CN111889141A - 一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂 - Google Patents
一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂 Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 31
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- 229920000642 polymer Polymers 0.000 title claims abstract description 26
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- XCMRHOMYGPXALN-UHFFFAOYSA-N 4-(bromomethyl)-2-[4-(bromomethyl)pyridin-2-yl]pyridine Chemical group BrCC1=CC=NC(C=2N=CC=C(CBr)C=2)=C1 XCMRHOMYGPXALN-UHFFFAOYSA-N 0.000 claims description 7
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- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
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- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
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- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂。合理设计咪唑离子液体和功能化联吡啶配合物单体，通过自由基聚合反应，制备得到具有高比表面积和丰富多级孔结构的联吡啶基多孔离子聚合物。该聚合物催化剂能高效、高选择性的催化二氧化碳和环氧化物环加成反应生成环碳酸酯。本发明的聚合物催化剂具有结构新颖、制备简单、催化选择性好、底物相容性优异、可重复利用的特点，丰富了环碳酸酯和多孔聚合物等相关领域的研究，具有很好的研究意义和应用价值。
Description
技术领域
本发明涉及多孔聚合物催化剂及其应用，特别是涉及一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂。
背景技术
二氧化碳(CO2)是一种温室气体，也是一种无毒、丰富和可再生的碳一资源。近年来，将CO2转化为精细化学品、化工基础原料和燃料已成为环境、能源和材料等领域的研究前沿。然而，CO2分子中的C处于最高价态而显化学惰性，需要较高的能量或在催化剂作用下才能进行活化。其中利用催化剂和环氧化物环张力在温和条件下将CO2转化成环状碳酸酯，是提高原子利用率、绿色可持续发展的途径之一，具有极高的基础研究意义和工业应用价值。
为实现CO2和环氧化物环加成制备环碳酸酯的反应，研究人员发展了丰富多样的均相和多相催化体系。如金属卤化物、金属配合物、金属氧化物、离子液体、有机碱、金属有机框架材料(MOFs)、共价有机骨架材料(COFs)以及多孔有机聚合物(POPs)等。通过对其反应机理的调研和分析，目前酸碱协同活化机制最具代表性。然而，当前协同催化体系多为均相催化体系，具有催化剂难分离与循环使用、产物纯化过程复杂的问题；非均相催化体系也存在着催化剂制备困难等问题。
法国专利FR3052776-A1，通过制备胺化合物或其互变异构形式化合物为催化剂，在二氧化碳存在下将环氧化合物转化为环碳酸酯。但此类催化剂回收困难，产品纯化过程复杂。
韩国专利KR1864998-B1，报道了一种2,20-dioxa-10,12-diaza-1-aluminapentacyclo-icosa-3(8),4,6,9,14,16,18-heptaene化合物催化CO2和环氧化物制备环碳酸酯。但此化合物合成复杂，催化过程中需要加入铵基或胺基共催化剂。
中国发明专利申请CN 108993610 A，报道了一种有机-无机杂化无定形介孔钛硅材料的制备及其催化CO2和环氧化物生成环碳酸酯的用途。但该催化剂制备需要调节酸碱性和选取合适的钛硅比材料，增加制备难度和成本。
发明内容
基于开发高效、稳定和易循环的多相催化体系的巨大挑战。本发明通过由下而上(bottom-up)的策略设计了离子液体功能化联吡啶配合物单体，利用自由基聚合反应制备得到同时包含丰富的卤素离子和路易斯酸性位点、具有高比表面积和丰富多级孔结构的双功能联吡啶基多孔离子聚合物催化剂。该催化剂能在无溶剂和无助剂条件下协同催化CO2与环氧化物的环加成反应制备环碳酸酯。
为实现本发明的目的，所采用的技术方案是：
一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂，以离子液体和功能化联吡啶配合物为单体，通过自由基聚合反应，制备得到具有高比表面积和丰富多级孔结构的联吡啶基多孔离子聚合物催化剂，结构见通式(Ⅰ)：
通式(1)中M为金属中心，选自Al、Cr、Mn、Fe、Co、Ni、Cu或Zn中的一种；IL为带有双键的咪唑功能结构，选自
B为带有2个双键的苯类功能结构，选自
上述的一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂，由4,4’-二羟甲基-2,2’-联吡啶在氢溴酸和浓硫酸作用下合成4,4’-二溴甲基-2,2’-联吡啶；然后将其与带有双键的咪唑功能物质作用生成离子液体和功能化联吡啶前体；接着将此前体与金属络合制备离子液体和功能化联吡啶配合物单体；最后通过自由基聚合将此配合物单体和带有2个双键的苯类聚合成多孔聚合物催化剂。
上述离子液体功能化联吡啶类多孔聚合物催化剂能用于催化二氧化碳与环氧化物环加成反应制备相应的环碳酸酯的应用。所述的环氧化物结构选自通式(Ⅱ)，催化剂用量为0.05～5.0mmol％，二氧化碳压力0.1～6MPa，反应温度为25～150℃：
通式(Ⅱ)中R1选自甲基、乙基、丙基、丁基、苯基、氯苯基、氯甲基。
与现有技术相比，本发明具有如下有益效果：
1.本发明利用双键自由基聚合反应合成多孔有机材料，聚合效率高、产物收率高，所得聚合物比表面积高。
2.本发明的离子液体功能化联吡啶类多孔聚合物催化剂具有高比表面积、多孔性的特点，增强化对CO2的富集和催化转化。
3.本发明的离子液体功能化联吡啶类多孔聚合物催化剂具有低密度性和高化学物理稳定性，提高催化剂的稳定性和可回收性。
4.本发明的反应条件温和，不需加入任何有机溶剂或助催化剂，产品经过滤即可分离，无毒无害，环境友好，符合绿色化学要求。
5.本发明的催化剂制备和催化操作简单，重现性好，降低了反应能耗，降低了生产成本，提高经济性。
具体实施方式
下面结合实施例对本发明做进一步的说明，但本发明的保护范围并不局限于实施例表示的范围。
实施例1
在氮气保护下，4,4’-二溴甲基-2,2’-联吡啶与N-乙烯基咪唑反应制备离子液体功能化联吡啶配体(IL-Bpy-1)。1H NMR(500MHz,DMSO-d6,25℃)δ(ppm)＝5.43(dd,J＝2.5,8.7Hz,2H),5.63(s,4H),5.98(dd,J＝2.4,15.6Hz,2H),7.33(dd,J＝8.8,15.6Hz,2H),8.04(s,2H),8.09(d,J＝8.5Hz,2H),8.27(s,2H),8.43(d,J＝8.2Hz,2H),8.86(s,2H),9.73(s,2H)；13C NMR(126MHz,DMSO-d6,25℃)δ(ppm)＝50.0,109.40,120.1,121.2,123.8,129.4,131.4,136.4,138.5,150.0.
该IL-Bpy-1配体与无水溴化锌反应制备离子液体功能化联吡啶锌配合物(IL-BpyZn-1)°最后该IL-BpyZn-1配合物与二乙烯基苯在偶氮二异丁腈(AIBN)催化下得到锌基离子液体功能化联吡啶类多孔聚合物(IL-BpyZn-POP-1)。
10mL的不锈钢高压反应釜中加入2.0mmol环氧氯丙烷、0.01mmol％IL-BpyZn-POP-1催化剂，充入1MPa CO2气体，80℃下反应24h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到95％转化率和99％选择性。
实施例2
在氮气保护下，4,4’-二溴甲基-2,2’-联吡啶与N-乙烯基咪唑反应制备离子液体功能化联吡啶配体(IL-Bpy-1)；该IL-Bpy-1配体与无水溴化锌反应制备离子液体功能化联吡啶锌配合物(IL-BpyZn-1)；最后该IL-BpyZn-1配合物与二乙烯基联苯在偶氮二异丁腈(AIBN)催化下得到锌基离子液体功能化联吡啶类多孔聚合物(IL-BpyZn-POP-2)。
10mL的不锈钢高压反应釜中加入2.0mmol环氧氯丙烷、0.01mmol％IL-BpyZn-POP-2催化剂，充入1MPa CO2气体，80℃下反应24h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到96％转化率和99％选择性。
实施例3
在氮气保护下，4,4’-二溴甲基-2,2’-联吡啶与4-乙烯基苯基咪唑反应制备离子液体功能化联吡啶配体(IL-Bpy-1)；该IL-Bpy-1配体与无水氯化铝反应制备离子液体功能化联吡啶铝配合物(IL-BpyAl-1)；最后该IL-BpyAl-1配合物与二乙烯基苯在偶氮二异丁腈(AIBN)催化下得到铝基离子液体功能化联吡啶类多孔聚合物(IL-BpyAl-POP-1)。
10mL的不锈钢高压反应釜中加入2.0mmol环氧氯丙烷、0.05mmol％IL-BpyZn-POP-1催化剂，充入2MPa CO2气体，100℃下反应24h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到85％转化率和99％选择性。
实施例4
在氮气保护下，4,4’-二溴甲基-2,2’-联吡啶与4-乙烯基苯基咪唑反应制备离子液体功能化联吡啶配体(IL-Bpy-1)；该IL-Bpy-1配体与无水溴化铁反应制备离子液体功能化联吡啶铁配合物(IL-BpyFe-1)；最后该IL-BpyFe-1配合物与二乙烯基苯在偶氮二异丁腈(AIBN)催化下得到铝基离子液体功能化联吡啶类多孔聚合物(IL-BpyFe-POP-1)。
10mL的不锈钢高压反应釜中加入2.0mmol环氧氯丙烷、5mmol％IL-BpyFe-POP-1催化剂，充入2MPa CO2气体，150℃下反应24h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到63％转化率和97％选择性。
实施例5
在氮气保护下，4,4’-二溴甲基-2,2’-联吡啶与N-乙烯基咪唑反应制备离子液体功能化联吡啶配体(IL-Bpy-1)；该IL-Bpy-1配体与无水溴化铜反应制备离子液体功能化联吡啶铝铜配合物(IL-BpyCu-1)；最后该IL-BpyAl-1配合物与二乙烯基苯在偶氮二异丁腈(AIBN)催化下得到铝基离子液体功能化联吡啶类多孔聚合物(IL-BpyCu-POP-1)。
10mL的不锈钢高压反应釜中加入2.0mmol环氧苯乙烯、0.05mmol％IL-BpyZn-POP-1催化剂，充入5MPa CO2气体，150℃下反应24h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到66％转化率和98％选择性。
实施例6
10mL的不锈钢高压反应釜中加入2.0mmol环氧环己烯、0.5mmol％IL-BpyZn-POP-1催化剂，充入3MPa CO2气体，25℃下反应12h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到95％转化率和98％选择性。
实施例7
10mL的不锈钢高压反应釜中加入2.0mmol环氧环己烯、0.5mmol％IL-BpyZn-POP-2催化剂，充入1MPa CO2气体，25℃下反应12h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到95％转化率和98％选择性。
实施例8
10mL的不锈钢高压反应釜中加入2.0mmol环氧丁烷、0.5mmol％IL-BpyZn-POP-2催化剂，充入2MPa CO2气体，50℃下反应6h。反应结束后，冷却至0℃，缓慢释放出釜内CO2。加入乙酸乙酯萃取反应混合液，过滤回收催化剂，催化剂经乙酸乙酯和丙酮洗涤、干燥等操作后直接用作下一次反应中。通过GC-2010分析反应得到93％转化率和98％选择性。
Claims (5)
1.一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂，其特征在于，其结构见通式(1)：
通式(1)中M为金属中心，选自Al、Cr、Mn、Fe、Co、Ni、Cu或Zn中的一种；IL为带有双键的咪唑功能结构，选自
B为带有2个双键的苯类功能结构，选自
2.权利要求1所述催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂的制备方法，其特征在于包括如下步骤：由4,4’-二羟甲基-2,2’-联吡啶在氢溴酸和浓硫酸作用下合成4,4’-二溴甲基-2,2’-联吡啶；然后将其与带有双键的咪唑功能物质作用生成离子液体和功能化联吡啶前体；接着将此前体与金属络合制备离子液体和功能化联吡啶配合物单体；最后通过自由基聚合将此配合物单体聚合成多孔聚合物催化剂。
3.权利要求1所述离子液体功能化联吡啶类多孔聚合物催化剂在催化二氧化碳与环氧化物环加成反应制备环碳酸酯中的应用。
4.根据权利要求3所述的应用，其特征在于，所述的环氧化物结构选自通式(Ⅱ)：
通式(Ⅱ)中R1选自甲基、乙基、丙基、丁基、苯基、氯苯基、氯甲基。
5.根据权利要求3所述的应用，其特征在于，所述催化剂的用量为0.01～5.0mmol％，二氧化碳压力0.1～6MPa，反应温度为25～150℃。
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