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An efficient transformation of cellulose into cellulose carbamates assisted by microwave irradiation

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Abstract

Cellulose carbamates (CCs) were microwave-assisted synthesized from the native cellulose and urea under solvent-free and catalyst-free conditions. Types of raw materials, the effects of the reaction condition on the nitrogen content of CCs were investigated. CCs were characterized with infrared spectroscopy (FT-IR), 13C NMR spectrometry, X-ray diffraction, scanning electron microscopy and thermogravimetry. The results indicated that various source of native celluloses such as cotton linter, reed, bagasse and wood pulps with different degree of polymerization could be successfully converted to CCs by the efficient and environmentally friendly procedure. The nitrogen content of CCs increased with an increase of the urea content and the mass of the mixtures, as well as the pulsed times of microwave irradiation. CCs retained the cellulose I crystalline form of the native cellulose and the degree of crystallinity decreased with the incorporation of carbamates. This work provided a novel pathway for the preparation of cellulose carbamate, which is expected to be useful for the CarbaCell process.

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Abbreviations

BA:

Bagasse pulps

CCs:

Cellulose carbamates

CL:

Cotton linter pulps

DP:

Degree of polymerization

DTG:

Differential thermogravimetry

FT-IR:

Infrared spectroscopy

RE:

Reed pulps

SEM:

Scanning electron microscopy

TG:

Thermogravimetry

WD:

Wood pulps

XRD:

X-ray diffraction

References

  • Conner WC, Tompsett GA (2008) How could and do microwave influence chemistry at interfaces? J Phys Chem B 112:2110–2118. doi:10.1021/jp0775247

    Article  CAS  Google Scholar 

  • Crépy L, Chaveriat L, Banoub J, Martin P, Joly N (2009) Synthesis of cellulose fatty esters as plastics-influence of the degree of substitution and the fatty chain length on mechanical properties. Chem Sus Chem 2:165–170. doi:10.1002/cssc.200800171

    Google Scholar 

  • Dogan H, Hilmioglu ND (2009) Dissolution of cellulose with NMMO by microwave heating. Carbohydr Polym 75:90–94. doi:10.1016/j.carbpol.2008.06.014

    Article  CAS  Google Scholar 

  • Gospodinova N, Grelard A, Jeannin M, Chitanu GC, Carpov A, Thiéry V, Besson T (2002) Efficient solvent-free microwave phosphorylation of microcrystalline cellulose. Green Chem 4:220–222. doi:10.1039/b200295g

    Article  CAS  Google Scholar 

  • Guo Y, Zhou J, Song Y, Zhang L (2009) An efficient and environmental-friendly method for the synthesis of cellulose carbamate by microwave. Macromol Rapid Commun 30:1504–1508. doi:10.1002/marc.200900238

    Article  CAS  Google Scholar 

  • Hong SM, Park JK, Lee YO (2004) Mechanisms of microwave irradiation involved in the destruction of fecal coliforms from biosolids. Water Res 38:1615–1625. doi:10.1016/j.watres.2003.12.011

    Article  CAS  Google Scholar 

  • Hou A, Wang X, Wu L (2008) Effect of microwave irradiation on the physical properties and morphological structures of cotton cellulose. Carbohydr Polym 74:934–937. doi:10.1016/j.carbpol.2008.05.011

    Article  CAS  Google Scholar 

  • Kappe CO (2004) Controlled microwave heating in modern organic synthesis. Angew Chem Int Ed 43:6250–6284. doi:10.1002/anie.200400655

    Article  CAS  Google Scholar 

  • Kappe CO, Stadler A (2005) Microwaves in organic and medicinal chemistry. Wiley-VCH, Weinheim, p 410

    Book  Google Scholar 

  • Keunecke G, Struszczyk H, Mikolajczyk W, Starostka P, Urbanowski A (1999) Method for modified manufacture of cellulose carbamate. US Patent 5,906,926

  • Klemm D, Philipp B, Heinze T, Heinze U, Wagenknecht W (1998a) Comprehensive cellulose chemistry, vol 1, fundamentals and analytical methods. Wiley-VCH, Weinheim, p 173

  • Klemm D, Philipp B, Heinze T, Heinze U, Wagenknecht W (1998b) Comprehensive cellulose chemistry, vol 2, functionalization of cellulose. Wiley-VCH, Weinheim, pp 161–164

  • Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393. doi:10.1002/anie.200460587

    Article  CAS  Google Scholar 

  • Kuester JL (1994) Design, operation and analysis of microwave heated chemical reactors. Res Chem Intermed 20:51–59. doi:10.1163/156856794X00063

    Article  CAS  Google Scholar 

  • Li J, Zhang L, Peng F, Bian J, Yuan T, Xu F, Sun R (2009) Microwave-assisted solvent-Free acetylation of cellulose with acetic anhydride in the presence of iodine as a catalyst. Molecules 14:3551–3566. doi:10.3390/molecules14093551

    Article  CAS  Google Scholar 

  • Loth F, Schaaf E, Fink HP, Kunze J, Gensrich J (2002) Verfahren zur Herstellung von Cellulosecarbamat in einem inerten organischen Reaktionsmedium. AZ Patent 102 53 672.4

  • Ludlow-Palafox C, Chase HA (2001) Microwave-induced pyrolysis of plastic wastes. Ind Eng Chem Res 40:4749–4756. doi:10.1021/ie010202j

    Article  CAS  Google Scholar 

  • Ma H, Liu W, Chen X, Wu Y, Yu Z (2009) Enhanced enzymatic saccharification of rice straw by microwave pretreatment. Bioresource Technol 100:1279–1284. doi:10.1016/j.biortech.2008.08.045

    Article  CAS  Google Scholar 

  • Maunu S, Liitiä T, Kauliomäki S, Hortling B, Sundquist J (2000) 13C CPMAS NMR investigations of cellulose polymorphs in different pulps. Cellulose 7:147–159. doi:10.1023/A:1009200609482

    Article  CAS  Google Scholar 

  • Moharram MA, Mahmoud OM (2007) X-ray diffraction methods in the study of the effect of microwave heating on the transformation of cellulose I into cellulose II during mercerization. J Appl Polym Sci 105:2978–2983. doi:10.1002/app.26580

    Article  CAS  Google Scholar 

  • Moharram MA, Mahmoud OM (2008) FTIR spectroscopic study of the effect of microwave heating on the transformation of cellulose I into cellulose II during mercerization. J Appl Polym Sci 107:30–36. doi:10.1002/app.26748

    Article  CAS  Google Scholar 

  • Nada AMA, Hassan ML (2000) Thermal behavior of cellulose and some cellulose derivatives. Polym Degrad Stabil 67:111–115. doi:10.1016/S0141-3910(99)00100-7

    Article  CAS  Google Scholar 

  • Nada AMA, Kamel S, El-Sakhawy M (2000) Thermal behaviour and infrared spectroscopy of cellulose carbamates. Polym Degrad Stabil 70:347–355. doi:10.1016/S0141-3910(00)00119-1

    Article  CAS  Google Scholar 

  • Nadagouda MN, Varma RS (2007) Synthesis of thermally stable carboxymethyl cellulose/metal biodegradable nanocomposites for potential biological applications. Biomacromolecules 8:2762–2767. doi:10.1021/bm700446p

    Article  CAS  Google Scholar 

  • Palm M, Zacchi G (2003) Extraction of Hemicellulosic oligosaccharides from spruce using microwave oven or steam treatment. Biomacromolecules 4:617–623. doi:10.1021/bm020112d

    Article  CAS  Google Scholar 

  • Possidonio S, Fidale LC, Seoud OAE (2009) Microwave-assisted derivatization of cellulose in an ionic liquid: an efficient, expedient synthesis of simple and mixed carboxylic esters. J Polym Sci Part A Polym Chem 48:134–143. doi:10.1002/pola.23770

    Article  Google Scholar 

  • Sarotti AM, Spanevello RA, Suárez AG (2007) An efficient microwave-assisted green transformation of cellulose into levoglucosenone. Advantages of the use of an experimental design approach. Green Chem 9:1137–1140. doi:10.1039/b703690f

    Article  CAS  Google Scholar 

  • Semsarilar M, Perrier S (2009) Solubilization and functionalization of cellulose assisted by microwave irradiation. Aust J Chem 62:223–226. doi:10.1071/CH08491

    Article  CAS  Google Scholar 

  • Shen X, Sugie N, Duan Q (2005) Synthesis and characterization of cellulose carbamates having α-amino acid moieties. Polym Bull 55:317–322. doi:10.1007/s00289-005-0442-x

    Article  CAS  Google Scholar 

  • Strauss CR, Varma RS (2006) Microwaves in green and sustainable chemistry. Top Curr Chem 266:199–231. doi:10.1007/128_060

    Article  CAS  Google Scholar 

  • Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975. doi:10.1021/ja025790m

    Article  CAS  Google Scholar 

  • Valta K, Sivonen E (2003) Method for manufacturing cellulose carbamate. WO Pat 2003064476

  • Voges M, Brück M, Fink HP, Gensrich J (2000) In: Proceedings of the Akzo-Nobel cellulosic man-made fibre seminar. Stenung-sund

  • Yin C, Li J, Xu Q, Peng Q, Liu Y, Shen X (2007) Chemical modification of cotton cellulose in supercritical carbon dioxide: synthesis and characterization of cellulose carbamate. Carbohydr Polym 67:147–154. doi:10.1016/j.carbpol.2006.05.010

    Article  CAS  Google Scholar 

  • Zhang Z, Zhao ZK (2010) Microwave-assisted conversion of lignocellulosic biomass into furans in ionic liquid. Bioresource Technol 101:1111–1114. doi:10.1016/j.biortech.2009.12.110

    Article  CAS  Google Scholar 

  • Zhu S, Wu Y, Yu Z, Liao J, Zhang Y (2005) Pretreatment by microwave/alkali of rice straw and its enzymic hydrolysis. Process Biochem 40:3082–3086. doi:10.1016/j.procbio.2005.03.016

    Article  CAS  Google Scholar 

  • Zhu S, Wu Y, Yu Z, Zhang X, Li H, Gao M (2006) The effect of microwave irradiation on enzymatic hydrolysis of rice straw. Bioresource Technol 97:1964–1968. doi:10.1016/j.biortech.2005.08.008

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Basic Research Program of China (973 Program, 2010CB732203), the National Natural Science Foundation of China (50973085), the Natural Science Foundation of Hubei Province (2009CDA040), and Engineering Research Center for Biomass Modified Materials, Sichuan Province, China.

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Authors and Affiliations

  1. Department of Chemistry, Wuhan University, 430072, Wuhan, China

    Yi Guo, Jinping Zhou, Yuchen Wang & Lina Zhang

  2. Engineering Research Center for Biomass Modified Materials, 621010, Mianyang, Sichuan Province, China

    Xiaoyan Lin

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  1. Yi Guo
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  2. Jinping Zhou
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  3. Yuchen Wang
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  4. Lina Zhang
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  5. Xiaoyan Lin
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Correspondence to Jinping Zhou.

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Guo, Y., Zhou, J., Wang, Y. et al. An efficient transformation of cellulose into cellulose carbamates assisted by microwave irradiation. Cellulose 17, 1115–1125 (2010). https://doi.org/10.1007/s10570-010-9446-2

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