Optimal Acyl Chain Length for Imparting Rigidity and Water Resistance to Cellulose–Hydroxyapatite Composites

Abstract

An acylation reaction was performed on the crystalline surface of cellulose in a composite consisting of microfibrillated cellulose (MFC) and hydroxyapatite (HAP) with an inorganic weight fraction of 68%. The composite was acylated using acetic anhydride, propanoic anhydride, and butanoic anhydride in pyridine in the presence of potassium carbonate at 120 °C for 1 h. The formation of ester linkages was confirmed by infrared spectroscopy, and X-ray diffraction analysis showed that the crystalline structure of cellulose was retained after acylation. From the intensity of the carbonyl stretching vibration in the infrared spectra, the degree of substitution of the acetylated sample was estimated to be approximately 0.2. The acylated MFC–HAP composites were uniaxially hot-pressed at 120 °C and 300 MPa, and the resulting molded specimens were subjected to three-point bending tests. A yield point appeared at a bending strain of 1.1–1.4%, followed by plastic deformation and final fracture, indicating that they exhibited ductile fracture. The elastic moduli were 5.9 GPa (acetyl), 7.6 GPa (propanoyl), 7.4 GPa (butanoyl), 3.6 GPa (hexanoyl), and 7.1 GPa (before acylation), indicating that acyl groups with medium chain lengths did not reduce the rigidity of the composites. When the molded specimens were immersed in water at room temperature for 24 h, the water absorption ratios were 29% (acetyl), 24% (propanoyl), 17% (butanoyl), and 18% (hexanoyl), demonstrating that water resistance improved with increasing acyl chain length. In summary, propanoylation and butanoylation improved the water resistance of the composites without compromising their rigidity in the dry state.