Study of the Effect of Grafting Method on Surface Polarity of Tempo-Oxidized Nanocellulose Using Polycaprolactone as the Modifying Compound: Esterification versus Click-Chemistry
Esterification and click-chemistry were evaluated as surface modification treatments for TEMPO-oxidized nanocelluloses (TONC) using Polycaprolactone-diol (PCL) as modifying compound in order to improve the dispersion of nanofibers in organic media. These two grafting strategies were analyzed and compared. The first consists of grafting directly the PCL onto TONC, and was carried out by esterification between hydroxyl groups of PCL and carboxyl groups of TONC. The second strategy known as click-chemistry is based on the 1,3-dipolar cycloaddition reaction between azides and alkyne terminated moieties to form the triazole ring between PCL and TONC. The grafted samples were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and Thermogravimetry analysis (TGA). Further, the effects of the two treatments on the surface hydrophobization of TONC were investigated by contact angle measurements. The results show that both methods confirm the success of such a modification and the click reaction was significantly more effective than esterification.
References
[1]
Dong, S.; Roman, M. Fluorescently labeled cellulose nanocrystals for bioimaging applications. J. Am. Chem. Soc. 2007, 129, 13810–13811, doi:10.1021/ja076196l.
[2]
Song, Y.B.; Zhou, J.P.; Li, Q.; Guo, Y.; Zhang, L.N. Preparation and characterization of novel quaternized cellulose nanoparticles as protein carriers. Macromol. Biosci. 2009, 9, 857–863, doi:10.1002/mabi.200800371.
[3]
Backdahl, H.; Helenius, G.; Bodin, A.; Nannmark, U.; Johansson, B.R.; Risberg, B.; Gatenholm, P. Mechanical properties of bacterial cellulose and interactions with smooth muscle cells. Biomaterials 2006, 27, 2141–2149, doi:10.1016/j.biomaterials.2005.10.026.
[4]
Helenius, G.; Backdahl, H.; Bodin, A.; Nannmark, U.; Gatenholm, P.; Risberg, B. In vivo biocompatibility of bacterial cellulose. J Biomed. Mater. Res. A 2006, 76A, 431–438, doi:10.1002/jbm.a.30570.
[5]
Svensson, A.; Nicklasson, E.; Harrah, T.; Panilaitis, B.; Kaplan, D.L.; Brittberg, M.; Gatenholm, P. Bacterial cellulose as a potential scaffold for tissue engineering of cartilage. Biomaterials 2005, 26, 419–431.
[6]
Cai, Z.; Kim, J. Bacterial cellulose/poly(ethylene glycol) composite: Characterization and first evaluation of biocompatibility. Cellulose 2010, 17, 83–91, doi:10.1007/s10570-009-9362-5.
[7]
Xing, Q.; Zhao, F.; Chen, S.; DeCoster, M.A.; Lvov, Y.M. Porous biocompatible three dimensional scaffolds of cellulose microfiber/gelatin composites for cell culture. Acta Biomater. 2010, 6, 2132–2139, doi:10.1016/j.actbio.2009.12.036.
Grunert, M.; Winter, W.T. Nanocomposites of cellulose acetate butyrate reinforced with cellulose nanocrystals. J. Polym. Environ. 2002, 10, 27–30.
[13]
Siqueira, G.; Bras, J.; Dufresne, A. Cellulose whiskers versus microfibrils: Influence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites. Biomacromolecules 2009, 10, 425–432, doi:10.1021/bm801193d.
[14]
Schandler, L.S.; Brinson, L.C.; Sawyer, W.G. Polymer nanocomposites: A small part of the story. JOM 2007, 59, 53–60.
[15]
Klemm, D.; Schumann, D.; Kramer, F.; Hessler, N.; Hornung, M.; Schmauder, H.P.; Marsch, S. Nanocelluloses as innovative polymers in research and application. Adv. Polym. Sci. 2006, 205, 49–96, doi:10.1007/12_097.
Ranby, B.G. Fibrous macromolecular systems. Cellulose and muscle. The colloidal properties of cellulose micelles. Discuss. Faraday Soc. 1951, 11, 158–164, doi:10.1039/df9511100158.
[19]
Nakagaito, A.N.; Yano, H. Novel high-strength biocomposites based on microfibrillated cellulose having nano-order-unit web-like network structure. Appl. Phys. A 2005, 80, 155–159, doi:10.1007/s00339-003-2225-2.
[20]
Baiardo, M.; Frisoni, G.; Scandola, M.; Licciardello, A. Surface chemical modification of natural cellulose fibers. J. Appl. Polym. Sci. 2002, 83, 38–45, doi:10.1002/app.2229.
[21]
Dong, X.M.; Revol, J.F.; Gray, D.G. Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 1998, 5, 19–32, doi:10.1023/A:1009260511939.
[22]
Nakagaito, A.N.; Yano, H. The effect of morphological changes from pulp fiber towards nano-scale fibrillated cellulose on the mechanical properties of high-strength plant fiber based composites. Appl. Phys. A 2004, 78, 547–552, doi:10.1007/s00339-003-2453-5.
[23]
Andresen, M.; Johansson, L.S.; Tanem, B.S.; Stenius, P. Properties and characterization of hydrophobized microfibrillated cellulose. Cellulose 2006, 13, 665–677, doi:10.1007/s10570-006-9072-1.
[24]
Gousse, C.; Chanzy, H.; Excoffier, G.; Soubeyrand, L.; Fleury, E. Stable suspensions of partially silylated cellulose whiskers dispersed in organic solvents. Polymer 2002, 43, 2645–2651, doi:10.1016/S0032-3861(02)00051-4.
[25]
Yuan, H.H.; Nishiyama, Y.; Wada, M.; Kuga, S. Surface acylation of cellulose whiskers by drying aqueous emulsion. Biomacromolecules 2006, 7, 696–700, doi:10.1021/bm050828j.
[26]
Araki, J.; Wada, M.; Kuga, S. Steric stabilization of a cellulose microcrystal suspension by poly(ethylene glycol) grafting. Langmuir 2001, 17, 21–27, doi:10.1021/la001070m.
[27]
Ahmed Said Azizi, S.; Lonnberg, H.; Fogelstrom, L.; Berglund, L.; Malmstrom, E.; Anders, H. Surface grafting of microfibrillated cellulose with poly(caprolactone)—Synthesis and characterization. Eur. Polym. J. 2008, 44, 2991–2997, doi:10.1016/j.eurpolymj.2008.06.023.
[28]
Heux, L.; Chauve, G.; Bonini, C. Nonflocculatingand chiral-nematic self-ordering of cellulose microcrystals suspensions in nonpolar solvents. Langmuir 2000, 16, 8210–8212, doi:10.1021/la9913957.
[29]
Zhou, Q.; Brumer, H.; Teeri, T.T. Self-organization of cellulose nanocrystals adsorbed with xyloglucan oligosaccharide-poly(ethylene-glycol)-polystyrene triblock copolymer. Macromolecules 2009, 42, 5430–5432, doi:10.1021/ma901175j.
[30]
Saito, T.; Kimura, S.; Nishiyama, Y.; Isogai, A. Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 2007, 8, 2485–2491, doi:10.1021/bm0703970.
[31]
Saito, T.; Nishiyama, Y.; Putaux, J.L.; Vignon, M.; Isogai, A. Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 2006, 7, 1687–1691, doi:10.1021/bm060154s.
[32]
Barner-Kowollik, C.; Du Prez, F.E. “Clicking” polymers or just efficient linking: What is the difference? Angew. Chem. Int. Ed. 2011, 50, 60–62, doi:10.1002/anie.201003707.
[33]
Habibi, Y.; Goffin, A.-L.; Schiltz, N.; Duquesne, E.; Dubois, P.; Dufresne, A. Bionanocomposites based on poly(epsilon-caprolactone)-grafted cellulose nanocrystals by ring-opening polymerization. J. Mater. Chem. 2008, 41, 5002–5010.
[34]
Krouit, M.; Bras, J. Cellulose surface grafting with polycaprolactone by heterogeneous click-chemistry. Eur. Polym. J. 2008, 44, 4074–4081, doi:10.1016/j.eurpolymj.2008.09.016.
[35]
Julien, O.; Krouit, M.; Bras, P.; Thielemans, W.; Belgacem, M.N. Surface modification of cellulose by PCL grafts. Acta Mater. 2010, 58, 792–801, doi:10.1016/j.actamat.2009.09.057.
[36]
Benkaddour, A.; Jradi, K.; Daneault, C.; Sylvain, R. Grafting of polycaprolactone on oxidized nanocelluloses by click chemistry. Nanomaterials 2013, 3, 141–157, doi:10.3390/nano3010141.
[37]
Varma, A.J.; Chavan, V.B. Thermal properties of oxidized cellulose. Cellulose 1995, 2, 41–49.
[38]
Lerdkanchanaporn, S.; Dollimore, D.; Alexander, K.S. A simultaneous TG-DTA study of the degradation in nitrogen of cellulose to carbon, alone and in the presence of other pharmaceutical excipients. Thermochim. Acta 1998, 324, 25–32, doi:10.1016/S0040-6031(98)00520-6.
[39]
Fukuzumi, H.; Saito, T.; Okita, Y.; Isogai, A. Thermal stabilization of TEMPO-oxidized cellulose. Polym. Degrad. Stab. 2010, 95, 1502–1508, doi:10.1016/j.polymdegradstab.2010.06.015.
[40]
Biresaw, G.; Carriere, C.J.J. Correlation between mechanical adhesion and interfacial properties of starch/biodegradable polyester blends. Polym. Sci. B 2001, 39, 920–930, doi:10.1002/polb.1067.
[41]
Habibi, Y.; Dufresne, A. Highly filled bionanocomposites from functionalized polysaccharide nanocrystals. Biomacromolecules 2008, 9, 1974–1980, doi:10.1021/bm8001717.
[42]
Mishra, S.P.; Thirree, J.; Manent, A.S.; Chabot, B.; Daneault, C. Ultrasound-catalyzed TEMPO-mediated oxydation of native cellulose for the production of nanocellulose: Effect of process variables. BioResources 2011, 6, 121–143.
[43]
Saito, T.; Isogai, A. Ion-exchange behavior of carboxylate groups in fibrous cellulose oxidized by the TEMPO mediated system. Carbohydr. Polym. 2005, 61, 183–190, doi:10.1016/j.carbpol.2005.04.009.
[44]
Benoit, D.; Grimaldi, S.; Robin, S.; Finet, J.P.; Tordo, P.; Gnanou, Y. Kinetics and mechaism of controlled free-radical polymerization of styrene and n-butyl acrylate in the presence of an acyclic phosphonylated nitroxide. J. Am. Chem. Soc. 2000, 122, 5929–5939, doi:10.1021/ja991735a.
[45]
Stenzel, M.H.; Davis, T.P.; Fane, A.G. Honeycomb structured porous films prepared from carbohydrate based polymers synthesised via the RAFT process. J. Mater. Chem. 2003, 13, 2090–2097, doi:10.1039/b304204a.
