Abstract
High performance fibers and improved interfacial interaction can enhance the properties of polymer composites. Herein, microcrystalline cellulose (MCC) was oxidized by H2O2/CuSO4, a new Fenton process, to achieve oxidized MCC (OCNCs) with 16 ± 1% carboxyl content. Noteworthy, the thermal stability of OCNCs was superior to CNCs prepared by acid hydrolysis. Interestingly, the primary alcohol groups of MCC were selectively oxidized and OCNCs achieved 11.0 nm, 231.6 nm and 72% of average diameter, length and degree of crystallinity, respectively. Then glycerol, starch and OCNCs were reactive extruded to fabricate TPS/OCNC bionanocomposites and their structure and performance were evaluated systematically. Strikingly, significant improvement in glass transition temperature (from 63.1 to 94.5 °C) and notch impact strength (from 1.3 to 3.9 kJ/m2) were noted for the amorphous TPS/OCNCs with 1 wt % OCNCs, and its tensile strength achieved 20.5 MPa, simultaneously. The improved performance was ascribed to in situ formation of “carboxyl-hydroxyl” hydrogen bonds that acted as cross-links and improved the interfacial compatibility. We showcase the Fenton reaction and reactive extrusion as a facile strategy to prepare sustainable and biodegradable TPS/OCNC bionanocomposites with properties more suitable for everyday applications to replace petroleum-based plastic and eliminate the pollution by “microplastics”.
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References
Alemdar A, Sain M (2008) Biocomposites from wheat straw nanofibers: Morphology, thermal and mechanical properties. Compos Sci Technol 68:557–565. https://doi.org/10.1016/j.compscitech.2007.05.044
Bao C et al (2021) Extraction of cellulose nanocrystals from microcrystalline cellulose for the stabilization of cetyltrimethylammonium bromide-enhanced Pickering emulsions. Colloids Surf, A 608:125442. https://doi.org/10.1016/j.colsurfa.2020.125442
Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromol 6:1048–1054. https://doi.org/10.1021/bm049300p
Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171. https://doi.org/10.1007/s10570-006-9061-4
Brisson J, Chanzy H, Winter WT (1991) The crystal and molecular structure of VH amylose by electron diffraction analysis. Int J Biol Macromol 13:31–39. https://doi.org/10.1016/0141-8130(91)90007-H
Calvino C, Macke N, Kato R, Rowan SJ (2020) Development, processing and applications of bio-sourced cellulose nanocrystal composites. Progr Polym Sci 103:101221. https://doi.org/10.1016/j.progpolymsci.2020.101221
Canché-Escamilla G, Canché-Canché M, Duarte-Aranda S, Cáceres-Farfán M, Borges-Argáez R (2011) Mechanical properties and biodegradation of thermoplastic starches obtained from grafted starches with acrylics. Carbohyd Polym 86:1501–1508. https://doi.org/10.1016/j.carbpol.2011.06.052
Cao X, Xu C, Liu Y, Chen Y (2013) Preparation and properties of carboxylated styrene-butadiene rubber/cellulose nanocrystals composites. Carbohyd Polym 92:69–76. https://doi.org/10.1016/j.carbpol.2012.09.054
Chen J, Lin N, Huang J, Dufresne A (2015) Highly alkynyl-functionalization of cellulose nanocrystals and advanced nanocomposites thereof via click chemistry. Polym Chem 6:4385–4395. https://doi.org/10.1039/C5PY00367A
Chen J, Chen F, Meng Y, Wang S, Long Z (2019) Oxidized microcrystalline cellulose improve thermoplastic starch-based composite films: thermal, mechanical and water-solubility properties. Polymer 168:228–235. https://doi.org/10.1016/j.polymer.2019.02.026
Coelho CCdS, Silva RBS, Carvalho CWP, Rossi AL, Teixeira JA, Freitas-Silva O, Cabral LMC (2020) Cellulose nanocrystals from grape pomace and their use for the development of starch-based nanocomposite films. Int J Biol Macromol 159:1048–1061. https://doi.org/10.1016/j.ijbiomac.2020.05.046
D’Acierno F, Hamad WY, Michal CA, MacLachlan MJ (2020) Thermal degradation of cellulose filaments and nanocrystals. Biomacromolecules 21:3374–3386. https://doi.org/10.1021/acs.biomac.0c00805
Dufresne A (2018) Cellulose nanomaterials as green nanoreinforcements for polymer nanocomposites philosophical transactions of the royal society a: mathematical. Phys Eng Sci 376:20170040. https://doi.org/10.1098/rsta.2017.0040
Du H, Liu C, Zhang Y, Yu G, Si C, Li B (2016) Preparation and characterization of functional cellulose nanofibrils via formic acid hydrolysis pretreatment and the followed high-pressure homogenization. Ind Crops Prod 94:736–745. https://doi.org/10.1016/j.indcrop.2016.09.059
Eichhorn SJ (2011) Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7:303–315. https://doi.org/10.1039/C0SM00142B
Ghimire G et al (2020) Influences of hydrogen bonding-based stabilization of bolaamphiphile layers on molecular diffusion within organic nanotubes having inner carboxyl groups. Langmuir 36:6145–6153. https://doi.org/10.1021/acs.langmuir.0c00556
González K, Iturriaga L, González A, Eceiza A, Gabilondo N (2020) Improving mechanical and barrier properties of thermoplastic starch and polysaccharide nanocrystals nanocomposites. Eur Polym J 123:109415. https://doi.org/10.1016/j.eurpolymj.2019.109415
González K, Retegi A, González A, Eceiza A, Gabilondo N (2015) Starch and cellulose nanocrystals together into thermoplastic starch bionanocomposites. Carbohyd Polym 117:83–90. https://doi.org/10.1016/j.carbpol.2014.09.055
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500. https://doi.org/10.1021/cr900339w
Huang L et al (2019) Properties of thermoplastic starch films reinforced with modified cellulose nanocrystals obtained from cassava residues. New J Chem 43:14883–14891. https://doi.org/10.1039/C9NJ02623A
Huang P, Wu M, Kuga S, Huang Y (2013) Aqueous pretreatment for reactive ball milling of cellulose. Cellulose 20:2175–2178. https://doi.org/10.1007/s10570-013-9940-4
Kang X, Kuga S, Wang C, Zhao Y, Wu M, Huang Y (2018) Green preparation of cellulose nanocrystal and its application. ACS Sustain Chem Eng 6:2954–2960. https://doi.org/10.1021/acssuschemeng.7b02363
Kargarzadeh H et al (2018) Recent developments in nanocellulose-based biodegradable polymers, thermoplastic polymers, and porous nanocomposites. Progr Polym Sci 87:197–227. https://doi.org/10.1016/j.progpolymsci.2018.07.008
Kargarzadeh H, Johar N, Ahmad I (2017) Starch biocomposite film reinforced by multiscale rice husk fiber. Compos Sci Technol 151:147–155. https://doi.org/10.1016/j.compscitech.2017.08.018
Koshani R, van de Ven TGM, Madadlou A (2018) Characterization of carboxylated cellulose nanocrytals isolated through catalyst-assisted H2O2 oxidation in a one-step procedure. J Agric Food Chem 66:7692–7700. https://doi.org/10.1021/acs.jafc.8b00080
Li B et al (2015) Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation. Carbohyd Polym 133:605–612. https://doi.org/10.1016/j.carbpol.2015.07.033
Lu P, Hsieh Y-L (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82:329–336. https://doi.org/10.1016/j.carbpol.2010.04.073
Lv D et al (2019) Tailored and integrated production of functional cellulose nanocrystals and cellulose nanofibrils via sustainable formic acid hydrolysis: kinetic study and characterization. ACS Sustain Chem Eng 7:9449–9463. https://doi.org/10.1021/acssuschemeng.9b00714
Matsumoto A, Ueda A, Aota H, Ikeda J-i (2002) Effect of hydrogen bonds on intermolecular crosslinking reaction by introduction of carboxyl groups in free-radical crosslinking monomethacrylate/dimethacrylate copolymerizations. Eur Polym J 38:1777–1782. https://doi.org/10.1016/S0014-3057(02)00055-1
Mittal G, Rhee KY, Mišković-Stanković V, Hui D (2018) Reinforcements in multi-scale polymer composites: Processing, properties, and applications. Compos Part B: Eng 138:122–139. https://doi.org/10.1016/j.compositesb.2017.11.028
Mokhena TC, John MJ (2020) Cellulose nanomaterials: new generation materials for solving global issues. Cellulose 27:1149–1194. https://doi.org/10.1007/s10570-019-02889-w
Nessi V et al (2019) Cellulose nanocrystals-starch nanocomposites produced by extrusion: structure and behavior in physiological conditions. Carbohyd Polym 225:115123. https://doi.org/10.1016/j.carbpol.2019.115123
Peng H, Zhang S, Yin Y, Jiang S, Mo W (2017) Fabrication of C-6 position carboxyl regenerated cotton cellulose by H2O2 and its promotion in flame retardency of epoxy resin. Polym Degrad Stabil 142:150–159. https://doi.org/10.1016/j.polymdegradstab.2017.05.026
Putaux J-L, Buléon A, Chanzy H (2000) Network formation in dilute amylose and amylopectin studied by TEM. Macromolecules 33:6416–6422. https://doi.org/10.1021/ma000242j
Ranby BG (1949) Aqueous colloidal solutions of cellulose micelles. Acta Chem Scand 3(5):649–65. https://doi.org/10.3891/acta.chem.scand.03-0649
Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules 5:1671–1677. https://doi.org/10.1021/bm034519+
Rosa MF et al (2010) Cellulose nanowhiskers from coconut husk fibers: effect of preparation conditions on their thermal and morphological behavior. Carbohyd Polym 81:83–92. https://doi.org/10.1016/j.carbpol.2010.01.059
Sang X, Qin C, Tong Z, Kong S, Jia Z, Wan G, Liu X (2017) Mechanism and kinetics studies of carboxyl group formation on the surface of cellulose fiber in a TEMPO-mediated system. Cellulose 24:2415–2425. https://doi.org/10.1007/s10570-017-1279-9
Sapkota J, Natterodt JC, Shirole A, Foster EJ, Weder C (2017) Fabrication and properties of polyethylene/cellulose nanocrystal composites. Macromol Mater Eng 302:1600300. https://doi.org/10.1002/mame.201600300
Shuidong Z, Lingcao T, Jizhao L, Hanxiong H, Guo J (2014) Relationship between structure and properties of reprocessed glass fiber reinforced flame retardant poly(butylene terephthalate). Polym Degrad Stabil 105:140–149. https://doi.org/10.1016/j.polymdegradstab.2014.04.009
Tao Y et al (2021) Cotton/alginate blended knitted fabrics: flame retardancy, flame-retardant mechanism, water absorption and mechanical properties. Cellulose 28:4495–4510. https://doi.org/10.1007/s10570-021-03772-3
Tavares KM, Campos Ad, Luchesi BR, Resende AA, Oliveira JEd, Marconcini JM (2020) Effect of carboxymethyl cellulose concentration on mechanical and water vapor barrier properties of corn starch films. Carbohydr Polym 246:116521. https://doi.org/10.1016/j.carbpol.2020.116521
Wang Y et al (2019) Hydrogen bonding derived self-healing polymer composites reinforced with amidation carbon fibers. Nanotechnology 31:025704. https://doi.org/10.1088/1361-6528/ab4743
Wang D, Yang T, Li J, Zhang J, Yu J, Zhang X, Zhang J (2020) Thermostable and redispersible cellulose nanocrystals with thixotropic gelation behavior by a facile desulfation process. ACS Sustain Chem Eng 8:11737–11746. https://doi.org/10.1021/acssuschemeng.0c03838
Wen J, Yin Y, Peng X, Zhang S (2019) Using H2O2 to selectively oxidize recyclable cellulose yarn with high carboxyl content. Cellulose 26:2699–2713. https://doi.org/10.1007/s10570-018-2217-1
Yang Y, Chen Z, Zhang J, Wang G, Zhang R, Suo D (2019) Preparation and applications of the cellulose nanocrystal. Int J Polym Sci 2019:1767028. https://doi.org/10.1155/2019/1767028
Yang Z, Liu X, Yang Z, Zhuang G, Bai Z, Zhang H, Guo Y (2013) Preparation and formation mechanism of levoglucosan from starch using a tubular furnace pyrolysis reactor. J Anal Appl Pyrol 102:83–88. https://doi.org/10.1016/j.jaap.2013.03.012
Yao W, Weng Y, Catchmark JM (2020) Improved cellulose X-ray diffraction analysis using Fourier series modeling. Cellulose 27:5563–5579. https://doi.org/10.1007/s10570-020-03177-8
Ye H-l, Liu Y-f, Zhang X-h, Di D-l (2013) DFT study on hydrogen-bonding adsorption mechanism of rutin onto macroporous adsorption resins functionalized with amino, hydroxyl, and carboxyl groups. Struct Chem 24:1443–1449. https://doi.org/10.1007/s11224-012-0174-0
Zhang Q-X, Yu Z-Z, Xie X-L, Naito K, Kagawa Y (2007) Preparation and crystalline morphology of biodegradable starch/clay nanocomposites. Polymer 48:7193–7200. https://doi.org/10.1016/j.polymer.2007.09.051
Zhang S, Liu F, Peng H, Peng X, Jiang S, Wang J (2015) Preparation of novel C-6 position carboxyl corn starch by a green method and its application in flame retardance of epoxy resin. Ind Eng Chem Res 54:11944–11952. https://doi.org/10.1021/acs.iecr.5b03266
Zhu J et al (2020) Lightweight, high-strength, and anisotropic structure composite aerogel based on hydroxyapatite nanocrystal and chitosan with thermal insulation and flame retardant properties. ACS Sustain Chem Eng 8:71–83. https://doi.org/10.1021/acssuschemeng.9b03953
Acknowledgments
The authors wish to acknowledge the academic discussion from Prof. Baochun Guo and financial support of the National Natural Science Foundation of China (No. 51773068), Fund Research Grant for Science and Technology in Guangzhou (202002030143), Natural Science Foundation of Guangdong Province (2021A1515010551), SKL of Bio-Fibers and Eco-Textiles (Qingdao University) K2019-05, and The Scientific and Technological Plan of Guangdong Province, China (No. 2019B090905005)”.
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Conceptualization: SZ; formal analysis and investigation: JY and BG; writing—original draft preparation: BG; writing—review and editing: SZ; funding acquisition: SZ; resources: SZ; supervision: SZ notes.
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Gao, B., Yang, J., Zhang, S. et al. Green fabrication of thermally-stable oxidized cellulose nanocrystals by evolved Fenton reaction and in-situ nanoreinforced thermoplastic starch. Cellulose 28, 8405–8418 (2021). https://doi.org/10.1007/s10570-021-04039-7
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DOI: https://doi.org/10.1007/s10570-021-04039-7