双金属氰化络合催化剂催化环氧烷烃与二氧化碳共聚研究进展

doi:10.16085/j.issn.1000-6613.2016.07.020

摘要/Abstract

摘要： 针对CO₂与环氧烷烃共聚制备脂肪族聚碳酸酯反应体系,本文在综合分析脂肪族聚碳酸酯应用前景的基础上,着重介绍了双金属氰化络合催化剂在该工艺中的研究进展,并对不同种类活性中心金属的组合在不同反应体系中的催化效果进行了分析。共沉淀法制得的Zn-Co双金属氰化络合催化剂在CO₂与环氧烷烃的催化体系中,通过改变制备方法、配体等条件可以实现对催化剂形貌的控制,有利于催化活性的提升。Zn-Fe双金属氰化络合催化剂对于环氧丙烷开环活性较好。同时还介绍了采用其他活性中心金属组合制得的双金属氰化络合催化剂,发现对于CO₂与环氧烷烃共聚活性受中心金属及配体的影响较大。最后,对该共聚反应的机理进行了分析,为双金属氰化络合催化剂的设计研究指明了方向。

关键词: 双金属络合催化剂, 二氧化碳, 反应机理, 脂肪族聚碳酸酯

Abstract: Considering the copolymeration of carbon dioxide (CO₂) and alkylene oxides to synthesize aliphatic polycarbonate, we introduced the research progress of double metal cyanide (DMC) complex catalyst used in the process following the comprehensive analysis of the application of aliphatic polycarbonate. In addition, we also analyzed the catalytic effect for different kinds of active center metal combinations in different reaction systems. The Zn-Co-DMC catalyst prepared by precipitation method was used in the catalytic system. By changing the preparation method, ligands and other conditions, we can control the morphology of the catalyst, and thus improve the catalytic activity. The Zn-Fe-DMC catalyst has good activity in the ring-opening of alkylene oxides. At the same time, we also described the combinations of other active center metals for the preparation of DMC catalyst, and got the conclusion that the activity of the copolymerization of CO₂ and alkylene oxide was strongly affected by the central metal and ligand. Finally, the mechanism of the copolymerization was introduced, and then we pointed out the direction for the design of the DMC catalyst.

Key words: double metal cyanide catalyst, carbon dioxide, reaction mechanism, aliphatic polycarbonate

中图分类号:

TQ316.33

张鹏, 刘定华. 双金属氰化络合催化剂催化环氧烷烃与二氧化碳共聚研究进展[J]. 化工进展, 2016, 35(07): 2081-2090.

ZHANG Peng, LIU Dinghua. The progress of copolymerization of alkylene oxide with carbon dioxide catalyzed by double metal cyanide complex catalysts[J]. Chemical Industry and Engineering Progree, 2016, 35(07): 2081-2090.

参考文献

[1] GERNGROSS T U,SLATER S C. How green are green plastics?[J].Sci.Am.,2000,283(2):24-29.
[2] ARAKAWA H,ARESTA M,ARMOR J N,et al. Catalysis research of relevance to carbon management: progress,challenges,and opportunities[J].Chem. Rev.,2001,101(4):953-996.
[3] BOLMm C,BECKMANN O,DABARD O A G. The search for new environmentally friendly chemical processes[J].Angew.Chem. Int.
Edit.,1999,38(7):907-909.
[4] COOPER A I. Polymer synthesis and processing using supercritical carbon dioxide[J].J.Mater.Chem.,2000,10(2):207-234.
[5] LEITNER W. Homogeneous catalysts for application in supercritical carbon dioxide as a ‘green' solvent[J].Comptes Rendus de l Academie des Sciences SerieⅡ C:Chimistry,2000,3(7):595-600.
[6] BECKMAN E J. Polymer synthesis-making polymers from carbon dioxide[J].Science,1999,283(5404):946-947.
[7] DARENSBOURG D J,HOLTCAMP M W. Catalysts for the reactions of epoxides and carbon dioxide[J].Coord.Chem.Rev.,1996,153:155-174.
[8] JESSOP P G,IKARIYA T,NOYORI R. Homogeneous catalysis in supercritical fluids[J].Chem.Rev.,1999,99(2):475-493.
[9] KENDALL J L,CANELAS D A,YOUNG J L,et al. Polymerizations in supercritical carbon dioxide[J].Chem.Rev.,1999,99(2):543-563.
[10] NAKAMURA I,INOUE S,ONO T,et al. Chronic arsenical poisoning due to environmental pollution.Seven cases among inhabitants near an abandoned mine[J].The Kumamoto Medical Journal,1976,29(4):172-186.
[11] ROKICKI A,KURAN W. The application of carbon-dioxide as a direct material for polymer synthesis in polymerization and polycondensation reactions[J].J.Macro.Sci.R.M.C.,1981,21(1):135-186.
[12] SUPER M S,BECKMAN E J. Copolymerizations involving carbon dioxide:the use of CO₂ as a monomer[J].Trends in Polymer Science,1997,5(7):236-240.
[13] WANG D X,KANG M Q,WANG X K. Aliphatic polycarbonates synthesized with carbon dioxide[J]. Prog.Chem.,2002,14(6):462-468.
[14] LIU B H,CHEN L B,ZHANG M,et al. Degradation and stabilization of poly(propylene carbonate)[J].Macromol.Rapid.Commun.,2002,23(15):881-884.
[15] Guven O. Radiolysis of a vinyl chloride vinyl acetate copolymer[J]. Angew. Makromol. Chem.,1979,82:217-220.
[16] 李复生,殷金柱,魏东炜,等. 聚碳酸酯应用与合成工艺进展[J].化工进展,2002,21(6):395-398.
[17] KAWAGUCHI T,NAKANO M,JUNI K,et al. Examination of biodegradability of poly(ethylene carbonate) and poly(propylene carbonate) in the peritoneal-cavity in rats[J].Chem.& Pharm.Bull.,1983,31(4):1400-1403.
[18] 蒋晶,王小峰,侯建华,等. 注射压缩成型聚碳酸酯制品的低温拉伸力学性能[J].化工学报,2015,66(10):4268-4274.
[19] TAKANASHI M,NOMURA Y,YOSHIDA Y,et al. Functional polycarbonate by copolymerization of carbon-dioxide and epoxide-synthesis and hydrolysis[J].Macromol.Chem.Phys.,1982,183(9):2085-2092.
[20] YANG S Y,FANG X G,CHEN L B. Biodegradability of CO₂ copolymers synthesized by using macromolecule-bimetal catalysts[J]. Polym. Adv. Technol.,1996,7(8):605-608.
[21] 陈立班,黄斌. 脂肪族聚碳酸酯多醇的制备:1060299[P].1992-04-
15.
[22] 王东山,余爱芳,何树杰,等. 聚碳酸亚丙酯聚氨酯的合成与性能[J].高分子学报,1999(2):162-166.
[23] 杨淑英,陈立班,余爱芳,等. 二氧化碳与环氧化物的调节共聚合反应速率[J].高分子学报,1998(3):83-88.
[24] 方兴高,陈立班,杨淑英. 生物降解型聚碳酸顺丁烯二酸亚乙酯1. 合成和表征[J].功能材料,1993(5):433-437.
[25] 王景霞,范晓东,周志勇,等. 双金属氰化物催化环氧化物开环聚合的研究进展[J].化工进展,2008,27(7):1012-1016.
[26] KUYPER J,BOXHOORN G. Hexacyanometallate salts used as alkene-oxide polymerization catalysts and molecular-sieves[J]. J.Catal.,1987,105(1):163-174.
[27] CHEN S,HUA Z J,FANG Z,et al. Copolymerization of carbon dioxide and propylene oxide with highly effective zinc hexacyanocobaltate(III)-based coordination catalyst[J].Polymer,2004,45(19):6519-6524.
[28] CHEN S,ZHANG X H,LIN F,et al. Preparation of double metal cyanide complexes from water-insoluble zinc compounds and their catalytic performance for copolymerization of epoxide and CO₂[J].React.Kinet.Catal.Lett.,2007,91(1):69-75.
[29] ZHANG X H,WEI R J,SUN X K,et al. Selective copolymerization of carbon dioxide with propylene oxide catalyzed by a nanolamellar double metal cyanide complex catalyst at low polymerization temperatures[J].Polymer,2011,52(24):5494-5502.
[30] ZHANG X H,WEI R J,ZHANG Y Y,et al. Carbon dioxide/epoxide copolymerization via a nanosized Zinc-Cobalt(Ⅲ) double metal cyanide complex: substituent effects of epoxides on polycarbonate selectivity,regioselectivity and glass transition temperatures[J].Macromolecules,2015,48(3):536-544.
[31] HONG J L,ZHANG X H,WEI R J,et al. Inhibitory effect of hydrogen bonding on thermal decomposition of the nanocrystalline cellulose/poly(propylene carbonate)nanocomposite[J].J.Appl.
Polym.Sci.,2014,131(3):1-7.
[32] DONG Y L,WANG X H,ZHAO X J,et al. Facile synthesis of poly(ether carbonate)s via copolymerization of CO₂ and propylene oxide under combinatorial catalyst of rare earth ternary complex and double metal cyanide complex[J].J.Polym.Sci.Part A:Polym.Chem.,2012,50(2):362-370.
[33] GAO Y G,GU L,QIN Y S,et al. Dicarboxylic acid promoted immortal copolymerization for controllable synthesis of low-molecular weight oligo(carbonate-ether) diols with tunable carbonate unit content[J].J.Polym.Sci.Part A:Polym.Chem.,2012,50(24):5177-5184.
[34] GAO Y G,QIN Y S,ZHAO X J,et al. Selective synthesis of oligo(carbonate-ether) diols from copolymerization of CO₂ and propylene oxide under zinc-cobalt double metal cyanide complex[J].J.Polym.Res.,2012,19(5):1-9.
[35] 李志峰,秦玉升,赵晓江,等. 双金属氰化物/稀土配合物催化二氧化碳和环氧丙烷的共聚合[J].应用化学,2012,29(9):985-989.
[36] LIU S J,QIN Y S,CHEN X S,et al. One-pot controllable synthesis of oligo(carbonate-ether) triol using a Zn-Co-DMC catalyst:the special role of trimesic acid as an initiation-transfer agent[J].Polym. Chem.,2014,5(21):6171-6179.
[37] SEBASTIAN J,DARBHA S. Structure-induced catalytic activity of Co-Zn double-metal cyanide complexes for terpolymerization of propylene oxide,cyclohexene oxide and CO₂[J].RSC Adv.,2015,5(24):18196-18203.
[38] KIM I,YI M J,LEE K J,et al. Aliphatic polycarbonate synthesis by copolymerization of carbon dioxide with epoxides over double metal cyanide catalysts prepared by using ZnX₂ (X = F,Cl,Br,I)[J].Catal.Today,2006,111(3/4):292-296.
[39] BYUN S H,SEO H S,LEE S H,et al. Zn(II)-Co(III)-Fe(III) multi-metal cyanide complexes as highly active catalysts for ring-opening polymerization of propylene oxide[J].Macromol.Res.,2007,15(5):393-395.
[40] LIU H X,WANG X K,GU Y,et al. Preparation and characterization of double metal cyanide complex catalysts[J].Molecules,2003,8(1):67-73.
[41] VARGHESE J K,PARK D S,JEON J Y,et al. Double metal cyanide catalyst prepared using H₃Co(CN)₆ for high carbonate fraction and molecular weight control in carbon dioxide/propylene oxide copolymerization[J].J.Polym.Sci.Part A:Polym.Chem.,2013,51(22):4811-4818.
[42] 邹志强,张多佑,刘言平,等. 高结晶度DMC催化二氧化碳-环氧丙烷共聚[J].高分子材料科学与工程,2010,26(5):5-8.
[43] CHEN S,QI G R,HUA Z J,et al. Double metal cyanide complex based on Zn₃Co(CN)₆ as highly active catalyst for copolymerization of carbon dioxide and cyclohexene oxide[J].J.Polym.Sci.Part A:Polym.Chem.,2004,42(20):5284-5291.
[44] 陈上,张兴宏,戚国荣. Zn-Co双金属氰化络合物催化氧化环己烯/二氧化碳共聚反应[J].催化学报,2006,27(4):355-360.
[45] SUN X K,ZHANG X H,LIU F,et al. Alternating copolymerization of carbon dioxide and cyclohexene oxide catalyzed by silicon dioxide/Zn-Co^III double metal cyanide complex hybrid catalysts with a nanolamellar structure[J].J.Polym.Sci.Part A:Polym.Chem.,2008,46(9):3128-3139.
[46] SUN X K,ZHANG X H,CHEN S,et al. One-pot terpolymerization of CO₂,cyclohexene oxide and maleic anhydride using a highly active heterogeneous double metal cyanide complex catalyst[J].Polymer,2010,51(24):5719-5725.
[47] LUO M,ZHANG X H,DU B Y,et al. Alternating copolymerization of carbonyl sulfide and cyclohexene oxide catalyzed by zinc-cobalt double metal cyanide complex[J].Polymer,2014,55(16):3688-3695.
[48] YI M J,BYUN S H,HA C S,et al. Copolymerization of cyclohexene oxide with carbon dioxide over nano-sized multi-metal cyanide catalysts[J].Solid State Ionics,2004,172(1/2/3/4):139-144.
[49] DHARMAN M M,AHN J Y,LEE M K,et al. Moderate route for the utilization of CO₂-microwave induced copolymerization with cyclohexene oxide using highly efficient double metal cyanide complex catalysts based on Zn₃Co(CN)₆[J].Green Chem.,2008,10(6):678-684.
[50] LEE I K,HA J Y,CAO C,et al. Effect of complexing agents of double metal cyanide catalyst on the copolymerizations of cyclohexene oxide and carbon dioxide[J].Catal.Today.,2009,148(3/4):389-397.
[51] OH H J,KO Y S. Effect of polymerization conditions on the polymer properties of CO₂-cyclohexene oxide copolymer prepared by double metal cyanide catalyst[J].J.Ind.Eng.Chem.,2013,19(6):1939-1943.
[52] SEBASTIAN J,SRINIVAS D. Effects of method of preparation on catalytic activity of Co-Zn double-metal cyanide catalysts for copolymerization of CO₂ and epoxide[J]. Appl. Catal.A:Gen.,2014,482:300-308.
[53] HUA Z J,QI G R,CHEN S. Ring-opening copolymerization of maleic anhydride with propylene oxide by double-metal cyanide[J].J.Appl.Polym.Sci.,2004,93(4):1788-1792.
[54] 华正江,陈上,方佐,等. 双金属氰化络合物催化环氧丙烷和邻苯二甲酸酐共聚[J].高分子学报,2004(4):551-555.
[55] WEI R J,ZHANG X H,DU B Y,et al. Selective production of poly(carbonate-co-ether) over cyclic carbonate for epichlorohydrin and CO₂ copolymerization via heterogeneous catalysis of Zn-Co (III) double metal cyanide complex[J].Polymer,2013,54(23):6357-6362.
[56] WEI R J,ZHANG X H,DU B Y,et al. Highly regioselective and alternating copolymerization of racemic styrene oxide and carbon dioxide via heterogeneous double metal cyanide complex catalyst[J].Macromolecules,2013,46(9):3693-3697.
[57] WEI R J,ZHANG X H,ZHANG Y Y,et al. Functional poly(carbonate-co-ether) synthesis from glycidyl methacrylate/CO₂ copolymerization catalyzed by Zn-Co(III) double metal cyanide complex catalyst[J].RSC Adv.,2014,4(7):3188-3194.
[58] LI Y,HONG J L,WEI R J,et al. Highly efficient one-pot/one-step synthesis of multiblock copolymers from three-component polymerization of carbon dioxide,epoxide and lactone[J].Chem.Sci.,2015,6(2):1530-1536.
[59] ZHANG Y Y,WEI R J,ZHANG X H,et al. Efficient solvent-free alternating copolymerization of CO₂ with 1,2-epoxydodecane and terpolymerization with styrene oxide via heterogeneous catalysis[J].J.Polym.Sci.Pol.Chem.,2015,53(6):737-744.
[60] KIM I,YI M J,BYUN S H,et al. Biodegradable polycarbonate synthesis by copolymerization of carbon dioxide with epoxides using a heterogeneous zinc complex[J].Macromol.Symp.,2005,224:181-191.
[61] SUH H S,HA J Y,YOON J H,et al. Polyester polyol synthesis by alternating copolymerization of propylene oxide with cyclic acid anhydrides by using double metal cyanide catalyst[J].React.& Funct.Polym.,2010,70(5):288-293.
[62] DIENES Y,LEITNER W,MUELLER M G J,et al. Hybrid sol-gel double metal cyanide catalysts for the copolymerisation of styrene oxide and CO₂[J].Green Chem.,2012,14(4):1168-1177.
[63] SRIVASTAVA R,SRINIVAS D,RATNASAMY P. Fe-Zn double-metal cyanide complexes as novel,solid transesteritication catalysts[J].J.Catal.,2006,241(1):34-44.
[64] SAIKIA L,SATYARTHI J K,GONNADE R,et al. Double metal cyanides as efficient solid acid catalysts for synthesis of beta-amino alcohols under solvent-free conditions[J].Catal.Lett.,2008,123(1/2):24-31.
[65] SEBASTIAN J,SRINIVAS D. Novel application of a Fe-Zn double-metal cyanide catalyst in the synthesis of biodegradable,hyperbranched polymers[J].Chem.Commun.,2011,47(37):10449-10451.
[66] ZHANG W Y,LIN Q,CHENG Y,et al. Double metal cyanide complexes synthesized by solvent-free grinding method for copolymerization of CO₂ and propylene oxide[J]. J.Appl.Polym.
Sci.,2012,123(2):977-985.
[67] GUO Z F,LIN Q. Coupling reaction of CO₂ and propylene oxide catalyzed by DMC with co-complexing agents incorporated via ball milling[J].J.Mol.Catal.A:Chem.,2014,390:63-68.
[68] GUO Z F,LIN Q,WANG X H,et al. Rapid synthesis of nanoscale double metal cyanide catalysts by ball milling for the cycloaddition of CO₂ and propylene oxide[J].Mater.Lett.,2014,124:184- 187.
[69] DARENSBOURG D J,ADAMS M J,YARBROUGH J C,et al. Synthesis and structural characterization of double metal cyanides of iron and zinc:catalyst precursors for the copolymerization of carbon dioxide and epoxides[J].Inorg.Chem.,2003,42(24):7809-7818.
[70] ZHANG X H,CHEN S,WU X M,et al. Highly active double metal cyanide complexes:effect of central metal and ligand on reaction of epoxide/CO₂[J].Chin.Chem.Lett.,2007,18(7):887-890.
[71] CHEN S,XIAO Z B,MA M Y.Copolymerization of carbon dioxide and epoxides with a novel effective Zn-Ni double-metal cyanide complex[J].J.Appl.Polym.Sci.,2008,107(6):3871-3877.
[72] GUO Z F,LIN Q,ZHU L H,et al. Nanolamellar Zn-Ni/Co-Ni catalysts introduced by ball milling for the copolymerization of CO₂ with propylene oxide[J].Nanosci.Nanotech.Lett.,2014,6(4):353-356.
[73] LIN Q,GUO Z F,PAN L S,et al. Zn-Cr double metal cyanide catalysts synthesized by ball milling for the copolymerization of CO₂/propylene oxide,phthalic anhydride/propylene oxide,and CO₂/propylene oxide/phthalic anhydride[J].Catal.Commun.,2015,64:114-118.