Homogenous esterification of cellulose pulp in [DBNH][OAc]

Cellulose acetate is widely used in films, filters, textiles, lacquer and cosmetic products. Herein we demonstrate the production of cellulose esters under homogeneous conditions using 1,5-diazabicyclo[4.3.0]non-5-ene acetate ([DBNH][OAc]) as solvent. The reagents have been chosen such that the system is recyclable, i.e. by-products are low boiling and easy to remove. It is demonstrated that cellulose acetate can be synthesized with different degree of substitution (DS) values, and that some commonly used acylation regents, like vinyl carboxylates react well without additional base catalyst. Low to high DS values are possible with good recovery of high purity ionic liquid (IL). A linear correlation method of two separate methods, IR and P-31 NMR, is proposed to reliably assess the DS of the products. The recyclability of the solvent is demonstrated by acetylating cellulose with isopropenyl acetate to high degree and regeneration into water. After regeneration of cellulose acetate from the IL with addition of water, the residual water was entrained using n-butanol to minimize hydrolysis of [DBNH][OAc], to allow for high recovery and high purity of the ionic liquid. Thus, an overall scheme for batch cellulose acetylation and recovery of [DBNH][OAc] from aqueous solutions is proposed.Peer reviewe

Obligatory integration of face features in expression discrimination

Previous composite face studies have shown that an unattended face half that differs in identity or in expression from the attended face half distracts face perception. These studies have typically not controlled for the amount of information in different face halves. We investigated feature integration while participants discriminated angry and happy expressions. The stimuli were scaled using individual thresholds to control the expression strength in face halves. In the first experiment, we varied the relative amount of information in upper and lower parts. In the second experiment, participants tried to ignore one half of the face, which was either congruent or incongruent with the attended half. We found both beneficial and obligatory integration of face halves. A robust face composite effect was found both when attending eyes or mouth, and both for congruent and incongruent expressions, suggesting similar processing of face halves when the amount of information is controlled for.Peer reviewe

Incorporated Diffusion Ordered Heteronuclear Multiple Bond Correlation Spectroscopy, 3D iDOSY-HMBC. Merging of Diffusion Delay with Long Polarization Transfer Delay of HMBC

3D iDOSY-HMBC pulse sequences allow the simplification of HMBC data of mixtures via separation in the diffusion domain. The presented methods utilize incorporated DOSY approach, iDOSY, where the existing delays of the basic pulse sequence are utilized for diffusion attenuation. In the simplest form of the proposed 3D iDOSY-HMBC sequences, no extra delays or RF-pulses were required, only two diffusion gradients were added within HMBC polarization transfer delay.Peer reviewe

Clustered Single Cellulosic Fiber Dissolution Kinetics and Mechanisms through Optical Microscopy under Limited Dissolving Conditions

Herein, we describe a new method of assessing the kinetics of dissolution of single fibers by dissolution under limited dissolving conditions. The dissolution is followed by optical microscopy under limited dissolving conditions. Videos of the dissolution were processed in Image) to yield kinetics for dissolution, based on the disappearance of pixels associated with intact fibers. Data processing was performed using the Python language, utilizing available scientific libraries. The methods of processing the data include clustering of the single fiber data, identifying clusters associated with different fiber types, producing average dissolution traces and also extraction of practical parameters, such as, time taken to dissolve 25, SO, 75, 95, and 99.5% of the clustered fibers. In addition to these simple parameters, exponential fitting was also performed yielding rate constants for fiber dissolution. Fits for sample and cluster averages were variable, although demonstrating first-order kinetics for dissolution overall. To illustrate this process, two reference pulps (a bleached softwood kraft pulp and a bleached hardwood pre hydrolysis kraft pulp) and their cellulase-treated versions were analyzed. As expected, differences in the kinetics and dissolution mechanisms between these samples were observed. Our initial interpretations are presented, based on the combined mechanistic observations and single fiber dissolution kinetics for these different samples. While the dissolution mechanisms observed were similar to those published previously, the more direct link of mechanistic information with the kinetics improve our understanding of cell wall structure and pre-treatments, toward improved processability.Peer reviewe

The impact of thermomechanical pulp fiber modifications on thermoplastic lignin composites

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High-Performance Acetylated Ioncell‑F Fibers with Low Degree of Substitution

Cellulose acetate is one of the most important cellulose derivatives. Herein we present a method to access cellulose acetate with a low degree of substitution through a homogeneous reaction in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]). This ionic liquid has also been identified as an excellent cellulose solvent for dry-jet wet fiber spinning. Cellulose was dissolved in [DBNH] [OAc] and esterified in situ to be immediately spun into modified cellulose filaments with a degree of substitution (DS) value of 0.05-0.75. The structural properties of the resulting fibers, which are characterized by particularly high tensile strength values (525-750 MPa conditioned and 315-615 MPa wet) and elastic moduli between 10-26 GPa, were investigated by birefringence measurements, wide-angle X-ray scattering, and molar mass distribution techniques while their unique interactions with water have been studied through dynamic vapor sorption. Thus, an understanding of the novel process is gained, and the advantages are demonstrated for producing high-value products such as textiles, biocomposites, filters, and membranes.Peer reviewe

Efficiency of hydrophobic phosphonium ionic liquids and DMSO as recyclable cellulose dissolution and regeneration media

Hydrophobic, long-chain tetraalkylphosphonium acetate salts (ionic liquids) were combined with a dipolar aprotic co-solvent, dimethylsulfoxide (DMSO), and the feasibility of these solvent systems for cellulose dissolution and regeneration was studied. A 60 : 40 w/w mixture of the ionic liquid tetraoctylphosphonium acetate ([P-8888][OAc]) and DMSO was found to dissolve up to 8 wt% cellulose, whilst trioctyl(tetradecyl) phosphonium acetate ([P-14888][OAc]) dissolved up to 3 wt% cellulose. Water (an anti-solvent for cellulose) was found to give rise to biphasic liquid-liquid systems when combined with these mixtures, yielding an upper phase rich in ionic liquid and a lower aqueous phase. The liquid-liquid equilibria of the ternary systems were experimentally determined, finding that DMSO strongly partitioned towards the aqueous phase. Thus, a process scheme involving simultaneous regeneration of cellulose and recycling of the solvent system was envisioned, and demonstrated on a large scale using [P-8888] [OAc]. A large portion of the ionic liquid (ca. 60 wt%) was directly recovered via phase separation, with a further 37 wt% being recovered from the swollen cellulose phase and residual materials, bringing recovery to 97%. XRD analysis of the recovered cellulose materials showed a loss of crystallinity and conversion from Cellulose I to Cellulose II. Non-dissolving compositions of ionic liquid and DMSO did not affect cellulose crystallinity after cellulose pulp treatment.Peer reviewe

Crystallinity reduction and enhancement in the chemical reactivity of cellulose by non-dissolving pre-treatment with tetrabutylphosphonium acetate

Herein, we demonstrate the activation of commercial chemical cellulose pulps towards chemical modification by a pre-treatment step with tetrabutylphosphonium acetate ([P-4444][OAc]). A heterogeneous (non-dissolving) pre-treatment was applied allowing for a significant reduction in crystallinity, without concomitant formation of the thermodynamically stable cellulose II. An increase in chemical reactivity was demonstrated using two model reactions; (1) acetylation (organic swelling conditions), where high degrees of substitution (DS) were obtained without the need for a catalyst, and (2) 4-acetamido-TEMPO oxidation (aqueous swelling conditions), where significant degrees of oxidation (DO) were obtained, beyond those for the untreated pulps. In both tests a notable improvement in cellulose reactivity was observed. Regioselectivity of acetylation was assessed using 2D NMR for one low and one high DS sample. The low DS showed a small degree of acetylation of the 6-OH, whereas, the high DS from the pre-treated sample showed mainly mixtures of triacetate and diacetates. Important mechanistic information is attained for future development of aqueous and organic-based reactions involving this ionic liquid pre-treatment.Peer reviewe

On the solubility of wood in non-derivatising ionic liquids

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