Abstract
Cellulose acetate propionate (CAP), a high value-added chemical, is traditionally prepared using H2SO4 as catalyst. Replacement of the mineral acids by solid acids is current research focus for green and sustainable production of CAP. Herein, we reported the fabrication of novel solid acid catalyst HPW/Si(Et)Si-Dim-SO3H (Si(Et)Si = ethyl-bridged organosilica and Dim = dihydroimidazole) by incorporating phosphotungstic acid (HPW) and sulfonic acid-based Brønsted acidic ionic liquids onto the organosilica nanospheres of the designed catalyst for efficient manufacture CAP via esterification. The results indicated that the as-prepared HPW/Si(Et)Si-Dim-SO3H with 7.5% HPW loading showed the best catalytic performance at 45 °C in 3 h and the resulting CAP exhibited viscosity of 447 mPa s, Mw of 102,882 and DS of 2.69. Most importantly, the HPW/Si(Et)Si-Dim-SO3H exhibited high catalytic stability over six consecutive cycles and the obtained products were stable too with similar DS, Mw and viscosity. As such, the designed heteropolyacids and sulfonic acid-bifunctionalized heterogeneous catalyst is highly promising for biomass conversion under mild conditions.
Graphic abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abbott AP, Bell TJ, Handa S, Stoddart B (2005) O-Acetylation of cellulose and monosaccharides using a zinc based ionic liquid. Green Chem 7:705–707. https://doi.org/10.1039/B511691K
An S, Sun Y, Song D, Zhang Q, Guo Y, Shang Q (2016) Arenesulfonic acid-functionalized alkyl-bridged organosilica hollow nanospheres for selective esterification of glycerol with lauric acid to glycerol mono- and dilaurate. J Catal 342:40–54. https://doi.org/10.1016/j.jcat.2016.07.004
An S, Liu J-C, Zhang H, Wu L, Qi B, Song Y-F (2019) Recent progress on the frontiers of polyoxometalates structures and applications. Sci China Chem 62:159–161. https://doi.org/10.1007/s11426-018-9378-4
Barthel S, Heinze T (2006) Acylation and carbanilation of cellulose in ionic liquids. Green Chem 8:301–306. https://doi.org/10.1039/B513157J
Biganska O, Navard P (2005) Kinetics of precipitation of cellulose from cellulose−NMMO−water solutions. Biomacromol 6:1948–1953. https://doi.org/10.1021/bm040079q
Cao Y, Wu J, Meng T, Zhang J, He J, Li H, Zhang Y (2007) Acetone-soluble cellulose acetates prepared by one-step homogeneous acetylation of cornhusk cellulose in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). Carbohydr Polym 69:665–672. https://doi.org/10.1016/j.carbpol.2007.02.001
Cao Y, Wu J, Zhang J, Li H, Zhang Y, He J (2009) Room temperature ionic liquids (RTILs): a new and versatile platform for cellulose processing and derivatization. Chem Eng J 147:13–21. https://doi.org/10.1016/j.cej.2008.11.011
Cao Z, Zhao X, He F, Zhou Y, Huang K, Zheng A, Tao D (2018) Highly efficient indirect hydration of olefins to alcohols using superacidic polyoxometalate-based ionic hybrids catalysts. Ind Eng Chem Res 57:6654–6663. https://doi.org/10.1021/acs.iecr.8b00535
Chen Z, Zhang J, Xiao P, Tian W, Zhang J (2018) Novel thermoplastic cellulose esters containing bulky moieties and soft segments. ACS Sustain Chem Eng 6:4931–4939. https://doi.org/10.1021/acssuschemeng.7b04466
Cheng HN, Dowd MK, Shogren RL, Biswas A (2011) Conversion of cotton byproducts to mixed cellulose esters. Carbohydr Polym 86:1130–1136. https://doi.org/10.1016/j.carbpol.2011.06.002
Edgar KJ, Buchanan CM, Debenham JS, Rundquist PA, Seiler BD, Shelton MC, Tindall D (2001) Advances in cellulose ester performance and application. Prog Polym Sci 26:1605–1688. https://doi.org/10.1016/S0079-6700(01)00027-2
El Seoud OA, Marson GA, Ciacco GT, Frollini E (2000) An efficient, one-pot acylation of cellulose under homogeneous reaction conditions. Macromol Chem Phys 201:882–889. https://doi.org/10.1002/(SICI)1521-3935(20000501)201:8%3c882:AID-MACP882%3e3.0.CO;2-I
Fan G, Wang M, Liao C, Fang T, Li J, Zhou R (2013) Isolation of cellulose from rice straw and its conversion into cellulose acetate catalyzed by phosphotungstic acid. Carbohydr Polym 94:71–76. https://doi.org/10.1016/j.carbpol.2013.01.073
Geng Y, Xiong S, Li B, Liao Y, Xiao X, Yang S (2018) H3PW12O40 grafted on CeO2: a high-performance catalyst for the selective catalytic reduction of NOx with NH3. Ind Eng Chem Res 57:856–866. https://doi.org/10.1021/acs.iecr.7b03947
Heinze T, Liebert T (2001) Unconventional methods in cellulose functionalization. Prog Polym Sci 26:1689–1762. https://doi.org/10.1016/S0079-6700(01)00022-3
Heinze T, Dicke R, Koschella A, Kull AH, Klohr E, Koch W (2000) Effective preparation of cellulose derivatives in a new simple cellulose solvent. Macromol Chem Phys 201:627–631. https://doi.org/10.1002/(SICI)1521-3935(20000301)201:6%3c627:AID-MACP627%3e3.0.CO;2-Y
Hu J, Wu Q, Li W, Ma L, Su F, Guo Y, Qiu Y (2011) Epoxidation of alkenes catalyzed by phenyl group-modified, periodic mesoporous organosilica-entrapped, dimeric manganese-salen complexes. Chemsuschem 4:1813–1822. https://doi.org/10.1002/cssc.201100382
Huang K, Wang B, Cao Y, Li H, Wang J, Lin W, Mu C, Liao D (2011) Homogeneous preparation of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from sugarcane bagasse cellulose in ionic liquid. J Agric Food Chem 59:5376–5381. https://doi.org/10.1021/jf104881f
Hussain MA, Liebert T, Heinze T (2004) Acylation of cellulose with N, N′-carbonyldiimidazole-activated acids in the novel solvent dimethyl sulfoxide/tetrabutylammonium fluoride. Macromol Rapid Commun 25:916–920. https://doi.org/10.1002/marc.200300308
Inagaki S, Guan S, Fukushima Y, Ohsuna T, Terasaki O (1999) Novel mesoporous materials with a uniform distribution of organic groups and inorganic oxide in their frameworks. J Am Chem Soc 121:9611–9614. https://doi.org/10.1021/ja9916658
Inagaki S, Guan S, Ohsuna T, Terasak O (2002) An ordered mesoporous organosilica hybrid material with a crystal-like wall structure. Nature 416:304–307. https://doi.org/10.1038/416304a
Kasztelan S, Payen E, Moffat JB (1990) The existence and stability of the silica-supported 12-molybdophosphoric acid Keggin unit as shown by Raman, XPS, and 31P NMR spectroscopic studies. J Catal 125:45–53. https://doi.org/10.1016/0021-9517(90)90076-V
Klemm D, Heublein B, Fink H, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393. https://doi.org/10.1002/anie.200460587
Köhler S, Heinze T (2007) Efficient synthesis of cellulose furoates in 1-N-butyl-3-methylimidazolium chloride. Cellulose 14:489–495. https://doi.org/10.1007/s10570-007-9138-8
Kozhevnikov IV, Kloetstra KR, Sinnema A, Zandbergen HW, Vanbekkum H (1996) Study of catalysts comprising heteropoly acid H3PW12O40 supported on MCM-41 molecular sieve and amorphous silica. J Mol Catal A 114:287–298. https://doi.org/10.1016/S1381-1169(96)00328-7
Kuzminska M, Kovalchuk TV, Backov R, Gaigneaux EM (2014) Immobilizing heteropolyacids on zirconia-modified silica as catalysts for oleochemistry transesterification and esterification reactions. J Catal 320:1–8. https://doi.org/10.1016/j.jcat.2014.09.016
Lefebvre F (1992) 31P MAS NMR study of H3PW12O40 supported on silica: formation of (≡SiOH2+)(H2PW12O40–). J Chem Soc Chem Commun. https://doi.org/10.1039/C39920000756
Li X, Wang K, Helmer B, Chung T (2012) Thin-film composite membranes and formation mechanism of thin-film layers on hydrophilic cellulose acetate propionate substrates for forward osmosis processes. Ind Eng Chem Res 51:10039–10050. https://doi.org/10.1021/ie2027052
Li J, Li D, Xie J, Liu Y, Guo Z, Wang Q, Lyu Y, Zhou Y, Wang J (2016) Pyrazinium polyoxometalate tetrakaidecahedron-like crystals esterify oleic acid with equimolar methanol at room temperature. J Catal 339:123–134. https://doi.org/10.1016/j.jcat.2016.03.036
Li T, Wang Z, Chen W, Miras HN, Song Y-F (2017) Rational design of a polyoxometalate intercalated layered double hydroxide: highly efficient catalytic epoxidation of allylic alcohols under mild and solvent-free conditions. Chem Eur J 23:1069–1077. https://doi.org/10.1002/chem.201604180
Marson GA, El Seoud OA (1999) A novel, efficient procedure for acylation of cellulose under homogeneous solution conditions. J Appl Polym Sci 74:1355–1360. https://doi.org/10.1002/(SICI)1097-4628(19991107)74:6%3c1355:AID-APP5%3e3.0.CO;2-M
Meng C, Cao G, Li X, Yan Y, Zhao E, Hou L, Shi H (2017) Structure of the SO42−/TiO2 solid acid catalyst and its catalytic activity in cellulose acetylation. React Kinet Mech Catal 121:719–734. https://doi.org/10.1007/s11144-017-1165-3
Omwoma S, Chen W, Tsunashima R, Song Y-F (2014) Recent advances on polyoxometalates intercalated layered double hydroxides: from synthetic approaches to functional material applications. Coord Chem Rev 258–259:58–71. https://doi.org/10.1016/j.ccr.2013.08.039
Schnee J, Eggermont A, Gaigneaux EM (2017) Boron nitride: a support for highly active heteropolyacids in the methanol-to-DME reaction. ACS Catal 7:4011–4017. https://doi.org/10.1021/acscatal.7b00808
Shi Y, Guo Z, Wang Q, Zhang L, Li J, Zhou Y, Wang J (2017) Amphiphilic mesoporous poly(ionic liquid) immobilized heteropolyanions towards the efficient heterogeneous epoxidation of alkenes with stoichiometric hydrogen peroxide. ChemCatChem 9:4426–4436. https://doi.org/10.1002/cctc.201700906
Song Y-F, Tsunashima R (2012) Recent advances on polyoxometalate-based molecular and composite materials. Chem Soc Rev 41:7384–7402. https://doi.org/10.1039/C2CS35143A
Song D, An S, Sun Y, Guo Y (2016) Efficient conversion of levulinic acid or furfuryl alcohol into alkyl levulinates catalyzed by heteropoly acid and ZrO2 bifunctionalized organosilica nanotubes. J Catal 333:184–199. https://doi.org/10.1016/j.jcat.2015.10.018
Su F, Guo Y (2014) Advancements in solid acid catalysts for biodiesel production. Green Chem 16:2934–2957. https://doi.org/10.1039/C3GC42333F
Tao M, Yi X, Delidovich I, Palkovits R, Shi J, Wang X (2015) Hetropolyacid-catalyzed oxidation of glycerol into lactic acid under mild base-free conditions. Chemsuschem 8:4195–4201. https://doi.org/10.1002/cssc.201501200
Tao M, Sun N, Li Y, Tong T, Wielicako M, Wang S, Wang X (2017) Heteropolyacids embedded in a lipid bilayer covalently bonded to graphene oxide for the facile one-pot conversion of glycerol to lactic acid. J Mater Chem A 5:8325–8333. https://doi.org/10.1039/C7TA01334E
Wu J, Zhang J, Zhang H, He JS, Ren Q, Guo ML (2004) Homogeneous acetylation of cellulose in a new ionic liquid. Biomacromol 5:266–268. https://doi.org/10.1021/bm034398d
Xu Q, Song L, Zhang L, Hu G, Chen Q, Liu E, Liu Y, Zheng Q, Xie H, Li N (2018) Synthesis of cellulose acetate propionate and cellulose acetate butyrate in a CO2/DBU/DMSO system. Cellulose 25:205–216. https://doi.org/10.1007/s10570-017-1539-8
Yan L, Li W, Qi Z, Liu S (2006) Solvent-free synthesis of cellulose acetate by solid superacid catalysis. J Polym Res 13:375–378. https://doi.org/10.1007/s10965-006-9054-x
Yan H, Yang Y, Tong D, Xiang X, Hu C (2009) Catalytic conversion of glucose to 5-hydroxymethylfurfural over SO42−/ZrO2 and SO42−/ZrO2-Al2O3 solid acid catalysts. Catal Commun 10:1558–1563. https://doi.org/10.1016/j.catcom.2009.04.020
Yu Y, Miao J, Jiang Z, Sun H, Zhang L (2016) Cellulose esters synthesized using a tetrabutylammonium acetate and dimethylsulfoxide solvent system. Appl Phys A 122:656. https://doi.org/10.1007/s00339-016-0205-6
Zhang X, Zhao Y, Xu S, Yang Y, Liu J, Wei Y, Yang Q (2014) Polystyrene sulphonic acid resins with enhanced acid strength via macromolecular self-assembly within confined nanospace. Nature Commun 5:3170. https://doi.org/10.1038/ncomms4170
Zhang Y, Chen X, Li L, Chen W, Miras NH, Song Y-F (2019) Mesoporous polymer loading heteropolyacid catalysts: one-step strategy to manufacture high value-added cellulose acetate propionate. ACS Sustain Chem Eng 7:4975–4982. https://doi.org/10.1021/acssuschemeng.8b05627
Zhu F, Wang W, Li H (2011) Water-medium and solvent-free organic reactions over a bifunctional catalyst with Au nanoparticles covalently bonded to HS/SO3H functionalized periodic mesoporous organosilica. J Am Chem Soc 133:11632–11640. https://doi.org/10.1021/ja203450g
Acknowledgments
This research was supported by the National Key Research and Development Program of China (2017YFB0307303), the National Nature Science Foundation of China (21625101, 21521005, 21808011), Postdoctoral Science Foundation of China (2018M631313) and the Fundamental Research Funds for the Central Universities (XK1802-6, XK1803-05, XK1902, 12060093063).
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Zhang, H., Wu, L., Zhang, Y. et al. Heteropolyacids and sulfonic acid-bifunctionalized organosilica spheres for efficient manufacture of cellulose acetate propionate with high viscosity. Cellulose 27, 2437–2453 (2020). https://doi.org/10.1007/s10570-019-02936-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-019-02936-6