CN106391119B - 一种有机框架材料催化二氧化碳高效合成环碳酸酯的方法 - Google Patents
一种有机框架材料催化二氧化碳高效合成环碳酸酯的方法 Download PDFInfo
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Abstract
一种有机框架材料催化二氧化碳高效合成环碳酸酯的方法,该催化剂是有机共价大分子平面化合物,具有结构稳定的优点;其催化位点多具有较高的催化转化效率;该催化剂容易与反应物分离,具有非常好的循环作用;该催化剂稳定性较好,不易分解。本发明能够解决以往催化CO2与环氧化合物生成环氧碳酸酯反应中催化剂不稳定,不能重复利用的问题。该催化剂能够多次、高效的循环使用。
Description
技术领域
本发明公开了一种共价键连接的有机框架结构的催化剂并用于催化CO2与环氧烷烃生成环氧碳酸酯的反应。实现多位点催化、重复性好、催化效率高的特点。测试了该催化剂的循环次数。实验结果表明:该催化剂催化该类反应具有60-95%的产率,并且此催化剂循环使用6次后催化活性依然保持不变,本发明涉及催化化学领域。
技术背景
随着温室气体的含量不断增加,温室效应越来越明显,以至于近年来天气极端反常;而CO2是温室气体的主要成分,并且在大气中的含量非常的高,同时CO2又是一种很重要的C1资源,因此能将CO2转化为化工原料或者化工产品是非常有价值和意义。近些年来关于催化CO2的捕获活化转化的研究报道很多,由于CO2具有热力学和动力学上的稳定性,造成活化利用CO2需要较高的温度和苛刻的反应条件,因此开发一种高效的,条件温和的催化剂是非常有必要的。关于催化CO2与环氧烷烃生成环状碳酸酯的报道非常多,主要有有无机金属催化剂,金属有机催化剂,有剂催化剂,但是这些催化剂主要缺点是催化剂不稳定,无法多次的重复利用,从而给大规模工业化带来极大的障碍。
鉴于此,本发明设计并合成一种具有可重复利用的多相催化剂,催化CO2与环氧烷烃生成环状碳酸酯反应,从而解决上述迫切的问题。
发明内容
本发明的目的是针对现有技术不足提供一种有机框架材料催化二氧化碳高效合成环碳酸酯的方法,该催化剂能够解决其他催化剂催化CO2与环氧烷烃反应中催化剂不稳定,无法循环重利用的难题。为解决上述技术问题,本发明采用全新的策略,设计和合成一系列的共价键连接的有机框架材料,并应用于催化CO2与环氧烷烃生成环氧碳酸酯的反应。
本发明所述方法的工艺步骤如下:
(1)共价键连接的有机框架材料的合成:在反应容器中,加入1:10至10:1的不同比例的正丁醇和三甲基苯作为溶剂,加入与反应物摩尔比为0.5%-5%有机酸作为催化剂,所用有机酸为甲酸、乙酸、丙酸、苯甲酸中的一种,按照2:1的比例加入对苯二甲醛和四对氨基苯基卟啉,并在用超声波仪器超声5-20分钟,并抽出空气—通入氮气—抽出空气—通入氮气,并循环2-9次,在30-200℃,氮气保护下反应;
(2)反应结束后离心分离,并用四氢呋喃和丙酮分别洗涤3-11次,真空干燥24小时;得到反应所需的共价键连接的有机框架材料即COF-366;
(3)将步骤(2)得到的COF-366和金属醋酸盐溶解在DMF溶剂中,加热到20-110℃,在氮气保护搅拌3-9小时;反应结束后过滤,并用水和甲醇洗涤多次,即可得到COF-366(M)化合物,M为Cu,Cr,Co,Zn中的一种,真空干燥;
(4)称取催化剂COF-366(M),反应助催化剂PTAT即苯基三甲基三溴化铵、DMAP即N,N-二甲基甲酰胺、N-甲基咪唑即TBAB、四苯基溴化膦即TPPB和碘化钾(KI)中的一种以及反应物环氧烷烃,加入高压反应釜中;上述催化剂、反应助催化剂和反应物的摩尔比为1:1:85至1:1:95,通入二氧化碳,设置压力为0.1MPa-2MPa,在0-120℃的条件下反应;
(5)反应结束后将反应中的催化剂离心分离取其上清液用气相色谱仪进行检测。
所述催化材料的制备方法适合COF-366(Cu),COF-366(Cr)COF-366(Co)COF-366(Cu)等有机框架材料的合成;其催化反应适合所有液态环氧烷烃与CO2反应生成环状碳酸酯的反应;反应在不同0-120℃和CO2压强为0.1-2MP条件下进行。
本发明的有益效果:本发明的催化剂易制备,通过实验证明了该类催化剂催化CO2与环氧烷烃生成环氧碳酸酯的反应有很高的催化效果,同时研究表明催化剂重复利用6次以上催化产率不变。
附图说明
图1是共价键连接的有机框架分子催化剂合成路线图;
图2a是COF-366催化剂的粉末衍射图谱;
图2b是COF-366(Co)催化剂的粉末衍射图谱;
图2c是COF-366(Zn)催化剂的粉末衍射图谱;
图3是催化反应示意图;R=为烷烃和芳香烃基团;
图4是催化剂的催化该反应的重复使用效率图。
具体实施方式
下面结合附图对本发明的实施进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。请参阅图1和图2、图3,图4和表1。
实施例1
在25ml烧瓶中分别加四对氨基苯基卟啉50mg(0.0739mmol),对苯二甲醛24.8mg(0.147mmol),正丁醇/三甲基苯(8ml,体积比1/1),1ml乙酸(6mol/L),超声10min并抽出空气——通入氮气——抽出空气通入氮气循环三次,在氮气保护下加热到85℃反应五天。反应结束后离心分离,并用四氢呋喃洗10次,用丙酮洗两次。真空干燥24小时。即得到COF-366,然后把50mg的COF-366和40mg的Co(CH3COO)2溶解在10ml的DMF溶液中,在氮气保护下加热到70℃搅拌4h。反应结束后过滤,用水和甲醇洗涤三次,即可得到COF-366(Co),真空干燥24小时,对催化剂进行粉末X-衍射实验图谱(图2)从图2a中可知在2θ=3.5°处有一个比较高的峰,这说明COF-366是一个平面堆叠的层状微晶结构。图2b是COF-366(Co)的粉末单晶衍射图谱,从图2b可以看出原有的COF-366的平面堆叠发生了改变,由卟啉环与卟啉环对应堆叠变成了错位堆叠。
称取催化剂10mg,助催化剂(TPPB)10mg,取环氧丙烷1ml,放在高压反应釜中,反应釜中CO2压力为1MPa,在温度为60℃的条件下反应6小时。反应结束后将反应釜中的催化剂离心分离取其上清液用气相色谱仪进行检测。从表1可以看出,该类催化剂有很好的催化效果,产率为93%。
将反应后的液体进行离心,然后去沉淀在80℃的条件下烘焙12h,再在冷冻干燥机中干燥24h。再将干燥后的催化剂直接投入催化反应并加入与前面等量的助催化剂,其他步骤保持不变。从图4中可以看出,催化剂重复使用6次,催化活性没有显著的下降。
实施例2
在25ml烧瓶中分别加四对氨基苯基卟啉50mg(0.0739mmol),对苯二甲醛24.8mg(0.147mmol),正丁醇/三甲基苯(8ml,体积比3/1),1ml甲酸(6mol/L),超声10min并抽出空气——通入氮气——抽出空气通入氮气循环三次,在氮气保护下加热到85℃反应五天。反应结束后离心分离,并用四氢呋喃洗7次,用丙酮洗两次。真空干燥24小时。即COF-366,然后把50mg的COF-366和40mg的Zn(CH3COO)2溶解在10ml的DMF溶液中,在氮气保护下加热到70℃搅拌4h。反应结束后过滤,用水和甲醇洗涤三次,即可得到COF-366(Zn),真空干燥24小时,对催化剂进行粉末X-衍射实验图谱(图2c)。从图2c中可知原有的COF-366的平面堆叠发生了改变,由卟啉环与卟啉环对应堆叠变成了错位堆叠。
称取催化剂10mg,助催化剂(KI)10mg,取环氧丙烷1ml,放在高压反应釜中,通入CO2,压力为1MP,温度为60℃的条件下反应6小时。反应结束后将反应液离心分离取其上清液做气象色谱。从表1可以看出,该类催化剂有很好的催化效果,产率为93%。
表1 COF-366(M)催化剂催化CO2与环氧丙烷/环氧丁烷加成合成环状碳酸酯的结果
。
Claims (1)
1.一种有机框架材料催化二氧化碳高效合成环碳酸酯的方法,其特征在于:
所述方法工艺步骤如下:
(1)共价键连接的有机框架材料的合成:在反应容器中,加入1:10至10:1的不同比例的正丁醇和三甲基苯作为溶剂,加入与反应物摩尔比为0.5%-5%有机酸作为催化剂,所用有机酸为甲酸、乙酸、丙酸、苯甲酸中的一种,按照2:1的比例加入对苯二甲醛和四对氨基苯基卟啉,并在用超声波仪器超声5-20分钟,并抽出空气—通入氮气—抽出空气—通入氮气,并循环2-9次,在30-200℃,氮气保护下反应;
(2)反应结束后离心分离,并用四氢呋喃和丙酮分别洗涤3-11次,真空干燥24小时;得到反应所需的共价键连接的有机框架材料即COF-366;
(3)将步骤(2)得到的COF-366和金属醋酸盐溶解在DMF溶剂中,加热到20-110℃,在氮气保护搅拌3-9小时;反应结束后过滤,并用水和甲醇洗涤多次,即可得到COF-366(M)化合物,M为Cu,Cr,Co,Zn中的一种,真空干燥;
(4)称取催化剂COF-366(M),反应助催化剂PTAT即苯基三甲基三溴化铵、DMAP即N,N-二甲基甲酰胺、N-甲基咪唑即TBAB、四苯基溴化膦即TPPB和碘化钾中的一种以及反应物环氧烷烃,加入高压反应釜中;上述催化剂、反应助催化剂和反应物的摩尔比为1:1:85至1:1:95,通入二氧化碳,设置压力为0.1MPa-2MPa,在0-120℃的条件下反应;
(5)反应结束后将反应中的催化剂离心分离取其上清液用气相色谱仪进行检测。
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