CN109970699B - 一种新型低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法 - Google Patents
一种新型低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法 Download PDFInfo
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Abstract
本发明涉及一种新型低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，该方法以二氧化碳和不同取代基环氧化合物为原料，以季鏻溴盐、氨基苯酚按照摩尔比1:2~1:3合成的新型低共熔离子液体为催化剂，在催化剂用量为环氧化合物摩尔量的5%~10%，反应压力为0.1 MPa，反应温度为25℃，反应时间为12~24小时的条件下合成相应的环状碳酸酯。本发明所提出的新型低共熔离子液体制备简单高效、原料廉价易得、催化性能优异，可以实现常温、常压条件下环状碳酸酯的高选择性合成。同时本发明避免了有毒过渡金属、挥发性有机溶剂及助催化剂的使用，催化剂与产物易分离，属于环境友好型催化剂。
Description
技术领域
本发明涉及一种新型低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，属于CO2清洁资源化利用领域。
背景技术
由于发热发电需要，化石燃料燃烧产生的二氧化碳(CO2)每年超过130亿吨，这严重加剧了气候变化和海洋酸化问题。政府间气候变化专门委员会(IPCC)预测，到2100年，全球平均温度上升1.9℃。因此，降低全球温室气体排放势在必行。同时CO2还是环境友好、储量丰富、价格低廉且可再生的C1资源，将捕集的CO2经过化学转化合成用途广泛、高附加值的化学品，从环境保护及可持续发展化学的角度来讲，具有重大意义。其中具有代表性的一类化学品就是环状碳酸酯，该类产品通过CO2与环氧化物通过100％原子经济性反应制备而成，且环状碳酸酯在锂离子电池电解质、极性高沸点非质子溶剂及药物中间体等方面均具有广泛的应用。
目前，已开发出系列均相和非均相催化剂应用于催化CO2与环氧化物环加成反应，例如金属氧化物、碱金属盐、Salen金属配合物、金属有机骨架、离子液体以及金属功能聚合物等。以上报道催化剂中，金属基催化剂占很大比例，考虑到过渡金属离子长期过渡使用对人类以及生态环境的安全隐患，非过渡金属类催化剂的设计开发引起人们的关注。其中，离子液体被认为是最具有吸引力的非金属催化剂之一，主要归因于离子液体独特的Lewis酸碱双功能性以及对CO2较强的溶解能力。然而，目前报道的离子液体在温和条件下均不能得到令人满意的催化活性，为了提高催化活性，需要额外加入助催化剂，如过渡金属卤化物、氢键供体等活化环氧化物，以促进其开环反应的进行；或者将活性基团，如羟基、羧基或氨基等对离子液体进行功能化改性，以提高催化活性。据我们所知，大部分报道的离子液体存在合成工艺复杂、价格昂贵以及分离提纯困难等问题，限制了实际大规模工业应用，而且催化剂与环状碳酸酯的分离通常采用高温蒸馏手段，能耗较高，容易带来CO2二次排放，不符合“绿色化学”及“可持续发展”的观念。
为了解决以上问题，低共熔离子液体被提出应用于催化CO2与环氧化物环加成反应。低共熔离子液体除了具有离子液体自身的优良性能外，还具有无毒或低毒、价格低廉、合成简单高效、无需提纯等优点，有望成为传统有机溶剂/催化剂的优良替代品。目前报道的用于催化转化CO2合成环状碳酸酯的低共熔离子液体大体包括以下几种：氯化胆碱/尿素、尿素/卤化锌、氯化胆碱/醋酸以及氯化胆碱/聚乙二醇，但是仍然存在催化活性低、反应条件苛刻的问题，未发现有关低共熔离子液体常温、常压条件下催化转化CO2合成环状碳酸酯的报道。基于此，我们提出本项发明研究。
发明内容
本发明要解决的技术问题是提供一种新型低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，而且该低共熔离子液体合成简单、价格低廉、稳定性高、可重复利用、环境友好，同时避免过渡金属、挥发性有机溶剂及助催化剂的使用，对CO2实现清洁资源化利用。其中，CO2与环氧化物环加成制备环状碳酸酯反应方程式如下：
为了解决上述技术问题，本发明提出了一种新型低共熔离子液体常温常压条件下化学固定CO2合成环状碳酸酯的方法，即以新型低共熔离子液体为催化剂，使环氧化物和CO2通过环加成反应合成环状碳酸酯，所述低共熔离子液体以氨基苯酚作为氢键供体组分，以季鏻溴盐作为氢键受体组分，二者通过分子间氢键作用可生成低共熔离子液体。在催化CO2与环氧化物环加成反应中，氨基苯酚结构中氨基可以活化惰性CO2分子，酚羟基通过氢键作用可以活化环氧化物，季鏻溴盐结构中溴阴离子作为亲核试剂可以进攻活化后的环氧化物，二者的协同作用可以显著提高低共熔离子液体的催化活性。氨基苯酚选自邻氨基苯酚(2-AP)、间氨基苯酚(3-AP)或对氨基苯酚(4-AP)中的一种，季鏻溴盐结构通式如下：
式中R1，R2，R3，R4均选自苯基、苄基或碳数≤8的烷基中的一种。
作为本发明的进一步优化，所述环氧化物结构式为
中的任意一种。
作为本发明的进一步优化，所述低共熔离子液体由季鏻溴盐与氨基苯酚在50℃条件下搅拌反应0.5小时制备而成，季鏻溴盐与氨基苯酚摩尔比为1:2～1:3。
作为本发明的进一步优化，所述季鏻溴盐为四丁基溴化鏻(TBPB)、甲基三苯基溴化鏻(MTPB)、烯丙基三苯基溴化鏻(ATPB)或苄基三苯基溴化鏻(BTPC)中的任意一种。
作为本发明的进一步优化，二氧化碳与环氧化物环加成反应温度为25℃，反应压力为0.1MPa。
作为本发明的进一步优化，低共熔离子液体用量为环氧化合物摩尔量的5％～10％。
作为本发明的进一步优化，季鏻溴盐与氨基苯酚摩尔比为1:2。
作为本发明的进一步优化，所述季鏻溴盐为四丁基溴化鏻(TBPB)。
作为本发明的进一步优化，低共熔离子液体用量为环氧化物摩尔量的6％～8％。
作为本发明的进一步优化，二氧化碳与环氧化物环加成反应时间为12～24小时。
采用上述技术方案所产生的有益效果在于：本发明所提出的新型低共熔离子液体可通过氢键作用来取代过渡金属离子对环氧化物的活化开环，该低共熔离子液体氨基基团同时能够对惰性CO2气体进行吸收活化，可以实现常温、常压条件下高选择性合成环状碳酸酯，同时环加成反应过程中避免了助催化剂及挥发性有机溶剂的使用，具有环境友好性；该新型低共熔离子液体能够催化不同取代基环氧化物与二氧化碳的环加成反应，且反应结束后催化剂与产物经过简单萃取即可实现分离，具有优异的普适性与循环回用性能；此外，该类低共熔离子液体合成简单高效、价格低廉、环境友好，无需额外提纯，易于实现大规模合成及应用。本发明相比于已报道诸多离子液体，在催化剂合成及催化活性方面均得到明显改善，能够实现常温、常压条件下清洁催化转化CO2合成环状碳酸酯，表现出很大的发展潜力。
附图说明
图1是本发明其中一种低共熔离子液体TBPB/3-AP红外谱图；
图2是本发明其中一种低共熔离子液体TBPB/3-AP核磁氢谱图；
图3是本发明其中一种低共熔离子液体TBPB/3-AP对CO2活化红外谱图。
具体实施方式
本发明将结合具体实施方式作进一步详细的说明，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新型低共熔离子液体的合成
将四丁基溴化鏻(TBPB)与间氨基苯酚(3-AP)按照摩尔比为1:2的比例，分别加入到单口烧瓶中，在50℃条件下加热磁力搅拌0.5小时，制备而成得到TBPB/3-AP。附图1采用红外表征了TBPB/3-AP的结构；附图2采用核磁表征了TBPB/3-AP的结构；附图3采用红外表征了TBPB/3-AP对CO2的活化作用。
将甲基三苯基溴化鏻(MTPB)与对氨基苯酚(4-AP)按照摩尔比为1:3的比例，分别加入到单口烧瓶中，在50℃条件下加热磁力搅拌0.5小时，制备而成得到MTPB/4-AP。
将烯丙基三苯基溴化鏻(ATPB)与邻氨基苯酚(2-AP)按照摩尔比为1:2的比例，分别加入到单口烧瓶中，在50℃条件下加热磁力搅拌0.5小时，制备而成得到ATPB/2-AP。
将苄基三苯基溴化鏻(BTPC)与间氨基苯酚(3-AP)按照摩尔比为1:2的比例，分别加入到单口烧瓶中，在50℃条件下加热磁力搅拌0.5小时，制备而成得到BTPC/3-AP。
实施例2
取实施例1制备的催化剂TBPB/3-AP和反应物环氧氯丙烷依次加入100mL连接CO2气球的Schlenk(施伦克)反应瓶，其中，环氧氯丙烷10mmol，TBPB/3-AP0.8mmol，催化剂占环氧氯丙烷摩尔含量为8mol％，减压排除内部残存的空气；将反应瓶与CO2气球相连，在反应温度为25℃，0.1MPa CO2压力条件下，持续反应24小时；反应结束后，产物经气相色谱进行定量分析，对应产品收率96％，选择性99％。
实施例3
具体实验过程与检测方法同实施例2，将低共熔离子液体改为实施例1制备的MTPB/4-AP，催化剂用量改为占环氧氯丙烷摩尔含量的5mol％，反应时间改为12小时，对应产品收率83％，选择性99％。
实施例4
具体实验过程与检测方法同实施例2，将低共熔离子液体改为实施例1制备的ATPB/2-AP，催化剂用量改为占环氧氯丙烷摩尔含量的6mol％，对应产品收率92％，选择性99％。
实施例5
具体实验过程与检测方法同实施例2，将低共熔离子液体用量改为占环氧氯丙烷摩尔含量的10mol％，反应时间改为18小时，对应产品收率89％，选择性99％。
实施例6
具体实验过程与检测方法同实施例2，将环氧氯丙烷改为不同取代基其他环氧化物，分别与二氧化碳进行环加成反应，所得结果见表1。
表1 TBPB/3-AP催化不同环氧化物与二氧化碳环加成反应结果
实施例7-11
具体实验条件与步骤同实施例2，反应结束后使用甲基叔丁基醚萃取分离回收低共熔离子液体TBPB/3-AP，利用回收的TBPB/3-AP在相同条件下进行5次循环实验，所得结果见表2。
表2实施例7-11催化剂循环使用结果
实施例12
为了进一步说明本发明的优势，以下表3将本发明所提出的其中一种新型低共熔离子液体TBPB/3-AP与系列催化剂进行对比试验，并与已报道其他低共熔类离子液体进行催化反应条件及活性的对比，本发明可以实现常温、常压条件下环状碳酸酯的高选择性合成，反应条件及活性均得到明显改善。
表3催化反应条件及活性对比
Claims (9)
1.一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于使用低共熔离子液体作为催化剂，使环氧化合物与二氧化碳环加成合成环状碳酸酯，所述低共熔离子液体以氨基苯酚作为氢键供体组分，以季鏻溴盐作为氢键受体组分，其中，氨基苯酚选自邻氨基苯酚、间氨基苯酚或对氨基苯酚中的一种，季鏻溴盐结构通式如下：
式中R1，R2，R3，R4均选自苯基、苄基或碳数≤8的烷基中的一种。
2.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于所述环氧化合物结构式如下：
3.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于所述低共熔离子液体由季鏻溴盐与氨基苯酚在50℃条件下搅拌反应0.5小时制备而成，季鏻溴盐与氨基苯酚摩尔比为1:2~1:3。
4.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于所述季鏻溴盐为：
中的任意一种。
5.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于催化剂用量为环氧化合物摩尔量的5%~10%。
6.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于季鏻溴盐与氨基苯酚摩尔比为1:2。
7.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于所述季鏻溴盐为四丁基溴化鏻。
8.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于催化剂用量为环氧化物摩尔量的6%~8%。
9.根据权利要求1所述的一种低共熔离子液体常温常压条件下化学固定二氧化碳合成环状碳酸酯的方法，其特征在于环加成反应时间为12~24小时。
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