CN110746602B - 一种金属钴卟啉基多孔有机聚合物及其制备方法和应用 - Google Patents
一种金属钴卟啉基多孔有机聚合物及其制备方法和应用 Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明公开了一种金属钴卟啉基多孔有机聚合物及其制备方法和应用,属于功能材料技术领域。该聚合物以5,10,15,20‑四(4‑(2,4‑二氨基三氰基)苯基)‑卟啉和对苯二甲醛为原料制备成,先通过加热搅拌的聚合反应得到粗产品,再通过纯化得到最终的产物。本发明提供的聚合物可作为催化剂,用于催化二氧化碳与环碳酸酯的环加成反应。该聚合物具有较大的比表面积、优秀的稳定性、较高的催化活性和循环利用性,可广泛应用于二氧化碳有机蒸汽捕获、催化合成环碳酸酯等工业领域。同时,聚合物材料骨架中存在大量的卟啉基结构单元,可以通过各种修饰手段引入不同的基团,从而实现多领域的应用,具有巨大的潜在应用价值。
Description
技术领域
本发明属于功能材料技术领域,具体涉及一种金属钴卟啉基多孔有机聚合物及其制备方法和其在催化二氧化碳环加成反应中的应用。
背景技术
随着人类社会的发展,大量化石能源被消耗,使大气中二氧化碳含量呈上升趋势,从而导致温室效应和全球气候变化。但是与此同时,二氧化碳又是最丰富、最廉价且可再生的碳源。因此,将二氧化碳经由化学固定成有机化合物对化学和环境来讲都具有重要意义。目前,人类在利用二氧化碳合成具有附加值的化学品和燃料等方面已经取得了一系列的成就,例如合成环碳酸盐、甲醇、烃类等各种物质。其中,利用二氧化碳和环氧化合物合成环碳酸酯是非常具有潜在应用价值的策略之一。因为该反应具有原子经济性,符合绿色化学的要求。产物环碳酸酯具有广阔的工业应用价值,可用作锂离子电池电解液、极性非质子溶剂、燃料添加物和机合成中间体等。
目前,针对环氧化合物与二氧化碳的环加成反应,已有各种催化体系被开发出来。例如碱金属卤化物、离子液体、金属卟啉等均相催化剂以及离子液体多孔聚合物、离子交换树脂、金属有机骨架等非均相催化剂。然而,应用上述催化剂合成条件较为繁琐,且催化剂难以重复使用,或者是在很苛刻的条件下才能得到好的催化活性和效果,以上不仅提高了生产成本又增加了能源消耗。因此,开发出温和高效的催化剂,仍然是目前的研究热点和难点之一。
发明内容
基于上述问题,本发明的目的是提供一种金属配位的卟啉基多孔有机聚合物,该聚合物的制备方法工艺简单、整个聚合过程无需使用任何催化剂,得到的聚合物具有较大的比表面积、优秀的稳定性、较高的催化活性和循环利用性,可广泛应用于二氧化碳有机蒸汽捕获、催化合成环碳酸酯等工业领域。同时,聚合物材料骨架中存在大量的卟啉基结构单元,可以通过各种修饰手段引入不同的基团,从而实现多领域的应用,具有巨大的潜在应用价值。
本发明的技术方案:
一种金属钴卟啉基多孔有机聚合物,其结构式如下:
一种金属钴卟啉基多孔有机聚合物的制备方法,以5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴和对苯二甲醛为原料,先通过加热搅拌的聚合反应得到粗产品,再通过纯化得到最终的产物;合成路线如下:
具体包括以下步骤:
步骤1.将反应装置除水除氧;
步骤2.将5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴、对苯二甲醛和二甲基亚砜三者混合,其中,5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴、对苯二甲醛以及二甲基亚砜三种物质的摩尔比为1:1.8~2.2:0.28~0.42,将体系在160~185℃下加热回流60~84小时,直至反应完毕;
步骤3.将步骤2得到的产物静置冷却至室温,洗涤所收集的固体,得到粗产物。将粗产物用四氢呋喃索氏提取20~28小时,70~100℃真空干燥12~24小时,得到金属钴卟啉基多孔有机聚合物。
所述的洗涤所用的洗涤剂为N,N-二甲基甲酰胺、甲醇、四氢呋喃中的一种或两种以上混合。
所述的金属钴卟啉基多孔有机聚合物在催化二氧化碳与环氧化合物环加成反应中的应用。
本发明的有益之处在于:
(1)卟啉是一类富含N元素、拥有大π键的理想多孔材料,以卟啉作为聚合物的基底,有助于增加其与二氧化碳间的相互作用。本发明提供的金属钴卟啉基多孔有机聚合物,具有较高的表面积和孔隙率,因而可以使得有聚合物外部暴露出大量的催化活性位点,从而表现出较高的催化活性。经验证,该金属钴卟啉基多孔有机聚合物在二氧化碳与环氧化合物的环加成反应中表现出了优异的选择性和催化活性,其催化产率均在90%以上,绝大多数产物的选择性在99%以上,同时,聚合物催化剂具有较好的循环稳定性,可以循环使用数次而不失活。
(2)本发明提供的金属钴卟啉基多孔有机聚合物的原料廉价易得,制备方法简单,易操作,环境污染小。
附图说明
图1是PAN-TPD(Co)的红外-可见光谱图。
图2是PAN-TPD(Co)的扫描电镜图。
图3是PAN-TPD(Co)对环氧丁烷的环加成反应循环实验图。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步详细介绍,但不限制本发明的保护范围。如无特殊说明,本发明所采用的实验方法均为常规方法,所用实验器材、材料、试剂等均可从化学公司购买。
一.PAN-TPD(Co)的制备方法
本发明提供的金属钴卟啉基多孔有机聚合物(PAN-TPD(Co))是以5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴和对苯二甲醛为原料制备成,先通过加热搅拌的聚合反应得到粗产品,再通过纯化得到最终的产物。
PAN-TPD(Co)的合成路线如下:
实施例1:
步骤1.将装有搅拌和冷凝装置的三口瓶利用双排管反复抽真空三次,以除去体系中的水分和氧气。
步骤2.在氮气流下,将5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴(0.25g,0.226mmol)、对苯二甲醛(54.47mg,0.406mool)和20mL二甲基亚砜加入到圆底烧瓶中。将油浴锅加热到160℃,打开搅拌,恒温反应84小时。
步骤3.反应完毕后将体系静置冷却至室温,将固体用N,N-二甲基甲酰胺和甲醇洗涤数次,过滤得到粗产物。将粗产物用四氢呋喃索氏提取20小时,70℃真空干燥24小时。得到紫色固体。
实施例2:
步骤1.将装有搅拌和冷凝装置的三口瓶利用双排管反复抽真空三次,以除去体系中的水分和氧气。
步骤2.在氮气流下,将5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴(0.25g,0.226mmol)、对苯二甲醛(60.53mg,0.451mool)和25mL二甲基亚砜加入到圆底烧瓶中。将油浴锅加热到180℃,打开搅拌,恒温反应72小时。
步骤3.反应完毕后将体系静置冷却至室温,将固体分别用N,N-二甲基甲酰胺、甲醇和四氢呋喃洗涤数次,过滤得到粗产物。将粗产物用四氢呋喃索氏提取24小时,100℃真空干燥12小时。得到紫色固体。
实施例3:
步骤1.将装有搅拌和冷凝装置的三口瓶利用双排管反复抽真空三次,以除去体系中的水分和氧气。
步骤2.在氮气流下,将5,10,15,20-四(4-(2,4-二氨基三氰基)苯基)-卟啉钴(0.25g,0.226mmol)、对苯二甲醛(66.58mg,0.496mmol)和30mL二甲基亚砜加入到圆底烧瓶中。将油浴锅加热到170℃,打开搅拌,恒温反应60小时。
步骤3.反应完毕后将体系静置冷却至室温,将固体分别用甲醇和四氢呋喃洗涤数次,过滤得到粗产物。将粗产物用四氢呋喃索氏提取28小时,90℃真空干燥20小时。得到紫色固体。
二.催化二氧化碳与环氧化合物的环加成反应
1.催化实验
二氧化碳与环氧化合物的环加成反应方程式如下:
选取以下底物分别与二氧化碳进行环加成反应:
精确量取12.5mmol环氧化合物(环氧丙烷(0.84mL)、环氧氯丙烷(0.98mL)、环氧溴丙烷(1.19mL)、环氧丁烷(1.09mL)、氧化苯乙烯(1.42mL)),加入到聚四氟乙烯内衬中,然后精确称量催化剂PAN-TPD(Co)20mg、四丁基溴化铵0.58g(1.8mmol),加入到聚四氟乙烯内衬中,再将内衬加到反应釜中。向反应釜中缓慢通入二氧化碳气体用来排除釜内空气,以防止釜内的其他气体对实验结果产生影响。将二氧化碳压力调节至2MPa,油浴锅温度调节至120℃,恒温恒压反应4小时。反应结束后,将反应釜静置冷却至室温,打开反应釜,将溶液吸出,用有机滤膜过滤,由于催化剂不透过滤膜,分离出产物溶液,用装备有FID探测器和毛细血管柱((DB-1701,30m×0.32mm×0.25μm)的气相分析色谱(GC-MS,Agilent 7890A-7000B)测定产率。
2.循环实验
将反应釜中的液体通过有机滤膜过滤,收集催化剂固体。将收集得到的固体用甲醇、二氯甲烷洗涤数次,四氢呋喃索氏提取24小时,100℃真空干燥48小时。以环氧丁烷作为模型底物,重复上述步骤,其它条件不变,进行催化实验,测定循环产率。
3.催化活性分析
表1催化剂PAN-TPD(Co)对二氧化碳环加成反应的催化活性数据表
从实验结果中可以看出,PAN-TPD(Co)作为催化剂在催化二氧化碳与环氧化合物的环加成反应中表现出了良好的催化效果,以上述化合物作为底物,产率均在90%以上,同时绝大多数产物的选择性在99%以上。其中,对环氧丙烷的催化作用更为优异,TON和TOF值分别达到了920.84和230.21h-1。
需要说明的是,上述实施例不以任何形式限制本发明,凡采用等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。
Claims (4)
2.一种金属钴卟啉基多孔有机聚合物的制备方法,其特征在于,以5,10,15,20-四(4-(2,4-二氨基三嗪基)苯基)-卟啉钴和对苯二甲醛为原料,先通过加热搅拌的聚合反应得到粗产品,再通过纯化得到最终的产物;合成路线如下:
具体包括以下步骤:
步骤1.将反应装置除水除氧;
步骤2.将5,10,15,20-四(4-(2,4-二氨基三嗪基)苯基)-卟啉钴、对苯二甲醛和二甲基亚砜三者混合,其中,5,10,15,20-四(4-(2,4-二氨基三嗪基)苯基)-卟啉钴、对苯二甲醛以及二甲基亚砜三种物质的摩尔比为1:1.8~2.2:0.28~0.42,将体系在160~185℃下加热回流60~84小时,直至反应完毕;
步骤3.将步骤2得到的产物静置冷却至室温,洗涤所收集的固体,得到粗产物;将粗产物用四氢呋喃索氏提取20~28小时,70~100℃真空干燥12~24小时,得到金属钴卟啉基多孔有机聚合物。
3.根据权利要求2所述的制备方法,其特征在于,所述的洗涤所用的洗涤剂为N,N-二甲基甲酰胺、甲醇、四氢呋喃中的一种或两种以上混合。
4.一种如权利要求1所述的金属钴卟啉基多孔有机聚合物在催化二氧化碳与环氧化合物环加成反应中的应用。
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