尔比例是2:3。
作为优选的，在上述的制备方法中，所述Pd(PPh3)4与9,10-二溴蒽的摩尔比例是1：10，K2CO3与9,10-二溴蒽的摩尔比例是20:1。
作为优选的，在上述的制备方法中，所述Suzuki偶联反应的溶剂是N,N-二甲基甲酰胺和水的混合溶剂，N,N-二甲基甲酰胺和水的体积比为5:1。
作为优选的，在上述的制备方法中，所述Suzuki偶联反应在氮气氛围下，在150℃下反应48h。
上述共轭多孔聚合物在光催化伯胺氧化制备亚胺中的应用。所述氧化的氧化剂为氧气、共轭多孔聚合物作为催化剂，乙腈和水(体积比1：1)为溶剂，白光LED(波长400-800nm)为光源，伯胺为反应底物。所述伯胺选自苄胺、对溴苄胺、3-氨甲基吡啶、R(+)-α-甲基苄胺、2-甲氧基苄胺、4-甲氧基苄胺中的一种或多种。具体包括如下步骤：将共轭多孔聚合物超声分散在乙腈和水的混合溶剂中，通入氧气鼓泡10分钟，加入伯胺，安装冷指回流冷凝器，在25℃和白光LED下照射24h，过滤回收催化剂，向滤液中加入二氯甲烷萃取，得到的有机相经干燥和浓缩后进行GC-MS分析。
在上述的制备方法中，所得D-π-D型共轭多孔聚合物是黄绿色粉末，比表面积是506m2/g，孔径范围是0.8～1.6nm。
与现有技术相比，本发明具有如下有益效果：
本发明合成的新型D-π-D型共轭多孔聚合物，具有大的比表面积和高化学稳定以及热稳定性。在可见光照射下温和地催化伯胺氧化制备亚胺，伯胺转化率达到90％以上，亚胺选择性达到95％以上。而且作为无金属催化的多相催化剂，易于分离和回收，具有重复使用的优势，产物亚胺易纯化，反应条件温和、催化效果好、底物适用范围宽、亚胺选择性高和催化剂可回收等优点。因此，本发明设计的D-π-D型共轭多孔聚合物对伯胺氧化偶联制备亚胺具有广泛的应用前景。
附图说明
图1为D-π-D型共轭多孔聚合物的合成经红外图谱。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明实施例的一部分，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
一种D-π-D型共轭多孔聚合物，其合成路线如下：
分别将50mL N,N-二甲基甲酰胺(DMF)和5mLK2CO3(2mol/L)水溶液用氮气鼓泡30min，然后将两者混合到250mL的两口烧瓶中。往混合溶液中分别加入单体三(4-硼酸频哪醇酯苯基)胺(312mg,0.5mmol)和9,10-二溴蒽(252mg,0.75mmol)，搅拌加热到80℃。在氮气氛围下，向混合物中加入Pd(PPh3)4(43mg,0.0375mmol)，搅拌加热到150℃，反应48h。冷却至室温后，抽滤，依次用水、1，4-二氧六环、四氢呋喃洗涤滤饼，再分别用1,4-二氧六环和四氢呋喃分别索提24h，真空干燥24h，得到黄绿色粉末(392mg，产率：70％)。
经红外图谱分析可知(图1)，单体三(4-硼酸频哪醇酯苯基)胺上的B-O伸缩振动吸收带出现在1359cm-1处，单体9,10-二溴蒽上的C-Br伸缩振动吸收带出现在577cm-1处,而共轭多孔聚合物相应位置上B-O伸缩振动吸收带和C-Br伸缩振动吸收带强度都明显减弱，说明在硼酸频哪醇酯和C-Br处发生偶联反应；此外，共轭多孔聚合物上1315cm-1和1285cm-1峰为叔胺C-N的特征峰；结合单体及聚合物的图谱和官能团出峰位置，峰强度等，我们可确定该反应的较充分进行。
本发明进行的光催化伯胺氧化制备亚胺主要利用D-π-D型共轭多孔聚合物催化剂，将伯胺和氧气溶解于液体混合溶剂中，在室温和可见光照射下进行多相催化反应。
实施例和对比例中的试剂均为市售的分析纯试剂。
实施例和对比例中所用的D-π-D型共轭多孔聚合物催化剂是按现有技术所描述的方法制得。
实施例1
以0.5mmol苄胺为原料，加入5mL乙腈和5mL水作为混合溶剂，并加入作为氧化剂的氧气鼓泡10min。加入20mg作为催化剂的D-π-D型共轭多孔聚合物。在室温和白光LED照射下搅拌进行催化反应24h。过滤除去催化剂，二氯甲烷萃取和旋蒸浓缩，即得相应产物亚胺。
实施例2
以0.5mmol对溴苄胺为原料，加入5mL乙腈和5mL水作为混合溶剂，并加入作为氧化剂的氧气鼓泡10min。加入20mg作为催化剂的D-π-D型共轭多孔聚合物。在室温和白光LED照射下搅拌进行催化反应24h。过滤除去催化剂，二氯甲烷萃取和旋蒸浓缩，即得相应产物亚胺。
实施例3
以0.5mmol3-氨甲基吡啶为原料，加入5mL乙腈和5mL水作为混合溶剂，并加入作为氧化剂的氧气鼓泡10min。加入20mg作为催化剂的D-π-D型共轭多孔聚合物。在室温和白光LED照射下搅拌进行催化反应24h。过滤除去催化剂，二氯甲烷萃取和旋蒸浓缩，即得相应产物亚胺。
实施例4
以0.5mmolR(+)-α-甲基苄胺为原料，加入5mL乙腈和5mL水作为混合溶剂，并加入作为氧化剂的氧气鼓泡10min。加入20mg作为催化剂的D-π-D型共轭多孔聚合物。在室温和白光LED照射下搅拌进行催化反应24h。过滤除去催化剂，二氯甲烷萃取和旋蒸浓缩，即得相应产物亚胺。
实施例5
以0.5mmol2-甲氧基苄胺为原料，加入5mL乙腈和5mL水作为混合溶剂，并加入作为氧化剂的氧气鼓泡10min。加入20mg作为催化剂的D-π-D型共轭多孔聚合物。在室温和白光LED照射下搅拌进行催化反应24h。过滤除去催化剂，二氯甲烷萃取和旋蒸浓缩，即得相应产物亚胺。
实施例6
以0.5mmol4-甲氧基苄胺为原料，加入5mL乙腈和5mL水作为混合溶剂，并加入作为氧化剂的氧气鼓泡10min。加入20mg作为催化剂的D-π-D型共轭多孔聚合物。在室温和白光LED照射下搅拌进行催化反应24h。过滤除去催化剂，二氯甲烷萃取和旋蒸浓缩，即得相应产物亚胺。
分别取实施例1-6中制备得到的亚胺样品，采用气相色谱法进行分析，结果如下表1所示：
表1
从上表1可以看到，通过本发明所述的D-π-D型共轭多孔聚合物催化剂光催化伯胺氧化制备亚胺的方法，其伯胺转化率均达到90％以上，且亚胺选择性达到95％以上，选择性好，效率高。
对比例1
取实施例1中催化剂通过过滤和干燥进行回收，重新用于苄胺光氧化制备亚胺的反应中，反应条件与实施例1相一致。
反应完成后，通过气相色谱法进行分析，结果显示，苄胺的转化率为99％，亚胺的选择性为98％。
进一步地，将上述反应完成后的催化剂通过过滤和干燥再次回收，重新用于苄胺光氧化制备亚胺的反应中，反应条件与实施例1相一致。
反应完成后，通过气相色谱法进行分析，结果显示，苄胺的转化率为97％，亚胺的选择性为99％。
由此可见，通过本发明所述的方法，可以实现催化剂的多次回收和重复利用，同时能够保证反应的效率和选择性，大大降低反应的成本和能耗，且反应条件温和，安全性显著提高。
以上具体实施方式部分对本发明所涉及的分析方法进行了具体的介绍。应当注意的是，上述介绍仅是为了帮助本领域技术人员更好地理解本发明的方法及思路，而不是对相关内容的限制。在不脱离本发明原理的情况下，本领域技术人员还可以对本发明进行适当的调整或修改，上述调整和修改也应当属于本发明的保护范围。
Claims (10)
1.一种共轭多孔聚合物，其特征在于其结构如式(I)：
其中，三苯胺是电子给体，蒽是π联结体。
2.权利要求1所述共轭多孔聚合物的制备方法，其特征在于包括如下步骤：由三(4-硼酸频哪醇酯苯基)胺和9,10-二溴蒽在Pd(PPh3)4催化下发生Suzuki偶联反应得到，如下所示：
3.根据权利要求2所述的制备方法，其特征在于，所述Suzuki反应中，三(4-硼酸频哪醇酯苯基)胺和9,10-二溴蒽的摩尔比例是2:3。
4.根据权利要求2所述的制备方法，其特征在于，所述Pd(PPh3)4与9,10-二溴蒽的摩尔比例是1：10；K2CO3与9,10-二溴蒽的摩尔比例是20:1。
5.根据权利要求2所述的制备方法，其特征在于，所述Suzuki偶联反应的溶剂是N,N-二甲基甲酰胺和水的混合溶剂，N,N-二甲基甲酰胺和水的体积比为5:1。
6.根据权利要求2所述的制备方法，其特征在于，所述Suzuki偶联反应在氮气氛围下，在150℃下反应48h。
7.权利要求1所述共轭多孔聚合物在光催化伯胺氧化制备亚胺中的应用。
8.根据权利要求7所述的应用，其特征在于，所述氧化的氧化剂为氧气、共轭多孔聚合物作为催化剂，乙腈和水为溶剂，白光LED为光源，伯胺为反应底物。
9.根据权利要求8所述的应用，其特征在于，所述伯胺选自苄胺、对溴苄胺、3-氨甲基吡啶、R(+)-α-甲基苄胺、2-甲氧基苄胺、4-甲氧基苄胺中的一种或多种。
10.根据权利要求8所述的应用，其特征在于，包括如下步骤：将共轭多孔聚合物超声分散在乙腈和水的混合溶剂中，通入氧气鼓泡10分钟，加入伯胺，安装冷指回流冷凝器，在25℃和白光LED下照射24h，过滤回收催化剂，向滤液中加入二氯甲烷萃取，得到的有机相经干燥和浓缩后进行GC-MS分析。
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