反相微乳法制备DMCC用于催化二氧化碳与环氧丙烷共聚
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摘要
通过反相微乳法和共沉淀法合成了钴锌双金属氰化物催化剂。研究了制备方式及共聚反应条件对其催化性能及聚碳酸酯组成的影响。结果表明,反相微乳法制备的DMCC-1具有较低的结晶度且可以配合更多的有机配体,在80℃、4 MPa条件下,采用一步加料法催化CO2与环氧丙烷共聚,所制备的聚碳酸酯中碳酸酯单元量达43.5%,数均分子量达36 400,且聚合物分散指数仅为2.07。共聚结果表明,一步加料法有利于提高聚合物的数均分子量,而逐步加料法有利于降低聚合物的相对分子量分布。
Cobalt zinc double metal cyanide catalysts were prepared by reverse micro emulsion method and coprecipitation method.The effect of preparation and reaction condition on catalytic performance and the polycarbonate composition were investigated.The results revealed that DMCC-1 prepared by reverse microemulsion method had lower crystallinity and complexed more organic ligand.The polycarbonate synthesized from CO2 and propylene oxide in the presence of DMCC-1 under the conditions of 80 ℃,4 MPa and one-step feed modepossessed the molar fraction of carbonate linkages in the produced polymer was 43. 5%,number average molecular mass up to 36 400 and polydispersity index was 2. 07.At the same time,it was found that the one-step feed mode could improve the number average molecular of the polycarbonate,but interval feed mode could reduce the polydispersity index of the polycarbonate.
Cobalt zinc double metal cyanide catalysts were prepared by reverse micro emulsion method and coprecipitation method.The effect of preparation and reaction condition on catalytic performance and the polycarbonate composition were investigated.The results revealed that DMCC-1 prepared by reverse microemulsion method had lower crystallinity and complexed more organic ligand.The polycarbonate synthesized from CO2 and propylene oxide in the presence of DMCC-1 under the conditions of 80 ℃,4 MPa and one-step feed modepossessed the molar fraction of carbonate linkages in the produced polymer was 43. 5%,number average molecular mass up to 36 400 and polydispersity index was 2. 07.At the same time,it was found that the one-step feed mode could improve the number average molecular of the polycarbonate,but interval feed mode could reduce the polydispersity index of the polycarbonate.
引文
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[22]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.
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[2]KOBAYASHI M,INOUE S,TSURUTA T.Diethylzinc-dihydric phenol system as catalyst for the copolymerization of carbon dioxide with propylene oxide[J].Macromolecules,1971,4(4):658-659.
[3]KEMBER M R,BUCHARD A,WILLIAMS C K.Catalysts for CO2/epoxide copolymerisation[J].Chem.Commun.,2010,47(1):141-163.
[4]SUGIMOTO H,OHSHIMA H,INOUE S.Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin:the first example of polycarbonate synthesis from 1 atm carbon dioxide[J].Stud.Sur.Sci.Catal.,2003,153(22):247-250.
[5]LEHENMEIER M W,BRUCKMEIER C,KLAUS S,et al.Differences in reactivity of epoxides in the copolymerisation with carbon dioxide by zinc-based catalysts:propylene oxide versus cyclohexene oxide[J].Chemistry,2011,17(32):8 858-8 869.
[6]ELLIS W C,JUNG Y,MULZER M,et al.Copolymerization of CO2and meso epoxides using enantioselectiveβ-diiminate catalysts:a route to highly isotactic polycarbonates[J].Chem.Sci.,2014,5(10):4 004-4 011.
[7]陈上,吴元祥.高效结晶型DMC催化剂制备及其催化性能[J].吉首大学学报(自然科学版),2010,31(5):89-92.
[8]赵瑞超,姚丽娜,盖东杰,等.用于合成聚醚多元醇的催化剂研究进展[J].上海塑料,2016,(1):16-25.
[9]王萍,刘顺杰,秦玉升,等.支化结构二氧化碳基六元醇的可控合成[J].高分子学报,2017,(2):259-265.
[10]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(7):2 081-2 090.
[11]SEASTIAN J,SRINIVAS D.Factors influencing catalytic activity of Co-Zn double-metal cyanide complexes for alternating polymerization of epoxides and CO2[J].Appl.Catal A-Gen.,2015,506(4):163-172.
[12]SEBASTIAN J,SRINIVAS D.Novel application of a FeZn double-metal cyanide catalyst in the synthesis of biodegradable,hyperbranched polymers[J].Chem.Commun.,2011,47(37):10 449-10 451.
[13]ZHANG Ming,YANG Yong,CHEN Li-ban.Preparation of crown ether complexing highly active double metal cyanide catalysts and copolymerization of CO2,and propylene oxide[J].Chin.J.Catal.,2015,36(8):1 304-1 311.
[14]YI M J,BYUN S H,HAC S,et al.Copolymerization of cyclohexene oxide with carbon dioxide over nano-sized multi-metal cyanide catalysts[J].Solid State Ionics,2004,172(1):139-144.
[15]马苏川,房晶瑞,汪澜,等.微乳法制备Fe-DMC催化剂用于CO2与环氧丙烷聚合[J].合成树脂及塑料,2015,32(2):15-18.
[16]GUO Zhi-fang,LIN Qiang,ZHU Lin-hua,et al.Nanolamellar Zn-Ni/Co-Ni catalysts introduced by ball milling for the copolymerization of CO2with propylene oxide[J].Nanosci.Nanotech.Lett.,2014,6(4):353-356.
[17]YU S J,LIU Yin-shan,BYEON S J,et al.Ring-opening polymerization of propylene oxide by double metal cyanide catalysts prepared by reacting Co Cl2,with various metal cyanide salts[J].Catal.Today,2014,232:75-81.
[18]ZHANG Xing-hong,HUA Zheng-jiang,CHEN Shang,et al.Role of zinc chloride and complexing agents in highly active double metal cyanide catalysts for ring-opening polymerization of propylene oxide[J].Appl.Catal.A-Gen.,2007,325(1):91-98.
[19]华正江,陈上,闵玉勤,等.双金属氰化络合物催化剂的形态及其对催化剂活性的影响[J].浙江大学学报(理学版),2004,31(1):74-78.
[20]SEASTIAN 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(5):300-308.
[21]LEE I K,JU Y H,CAO Chen-gong,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.
[22]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.
[23]黄亦军,戚国荣,钱锦文,等.Fe-Zn双金属氰化物催化环氧丙烷开环聚合的研究[J].高分子学报,2001,(2):210-214.