Copolymerization of epoxides and carbon dioxide by using double metal cyanide complex (DMC) with high crystallinity
Tóm tắt
Zn3 [Co(CN)6]2 based double metal cyanide complex(Co-Zn DMC) is synthesized and characterized by element analysis, FT-IR, TG-FTIR, XRD and TEM. The composition of Co-Zn DMC summarized by elemental analysis has been confirmed by TG-FTIR. The catalyst has high crystallinity according to strong crystalline peaks shown in XRD and diffraction spot observed by TEM. Copolymerization of epoxides and carbon dioxide are successfully catalyzed by Co-Zn DMC. The efficiency of catalysts is as high as 7488 g polymer/g catalyst for CO2/propylene oxide (PO), 1100 g polymer/g catalyst for CO2/ethylene oxide (EO), which are higher than that reported ever before. The effects of various reaction conditions such as amount of the catalyst, reaction time and temperature on the copolymerization are investigated. The results show that insertion of CO2 into chains is significantly affected by the catalyst quantity and ambient temperature. The weight percentage of byproduct cyclic carbonate can be easily controlled to be less than 5% while the molar fraction of CO2 in backbone (fco2) is more than 30%.
Tài liệu tham khảo
Inoue S, Koinuma H, Tsuruta T (1969) Polymer letter 7:287–292
Inoue S, Yokoo Y (1972) J Organomet Chem 39:11
Qin YS, Wang XH (2010) Biotechnology journal 5:1164–1180
Darensbourg DJ, Holtcamp MW (1996) Coordination Chemistry Reviews 153:155
Wu GP, Lu XB, Darensbourg DJ et al (2010) Macromolecular 43:4302
Chen XH, Shen ZQ, Zhang YF (1991) Macromolecules 24(19):5305
Darensbourg DJ, Yarbrough JC (2002) J Am Chem Soc 124:6335
Kruper WJ, Swart DJ (1985) US Patent 4500704
Mullica DF, Milligan WO, Beall GW (1978) Acta Crystallogr B34:3558
Kim I, Min JY, Kyoung JL, et al (2006) Catalysis Today: 292–296
Min JY, Seung HB, Ha CS et al (2004) Solid State Ionics 172:139–144
Kim I, Min JY, Seung HB et al (2005) Macromol. Symp 224:181–191
Kim I, Lee IK, Ha JY, Ha CS (2009) Catal. Today 148:389–397
Chen S, Qi GR, Hua ZJ et al (2004) J Polym Sci Pol Chem 42(20):5284–5291
Chen S, Hu ZJ, Fang Z et al (2004) Polymer 45:6519–6524
Huang YJ, Qi GR, Chen LS (2003) Applied Catalysis A: General 240:263–271
Chen LB (1992) Makromol Chem Macromol Symp 59:75–82
Chen LB, Huang B, Zhao J (1994) J Nat Gas Chem 4:368–378
Min JY, Seung HB, Ha CS et al (2004) Solid State Ionics 172:139–144
Dharman MM, Ahn JT, Lee MK et al (2008) ResChemIntermed 34:835–844
Zhang XH, Liu F, Sun XK et al (2008) Macromolecules 41:1587–1590
Kim I, Ahn JT, Ha CS et al (2003) Polymer 44:3417–3428