Abstract
The reversible reaction of the hydroxyl groups in cellulose with CO2 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) results in a rapid and effective derivative dissolution of cellulose in DMSO, by which a series of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) with various degrees of substitution (DS) were synthesized controllably without adding external catalysts. Wherein DBU not only achieves the dissolution of cellulose, but also acts as an efficient organocatalyst for the subsequent cellulose derivatization. The DS of CAB and CAP can be tuned by changing the feed molar ratio of propionic (butyric) anhydride/acetic anhydride and the reaction temperature. The structural and thermal properties of the products were characterized by several analytical techniques including NMR, FT-IR, and TGA. The CO2/DBU/DMSO dissolution system provides a new platform for controllable synthesis of mixed cellulose esters with high efficiency under mild conditions.
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Abbreviations
- DBU:
-
1,8-Diazabicyclo[5.4.0]undec-7-ene
- CAP:
-
Cellulose acetate propionate
- CAB:
-
Cellulose acetate butyrate
- DS:
-
Degrees of substitution
- CA:
-
Cellulose acetate
- CP:
-
Cellulose propionate
- AGU:
-
Anhydroglucose unit
- TGA:
-
Thermo gravimetric analysis
- DSC:
-
Differential scanning calorimetry
- FTIR:
-
Fourier transform infrared spectrometer
- AmimCl:
-
1-Allyl-3-methylimidazolium chloride
- BmimCl:
-
1-Buty-3-methylimidazolium chloride
- DMAP:
-
4-Dimethylaminopyridine
References
Abderahmane E, El Barkany S, Hassan A, Abdel-Karim M (2011) Synthesis and characterization of the new cellulose derivative films based on the hydroxyethyl cellulose prepared from “Stipa Tenacissima” cellulose of Eastern Morocco. I. Solubility study. J Appl Polym Sci 122:2952–2965
Ass BAP, Ciacco GT, Frollini E (2006) Cellulose acetates from linters and sisal: correlation between synthesis conditions in DMAc/LiCl and product properties. Bioresour Technol 97:1696–1702
Biganska O, Navard P (2005) Kinetics of precipitation of cellulose from cellulose-NMMO-water solutions. Biomacromolecules 6:1948–1953
Buchanan CM, Edgar KJ, Wilson AK (1991) Preparation and characterization of cellulose monoacetates: the relationship between structure and water solubility. Macromolecules 24:169–176
Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548
Cai J, Zhang L, Zhou J, Qi H, Chen H, Kondo T, Chen X, Chu B (2007) Multifilament fibers based on dissolution of cellulose in NaOH/urea aqueous solution: structure and properties. Adv Mater 19:821–825
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
Caruso RA, Schattka JH (2000) Cellulose acetate templates for porous inorganic network fabrication. Adv Mater 12:1921–1923
Chen X, Liu Y, Qin F, Kong L, Zou H (2003) Synthesis of covalently bonded cellulose derivative chiral stationary phases with a bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate. J Chromatogr A 1010:185–194
Cheng HN, Dowd MK, Shogren RL, Biswas A (2011) Conversion of cotton byproducts to mixed cellulose esters. Carbohydr Polym 86:1130–1136
Chou WL, Yu DG, Yang MC (2005) The preparation and characterization of silver-loading cellulose acetate hollow fiber membrane for water treatment. Polym Adv Technol 16:600–607
Chrapava S, Touraud D, Rosenau T, Potthast A, Kunz W (2003) The investigation of the influence of water and temperature on the LiCl/DMAc/cellulose system. PCCP 5:1842–1847
Dan A, Nishio Y (2010) Phosphorylated cellulose propionate derivatives as thermoplastic flame resistant/retardant materials: influence of regioselective phosphorylation on their thermal degradation behaviour. Cellulose 17:963–976
Deng M, Zhou Q, Du A, Kasteren JV, Wang Y (2009) Preparation of nanoporous cellulose foams from cellulose-ionic liquid solutions. Mater Lett 63:1851–1854
Ducéré V, Bernès A, Lacabanne C (2005) A capacitive humidity sensor using cross-linked cellulose acetate butyrate. Sens Act B Chem 106:331–334
Fischer S, Thümmler K, Pfeiffer K, Liebert T, Heinze T (2002) Evaluation of molten inorganic salt hydrates as reaction medium for the derivatization of cellulose. Cellulose 9:293–300
Fischer S, Leipner H, Thümmler K, Brendler E, Peters J (2003) Inorganic molten salts as solvents for cellulose. Cellulose 10:227–236
Gupta KM, Hu Z, Jiang J (2013a) Cellulose regeneration from a cellulose/ionic liquid mixture: the role of anti-solvents. RSC Adv 3:12794–12801
Gupta KM, Hu Z, Jiang J (2013b) Molecular insight into cellulose regeneration from a cellulose/ionic liquid mixture: effects of water concentration and temperature. RSC Adv 3:4425–4433
Heinze T, Liebert T (2001) Unconventional methods in cellulose functionalization. Prog Polym Sci 26:1689–1762
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
Hwang IT, Lee SA, Hwang JS, Lee KI (2011) A facile synthesis of highly functionalized 4-arylcoumarins via Kostanecki reactions mediated by DBU. Molecules 16:6313–6321
Jeon GW, An JE, Jeong YG (2012) High performance cellulose acetate propionate composites reinforced with exfoliated graphene. Compos Part B Eng 43:3412–3418
Kazakov OI, Datta PP, Isajani M, Kiesewetter ET, Kiesewetter MK (2014) Cooperative hydrogen-bond pairing in organocatalytic ring-opening polymerization. Macromolecules 47:7463–7468
Khan S, Ghosh AK, Ramachandhran V, Bellare J, Hanra MS, Trivedi MK, Misra BM (2000) Synthesis and characterization of low molecular weight cut off ultrafiltration membranes from cellulose propionate polymer. Desalination 128:57–66
Li J, Zhang LP, Peng F, Bian J, Yuan TQ, Xu F, Sun RC (2009a) Microwave-assisted solvent-free acetylation of cellulose with acetic anhydride in the presence of iodine as a catalyst. Molecules 14:3551–3566
Li WY, Jin AX, Liu CF, Sun RC, Zhang AP, Kennedy JF (2009b) Homogeneous modification of cellulose with succinic anhydride in ionic liquid using 4-dimethylaminopyridine as a catalyst. Carbohydr Polym 78:389–395
Li X, Wang KY, Helmer B, Chung TS (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
Liu CF, Zhang AP, Li WY, Yue FX, Sun RC (2009) Homogeneous modification of cellulose in ionic liquid with succinic anhydride using N-bromosuccinimide as a catalyst. J Agric Food Chem 57:1814–1820
Liu CF, Zhang AP, Li WY, Yue FX, Sun RC (2010) Succinoylation of cellulose catalyzed with iodine in ionic liquid. Ind Crops Prod 31:363–369
Luan Y, Zhang J, Zhan M, Wu J, Zhang J, He J (2013) Highly efficient propionylation and butyralation of cellulose in an ionic liquid catalyzed by 4-dimethylminopyridine. Carbohydr Polym 92:307–311
Mail WL, Lan WM, Chen D, Liu C (2011) DMAP-catalyzed phthalylation of cellulose with phthalic anhydride in [Bmim]Cl. BioResources 6:2375–2385
Meng X, Edgar KJ (2015) Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis. Carbohydr Polym 132:565–573
Meng X, Matson JB, Edgar KJ (2014a) Olefin cross-metathesis as a source of polysaccharide derivatives: cellulose ω-carboxyalkanoates. Biomacromolecules 15:177–187
Meng X, Matson JB, Edgar KJ (2014b) Olefin cross-metathesis, a mild, modular approach to functionalized cellulose esters. Polym Chem 5:7021–7033
Meng X, York EA, Liu S, Edgar KJ (2015) Hydroboration–oxidation: a chemoselective route to cellulose ω-hydroxyalkanoate esters. Carbohydr Poly 133:262–269
Meng X, Roy Choudhury S, Edgar KJ (2016) Multifunctional cellulose esters by olefin cross-metathesis and thiol-Michael addition. Polym Chem 7:3848–3856
Ostlund A, Lundberg D, Nordstierna L, Holmberg K, Nydén M (2009) Dissolution and gelation of cellulose in TBAF/DMSO solutions: the roles of fluoride ions and water. Biomacromolecules 10:2401–2407
Park JW, Doi Y, Iwata T (2005) Unique crystalline orientation of poly[(R)-3-hydroxybutyrate]/cellulose propionate blends under uniaxial drawing. Macromolecules 38:2345–2354
Peschel D, Zhang K, Aggarwal N, Brendler E, Fischer S, Groth T (2010) Synthesis of novel celluloses derivatives and investigation of their mitogenic activity in the presence and absence of FGF2. Acta Biomater 6:2116–2125
Pinkert A, Marsh KN, Pang S, Staiger MP (2009) Ionic liquids and their interaction with cellulose. Chem Rev 109:6712–6728
Son WK, Ji HY, Park WH (2006) Antimicrobial cellulose acetate nanofibers containing silver nanoparticles. Carbohydr Polym 65:430–434
Song Y, Sun Y, Zhang X, Zhou J, Zhang L (2008) Homogeneous quaternization of cellulose in NaOH/urea aqueous solutions as gene carriers. Biomacromol 9:2259–2264
Song L, Yang Y, Xie H, Liu E (2015) Cellulose dissolution and in situ grafting in a reversible system using an organocatalyst and carbon dioxide. Chemsuschem 8:3217–3221
Su J, Qian Y, Teo JF, Chung TS (2010) Cellulose acetate nanofiltration hollow fiber membranes for forward osmosis processes. J Membr Sci 355:36–44
Sugimura K, Teramoto Y, Nishio Y (2013) Blend miscibility of cellulose propionate with poly(N-vinyl pyrrolidone-co-methyl methacrylate). Carbohydr Polym 98:532–541
Takaragi A, Minoda M, Miyamoto T, Hai QL, Li NZ (1999) Reaction characteristics of cellulose in the LiCl/1,3-dimethyl-2-imidazolidinone solvent system. Cellulose 6:93–102
Tosh B, Saikia CN, Dass NN (2000) Homogeneous esterification of cellulose in the lithium chloride–N,N-dimethylacetamide solvent system: effect of temperature and catalyst. Carbohydr Res 327:345–352
Wu J, Zhang J, Zhang H, He J, Ren Q, Guo M (2004) Homogeneous acetylation of cellulose in a new ionic liquid. Biomacromol 5:266–268
Xie H, Yu X, Yang Y, Zhao ZK (2014) Capturing CO2 for cellulose dissolution. Green Chem 16:2422–2427
Yang Y, Xie H, Liu E (2014) Acylation of cellulose in reversible ionic liquids. Green Chem 16:3018–3023
Yang Y, Song L, Peng C, Liu E, Xie H (2015) Activating cellulose via its reversible reaction with CO2 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene for efficient synthesis of cellulose acetate. Green Chem 17:2758–2763
Yu N, Gray GR (1998) Analysis of the positions of substitution of acetate and propionate groups in cellulose acetate–propionate by the reductive-cleavage method. Carbohydr Res 313:29–36
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 122:1–8
Zhang C, Price LM, Daly WH (2006) Synthesis and characterization of a trifunctional aminoamide cellulose derivative. Biomacromolecules 7:139–145
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Grant No. 31270637 and 21574030); Science and Technology Department of Guizhou Province (Grant No. Natural Science Key Fund [2016]1402) (Grant No. Platform and Talents [2016]5652); Open research fund of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education of China (08031339); Foundation of State Key Laboratory of Coal Conversion (Grant No. J17-18-907); Excellent Scientific Innovative Talent Programme from Education Department of Guizhou Province (Grant No. KY[2015]479).
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Qinqin Xu and Longchu Song have contributed equally to the work.
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Xu, Q., Song, L., Zhang, L. et al. Synthesis of cellulose acetate propionate and cellulose acetate butyrate in a CO2/DBU/DMSO system. Cellulose 25, 205–216 (2018). https://doi.org/10.1007/s10570-017-1539-8
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DOI: https://doi.org/10.1007/s10570-017-1539-8