超临界二氧化碳中合成环碳酸酯的催化剂研究进展

doi:10.16085/j.issn.1000-6613.2016-2446

摘要/Abstract

摘要： 超临界二氧化碳（scCO₂）是一种环境友好型溶剂，它作为传统有机溶剂的替代品已被广泛应用于绿色化学过程的开发。其中，环氧化合物在超临界二氧化碳中制备环碳酸酯是实现二氧化碳高附加值转化的有效途径之一。本文回顾了近年来在超临界二氧化碳中合成环碳酸酯的研究进展，着重介绍了不同种类的催化剂，包括金属配合物、季盐、二元催化体系、离子液体、金属氧化物、有机小分子及其他类型催化剂在该反应体系中的应用，突出了超临界二氧化碳既作为溶剂，又作为反应物的双重优势。从经济和环境角度考虑，离子液体或季盐等有机催化剂具有更好的工业化应用前景。同时，指出了高效和绿色催化体系设计和创制是该研究领域的关键。

关键词: 超临界二氧化碳, 环碳酸酯, 环氧化物, 催化

Abstract: Supercritical carbon dioxide(scCO₂) has been widely used as an environmentally friendly solvent to replace the conventional organic solvent in green chemical processes. Among those applications reported,the synthesis of cyclic carbonates from epoxides in supercritical CO₂ has received a great interest. This review covered the recent progress in the synthesis of cyclic carbonates under supercritical carbon dioxide,with an emphasis on the state of the art of different kinds of catalysts employed in this reaction,including metal complex,quaternary onium salts,binary catalytic systems,ionic liquids,metal oxide,organocatalysts,et al. Furthermore,the advantages of supercritical carbon dioxide both as solvent and as reactant for this transformation were highlighted. From the economic and environmental point of view,organic catalysts,such as ionic liquids and quaternary onium salts,show promising potential application in the future development of chemical industry. It was also pointed out that the design and preparation of efficient and green catalysts are critical to this research field.

Key words: supercritical carbon dioxide, epoxides, cyclic carbonates, catalysis

中图分类号:

TQ072

范芳君, 张治国, 邢华斌, 杨启炜, 鲍宗必, 杨亦文, 任其龙. 超临界二氧化碳中合成环碳酸酯的催化剂研究进展[J]. 化工进展, 2017, 36(08): 2924-2933.

FAN Fangjun, ZHANG Zhiguo, XING Huabing, YANG Qiwei, BAO Zongbi, YANG Yiwen, REN Qilong. Progress in synthesis of cyclic carbonates under supercritical carbon dioxide[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 2924-2933.

参考文献

[1] GIBSON D H. The organometallic chemistry of carbon dioxide[J]. Chemical Reviews,1996,96(6):2063-2096.
[2] ARESTA M,DIBENEDETTO A. Utilisation of CO₂ as a chemical feedstock:opportunities and challenges[J]. Dalton Transactions,2007(28):2975-2992.
[3] SAKAKURA T,CHOI J,YASUDA H. Transformation of carbon dioxide[J]. Chemical Reviews,2007,107(6):2365-2387.
[4] SCHÄFFNER B,SCHÄFFNER F,VEREVKIN S P,et al. Organic carbonates as solvents in synthesis and catalysis[J]. Chemical Reviews,2010,110(8):4554-4581.
[5] PETERS M,KÖHLER B,KUCKSHINRICHS W,et al. Chemical technologies for exploiting and recycling carbon dioxide into the value chain[J]. Chemsuschem,2011,4(4):1216-1240.
[6] Dr. KAI M K Y,IGOR C,JOSEPH G,et al. Recent advances in CO₂ capture and utilization[J]. ChemSusChem,2008,1(11):893-899.
[7] MARKEWITZ P,KUCKSHINRICHS W,LEITNER W,et al. Worldwide innovations in the development of carbon capture technologies and the utilization of CO₂[J]. Energy & Environmental Science,2012,5(6):7281-7305.
[8] CLEMENTS J H. Reactive applications of cyclic alkylene carbonates[J]. Industrial & Engineering Chemistry Research,2003,42(4):663-674.
[9] DARENSBOURG D J. Making plastics from carbon dioxide:salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO₂[J]. Chemical Reviews,2007,107(6):2388-2410.
[10] YOSHIDA M,IHARA M. Novel methodologies for the synthesis of cyclic carbonates[J]. Chemistry:A European Journal,2004,10(12):2886-2893.
[11] 罗荣昌,周贤太,杨智,等. 均相体系中酸碱协同催化二氧化碳与环氧化物的环加成反应[J]. 化工学报,2016,67(1):258-276. LUO R C,ZHOU X T,YANG Z,et al. Acid-base synergistic effect promoted cycloaddition reaction from CO₂ with epoxide in homogenous catalysis systems[J]. CIESC Journal,2016,67(1):258-276.
[12] MIAO C X,WANG J Q,YING W,et al. Bifunctional metal-salen complexes as efficient catalysts for the fixation of CO₂ with epoxides under solvent-free conditions.[J]. ChemSusChem,2008,1(3):236-241.
[13] HAAK R M,WEZENBERG S J,KLEIJ A W. Cooperative multimetallic catalysis using metallosalens[J]. Chemical Communications,2010,46(16):2713-2723.
[14] YAMAGUCHI K,EBITANI K,YOSHIDA T,et al. Mg-Al mixed oxides as highly active acid-base catalysts for cycloaddition of carbon dioxide to epoxides[J]. Journal of the American Chemical Society,1999,121(18):4526-4527.
[15] BHANAGE B M,FUJITA S I,IKUSHIMA Y,et al. Synthesis of dimethyl carbonate and glycols from carbon dioxide,epoxides,and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity[J]. Applied Catalysis A:General,2001,219(1-2):259-266.
[16] SONG J,ZHANG B,ZHANG P,et al. Highly efficient synthesis of cyclic carbonates from CO₂ and epoxides catalyzed by KI/lecithin[J]. Catalysis Today,2012,183(1):130-135.
[17] KIHARA N,HARA N,ENDO T. Catalytic activity of various salts in the reaction of 2,3-epoxypropyl phenyl ether and carbon dioxide under atmospheric pressure[J]. Journal of Organic Chemistry,1993,58(23):6198-6202.
[18] ZHAO Y,TIAN J,QI X,et al. Quaternary ammonium salt-functionalized chitosan:an easily recyclable catalyst for efficient synthesis of cyclic carbonates from epoxides and carbon dioxide[J]. Journal of Molecular Catalysis A:Chemical,2007,271(1-2):284-289.
[19] CALÓ V,NACCI A,MONOPOLI A,et al. Cyclic carbonate formation from carbon dioxide and oxiranes in tetrabutylammonium halides as solvents and catalysts[J]. Organic Letters,2002,4(15):2561-2563.
[20] 张媛媛,罗胜联,尹双凤. 离子液体催化CO₂与环氧化物合成环状碳酸酯[J]. 化学进展,2012,24(05):674-685. ZHANG Y Y,LUO S L,YIN S S. Synthesis of cyclic carbonates from CO₂ and epoxides catalyzed by ionic liquids[J]. Progress in Chemistry,2012,24(05):674-685.
[21] PENG J,DENG Y. Cycloaddition of carbon dioxide to propylene oxide catalyzed by ionic liquids[J]. New Journal of Chemistry,2001,25(4):639-641.
[22] SUN J,ZHANG S,CHENG W,et al. Hydroxyl-functionalized ionic liquid:a novel efficient catalyst for chemical fixation of CO₂ to cyclic carbonate[J]. Tetrahedron Letters,2008,49(22):3588-3591.
[23] DAI W,JIN B,LUO S,et al. Cross-linked polymer grafted with functionalized ionic liquid as reusable and efficient catalyst for the cycloaddition of carbon dioxide to epoxides[J]. Journal of CO₂ Utilization,2013,3/4:7-13.
[24] LEE E,AHN J,DHARMAN M M,et al. Synthesis of cyclic carbonate from vinyl cyclohexene oxide and CO₂ using ionic liquids as catalysts[J]. Catalysis Today,2008,131(1-4):130-134.
[25] IKARIYA T,KAYAKI Y. Supercritical fluids as reaction media for molecular catalysis[J]. Catalysis Surveys from Japan,2000,4(1):39-50.
[26] 吕小兵. 超临界条件下环状碳酸酯的催化合成[D]. 大连:大连理工大学,2002. LU X B. Catalytic synthesis of cyclic carbonates under supercritical conditions[D]. Dalian:Dalian University of Technology,2002.
[27] 吕小兵,张华,何仁. 超临界条件下碳酸乙烯酯的均相催化合成[J]. 高等学校化学学报,2002,23(12):2309-2312. LU X B,ZHANG H,HE R. Homogeneous catalytic synthesis of ethylene carbonate under supercritical condition[J]. Chemical Journal of Chinese Universities,2002,23(12):2309-2312.
[28] LU X B,FENG X,HE R. Catalytic formation of ethylene carbonate from supercritical carbon dioxide/ethylene oxide mixture with tetradentate schiff-base complexes as catalyst[J]. Applied Catalysis A:General,2002,234(1-2):25-33.
[29] ALVARO M,BALEIZAO C,DAS D,et al. CO₂ fixation using recoverable chromium salen catalysts:use of ionic liquids as cosolvent or high-surface-area silicates as supports[J]. Journal of Catalysis,2004,228(1):254-258.
[30] ALVARO M,BALEIZAO C,CARBONELL E,et al. Polymer-bound aluminium salen complex as reusable catalysts for CO₂ insertion into epoxides[J]. Tetrahedron,2005,61(51):12131-12139.
[31] JUTZ F,GRUNWALDT J,BAIKER A. Mn(Ⅲ)(salen)-catalyzed synthesis of cyclic organic carbonates from propylene and styrene oxide in"supercritical"CO₂[J]. Journal of Molecular Catalysis A:Chemical,2008,279(1):94-103.
[32] JIANG J,GAO F,HUA R M,et al. Re(CO)₅ Br-catalyzed coupling of epoxides with CO₂ affording cyclic carbonates under solvent-free conditions[J]. The Journal of Organic Chemistry,2005,70(1):381-383.
[33] ARESTA M,DIBENEDETTO A,DILEO C,et al. The first synthesis of a cyclic carbonate from a ketal in sc-CO₂[J]. The Journal of Supercritical Fluids,2003,25(2):177-182.
[34] WANG J,KONG D,CHEN J,et al. Synthesis of cyclic carbonates from epoxides and carbon dioxide over silica-supported quaternary ammonium salts under supercritical conditions[J]. Journal of Molecular Catalysis A:Chemical,2006,249(1-2):143-148.
[35] DU Y,WANG J,CHEN J,et al. A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO₂ with epoxides under supercritical conditions[J]. Tetrahedron Letters,2006,47(8):1271-1275.
[36] HE L,YASUDA H,SAKAKURA T. New procedure for recycling homogeneous catalyst:propylene carbonate synthesis under supercritical CO₂ conditions[J]. Green Chemistry,2003,5(1):92-94.
[37] SONG Q,HE L N,WANG J,et al. Catalytic fixation of CO₂ to cyclic carbonates by phosphonium chlorides immobilized on fluorous polymer[J]. Green Chemistry,2013,15(1):110-115.
[38] LU X B,HE R,BAI C. Synthesis of ethylene carbonate from supercritical carbon dioxide/ethylene oxide mixture in the presence of bifunctional catalyst[J]. Journal of Molecular Catalysis A:Chemical,2002,186(1-2):1-11.
[39] LU X B,XIU J,HE R,et al. Chemical fixation of CO₂ to ethylene carbonate under supercritical conditions:continuous and selective[J]. Applied Catalysis A:General,2004,275(1-2):73-78.
[40] LU X B,PAN Y Z,DONG F J,et al. Catalytic formation of propylene carbonate from supercritical carbon dioxide/propylene oxide mixture[J]. Chinese Chemical Letters,2000,11(7):589-592.
[41] LU X B,WANG H,HE R. Aluminum phthalocyanine complex covalently bonded to mcm-41 silica as heterogeneous catalyst for the synthesis of cyclic carbonates[J]. Journal of Molecular Catalysis A:Chemical,2002,186(1-2):33-42.
[42] CUESTA-ALUJA L,DJOUFAK M,AGHMIZ A,et al. Novel chromium(Ⅲ)complexes with n4-donor ligands as catalysts for the coupling of CO₂ and epoxides in supercritical CO₂[J]. Journal of Molecular Catalysis A:Chemical,2014,381:161-170.
[43] TAHERIMEHR M,DECORTES A,AL-AMSYAR S M,et al. A highly active Zn(salphen) catalyst for production of organic carbonates in a green CO₂ medium[J]. Catalysis Science & Technology,2012,2(11):2231-2237.
[44] SUN J,FUJITA S,ZHAO F,et al. A highly efficient catalyst system of ZnBr₂/n-Bu₄NI for the synthesis of styrene carbonate from styrene oxide and supercritical carbon dioxide[J]. Applied Catalysis A:General,2005,287(2):221-226.
[45] TAHERIMEHR M,AL-AMSYAR S M,WHITEOAK C J,et al. High activity and switchable selectivity in the synthesis of cyclic and polymeric cyclohexene carbonates with iron amino triphenolate catalysts[J]. Green Chemistry,2013,15(11):3083-3090.
[46] JIANG H F,WANG A,LIU H L,et al. Reusable polymer-supported amine-copper catalyst for the formation of α-alkylidene cyclic carbonates in supercritical carbon dioxide[J]. European Journal of Organic Chemistry,2008(13):2309-2312.
[47] 戚朝荣,江焕峰,刘海灵,等. 超临界二氧化碳中马来酸锌催化合成环状碳酸酯[J]. 高等学校化学学报,2007,28(6):1084-1087. QI C R,JIANG H F,LIU H L,et al. Synthesis of cyclic carbonates catalyzed by zinc maleate under supercritical carbon dioxide conditions[J]. Chemical Journal of Chinese Universities,2007,28(6):1084-1087.
[48] YANO T,MATSUI H,KOIKE T,et al. Magnesium oxide-catalysed reaction of carbon dioxide with an epoxide with retention of stereochemistry[J]. Chemical Communications,1997(12):1129-1130.
[49] YAMAGUCHI K,EBITANI K,YOSHIDA T,et al. Mg-Al mixed oxides as highly active acid-base catalysts for cycloaddition of carbon dioxide to epoxides[J]. Journal of the American Chemical Society,1999,121(18):4526-4527.
[50] YASUDA H,HE L N,TAKAHASHI T,et al. Non-halogen catalysts for propylene carbonate synthesis from CO₂ under supercritical conditions[J]. Applied Catalysis A:General,2006,298:177-180.
[51] YASUDA H,HE L,SAKAKURA T. Cyclic carbonate synthesis from supercritical carbon dioxide and epoxide over lanthanide oxychloride[J]. Journal of Catalysis,2002,209(2):547-550.
[52] TOMISHIGE K,YASUDA H,YOSHIDA Y,et al. Novel route to propylene carbonate:selective synthesis from propylene glycol and carbon dioxide[J]. Catalysis Letters,2004,95(1):45-49.
[53] DU Y,KONG D,WANG H,et al. Sn-catalyzed synthesis of propylene carbonate from propylene glycol and CO₂ under supercritical conditions[J]. Journal of Molecular Catalysis A:Chemical,2005,241(1-2):233-237.
[54] KAWANAMI H,SASAKI A,MATSUI K,et al. A rapid and effective synthesis of propylene carbonate using a supercritical CO₂-ionic liquid system[J]. Chemical Communications,2003(7):896-897.
[55] WANG J,YUE X,CAI F,et al. Solventless synthesis of cyclic carbonates from carbon dioxide and epoxides catalyzed by silica-supported ionic liquids under supercritical conditions[J]. Catalysis Communications,2007,8(2):167-172.
[56] FOLTRAN S,ALSARRAF J,ROBERT F,et al. On the chemical fixation of supercritical carbon dioxide with epoxides catalyzed by ionic salts:an in situ FTIR and Raman study[J]. Catalysis Science & Technology,2013,3(4):1046-1055.
[57] WANG J,YUE X,CAI F,et al. Solventless synthesis of cyclic carbonates from carbon dioxide and epoxides catalyzed by silica-supported ionic liquids under supercritical conditions[J]. Catalysis Communications,2007,8(2):167-172.
[58] BERTELSEN S,JORGENSEN K A. Organocatalysis-after the gold rush[J]. Chemical Society Reviews,2009,38(8):2178-2189.
[59] KAWANAMI H,IKUSHIMA Y. Chemical fixation of carbon dioxide to styrene carbonateunder supercritical conditions with DMF in the absence of any additional catalysts[J]. Chemical Communications,2000(21):2089-2090.
[60] 戚朝荣,江焕峰. 超临界二氧化碳中组氨酸催化合成环状碳酸酯[J]. 中国科学:化学,2011,41(3):479-484. QI C R,JIANG H F. Histidine-catalyzed synthesis of cyclic carbonates in supercritical carbon dioxide[J]. Scientia Sinica Chimica,2011,41(3):479-484.
[61] 叶金武. 超临界二氧化碳中氨基酸催化合成噁唑烷酮和环状碳酸酯的研究[D]. 广州:华南理工大学,2010. YE J W. Synthesis of oxazolidinones and cyclic carbonates catalyzed by amino acids under supercritical carbon dioxide conditions[D]. Guangzhou:South China University of Technology,2010.
[62] KAYAKI Y,YAMAMOTO M,IKARIYA T. Stereoselective formation of α-alkylidene cyclic carbonates via carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide[J]. The Journal of Organic Chemistry,2007,72(2):647-649.
[63] CA' N D,GABRIELE B,RUFFOLO G,et al. Effective guanidine-catalyzed synthesis of carbonate and carbamate derivatives from propargyl alcohols in supercritical carbon dioxide[J]. Advanced Synthesis & Catalysis,2011,353(1):133-146.
[64] DU Y,CAI F,KONG D,et al. Organic solvent-free process for the synthesis of propylene carbonate from supercritical carbon dioxide and propylene oxide catalyzed by insoluble ion exchange resins[J]. Green Chemistry,2005,7(7):518-523.
[65] SAKO T,FUKAI T,SAHASHI R,et al. Cycloaddition of oxirane group with carbon dioxide in the supercritical homogeneous state[J]. Industrial & Engineering Chemistry Research,2002,41(22):5353-5358.
[66] KAWANAMI H,IKUSHIMA Y. Regioselectivity and selective enhancement of carbon dioxide fixation of 2-substituted aziridines to 2-oxazolidinones under supercritical conditions[J]. Tetrahedron Letters,2002,43(21):3841-3844.
[67] VIEVILLE C,YOO J W,PELET S,et al. Synthesis of glycerol carbonate by direct carbonatation of glycerol in supercritical CO₂ in the presence of zeolites and ion exchange resins[J]. Catalysis Letters,1998,56(4):245-247.

编辑推荐 0

Metrics

阅读次数

全文

600

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	0	0	0	600

来源	本网站	其他网站

次数	137	463
比例	23%	77%

摘要

345

最新录用	在线预览	正式出版

0	0	345

来源	本网站	其他网站

次数	154	191
比例	45%	55%