Abstract
To graft epoxy and ester functional groups onto cellulose nanofibrils (CNFs) and to overcome their poor hydrophobicity, we studied the modification of CNFs using graft copolymerization with glycidyl methacrylate (GMA) by a Fe2+–thiourea dioxide–H2O2 initiator system (Fe2+–TD–H2O2) in aqueous solution. The synthesized poly (GMA)-grafted CNF (CNF-g-PGMA) was characterized by FTIR, AFM, XRD, water contact angle, and TGA. GMA was successfully grafted onto the CNFs by Fe2+–TD–H2O2, the epoxy groups and ester groups of GMA were clearly present and intact in the CNF-g-PGMA, and TD is an important component of the initiator system under relatively mild graft conditions. CNF-g-PGMA may be an important intermediate because of its epoxy and ester functional groups. The main nanostructure of the CNFs was retained after graft copolymerization, and there were no obvious effects of graft copolymerization on the crystalline structure of the CNF backbone, although the crystalline index slightly decreased with the increased percentage of grafting. Graft copolymerization significantly modifies the CNF hydrophobicity. This strategy could extend the applications of CNFs into many areas.
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References
Battista OA (1950) Hydrolysis and crystallization of cellulose. Ind Eng Chem 42:502–507. https://doi.org/10.1021/ie50483a029
Bo S, Hou Q, Liu Z, Ni Y (2015) Sodium periodate oxidation of cellulose nanocrystal and its application as a paper wet strength additive. Cellulose 22:1135–1146. https://doi.org/10.1007/s10570-015-0575-5
El-Alfy E, Waly A, Hebeish A (1985) Graft copolymerization of perfluoroheptyl methacrylate/glycidyl methacrylate mixtures with cotton fabric using Fe2+-thioureadioxide-H2O2 redox system. Macromol Mater Eng 130:137–146. https://doi.org/10.1002/apmc.1985.051300111
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Griffiths PR (1991) The handbook of infrared and Raman characteristic frequencies of organic molecules. Academic Press, New York. https://doi.org/10.1016/0924-2031(92)87021-7
Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43:1519–1542. https://doi.org/10.1039/c3cs60204d
Henriksson G, Christiernin M, Agnemo R (2005) Monocomponent endoglucanase treatment increases the reactivity of softwood sulphite dissolving pulp. J Ind Microbiol Biot 32:211–214. https://doi.org/10.1007/s10295-005-0220-7
Huang J, Zhai HM (2008) Graft copolymerization of glycidyl methacrylate with eucalyptus pulp induced by Fe2+–H2O2–thiourea dioxide redox system. Chem Ind For Prod 28:58–62. http://www.cifp.ac.cn/EN/Y2008/V28/I2/58
Ibrahim NA, Wan MZWY, Abu-Ilaiwi FA, Rahman MZA, Ahmad MB, Dahlan KZM (2010) Graft copolymerization of methyl methacrylate onto oil palm empty fruit bunch fiber using H2O2/Fe2+ as an initiator. J Appl Polym Sci 89:2233–2238. https://doi.org/10.1002/app.12467
Isogai A (2015) Structural characterization and modifications of surface-oxidized cellulose nanofiber. J Jpn Pet Inst 58:365–375. https://doi.org/10.1627/jpi.58.365
Jorfi M, Foster EJ (2015) Recent advances in nanocellulose for biomedical applications. J Appl Polym Sci 132:41719. https://doi.org/10.1002/app.41719
Kalia S, Sabaa MW (2013) Polysaccharide based graft copolymers. Springer, Berlin. https://doi.org/10.1007/978-3-642-36566-9
Kargarzadeh H, Mariano M, Huang J, Lin N, Ahmad I, Dufresne A, Thomas S (2017) Recent developments on nanocellulose reinforced polymer nanocomposites: a review. Polymer 132:368–393. https://doi.org/10.1016/j.polymer.2017.09.043
Kargarzadeh H et al (2018) Advances in cellulose nanomaterials. Cellulose 25:1–39. https://doi.org/10.1007/s10570-018-1723-5
Kedzior SA, Graham L, Moorlag C, Dooley BM, Cranston ED (2016) Poly(methyl methacrylate)-grafted cellulose nanocrystals: one-step synthesis, nanocomposite preparation, and characterization. Can J Chem Eng 94:811–822. https://doi.org/10.1002/cjce.22456
Khalil HPSA, Bhat AH, Yusra AFI (2012) Green composites from sustainable cellulose nanofibrils: a review. Carbohydr Polym 87:963–979. https://doi.org/10.1016/j.carbpol.2011.08.078
Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466. https://doi.org/10.1002/anie.201001273
Kumar M, Mohanty S, Nayak SK, Rahail PM (2010) Effect of glycidyl methacrylate (GMA) on the thermal, mechanical and morphological property of biodegradable PLA/PBAT blend and its nanocomposites. Bioresour Technol 101:8406–8415. https://doi.org/10.1016/j.biortech.2010.05.075
Li X, Xu H, Long S, Yuan Y, Wang P, Qiu D, Ke K (2018) Improved compatibility in Recycled-PE/LDPE using glycidyl methacrylate, acrylic acid grafted mPE. Polym Test. https://doi.org/10.1016/j.polymertesting.2018.06.008
Littunen K, Hippi U, Johansson LS, Österberg M, Tammelin T, Laine J, Seppälä J (2011) Free radical graft copolymerization of nanofibrillated cellulose with acrylic monomers. Carbohydr Polym 84:1039–1047. https://doi.org/10.1016/j.carbpol.2010.12.064
Makarov SV, Horvath AK, Silaghi‐Dumitrescu R, Gao Q (2015) Recent developments in the chemistry of thiourea oxides. Chem Eur J 46:14164–14176. https://doi.org/10.1002/chem.201403453
Mao Y, Gleason KK (2004) Hot filament chemical vapor deposition of poly(glycidyl methacrylate) thin films using tert-butyl peroxide as an initiator. Langmuir 20:2484–2488. https://doi.org/10.1021/la0359427
Misra BN, Dogra R, Kaur I, Jassal JK (1979) Grafting onto cellulose. IV. Effect of complexing agents on fenton’s reagent (Fe2+–H2O2)-initiated grafting of poly(vinyl acetate). J Polym Sci Polym Chem Ed 17:1861–1863. https://doi.org/10.1002/pol.1979.170170631
Missoum K, Belgacem MN, Bras J (2013) Nanofibrillated cellulose surface modification: a review. Materials 6:1745–1766. https://doi.org/10.3390/ma6051745
Navarro JRG, Edlund UM (2017) A surface-initiated controlled radical polymerization approach to enhance nanocomposite integration of cellulose nanofibrils. Biomacromolecules 18:1947–1955. https://doi.org/10.1021/acs.biomac.7b00398
O’Connell DW, Birkinshaw C, O’Dwyer TF (2010) A chelating cellulose adsorbent for the removal of Cu(II) from aqueous solutions. J Appl Polym Sci 99:2888–2897. https://doi.org/10.1002/app.22568
Odian GG (1981) Principles of polymerization. Wiley, NewYork
Okita Y, Saito T, Isogai A (2010) Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation. Biomacromolecules 11:1696–1700. https://doi.org/10.1021/bm100214b
Osicka J, Mrlik M, Ilcikova M, Hanulikova B, Urbanek P, Sedlacik M, Mosnacek J (2018) Reversible actuation ability upon light stimulation of the smart systems with controllably grafted graphene oxide with poly (glycidyl methacrylate) and PDMS elastomer: effect of compatibility and graphene oxide reduction on the photo-actuation performance. Polym Basel 10:832. https://doi.org/10.3390/polym10080832
Poletto M, Zattera AJ, Forte MM, Santana RM (2012) Thermal decomposition of wood: influence of wood components and cellulose crystallite size. Bioresour Technol 109:148–153. https://doi.org/10.1016/j.biortech.2011.11.122
Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Chem Soc Rev 38:2046–2064. https://doi.org/10.1039/B808639G
Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Geng S, Yao K, Zhou Q, Oksman K (2018) High-strength, high-toughness aligned polymer-based nanocomposite reinforced with ultra-low weight fraction of functionalized nanocellulose. Biomacromolecules 19:4075–4083. https://doi.org/10.1021/acs.biomac.8b01086
Spinella S, Samuel C, Raquez JM, Mccallum SA, Gross R, Dubois P (2016) Green and efficient synthesis of dispersible cellulose nanocrystals in biobased polyesters for engineering applications. ACS Sustain Chem Eng 4:2517–2527. https://doi.org/10.1021/acssuschemeng.5b01611
Waly A, Abou-Zeid NY, El-Alfy EA, Hebeish A (1982) Polymerization of glycidyl methacrylate, methacrylic acid, acrylamide and their mixtures with cotton fabric using fe2+-thioureadioxide-H2O2redox system. Macromol Mater Eng 103:61–76. https://doi.org/10.1002/apmc.1982.051030106
Wang Y, Zhou J, Wu C, Tian L, Zhang B, Zhang Q (2018) Fabrication of micron-sized BSA-imprinted polymers with outstanding adsorption capacity based on poly(glycidyl methacrylate)/polystyrene (PGMA/PS) anisotropic microspheres. J Mater Chem B 6:5860–5866. https://doi.org/10.1039/c8tb01423j
Wei L, Mcdonald AG (2016) A Review on grafting of biofibers for biocomposites. Materials 9:303. https://doi.org/10.3390/ma9040303
Yano H, Omura H, Honma Y, Okumura H, Sano H, Nakatsubo F (2018) Designing cellulose nanofiber surface for high density polyethylene reinforcement. Cellulose 25:3351–3362. https://doi.org/10.1007/s10570-018-1787-2
Acknowledgments
The authors are grateful for the support of the National Natural Science Foundation of China (Grant No. 31070524), and the Major State Basic Research Development Program of China (Grant No. 2010CB732205).
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Guo, L., Li, D., Lennholm, H. et al. Structural and functional modification of cellulose nanofibrils using graft copolymerization with glycidyl methacrylate by Fe2+–thiourea dioxide–H2O2 redox system. Cellulose 26, 4853–4864 (2019). https://doi.org/10.1007/s10570-019-02411-2
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DOI: https://doi.org/10.1007/s10570-019-02411-2