Effects of Acid-Anhydride-Modified Cellulose Nanofiber on Poly(Lactic Acid) Composite Films

In this study, we investigated the effect of the addition of cellulose nanofiber (CNF) fillers on the performance of poly(lactic acid) (PLA). Modification of the hydroxyl group of cellulose to the acyl group by acid anhydrides changed the compatibility of the CNF with PLA. CNF was modified by acetic anhydride, propionic anhydride, and butyric anhydride to form surface-modified acetylated CNF (CNFa), propionylated CNF (CNFp), and butyrylated CNF (CNFb), respectively, to improve the compatibility with the PLA matrix. The effects of the different acid anhydrides were compared based on their rates of reaction in the acylation process. PLA with modified cellulose nanofiber fillers formed smoother surfaces with better transparency, mechanical, and wettability properties compared with the PLA/CNF composite film. The effects of CNFa, CNFp, and CNFb on the PLA matrix were compared, and it was found that CNFp was the best filler for PLA.

Production of Butyric Anhydride Using Single Reactive Distillation Column with Internal Material Circulation

The traditional two-column reactive distillation (RD) process is used for the production of butyric anhydride, which is synthesized with butyric acid and acetic anhydride via a reversible reaction. In this work, a novel process with a single RD column (SRDC) is designed for the production of butyric anhydride, where the second distillation column for separating excess reactant is removed based on the boiling point profile of the reaction system. Two applications of the proposed SRDC process, namely SRDC with excess butyric acid or acetic anhydride circulating internally, are economically optimized, and the results show that both SRDC processes have a lower total annual cost (TAC) than the traditional two-column process. Furthermore, from the perspective of TAC, the application with an excess feed of butyric acid is better than the application with excess acetic anhydride. The developed technique may also be applied to retrofit other traditional two-column RD processes, where the overhead and bottom products are the lightest and heaviest components of the reaction system, respectively, and no azeotrope is involved in the RD column.

Rheology of Polyacrylonitrile/Lignin Blends in Ionic Liquids under Melt Spinning Conditions

Lignin, while economically and environmentally beneficial, has had limited success in use in reinforcing carbon fibers due to harmful chemicals used in biomass pretreatment along with the limited physical interactions between lignin and polyacrylonitrile (PAN) during the spinning process. The focus of this study is to use lignin obtained from chemical-free oxidative biomass pretreatment (WEx) for blending with PAN at melt spinning conditions to produce carbon fiber precursors. In this study, the dynamic rheology of blending PAN with biorefinery lignin obtained from the WEx process is investigated with the addition of 1-butyl-3-methylimidazolium chloride as a plasticizer to address the current barriers of developing PAN/lignin carbon fiber precursors in the melt-spinning process. Lignin was esterified using butyric anhydride to reduce its hydrophilicity and to enhance its interactions with PAN. The studies indicate that butyration of the lignin (BL) increased non-Newtonian behavior and decreased thermo-reversibility of blends. The slope of the Han plot was found to be around 1.47 for PAN at 150 °C and decreased with increasing lignin concentrations as well as temperature. However, these blends were found to have higher elasticity and solution yield stress (47.6 Pa at 20%wt BL and 190 °C) when compared to pure PAN (5.8 Pa at 190 °C). The results from this study are significant for understanding lignin–PAN interactions during melt spinning for lower-cost carbon fibers.

Effect of Linear Chain Carboxylic Acid Anhydrides on Physical and Mechanical Properties of Rubber (Hevea brasiliensis), Acacia, (Acacia spp.), and Oil Palm (Tinnera spp.) Woods

The physical and mechanical properties of Rubber wood, Acacia wood, and Oil palm wood that reacted with acetic, propionic, and butyric anhydrides using a microwave heating for 4 minutes were investigated. A sample dimension of 300 mm × 100 mm × 25 mm (L×W×T) was used for modification and they were cut into smaller specimens for different testing method. This study found that the density increment and void volume changes were not significantly different from anhydrides. The modification of wood with anhydrides was not significantly affected by the static bending properties, except for the Oil palm. The compression strength for any anhydrides shows an improvement for the Rubber wood and Acacia spp. but not Oil palm. The hardness was also not significantly different from anhydrides for all wood species. The impact strength of Rubber wood and Oil palm significantly increased compared to the untreated wood, but this was not the case for Acacia spp. Generally, the highest improvement in mechanical properties was obtained by modification of Rubber and Acacia woods with butyric anhydride.

Solvent-free chemical modification of wood by acetic and butyric anhydride with iodine as catalyst

A solvent-free process has been developed concerning the chemical modification of rubberwood and the isolates from it (holocellulose and Klason lignin) by means of acetic anhydride (Ac2O) and butyric anhydride (But2O), with iodine as the catalyst. The effect of temperature and reaction time was in focus, and the conversion products were characterized by Fourier transform infrared (FTIR) spectroscopy. The acetylation of holocellulose and lignin with Ac2O was performed at 120°C, whereas the modification of wood with Ac2O and But2O was carried out in the temperature range of 90–120°C for different reaction times between 15 and 240 min. The extent of the chemical modification was measured by the weight percent gain, and the modified wood was characterized by FTIR-attenuated total reflectance (ATR) method. The presence of small amounts of iodine (0.02 or 0.035 M) elevated the conversion rate of modification. The dimensional stability of the modified woods was essentially improved.