Abstract
A surface-carboxylated nanocellulose was prepared from wood cellulose by catalytic oxidation with 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO). The fibrous TEMPO-oxidized cellulose with sodium carboxylate groups (TOC-Na) was surface-hydrophobized by counterion exchange with tetra-n-butylammonium [TOC-N(n-Bu)4]. This fibrous TOC-N(n-Bu)4 was mechanically disintegrated in water and N,N-dimethylformamide (DMF) to prepare dispersions of TEMPO-oxidized cellulose nanofibrils (TOCNs) with tetra-n-butylammonium counterions, i.e., TOCN-N(n-Bu)4/water and TOCN-N(n-Bu)4/DMF. TOCN-N(n-Bu)4/rubber composite films were prepared by mixing TOCN-N(n-Bu)4 and hydrogenated acrylonitrile–butadiene rubber (H-NBR), used as a polymer matrix, in heterogeneous and homogeneous systems with water and DMF, respectively, followed by casting and drying. The TOCN-N(n-Bu)4/H-NBR composite films prepared in the heterogeneous and homogeneous systems both had a high Young’s modulus of ~ 45 MPa and low coefficients of thermal expansion of ~ 20 ppm/K at a TOCN/H-NBR ratio of 5/100 (w/w). In contrast, the tensile strengths and strain-to-failure values of the composite films prepared using the two systems clearly differed. These different properties are probably caused by differences between the TOCN distributions in the H-NBR matrix and between the H-NBR matrix structures in the two systems. The composite films prepared in the homogeneous system with DMF as the medium are likely to have a more homogeneous distribution of TOCN elements in a homogeneous H-NBR polymer matrix, resulting in a higher tensile strength and work-of-fracture at TOCN/H-NBR = 5/100 (w/w) compared with those of the films prepared in the heterogeneous system with water.
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Acknowledgments
This research was supported by Core Research for Evolutional Science and Technology (CREST, Grant Number JPMJCR13B2) of the Japan Science and Technology Agency (JST). We thank Helen McPherson, Ph.D., from Edanz Group (www.edanzediting.com/ac) for editing a draft of this manuscript.
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Fukui, S., Ito, T., Saito, T. et al. Surface-hydrophobized TEMPO-nanocellulose/rubber composite films prepared in heterogeneous and homogeneous systems. Cellulose 26, 463–473 (2019). https://doi.org/10.1007/s10570-018-2107-6
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DOI: https://doi.org/10.1007/s10570-018-2107-6