Abstract
The fabrication of low-cost, recyclable, reusable, and heterogeneous catalysts is of considerable significance for green chemistry. In this study, a nanocomposite catalyst, MCM-41-supported Zn–Co double metal cyanide (MCM-41@DMC), was prepared using the synchronous dropping method. Thereafter, the composition, crystal structure, complexing state, morphology, and thermal stability of the catalyst were characterised using scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller analysis, and thermogravimetry. The effects of different organic ligands on the catalytic activity of samples were evaluated, and the results showed that ethyl acetoacetate exhibited the best catalytic activity owing to its ketone coordination. The use of the MCM-41 support was beneficial for improving the catalytic activity because it reduced the crystallinity and substantially increased the external specific surface area of the catalyst. The experimental results pertaining to the use of the MCM-41@DMC catalyst in the fabrication of polypropylene glycol showed that the conversion of propylene oxide and molecular weight reached 90.6% and 2900, respectively. This study provides a new strategy for the green synthesis of poly(propylene glycol) products.
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References
Almora-Barrios N, Pogodin S, Bellarosa L, García-Melchor M, Revilla-López G, García-Ratés M, López N (2015) Structure, activity, and deactivation mechanisms in double metal cyanide catalysts for the production of polyols. ChemCatChem 7:928–935. https://doi.org/10.1002/cctc.201402907
An N, Li Q, Yin N, Kang M, Wang J (2018) Effects of addition mode on Zn–Co double metal cyanide catalyst for synthesis of oligo(propylene-carbonate) diols. Appl Organomet Chem 32:e4509. https://doi.org/10.1002/aoc.4509
Blankenburg J, Kersten E, Maciol K, Wagner M, Zarbakhsh S, Frey H (2019) The poly(propylene oxide-co-ethylene oxide) gradient is controlled by the polymerization method: determination of reactivity ratios by direct comparison of different copolymerization models. Polym Chem 10:2863–2871. https://doi.org/10.1039/C9PY00500E
Blasco T, Corma A, Martínez A, Martínez-Escolano P (1998) Supported heteropolyacid (HPW) catalysts for the continuous alkylation of isobutane with 2-butene: the benefit of using MCM-41 with larger pore diameters. J Catal 177:306–313. https://doi.org/10.1006/jcat.1998.2105
Chen S, Chen L (2004) Fe/Zn double metal cyanide catalyzed ring-opening polymerization of propylene oxide: 2. Characterization of active structure of double metal cyanide catalysts. Colloid Polym Sci 282:1033–1038. https://doi.org/10.1007/s00396-003-1030-y
Chen L, Zhao J, Yin S-F, Au C-T (2013) A mini-review on solid superbase catalysts developed in the past two decades. RSC Adv 3:3799–3814. https://doi.org/10.1039/C2RA22252C
Dienes Y, Leitner W, Müller M-G-J, Offermans W-K, Reier T, Reinholdt A, Müller T-E (2012) Hybrid sol–gel double metal cyanide catalysts for the copolymerisation of styrene oxide and CO2. Green Chem 14:1168–1177. https://doi.org/10.1039/C2GC16485J
Gagnon SD (2002) Encyclopedia of polymer science and technology || propylene oxide and higher 1,2-epoxide polymers. Encycl Polymer Sci Technol. https://doi.org/10.1002/0471440264.pst530
Gao L, Shi Z, Etim U-J, Wu P, Han D, Xing W, Yan Z (2019) Beta-MCM-41 micro-mesoporous catalysts in the hydroisomerization of n-heptane: definition of an indexed isomerization factor as a performance descriptor. Microporous Mesoporous Mater 277:17–28. https://doi.org/10.1016/j.micromeso.2018.10.015
Herzberger J, Niederer K, Pohlit H, Seiwert J, Worm M, Wurm F, Frey H (2015) Polymerization of ethylene oxide, propylene oxide, and other alkylene oxides: synthesis, novel polymer architectures, and bioconjugation. Chem Rev 116:2170–2243. https://doi.org/10.1021/acs.chemrev.5b00441
Huang Y-J, Qi G-R, Chen L-S (2003) Effects of morphology and composition on catalytic performance of double metal cyanide complex catalyst. Appl Catal A Gen 240:263–271. https://doi.org/10.1016/S0926-860X(02)00452-0
Huang Y-J, Zhang X-H, Hua Z-J, Chen S-L, Qi G-R (2010) Ring-opening polymerization of propylene oxide catalyzed by a calcium-chloride-modified zinc-cobalt double metal-cyanide complex. Macromol Chem Phys 211:1229–1237. https://doi.org/10.1002/macp.200900666
Kang X, Sun X, Zhu Q, Ma X, Liu H, Ma J, Han B (2016) Synthesis of hierarchical mesoporous Prussian blue analogues in ionic liquid/water/MgCl2 and application in electrochemical reduction of CO2. Green Chem 18:1869–1873. https://doi.org/10.1039/C5GC02848E
Kim I, Ahn J-T, Ha C-S, Yang C-S, Park I (2003) Polymerization of propylene oxide by using double metal cyanide catalysts and the application to polyurethane elastomer. Polymer 44:3417–3428. https://doi.org/10.1016/S0032-3861(03)00226-X
Lawniczak-Jablonska K, Dynowska E, Sobczak J, Lisowski W, Chruściel A, Hreczuch W, Reszka A (2015) Structural properties and chemical bonds in double metal cyanide catalysts. X-Ray Spectrom 44:330–338. https://doi.org/10.1002/xrs.2636
Lee I-K, Ha J-Y, Cao C, Park D-W, Ha C-S, Kim I (2009) Effect of complexing agents of double metal cyanide catalyst on the copolymerizations of cyclohexene oxide and carbon dioxide. Catal Today 148:389–397. https://doi.org/10.1016/j.cattod.2009.07.073
Li X, Deng Q, Yu L, Gao R, Tong Z, Lu C, Deng S (2020) Double-metal cyanide as an acid and hydrogenation catalyst for the highly selective ring-rearrangement of biomass-derived furfuryl alcohol to cyclopentenone compounds. Green Chem 22:2549–2557. https://doi.org/10.1039/C9GC04432A
Ludi A, Guedel H-U, Ruegg M (1970) Structural chemistry of Prussian blue analogs. Single-crystal study of manganese(II) hexacyanocobaltate(III), Mn3[Co(DcN)6]2.xH2O. Inorg Chem 9:2224–2227. https://doi.org/10.1021/ic50092a005
Marquez C, Rivera-Torrente M, Paalanen P-P, Weckhuysen B-M, Cirujano F-G, De Vos D, De Baerdemaeker T (2017) Increasing the availability of active sites in Zn-Co double metal cyanides by dispersion onto a SiO2 support. J Catal 354:92–99. https://doi.org/10.1016/j.jcat.2017.08.008
Marquez C, Simonov A, Wharmby M, Goethem C, Vankelecom I, Bueken B, De Baerdemaeker T (2019) Layered Zn 2 [Co(CN) 6 ](CH 3 COO) double metal cyanide: a two-dimensional DMC phase with excellent catalytic performance. Chem Sci 10:4868–4875. https://doi.org/10.1039/C9SC00527G
Raghuraman A, Babb D, Miller M, Paradkar M, Smith B, Nguyen A (2016) Sequential DMC/FAB-catalyzed alkoxylation toward high primary hydroxyl, high molecular weight polyether polyols. Macromolecules 49:6790–6798. https://doi.org/10.1021/acs.macromol.6b01363
Robert J-H (1967) Method of epoxide or episulfide copolymer polymerization with nitro aromatic compound. US3301796 A.
Robertson N-J, Qin Z, Dallinger G-C, Lobkovsky E-B, Lee S, Coates G-W (2006) Two-dimensional double metal cyanide complexes: highly active catalysts for the homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide. Dalton Trans 45:5390–5395. https://doi.org/10.1039/B607963F
Sebastian J, Srinivas D (2014) Effects of method of preparation on catalytic activity of Co–Zn double-metal cyanide catalysts for copolymerization of CO2 and epoxide. Appl Catal A Gen 482:300–308. https://doi.org/10.1016/j.apcata.2014.06.007
Seneker S-D, Barksby N-J-E (1996) Aqueous polyurethane dispersions based on polyether polyols of low monol content. US5576382 A
Song Z, Subramaniam B, Chaudhari R-V (2019) Transesterification of propylene carbonate with methanol using Fe–Mn double metal cyanide catalyst. ACS Sustain Chem Eng 7:5698–5710. https://doi.org/10.1021/acssuschemeng.8b04779
Su C, Xu N, Shi J (2004) Structure and properties of polyether polyols catalyzed by Fe/Zn double metal cyanide complex catalyst. Prog Org Coat 49:125–129
Subhani M, Gürtler C, Leitner W, Müller T (2016) Nanoparticulate TiO2 -supported double metal cyanide catalyst for the copolymerization of CO2 with propylene oxide. Eur J Inorg Chem 2016:1944–1949. https://doi.org/10.1002/ejic.201501187
Sun X-K, Zhang X-H, Liu F, Chen S, Du B-Y, Wang Q, Qi G-R (2008) Alternating copolymerization of carbon dioxide and cyclohexene oxide catalyzed by silicon dioxide/Zn-CoIII double metal cyanide complex hybrid catalysts with a nanolamellar structure. J Polym Sci A Polym Chem 46:3128–3139. https://doi.org/10.1002/pola.22666
Tran C-H, Pham L-T-T, Lee Y, Jang H-B, Kim S, Kim I (2019) Mechanistic insights on Zn(II)−Co(III) double metal cyanide-catalyzed ring-opening polymerization of epoxides. J Catal 372:86–102. https://doi.org/10.1016/j.jcat.2019.02.028
Yi M-J, Byun S-H, Ha C-S, Park D-W, Kim I (2004) Copolymerization of cyclohexene oxide with carbon dioxide over nano-sized multi-metal cyanide catalysts. Solid State Ionics 172:139–144. https://doi.org/10.1016/j.ssi.2004.04.031
Yoon J-H, Lee I-K, Choi H-Y, Choi E-J, Yoon J-H, Shim S-E, Kim I (2011) Double metal cyanide catalysts bearing lactate esters as eco-friendly complexing agents for the synthesis of highly pure polyols. Green Chem 13:631–639. https://doi.org/10.1039/C0GC00554A
Zhang X-H, Hua Z-J, Chen S, Liu F, Sun X-K, Qi G-R (2007) Role of zinc chloride and complexing agents in highly active double metal cyanide catalysts for ring-opening polymerization of propylene oxide. Appl Catal A Gen 325:91–98. https://doi.org/10.1016/j.apcata.2007.03.014
Zhang W, Lin Q, Cheng Y, Lu L, Lin B, Pan L, Xu N (2012) Double metal cyanide complexes synthesized by solvent-free grinding method for copolymerization of CO2 and propylene oxide. J Appl Polym Sci 123:977–985. https://doi.org/10.1002/app.34544
Funding
This study was financially supported by the National Natural Science Foundation of China (21973045), China Petroleum & Chemical Corporation (J418013-3), and Jiangsu Scientific and Technological Transformative Project (SBA2018030374). The related measure and analysis instrument for this work were supported by Centre for Analysis, Nanjing Normal University.
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Cao, X., Wang, K., Mao, Q. et al. MCM-41-supported double metal cyanide nanocomposite catalyst for ring-opening polymerisation of propylene oxide. J Nanopart Res 24, 71 (2022). https://doi.org/10.1007/s11051-022-05443-1
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DOI: https://doi.org/10.1007/s11051-022-05443-1