CN115160232B - 一种二氧化碳与环氧化合物合成环状碳酸酯的方法及其催化剂 - Google Patents

一种二氧化碳与环氧化合物合成环状碳酸酯的方法及其催化剂 Download PDF

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CN115160232B
CN115160232B CN202210743782.2A CN202210743782A CN115160232B CN 115160232 B CN115160232 B CN 115160232B CN 202210743782 A CN202210743782 A CN 202210743782A CN 115160232 B CN115160232 B CN 115160232B
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carbon dioxide
epoxy compound
cyclic carbonate
quaternary ammonium
ammonium salt
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CN115160232A (zh
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陈雪君
曹朝伟
王帮应
涂凯
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Shenzhen Capchem Technology Co Ltd
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Abstract

本发明涉及绿色、清洁、高效催化技术领域，尤其涉及一种二氧化碳与环氧化合物通过催化反应合成环状碳酸酯的方法以及对应的催化剂。本发明以羟基氮杂环季铵盐为催化剂，用于催化二氧化碳与环氧化合物反应合成环状碳酸酯。本发明选用全新的羟基氮杂环季铵盐做催化剂，可在较温和的反应条件下高效、高选择性的合成环状碳酸酯，且催化剂成本低、选择性高、热稳定性好，并可重复使用。

Description

一种二氧化碳与环氧化合物合成环状碳酸酯的方法及其催 化剂
技术领域
本发明涉及绿色、清洁、高效催化技术领域，尤其涉及催化二氧化碳与环氧化合物反应合成环状碳酸酯的催化剂及合成环状碳酸酯的方法。
背景技术
二氧化碳是导致全球气候变暖的主要温室气体，也是地球上取之不竭、廉价、无毒、可循环再生的的绿色碳资源；实现二氧化碳的资源化利用对二氧化碳的减排、改善环境和降低人类对化石燃料的依赖具有重要的战略意义。二氧化碳的有效固定已经成为本世纪最具挑战性的课题之一，而合成环状碳酸酯就是其中一种很好的固定途径。近年来环状碳酸酯作为高附加值化学品在精细化工、锂电池制造、聚碳酸酯和聚氨酯的合成领域获得了广泛应用。环状碳酸酯的制备方法主要有光气法、酯交换法和二氧化碳与环氧化合物环加成法。而二氧化碳与环氧化合物环加成制备环状碳酸酯是一种具有100％原子经济性的绿色化学方法，一直备受学术界和工业界的关注。
在自然条件下，二氧化碳和环氧化合物将难以发生反应，或者二者反应生成环状碳酸酯的效率较低。因此，选择合适的催化剂能有效提高二氧化碳和环氧化合物反应生成环状碳酸酯的效率。目前已报道的生产环状碳酸酯大多使用路易斯酸金属和路易斯碱组成的二元催化剂，其中所使用的路易斯金属有：碱金属卤化物，碱土金属卤化物，过渡金属盐，过渡金属配合物或四齿希夫碱金属配合物；所用的路易斯碱有有机碱，季铵盐，咪唑盐，固体碱(如金属氧化物)，冠醚，分子筛等等。这些催化剂体系或多或少的存在催化活性不高，稳定性不好，反应条件苛刻，使用毒性很强的有机溶剂，催化剂成本高等问题。而用单组份催化剂催化合成环状碳酸酯的方法很少，故本发明以开发廉价，高效，组分简单，稳定性好，环境友好的催化剂为目的。
发明内容
本发明针对以上技术问题，提供了一种全新的羟基氮杂环季铵盐作为催化剂，来实现二氧化碳和环氧化合物反应合成环状碳酸酯，具有催化成本低、反应高效、高选择性的优点。
本发明解决上述技术问题所采用的技术方案如下：
本发明提供了一种羟基氮杂环季铵盐，所述羟基氮杂环季铵盐为下述结构式中的任一种所示的化合物：
其中，R3、R4、R5、R6、R7、R8各自独立地选自氢原子和C1-C16的烷基；X为卤素原子；m和n各自独立的选自1、2、3；且当n＝1时，m＝2或3；当n＝2时，m＝2；当n＝3时，m＝1。
进一步的，R3、R4、R5、R6、R7、R8各自独立地选自氢原子和甲基。
进一步的，X选自Cl、Br、I中的一种。
进一步的，X选自Cl、Br中的一种。
进一步的，所述羟基氮杂环季铵盐选自下述结构式所示化合物中的一种：
另一方面，本发明还提供一种二氧化碳与环氧化合物合成环状碳酸酯的方法，所述方法以二氧化碳和环氧化合物为原料，上述羟基氮杂环季铵盐为催化剂，反应合成环状碳酸酯。
进一步的，所述环氧化合物的结构式为：
其中，当R1＝H时，R2为H、CH3、C2H5、CH2Cl、C2H3、C4H9O、C4H9、C6H5、C7H7O的一种；当R1≠H时，所述环氧化合物为环氧环己烷。
具体的，所述环氧化合物的结构式为：
进一步的，所述羟基氮杂环季铵盐与环氧化合物的摩尔比为1×10-3-2.5×10-3：1。
进一步的，所述反应的压力为0.1-10MPa。
进一步的，所述反应的温度为40-220℃。
进一步的，所述反应的时间为0.5-6h。
本发明还提供上述羟基氮杂环季铵盐在催化二氧化碳与环氧化合物合成环状碳酸酯中的应用。
本发明具有如下有益效果：
(1)本发明提供了一种新的羟基氮杂环季铵盐，其可作为催化二氧化碳和环氧化合物反应合成环状碳酸酯的单一催化剂。发明人创新性地发现羟基氮杂环季铵盐上取代基的种类会影响其催化效果，并进一步研究获得了本发明结构式的羟基氮杂环季铵盐。所述羟基氮杂环季铵盐含有特定类型的取代基，催化性能得到明显改善，可环保、高效、高选择性地催化二氧化碳和环氧化合物通过环加成反应合成环状碳酸酯，有效提高环状碳酸酯的选择性和收率，制备得到的环状碳酸酯选择性可高达99.8％，收率可高达到99％。
(2)本发明的环状碳酸酯的合成方法，通过使用所述羟基氮杂环季铵盐为催化剂，可在较温和的反应条件下高效地合成环状碳酸酯，且所述羟基氮杂环季铵盐成本低、选择性高、热稳定性好，并可重复使用。
附图说明
为了更清楚的说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍，显而易见的，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它附图。
图1为本发明实施例2所得产品的气相色谱分析结果。
具体实施方式
下面将结合具体实施例，对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本发明的保护范围。
本发明所述羟基氮杂环季铵盐选自以下结构式中任一种所示的化合物：
其中，R3、R4、R5、R6、R7、R8各自独立的选自氢原子和C1-C16的烷基；X为卤素原子；m和n各自独立的选自1、2、3。
具体的，所述羟基氮杂环季铵盐的合成方法，以合成为例，包括以下步骤：
在磁力搅拌下，将5.2g 1-甲基咪唑(62.5mmol，5mL)和6.5g 2,2-双(溴甲基)-1,3-丙二醇(25mmol)的混合物在150℃加热8小时。冷却至室温后，所得固体用乙腈洗涤3次，残渣在100℃烘箱中干燥2h，得到10.14g 2,2-双[(1-甲基咪唑-3-基)甲基]丙烷-1,3-二醇，为白色粉末(收率：95.25％，熔点＝150℃)。再将2,2-双[(1-甲基咪唑-3-基)甲基]丙烷-1,3-二醇与一定含量的氢溴酸反应，即得对应季铵盐。
本发明的二氧化碳与环氧化合物合成环状碳酸酯的方法，其反应通式为：
其中，R1、R2为环氧化合物环上的取代基，当R1＝H时，R2为H(环氧乙烷)、CH3(环氧丙烷)、C2H5(环氧丁烷)、CH2Cl(环氧氯丙烷)、C2H3(环氧丁烯)、C4H9O(2-丙氧基甲基环氧乙烷)、C4H9(环氧己烷)、C6H5(环氧苯乙烷)、C7H7O(2-(苯氧基甲基)环氧乙烷)的一种；当R1≠H时，所述环氧化合物为环氧环己烷。
具体的，所述环氧化合物的结构式为：
所述羟基氮杂环季铵盐与环氧化合物的摩尔比为1×10-3-2.5×10-3：1，在反应压力为0.1-10MPa，温度为40-220℃，反应时间为0.5-6h的条件下合成环状碳酸酯。所述方法反应条件温和，所用所述羟基氮杂环季铵盐为单组分催化剂，具有成本低、选择性高、热稳定性好的优点。
下面将结合具体实施例对本发明的环状碳酸酯合成方法做进一步说明。
实施例1
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例1所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为3MPa，反应0.5h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例2
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例2所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至130℃，然后控制二氧化碳压力为4MPa，反应0.6h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致(图1)，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例3
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例3所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至140℃，然后控制二氧化碳压力为2MPa，反应0.7h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例4
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例4所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为3MPa，反应0.5h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例5
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例5所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为3MPa，反应0.5h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例6
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例6所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为5MPa，反应0.2h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例7
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例7所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为6MPa，反应0.2h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例8
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例8所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至130℃，然后控制二氧化碳压力为2MPa，反应2h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例9
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例9所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至130℃，然后控制二氧化碳压力为3MPa，反应3h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例10
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例10所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至140℃，然后控制二氧化碳压力为3MPa，反应2.5h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例11
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例11所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为3MPa，反应4h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例12
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例12所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至130℃，然后控制二氧化碳压力为3MPa，反应0.3h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例13
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例13所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至130℃，然后控制二氧化碳压力为8MPa，反应0.3h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例14
在带有四氟内衬的25mL不锈钢高压釜中，依次加入按表2中实施例14所示添加量的环氧化合物和催化剂，密闭反应釜，充入适量压力的二氧化碳，将反应釜缓慢升温至120℃，然后控制二氧化碳压力为10MPa，反应0.1h，冷却至室温，泄压，二氧化碳用饱和碳酸氢钠溶液吸收，将所得的液体减压蒸馏得产品，气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
实施例15-18
实施例15-18包括实施例1中大部分的操作步骤，区别仅在于按表2中实施例15-18所示的催化剂添加。气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
对比例1-2
对比例1-2包括实施例1中大部分的操作步骤，区别仅在于按表2中对比例1-2所示的催化剂添加。气相色谱分析，产品出峰时间与标样一致，说明产品为碳酸乙烯酯，产品性质如表2所示。
各实施例及对比例中所用催化剂分别为如表1中结构式所示的化合物。
表1
各实施例及对比例中所用催化剂及用量以及环状碳酸酯产物性质如表2所示。
表2
对比实施例1-14和对比例1-2的测试结果可知，以二氧化碳和环氧化合物为原料，以本发明羟基氮杂环季铵盐为催化剂，可在温和反应条件下制备得到环状碳酸酯，且制备得到的环状碳酸酯具有更高的选择性和收率。说明本发明含有特定类型取代基的羟基氮杂环季铵盐的催化性能得到明显改善，可环保、高效、高选择性地催化二氧化碳和环氧化合物通过环加成反应合成环状碳酸酯，有效提高环状碳酸酯的选择性和收率。
对比实施例1、实施例15-18的测试结果可知，当催化剂羟基氮杂环季铵盐与环氧化合物的摩尔比在较大范围内时，均可得到具有较高选择性和收率的环状碳酸酯；尤其是二者摩尔比在1×10-3-2.5×10-3范围内时，催化效果更佳。
由上可知，本发明通过全新的羟基氮杂环季铵盐做催化剂，可实现在温和反应条件下，高效、高选择性的由二氧化碳和环氧化合物通过环加成反应合成环状碳酸酯，且得到的环状碳酸酯的收率高，催化效果明显。
以上借助具体实施例对本申请做了进一步描述，但是应该理解的是，这里具体的描述，不应理解为对本申请的实质和范围的限定，本领域内的普通技术人员在阅读本说明书后对上述实施例做出的各种修改，都属于本申请所保护的范围。

Claims (11)

1.一种二氧化碳与环氧化合物合成环状碳酸酯的方法，其特征在于，以二氧化碳和环氧化合物为原料，以羟基氮杂环季铵盐为催化剂，反应合成环状碳酸酯；所述羟基氮杂环季铵盐为下述结构式中的任一种所示的化合物：
其中，R3、R4、R5、R6、R7、R8各自独立地选自氢原子和C1-C16的烷基；X为卤素原子；m和n各自独立的选自1、2、3；且当n＝1时，m＝2或3；当n＝2时，m＝2；当n＝3时，m＝1；
所述环氧化合物的结构式为：
其中，当R1＝H时，R2为H、CH3、C2H5、CH2Cl、C2H3、C4H9O、C4H9、C6H5、C7H7O的一种；当R1≠H时，所述环氧化合物为环氧环己烷。
2.如权利要求1所述的方法，其特征在于，R3、R4、R5、R6、R7、R8各自独立地选自氢原子和甲基。
3.如权利要求1所述的方法，其特征在于，X选自Cl、Br、I中的一种。
4.如权利要求1所述的方法，其特征在于，所述羟基氮杂环季铵盐选自下述结构式所示化合物中的一种：
5.根据权利要求1所述的二氧化碳与环氧化合物合成环状碳酸酯的方法，其特征在于，所述羟基氮杂环季铵盐与环氧化合物的摩尔比为1×10-3-2.5×10-3：1。
6.根据权利要求1所述的二氧化碳与环氧化合物合成环状碳酸酯的方法，其特征在于，反应的压力为0.1-10MPa；和/或，反应的温度为40-220℃。
7.根据权利要求1所述的二氧化碳与环氧化合物合成环状碳酸酯的方法，其特征在于，反应的时间为0.5-6h的条件下合成环状碳酸酯。
8.羟基氮杂环季铵盐在催化二氧化碳与环氧化合物合成环状碳酸酯中的应用，其特征在于，所述羟基氮杂环季铵盐为下述结构式中的任一种所示的化合物：
其中，R3、R4、R5、R6、R7、R8各自独立地选自氢原子和C1-C16的烷基；X为卤素原子；m和n各自独立的选自1、2、3；且当n＝1时，m＝2或3；当n＝2时，m＝2；当n＝3时，m＝1；
所述环氧化合物的结构式为：
其中，当R1＝H时，R2为H、CH3、C2H5、CH2Cl、C2H3、C4H9O、C4H9、C6H5、C7H7O的一种；当R1≠H时，所述环氧化合物为环氧环己烷。
9.如权利要求8所述的应用，其特征在于，R3、R4、R5、R6、R7、R8各自独立地选自氢原子和甲基。
10.如权利要求8所述的应用，其特征在于，X选自Cl、Br、I中的一种。
11.如权利要求8所述的应用，其特征在于，所述羟基氮杂环季铵盐选自下述结构式所示化合物中的一种：
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