Abstract
Cellulose nanocrystals (CNCs) are crystalline nano-rods that have high specific strength with hydroxyl surface chemistry. A wide range of chemical modifications have been performed on the surface of CNCs to increase their potential to be used in applications where compatibilization with other materials is required. Understanding the surface chemistry of CNCs and critically examining the functionalization technique are crucial to enable control over the extent of modification and the properties of CNCs. This work aims to optimize the surface modification of wood-derived CNCs with isocyanatoethyl methacrylate (IEM), a bifunctional molecule carrying both isocyanate and vinyl functional groups. We studied the effect of modification reaction time and temperature on the degree of substitution, crystallinity, and morphology of the CNCs. We found that the degree of modification is a strong and increasing function of reaction temperature over the range studied. However, the highest temperature (65 °C) and the longest time of reaction (6 h) resulted in shorter, thinner, and less crystalline CNCs. We obtained surface hydroxyl conversion of 60.1 ± 6% and percent crystallinity of 84% by keeping the reaction shorter (30 min) at 65 ºC. Also, the copolymerization ability of modified CNCs was verified by polymerizing attached IEM groups with acrylic monomers via solution polymerization. The polymer-grafted CNCs (6% w/w) dispersed better in an acrylic polymer matrix compared to unmodified CNCs (umCNCs), resulting in approximately 100% improvement in the tensile strength and about 53% enhancement in the hardness of the acrylic, whereas addition of 6% w/w umCNCs did not influence the strength and hardness.
Graphic abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abitbol T, Prevo BG, Galli C, Choudhary S, Corwin J, Villalpando-Páez F, Nguyen L, Komarov A, Villalobos M, Veldhuis SC, Cranston ED (2014) Comparison of nanocrystalline cellulose and fumed silica in latex coatings. Green Mater 2(4):206–221. https://doi.org/10.1680/gmat.14.00017
Abushammala H, Mao J (2019) A review of the surface modification of cellulose and nanocellulose using aliphatic and aromatic mono- and Di-isocyanates. Molecules. https://doi.org/10.3390/molecules24152782
Brinkmann A, Chen M, Couillard M, Jakubek ZJ, Leng T, Johnston LJ (2016) Correlating cellulose nanocrystal particle size and surface area. Langmuir 32(24):6105–6114. https://doi.org/10.1021/acs.langmuir.6b01376
Chambers J, Jiricny J, Reese CB (1981) The thermal decomposition of polyurethanes and polyisocyanurates. Fire Mater 5(4):133–141. https://doi.org/10.1002/fam.810050402
Chang H, Luo J, Bakhtiary Davijani AA, Chien A-T, Wang P-H, Liu HC, Kumar S (2016) Individually dispersed wood-based cellulose nanocrystals. ACS Appl Mater Interfaces 8(9):5768–5771. https://doi.org/10.1021/acsami.6b00094
Dogan-Guner EM, Brownell S, Schueneman GT, Shofner ML, Meredith JC (2021) Enabling zero added-coalescent waterborne acrylic coatings with cellulose nanocrystals. Prog Org Coat 150:105969. https://doi.org/10.1016/j.porgcoat.2020.105969
Espino-Pérez E, Bras J, Ducruet V, Guinault A, Dufresne A, Domenek S (2013) Influence of chemical surface modification of cellulose nanowhiskers on thermal, mechanical, and barrier properties of poly(lactide) based bionanocomposites. Eur Polym J 49(10):3144–3154. https://doi.org/10.1016/j.eurpolymj.2013.07.017
Eyley S, Thielemans W (2014) Surface modification of cellulose nanocrystals. Nanoscale 6(14):7764–7779. https://doi.org/10.1039/C4NR01756K
Girouard NM, Xu S, Schueneman GT, Shofner ML, Meredith JC (2016) Site-selective modification of cellulose nanocrystals with isophorone diisocyanate and formation of polyurethane-CNC composites. ACS Appl Mater Interfaces 8(2):1458–1467. https://doi.org/10.1021/acsami.5b10723
Gong J, Li J, Xu J, Xiang Z, Mo L (2017) Research on cellulose nanocrystals produced from cellulose sources with various polymorphs. RSC Adv 7(53):33486–33493. https://doi.org/10.1039/C7RA06222B
Gwon J-G, Cho H-J, Chun S-J, Lee S, Wu Q, Lee S-Y (2016a) Physiochemical, optical and mechanical properties of poly(lactic acid) nanocomposites filled with toluene diisocyanate grafted cellulose nanocrystals. RSC Adv 6(12):9438–9445. https://doi.org/10.1039/C5RA26337A
Gwon J-G, Cho H-J, Chun S-J, Lee S, Wu Q, Li M-C, Lee S-Y (2016b) Mechanical and thermal properties of toluene diisocyanate-modified cellulose nanocrystal nanocomposites using semi-crystalline poly(lactic acid) as a base matrix. RSC Adv 6(77):73879–73886. https://doi.org/10.1039/C6RA10993D
Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43(5):1519–1542. https://doi.org/10.1039/C3CS60204D
Henze M, Mädge D, Prucker O, Rühe J (2014) “Grafting through”: mechanistic aspects of radical polymerization reactions with surface-attached monomers. Macromolecules 47(9):2929–2937. https://doi.org/10.1021/ma402607d
Kedzior SA, Gabriel VA, Dubé MA, Cranston ED (2020) Nanocellulose in emulsions and heterogeneous water-based polymer systems: a review. Adv Mater. https://doi.org/10.1002/adma.202002404
Kedzior SA, Zoppe JO, Berry RM, Cranston ED (2019) Recent advances and an industrial perspective of cellulose nanocrystal functionalization through polymer grafting. Curr Opin Solid State Mater Sci 23(2):74–91. https://doi.org/10.1016/j.cossms.2018.11.005
Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromol 2(2):410–416. https://doi.org/10.1021/bm005612q
Leng T (2016) Cellulose Nanocrystals: Particle Size Distribution and Dispersion in Polymer Composites. MSc thesis, University of Ottowa
Limousin E, Rafaniello I, Schäfer T, Ballard N, Asua JM (2020) Linking film structure and mechanical properties in nanocomposite films formed from dispersions of cellulose nanocrystals and acrylic latexes. Langmuir 36(8):2052–2062. https://doi.org/10.1021/acs.langmuir.9b03861
Missoum K, Bras J, Belgacem MN (2012) Organization of aliphatic chains grafted on nanofibrillated cellulose and influence on final properties. Cellulose 19(6):1957–1973. https://doi.org/10.1007/s10570-012-9780-7
Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40(7):3941–3994. https://doi.org/10.1039/C0CS00108B
Moon RJ, Schueneman GT, Simonsen J (2016) Overview of cellulose nanomaterials, their capabilities and applications. JOM 68(9):2383–2394. https://doi.org/10.1007/s11837-016-2018-7
Morelli C, Belgacem N, Bretas RES, Bras J (2016a) Melt extruded nanocomposites of polybutylene adipate-co-terephthalate (PBAT) with phenylbutyl isocyanate modified cellulose nanocrystals. J Appl Polym Sci. https://doi.org/10.1002/app.43678
Morelli CL, Belgacem MN, Branciforti MC, Bretas RES, Crisci A, Bras J (2016b) Supramolecular aromatic interactions to enhance biodegradable film properties through incorporation of functionalized cellulose nanocrystals. Compos Part A Appl Sci Manuf 83:80–88. https://doi.org/10.1016/j.compositesa.2015.10.038
Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3(1):10. https://doi.org/10.1186/1754-6834-3-10
Pinheiro IF, Ferreira FV, Alves GF, Rodolfo A, Morales AR, Mei LHI (2019) Biodegradable PBAT-based nanocomposites reinforced with functionalized cellulose nanocrystals from pseudobombax munguba: rheological, thermal, mechanical and biodegradability properties. J Polym Environ 27(4):757–766. https://doi.org/10.1007/s10924-019-01389-z
Pu Y, Zhang J, Elder T, Deng Y, Gatenholm P, Ragauskas AJ (2007) Investigation into nanocellulosics versus acacia reinforced acrylic films. Compos Part B Eng 38(3):360–366. https://doi.org/10.1016/j.compositesb.2006.07.008
Qu Z, Schueneman GT, Shofner ML, Meredith JC (2020) Acrylic functionalization of cellulose nanocrystals with 2-isocyanatoethyl methacrylate and formation of composites with poly(methyl methacrylate). ACS Omega 5(48):31092–31099. https://doi.org/10.1021/acsomega.0c04246
Rämänen P, Penttilä PA, Svedström K, Maunu SL, Serimaa R (2012) The effect of drying method on the properties and nanoscale structure of cellulose whiskers. Cellulose 19(3):901–912. https://doi.org/10.1007/s10570-012-9695-3
Reid MS, Villalobos M, Cranston ED (2017) Benchmarking cellulose nanocrystals: from the laboratory to industrial production. Langmuir 33(7):1583–1598. https://doi.org/10.1021/acs.langmuir.6b03765
Rueda L, Fernández d’Arlas B, Zhou Q, Berglund LA, Corcuera MA, Mondragon I, Eceiza A (2011) Isocyanate-rich cellulose nanocrystals and their selective insertion in elastomeric polyurethane. Compos Sci Technol 71(16):1953–1960. https://doi.org/10.1016/j.compscitech.2011.09.014
Siqueira G, Bras J, Dufresne A (2010) New process of chemical grafting of cellulose nanoparticles with a long chain isocyanate. Langmuir 26(1):402–411. https://doi.org/10.1021/la9028595
Siqueira G, Bras J, Follain N, Belbekhouche S, Marais S, Dufresne A (2013) Thermal and mechanical properties of bio-nanocomposites reinforced by Luffa cylindrica cellulose nanocrystals. Carbohydr Polym 91(2):711–717. https://doi.org/10.1016/j.carbpol.2012.08.057
Sormana J-L, Chattopadhyay S, Meredith JC (2005) High-throughput mechanical characterization of free-standing polymer films. Rev Sci Instrum 76(6):062214. https://doi.org/10.1063/1.1926967
Viet D, Beck-Candanedo S, Gray DG (2007) Dispersion of cellulose nanocrystals in polar organic solvents. Cellulose 14(2):109–113. https://doi.org/10.1007/s10570-006-9093-9
Wohlhauser S, Delepierre G, Labet M, Morandi G, Thielemans W, Weder C, Zoppe JO (2018) Grafting polymers from cellulose nanocrystals: synthesis, properties, and applications. Macromolecules 51(16):6157–6189. https://doi.org/10.1021/acs.macromol.8b00733
Yu H-Y, Qin Z-Y (2014) Surface grafting of cellulose nanocrystals with poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Carbohydr Polym 101:471–478. https://doi.org/10.1016/j.carbpol.2013.09.048
Yu J, Wang C, Wang J, Chu F (2016) In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization. Carbohydr Polym 141:143–150. https://doi.org/10.1016/j.carbpol.2016.01.006
Zhang J, Li M-C, Zhang X, Ren S, Dong L, Lee S, Cheng HN, Lei T, Wu Q (2019) Surface modified cellulose nanocrystals for tailoring interfacial miscibility and microphase separation of polymer nanocomposites. Cellulose 26(7):4301–4312. https://doi.org/10.1007/s10570-019-02379-z
Zhang Z, Tam KC, Sèbe G, Wang X (2018) Convenient characterization of polymers grafted on cellulose nanocrystals via SI-ATRP without chain cleavage. Carbohydr Polym 199:603–609. https://doi.org/10.1016/j.carbpol.2018.07.060
Zoppe JO, Peresin MS, Habibi Y, Venditti RA, Rojas OJ (2009) Reinforcing poly(ε-caprolactone) nanofibers with cellulose nanocrystals. ACS Appl Mater Interfaces 1(9):1996–2004. https://doi.org/10.1021/am9003705
Acknowledgments
This research was financially supported by P3Nano program in the US Endowment for Forestry and Communities. The authors of this paper would like to thank the USDA Forest Service Forest Products Laboratory (FPL) for their collaboration. The authors also thank F. Joseph Schork from Georgia Institute of Technology and Stan Brownell from Dow Coating Materials for their valuable insights, Will Gutekunst and Mizhi Xu from Georgia Institute of Technology for GPC measurements. This work was performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (Grant ECCS-2025462).
Funding
This research was financially supported by P3Nano program in the US Endowment for Forestry and Communities (Grant 16-JV-11111106- 052).
Author information
Authors and Affiliations
Contributions
All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by EMDG. The first draft of the manuscript was written by EMDG, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
Corresponding author
Ethics declarations
Conflicts of interest
The authors have no relevant financial or non-financial interests to disclose.
Ethical approval
This work does not involve animal studies or human participants.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Dogan-Guner, E.M., Schueneman, G.T., Shofner, M.L. et al. Acryloyl-modified cellulose nanocrystals: effects of substitution on crystallinity and copolymerization with acrylic monomers. Cellulose 28, 10875–10889 (2021). https://doi.org/10.1007/s10570-021-04219-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-021-04219-5