CN113999170B - 吡啶基离子液体的制备以及利用其催化合成环状碳酸酯的方法 - Google Patents

吡啶基离子液体的制备以及利用其催化合成环状碳酸酯的方法 Download PDF

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CN113999170B
CN113999170B CN202111411204.0A CN202111411204A CN113999170B CN 113999170 B CN113999170 B CN 113999170B CN 202111411204 A CN202111411204 A CN 202111411204A CN 113999170 B CN113999170 B CN 113999170B
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pyridyl
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郭续更
王丽
张敬来
任铁钢
张正昆
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Abstract

本发明涉及一类新型吡啶基离子液体，其具有如下所示的任一结构式：。本发明还提供了利用该离子液体催化合成环状碳酸酯的方法。本发明解决了现有利用CO2和环氧化合物合成环状碳酸酯的方法中存在的催化剂性能不高、反应条件苛刻、使用有机溶剂或助催化剂的问题，以新型吡啶基离子液体为催化剂，在0.1~0.5 MPa、30~90℃下催化环氧化合物和CO2进行环加成反应生成环状碳酸酯，最高产率可达98.1%。

Description

吡啶基离子液体的制备以及利用其催化合成环状碳酸酯的 方法
技术领域
本发明属于环境友好催化技术领域，具体涉及一种新型吡啶基离子液体及其制备方法和在催化二氧化碳与环氧化合物反应合成环状碳酸酯中的应用。
背景技术
作为一种廉价、丰富、无毒、可再生的C1资源，二氧化碳可以替代一氧化碳或光气合成许多高附加值的化工产品，如尿素、甲醇和环状碳酸酯，从绿色可持续发展的角度来看具有重要意义。在众多的CO2转化和利用方法中，CO2与环氧化合物的环加成反应是最有效和应用最广泛的方法。一方面，环加成反应是原子经济性反应，副产物可以忽略不计；另一方面，生成的环状碳酸酯被广泛用作极性非质子溶剂、燃料电池或锂离子电池的电解质以及各种医药中间体。
由于环状碳酸酯具有重要的经济潜力和广阔的应用前景，因此有必要进一步提高催化剂的性能，以提高收率和降低成本。在目前报道的各种催化剂中，离子液体以其独特的优势在众多催化剂中脱颖而出。近十年来，各种离子液体取得了很大的进展，如功能离子液体、双阳离子离子液体、双功能离子液体等。然而，一般的离子液体可能仍然具有一个或多个缺点，例如低催化活性、苛刻的催化条件和低重复使用性。因此，有必要探索一种在温和条件下具有高催化活性的高效离子液体。
发明内容
为了解决现有合成环状碳酸酯方法中催化剂活性低、反应条件苛刻、使用有机溶剂等技术问题，本发明旨在提供一种新型吡啶基离子液体，利用该离子液体催化合成环状碳酸酯可以在常温常压下进行，催化活性高，不需要金属助催化剂和有机溶剂。
本发明还提供了上述新型吡啶基离子液体的制备方法。
为达到上述目的，本发明采用以下技术方案:
一类新型吡啶基离子液体，其具有如下所示的任一结构式：
一种上述吡啶基离子液体的制备方法，其包括如下步骤：
1)4-二甲氨基吡啶和3-溴丙酸反应生成羧基吡啶溴盐；具体为：4-二甲氨基吡啶和3-溴丙酸溶解于甲苯中，在70-90℃搅拌反应10-14h；
2)羧基吡啶溴盐与1,1,3,3-四甲基胍(TMG)、1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、或苄基三甲基氢氧化铵([BTMA][OH])在溶剂存在条件下常温反应6～18h，反应结束后经旋蒸、洗涤、干燥即得；
上述吡啶基离子液体的合成路线如下所示：
进一步的，4-二甲氨基吡啶与3-溴丙酸的摩尔比为1∶1～1.2；羧基吡啶溴盐与1,1,3,3-四甲基胍、1,8-二氮杂双环[5.4.0]十一碳-7-烯、或苄基三甲基氢氧化铵的摩尔比为1∶1～1.2；所述溶剂为甲醇或乙醇等。
本发明提供了一种利用所述吡啶基离子液体催化合成环状碳酸酯的方法，其将吡啶基离子液体与环氧化合物按照摩尔比1～9∶100加入反应釜，封闭反应釜并通入二氧化碳，在反应压强为0.1～0.5MPa、反应温度为30～90℃的条件下环加成反应1～12h，合成环状碳酸酯。
具体的，所述环氧化合物为下述任一结构的化合物：
为了获得较高的收率，进一步优选的，吡啶基离子液体与环氧化合物的摩尔比为5～7∶100；环加成反应的温度为60～70℃，反应时间为6～9h。在该条件下，产物环状碳酸酯的收率约97％，选择性＞99％。
本发明提供了一种利用新型吡啶基离子液体催化CO2和环氧化合物制备环状碳酸酯的方法，即以新型吡啶基离子液体为催化剂，在温和条件下，不使用助催化剂和溶剂，使CO2和环氧化合物通过环加成反应合成环状碳酸酯。CO2与环氧化合物通过环加成反应制备环状碳酸酯的反应方程式如下：
式中R为-CH3、-CH2Cl、-CH2OH、-C6H5、-CH2OCH2CH＝CH2或-CH2OC6H5等。
和现有技术相比，本发明的有益效果如下：
1)本发明所提供的三种新型吡啶基离子液体[DMAPBrPC][TMGH]、[DMAPBrPC][DBUH]和[DMAPBrPC][BTMA]能够在温和、无助催化剂、无有机溶剂条件下高效地催化CO2和环氧化合物生成环状碳酸酯。该催化剂能够催化不同环氧化合物与CO2的环加成反应，表现出了优异的普适性；
2)本发明解决了现有利用CO2和环氧化合物合成环状碳酸酯的方法中存在的催化剂性能不高、反应条件苛刻、使用有机溶剂或助催化剂的问题，以新型吡啶基离子液体为催化剂，在0.1～0.5MPa、30～90℃下催化环氧化合物和CO2进行环加成反应生成环状碳酸酯，最高产率可达98.1％；
3)本发明新型吡啶基离子液体催化CO2和环氧化合物能够循环使用多次，催化生成环状碳酸酯后可以在加入乙酸乙酯条件下很容易分离出来，经过简单的洗涤和干燥即可重新得到固体状的离子液体，循环利用性能较好，降低了成本。该催化剂催化CO2与环氧化合物的环加成反应中活性高、反应条件温和、无金属、无溶剂，操作安全性高，有非常好的工业应用前景。
附图说明
图1和图2分别为实施例1中制备的[DMAPBrPC][TMGH]催化剂的核磁共振氢谱和碳谱；
图3和图4分别为实施例1中制备的[DMAPBrPC][DBUH]催化剂的核磁共振氢谱和碳谱；
图5和图6分别为是实施例1中制备的[DMAPBrPC][BTMA]催化剂的核磁共振氢谱和碳谱。
具体实施方式
本发明将结合具体实施方式作进一步详细说明，以下实施例只用于说明本发明，并不是本发明的限定。
实施例1
本实施例制备的新型吡啶基离子液体催化剂结构式如下：
通过以下步骤合成离子液体[DMAPBrPC][TMGH]：
1)合成羧基吡啶溴盐[DMAPBrPC]：在100ml单口烧瓶中，将30mmol(3.6651g)4-二甲氨基吡啶和36mmol(5.5070g)3-溴丙酸溶解于30ml甲苯中。然后将混合物在80℃下搅拌12h，直至固体产物不增加。反应结束后，倒出上层液体，残渣用二氯甲烷洗涤三次，在50℃真空干燥12h，即得[DMAPBrPC]；
2)在100ml单口瓶中，将0.02mol(5.5028g)[DMAPBrPC]和0.024mol(2.7643g)TMG溶解于30ml甲醇中，在室温25℃下搅拌反应12h。反应结束后，旋蒸除去甲醇，然后用乙酸乙酯洗涤，在50℃条件下干燥12h得到白色固体[DMAPBrPC][TMGH]。其核磁共振氢谱、碳谱分别见图1和2。
参考上述方法，将第一步反应中的原料TMG分别替换为DBU、[BTMA][OH]，最终分别得到吡啶基离子液体[DMAPBrPC][DBUH]和[DMAPBrPC][BTMA]；其核磁共振氢谱、碳谱见图3、4和图5、6。
图1和2数据如下：[DMAPBrPC][TMGH]:1H NMR(300MHz,D2O)δ7.96–7.85(m,2H),6.80–6.70(m,2H),4.22(t,J＝6.5Hz,2H),3.07(s,5H),2.85(d,J＝0.7Hz,12H),2.61(t,J＝6.5Hz,2H).13C NMR(75MHz,Deuterium Oxide)δ177.41,161.23,156.16,141.53,107.55,54.77,39.58,39.11,38.22。
图3和4数据如下：[DMAPBrPC][DBUH]:1H NMR(300MHz,D2O)δ7.96–7.83(m,2H),6.85–6.67(m,2H),4.23(t,J＝6.5Hz,2H),3.56–3.35(m,4H),3.21(t,J＝5.9Hz,2H),3.07(s,6H),2.63(t,J＝6.5Hz,2H),2.51(dd,J＝7.1,3.1Hz,2H),1.90(p,J＝5.9Hz,2H),1.59(dq,J＝9.5,5.5,4.2Hz,6H).13C NMR(75MHz,Deuterium Oxide)δ177.32,165.85,156.18,141.53,107.54,54.69,54.17,48.28,39.55,38.08,38.00,32.80,28.48,25.94,23.38,19.00。
图5和6数据如下：[DMAPBrPC][BTMA]:1H NMR(400MHz,D2O)δ7.95(d,J＝7.3Hz,2H),7.61–7.46(m,5H),6.79(d,J＝7.4Hz,2H),4.45(s,2H),4.28(t,J＝6.5Hz,2H),3.12(s,6H),3.06(s,9H),2.67(t,J＝6.5Hz,2H).13C NMR(75MHz,Deuterium Oxide)δ177.23,155.94,141.42,132.80,130.82,129.22,127.30,107.46,69.20,54.73,52.46,52.40,52.35,39.54,38.23。
从图1至6的核磁图及相应的核磁数据分析中可知：所合成的催化剂为目标催化剂。
实施例2
在50mL带有数显压力表的不锈钢反应釜中，加入实施例1制备的0.25mmol TMG催化剂和5mmol环氧氯丙烷，催化剂占环氧氯丙烷的摩尔含量为5mol％，缓慢通入CO2排除反应釜内残留空气，封闭反应釜并控制温度为60℃，持续通入CO2气体保持压强为0.1MPa，环加成反应7h，反应结束后，产物经气相色谱分析，测得产物4-氯甲基-[1,3]二氧环戊-2-酮收率为85.4％，选择性＞99％。
实施例3
具体实验过程与检测方法同实施例2，区别仅在于所使用的催化剂为DMAPBrPC，测得产物收率为93.5％，选择性＞99％。
实施例4
具体实验过程与检测方法同实施例2，区别仅在于所使用的催化剂为[DMAPBrPC][TMGH]，测得的产物收率为97.4％，选择性＞99％。
实施例5
具体实验过程与检测方法同实施例2，区别仅在于所使用的催化剂为[DMAPBrPC][DBUH]，测得的产物收率为96.6％，选择性＞99％。
实施例6
具体实验过程与检测方法同实施例2，区别仅在于所使用的催化剂为[DMAPBrPC][BTMA]，测得的产物收率为98.1％，选择性＞99％。
实施例7
具体实验过程与检测方法同实施例2，区别仅在于催化剂为[DMAPBrPC][TMGH]，占环氧氯丙烷摩尔含量为1mol％，测得的产物收率为83.9％，选择性＞99％。
实施例8
具体实验过程与检测方法同实施例7，区别仅在于催化剂占环氧氯丙烷摩尔含量为3mol％，测得的产物收率为96.3％，选择性＞99％。
实施例9
具体实验过程与检测方法同实施例7，区别仅在于催化剂占环氧氯丙烷摩尔含量为5mol％，测得的产物收率为97.4％，选择性＞99％。
实施例10
具体实验过程与检测方法同实施例7，区别仅在于催化剂占环氧氯丙烷摩尔含量为7mol％，测得的产物收率为97.7％，选择性＞99％。
实施例11
具体实验过程与检测方法同实施例7，区别仅在于催化剂占环氧氯丙烷摩尔含量为9mol％，测得的产物收率为97.6％，选择性＞99％。
实施例12
具体实验过程与检测方法同实施例7，区别仅在于催化剂占环氧氯丙烷摩尔含量为5mol％，反应温度为30℃，测得的产物收率为52.7％，选择性＞99％。
实施例13
具体实验过程与检测方法同实施例12，区别仅在于反应温度为40℃，测得的产物收率为74.1％，选择性＞99％。
实施例14
具体实验过程与检测方法同实施例12，区别仅在于反应温度为50℃，测得的产物收率为86.6％，选择性＞99％。
实施例15
具体实验过程与检测方法同实施例12，区别仅在于反应温度为70℃，测得的产物收率为97.7％，选择性＞99％。
实施例16
具体实验过程与检测方法同实施例12，区别仅在于反应温度为60℃，反应时间为1h，测得的产物收率为64.6％，选择性＞99％。
实施例17
具体实验过程与检测方法同实施例16，区别仅在于反应时间为3h，测得的产物收率为81.5％，选择性＞99％。
实施例18
具体实验过程与检测方法同实施例16，区别仅在于反应时间为5h，测得的产物收率为92.1％，选择性＞99％。
实施例19
具体实验过程与检测方法同实施例16，区别仅在于反应时间为9h，测得的产物收率为97.8％，选择性＞99％。
实施例20
具体实验过程与检测方法同实施例16，区别仅在于反应时间为10h，反应温度为30℃，测得的产物收率为65.3％，选择性＞99％。
实施例21
具体实验过程与检测方法同实施例16，区别仅在于反应时间为9h，反应温度为40℃，测得的产物收率为84.7％，选择性＞99％。
实施例22
具体实验过程与检测方法同实施例16，区别仅在于反应时间为12h，反应温度为40℃，测得的产物收率为92.5％，选择性＞99％。
实施例23
具体实验过程与检测方法同实施例16，区别仅在于反应时间为9h，反应温度为40℃，测得的产物收率为84.7％，选择性＞99％。
实施例24
具体实验过程与检测方法同实施例16，区别仅在于反应时间为8h，反应温度为50℃，测得的产物收率为94.9％，选择性＞99％。
实施例25
具体实验过程与检测方法同实施例16，区别仅在于反应时间为6h，反应温度为70℃，测得的产物收率为97.8％，选择性＞99％。
实施例26
具体实验过程与检测方法同实施例16，区别仅在于反应时间为5h，反应温度为80℃，测得的产物收率为97.7％，选择性＞99％。
实施例27
具体实验过程与检测方法同实施例16，区别仅在于反应时间为4h，反应温度为90℃，测得的产物收率为98.1％，选择性＞99％。
实施例28
具体实验过程与检测方法同实施例4，区别仅在于使用的环氧化合物为环氧丙烷，测得的产物收率为64.6％，选择性＞97％。
本实验反应方程式为：
实施例29
具体实验过程与检测方法同实施例4，区别仅在于使用的环氧化合物为环氧丙醇，测得的产物收率为48.0％，选择性＞96％。
本实验反应方程式为：
实施例30
具体实验过程与检测方法同实施例4，区别仅在于使用的环氧化合物为苯基缩水甘油醚，测得的产物收率为69.5％，选择性＞96％。
本实验反应方程式为：
实施例31
具体实验过程与检测方法同实施例4，区别仅在于使用的环氧化合物为氧化苯乙烯，测得的产物收率为73.7％，选择性＞98％。
本实验反应方程式为：
实施例32
具体实验过程与检测方法同实施例31，区别仅在于使用的环氧化合物为烯丙基缩水甘油醚，测得的产物收率为84.6％，选择性＞97％。
本实验反应方程式为：
实施例33
具体实验过程与检测方法同实施例19，区别仅在于使用的环氧化合物为环氧环己烷，反应压力为0.5MPa，反应温度为90℃测得的产物收率为33.1％，选择性＞96％。
本实验反应方程式为：
实施例34-39
具体实验过程与检测方法同实施例19，区别仅在于使用的催化剂为实施例19中回收的[DMAPBrPC][TMGH]催化剂，在相同条件下进行6次循环回收实验，所得结果见表1。具体回收方法如下：反应结束后，加入约15mL乙酸乙酯，有白色固体析出，过滤后再次加入乙酸乙酯，反复洗涤三次，在50℃条件下干燥12h即可得到回收的[DMAPBrPC][TMGH]。表1可以看出：6次循环回收后，催化剂仍然具有较好的活性，产品收率在91.8％，选择性为99％。
表1实施例34-39催化剂回收使用催化结果

Claims (7)

1.吡啶基离子液体，其特征在于，具有如下所示的任一结构式：
。
2.权利要求1所述吡啶基离子液体的制备方法，其特征在于，包括如下步骤：
1）4-二甲氨基吡啶和3-溴丙酸反应生成羧基吡啶溴盐；
2）羧基吡啶溴盐与1,1,3,3-四甲基胍、1,8-二氮杂双环[5.4.0]十一碳-7-烯、或苄基三甲基氢氧化铵在溶剂存在条件下常温反应6~18 h，反应结束后经旋蒸、洗涤、干燥即得。
3.根据权利要求2所述吡啶基离子液体的制备方法，其特征在于，4-二甲氨基吡啶与3-溴丙酸的摩尔比为1∶1~1.2；羧基吡啶溴盐与1,1,3,3-四甲基胍、1,8-二氮杂双环[5.4.0]十一碳-7-烯、或苄基三甲基氢氧化铵的摩尔比为1∶1~1.2；所述溶剂为甲醇或乙醇。
4.利用权利要求1所述吡啶基离子液体催化合成环状碳酸酯的方法，其特征在于，将吡啶基离子液体与环氧化合物按照摩尔比1~9∶100加入反应釜，封闭反应釜并通入二氧化碳，在反应压强为0.1~0.5 MPa、反应温度为30~90℃的条件下环加成反应1~12 h，合成环状碳酸酯。
5.根据权利要求4所述利用吡啶基离子液体催化合成环状碳酸酯的方法，其特征在于，所述环氧化合物为下述任一结构的化合物：，，/>。
6.根据权利要求4所述利用吡啶基离子液体催化合成环状碳酸酯的方法，其特征在于，吡啶基离子液体与环氧化合物的摩尔比为5~7∶100。
7.根据权利要求4所述利用吡啶基离子液体催化合成环状碳酸酯的方法，其特征在于，环加成反应的温度为60~70℃，反应时间为6~9h。
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