金属锂盐-烷基铝活性阴离子聚合体系催化环氧环己烷与CO_2共聚反应
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摘要
近年来,利用环氧化合物与二氧化碳(CO_2)进行共聚反应制备聚碳酸酯(PC)成为绿色合成化学研究的热点领域。文中报道了一种由环境友好的轻金属Li/Al化合物构成的催化体系,可以有效催化环氧环己烷与CO_2的共聚反应,成功合成了一系列不同相对分子质量和窄相对分子质量分布的聚碳酸酯。同时,根据对合成产物的核磁分析,所合成的聚碳酸酯具有双官能度的异官能团端基,可通过简单聚合物链端基的有机反应来实现对聚碳酸酯链的接枝改性。
During the recent decades,synthesis of polycarbonates via the copolymerization of carbon dioxide(CO_2)with epoxides became one of attractive and important research topics in the green chemistry field.The key point of this research is to discover an efficient catalyst with environment benign characteristics.In this article,a new kind of catalytic system composed of lithium halide salts and alkyl aluminium was successfully developed for catalyzing the copolymerization of CO_2 and cyclohexane oxide,by which a series of polycarbonates with different molecular weights and narrow polydispersity indexes(PDI)can be easily synthesized.Meanwhile,the post modification of synthesized polycarbonates can be availably carried out through the reactions of functional terminal groups in the polymer main chain.
During the recent decades,synthesis of polycarbonates via the copolymerization of carbon dioxide(CO_2)with epoxides became one of attractive and important research topics in the green chemistry field.The key point of this research is to discover an efficient catalyst with environment benign characteristics.In this article,a new kind of catalytic system composed of lithium halide salts and alkyl aluminium was successfully developed for catalyzing the copolymerization of CO_2 and cyclohexane oxide,by which a series of polycarbonates with different molecular weights and narrow polydispersity indexes(PDI)can be easily synthesized.Meanwhile,the post modification of synthesized polycarbonates can be availably carried out through the reactions of functional terminal groups in the polymer main chain.
引文
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[7]Nakano K,Nakamura M,Nozaki K.Alternating copolymerization of cyclohexene oxide with carbon dioxide catalyzed by(salalen)CrCl complexes[J].Macromolecules,2009,42:6972-6980.
[8]Seong J E,Na S J,Cyriac A,et al.Terpolymerizations of CO2,propylene oxide,and various epoxides using a cobalt(III)complex of Salen-type ligand tethered by four quaternary ammonium salts[J].Macromolecules,2010,43:903-908.
[9]Chen X H,Shen Z Q,Zhang Y F.New catalytic systems for the fixation of carbon dioxide.1.Copolymerization of carbon dioxide and propylene oxide with new rare-earth catalysts-RE(P204)3-Al(i-Bu)3-R(OH)n[J].Macromolecules,1991,24:5305-5308.
[10]王献红,路宏伟,赵晓江,等.用于二氧化碳和环氧化物共聚合的负载稀土三元催化剂及制法:中国,10051413.7[P].2008-11-12.
[11]Nakano K,Kobayashi K,Nozaki K.Tetravalent metal complexes as a new family of catalysts for copolymerization of epoxides with carbon dioxide[J].J.Am.Chem.Soc.,2011,133:10720-10723.
[2]Mikkelsen M,Jφrgensena M,Krebs F C.The teraton challenge.A review of fixation and transformation of carbon dioxide[J].Energy Environ.Sci.,2010,3:43-81.
[3]赵晓江,董艳磊,王献红,等.一种二氧化碳与环氧化物共聚合的组合催化剂及制法:中国,10051414.1[P].2008-11-12.
[4]Inoue S,Koinuma H,Tsuruta T.Copolymerization of carbon dioxide and epoxide with organometallic compounds[J].Makromol.Chem.,1969,130:210-220.
[5]Cohen C T,Chu T,Coates G W.Cobalt catalysts for the alternating copolymerization of propylene oxide and carbon dioxide:?combining high activity and selectivity[J].J.Am.Chem.Soc.,2005,127:10869-10878.
[6]Lu X B,Shi L,Wang Y M,et al.Design of highly active binary catalyst systems for CO2/epoxide copolymerization:polymer selectivity,enantioselectivity,and stereochemistry control[J].J.Am.Chem.Soc.,2006,128:1664-1674.
[7]Nakano K,Nakamura M,Nozaki K.Alternating copolymerization of cyclohexene oxide with carbon dioxide catalyzed by(salalen)CrCl complexes[J].Macromolecules,2009,42:6972-6980.
[8]Seong J E,Na S J,Cyriac A,et al.Terpolymerizations of CO2,propylene oxide,and various epoxides using a cobalt(III)complex of Salen-type ligand tethered by four quaternary ammonium salts[J].Macromolecules,2010,43:903-908.
[9]Chen X H,Shen Z Q,Zhang Y F.New catalytic systems for the fixation of carbon dioxide.1.Copolymerization of carbon dioxide and propylene oxide with new rare-earth catalysts-RE(P204)3-Al(i-Bu)3-R(OH)n[J].Macromolecules,1991,24:5305-5308.
[10]王献红,路宏伟,赵晓江,等.用于二氧化碳和环氧化物共聚合的负载稀土三元催化剂及制法:中国,10051413.7[P].2008-11-12.
[11]Nakano K,Kobayashi K,Nozaki K.Tetravalent metal complexes as a new family of catalysts for copolymerization of epoxides with carbon dioxide[J].J.Am.Chem.Soc.,2011,133:10720-10723.
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