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Several literature reports describe the role of aqueous solutions of N-methylmorpholine-N-oxide monohydrate (NMMO) as a suitable medium for the generation of transition metal (nano)particles in or on cellulosic materials and further elaborate its role as a co-reactant of the transition metal salts that are reduced to the elemental metal. However, this would assign NMMO the role of a reductant, which is in contradiction of its obvious oxidative nature. In the present study, the exemplary cases of silver, gold, and platinum salts as the precursors of the respective metal (nano)particles in aqueous NMMO/cellulose mixtures were investigated. Naturally, NMMO did not act as a reducing agent in any case—this role was taken over by the frequently used NMMO stabilizer propyl gallate, or by cellulose itself, into which carbonyl and carboxyl groups were introduced. Also, hypochlorite—produced intermediately from chloride ions and subsequently undergoing disproportionation into chloride and chlorate—or transient N-methylene(morpholinium) ions generated from NMMO, which are in turn oxidized to formyl morpholide, can act as the corresponding reductants while the metal ions are reduced, depending on the reaction conditions. Apart from providing interesting mechanistic insights, the study points to the importance of a precise description of the composition of the chemical systems used, as well as the importance of seemingly inert auxiliaries, which turned out to be essential co-reactants in the metal (nano)particle generation. Graphic abstract

In the lyocell process, N-methylmorpholine-N-oxide (NMMO) with a high recovery rate is used as a solvent to directly dissolve cellulose, which is of great significance for the realization of industrialization. In this paper, the impurity removal process and side reactions in the NMMO recovery system are introduced. The NMMO recovery system is generally composed of three major processes: air flotation, ion exchange and evaporation. Air flotation and ion exchange are the processes of removing impurities. And evaporation, where side reactions occur, is the process of increasing the concentration of NMMO. In terms of conductivity and colority, organic flocculants are better than inorganic flocculants in the air flotation process which mainly removes undissolved particulate matter, part of hemicelluloses and some colored substances. The ion exchange process mainly removes ionic substances and propyl gallate (PG). Side reactions occur during evaporation, producing colored substances and black particulate matter. Through analysis, it can be known that the production of colored substances is caused by the condensation reaction of N-methylmorpholine (NMM, 1), morpholine (M, 2), 2-Amino-4-methyl-oxazole (3), furfuryl alcohol (4), Morpholinoacetonitrile (5), xylose and NMMO under alkaline and high-temperature conditions, rather than by PG. The black particles are due to thermal degradation of NMMO or NMM or M in the presence of oxygen and iron at high temperatures.

Abstract The cellulose solvent N-methylmorpholine-N-oxide monohydrate (NMMO) reacts violently with carbodiimide coupling agents, such as the widely used DCC (dicyclohexylcarbodiimide) and EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide), which can cause explosions, heavy smoke generation and complete charring of the reaction mixtures. For this reason it is clear that cellulose or other carbohydrates dissolved in NMMO (“Lyocell conditions”) cannot be safely esterified or amidified under DCC/EDC conditions. It is important to note that cellulosic material regenerated from NMMO solutions also poses a risk if it contains residual NMMO, which can then come into contact with DCC-type coupling agents in non-aqueous media, as recent accidents have unfortunately shown. Similarly, EDC/DCC traces in cellulose can have detrimental effects when trying to dissolve the material in NMMO. Working in aqueous systems generally reduces the risk of uncontrolled reactions, while alcohols or aprotic solvents are not very effective in this regard. Washing for NMMO removal or EDC/DCC removal should therefore always be carried out by aqueous media, if any possible, if there is a potential risk that the reagents might come into contact later. This warning describes the potential hazards of the reagent combination, highlights the underlying degradation mechanism and explains the precautions to be taken to avoid any “exothermic events”. Graphic abstract

In this work, an environmental micro-dissolution method to prepare Fe3O4 NPs@cotton composite fabrics without using binders is reported. The controlled N-methylmorpholine N-oxide (NMMO) treatment can micro-dissolve superficial layers of fibers through the strong hydrogen bonding force. The micro-dissolved superficial layers themselves can work like glue to physically adhere surrounding Fe3O4 NPs and then these Fe3O4 NPs can be embedded onto the layers. In the subsequent heating treatment, the micro-dissolved superficial layers would physically re-coagulate, immobilizing Fe3O4 NPs onto fibers’ surface. The as-obtained Fe3O4 NPs@cotton composite fabrics were systematically characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Additionally, through vibrating sample magnetometry tests, the Fe3O4 NPs@cotton fabrics exhibit para-magnetism, and the saturation magnetization can remain up to 90% after 20 washing cycles. Thermal gravimetric analysis and moisture absorption tests show that there are no obvious influences on thermal stability and moisture absorption capability of cotton fabrics. Even noticeable enhancements in mechanical properties can be observed.

The objective of the presented research was to determine the influence of cellulose coating, obtained from the cellulose solution in N-Methylmorpholine N-oxide (NMMO), on the structural and mechanical properties of paper. The effect of heating time of paper samples coated with cellulose dissolved in NMMO was also investigated. Depending on the heating time of the coating, a continuous or porous layer was obtained. Coating without any heating stage yielded a continuous cellulose layer of hydrophobic properties (higher contact angle in comparison to base paper), and paper of higher smoothness and increased tear resistance. Analysis of the paper samples showed that cellulose coating not only changed the surface properties of paper, but also significantly improved paper strength properties, such as the tensile index, elongation, bursting strength index and double folds number. Despite the process’ limitations (e.g. necessity of removing the NMMO), this method can be considered as a novel approach for paper property modification.

Phase separation of polymer solutions initiated by the addition of a nonsolvent is the main method for the preparation of polymer membranes. Depending on the application, such membranes must have a different pore size, which depends on the numerous parameters of the forming process. The liquid–liquid phase separation has been considered for cellulose solutions in N-methylmorpholine N-oxide (NMMO) interacting with various alcohols (methyl, ethyl, isopropyl, and isobutyl). Kinetics of cellulose regeneration was investigated by laser interferometry technique to understand the mechanism of cellulose film structure formation in the NMMO process. Influence of temperature, coagulant nature, and cellulose content on the process kinetics and morphology of the films was studied and corresponding interdiffusion coefficients were calculated. Based on the solubility parameters, triple phase diagrams of the systems were calculated. Formation of different morphologies was explained primarily by the different position of the composition path, the bimodal curve, and the gelation line in the phase diagrams. The second important parameter was the different rate of mutual diffusion of the NMMO and coagulants, due to the difference in the viscosity of the latter. Using methanol or ethanol as coagulation baths leads to obtaining the nanoporous structure of cellulose films, whereas isopropanol and isobutanol favors macropore formation.

N-Methylmorpholine-N-oxide (NMMO) cannot be completely separated by extraction from mixtures with common 1,3-dialkylimidazolium ionic liquids (ILs) due to strong ionic interactions between the two components. At elevated temperatures, above approx. 90 °C, especially under dry conditions and in the presence of acid, alkylating or acylating agents, remaining NMMO in ILs tends to undergo autocatalytic degradation. This is a highly exothermic, unstoppable process that results in explosions, flames, and complete charring of the reaction mixtures. Thus, caution must be exercised when drying or heating ILs that were in previous contact with NMMO, and the absence of amine oxide must be confirmed to avoid potential danger.

Alkali cellulose is an important intermediate in the production of cellulose derivatives. N-methylmorpholine-N-oxide (NMMO)/H2O was used as a homogeneous reaction medium for the cellulose alkalization process to intensify the alkalization degree and improve the substitution uniformity. The morphology, specific surface area and crystalline structure of pristine cellulose, the as-synthesized alkali cellulose and dissolved-regenerated cellulose were characterized by SEM, BET, XRD and FT-IR, respectively. The results showed that the homogeneous reaction medium not only offered a low mass transfer resistance, but also facilitated a disruption of the hydrogen bond in cellulose, thus resulting in the transformation of the cellulose structure from complicated stacking chains to simple glucose chains. The interior hydroxyl groups in the cellulose became accessible to the alkaline reagent NaOH to enhance the alkalization process for the increase in bonding alkali content and the improvement in substitution uniformity. The bonding alkali content was calculated by the difference between total added alkali and free alkali and was achieved as 0.61 g/g cellulose at the optimized operation conditions: reaction temperature of 95 °C, reaction time of 90 min, NMMO dosage of 90.00 g, cellulose 1.0 g and NaOH concentration of 1.40 wt%. Meanwhile, in the conventional alkalization process, the bonding alkali content was just 0.41 g/g cellulose. The alkali cellulose prepared in NMMO/H2O medium has a large specific surface area of 125 m2 g−1 and an extremely low crystallinity degree. The NMMO/H2O system represents a potential homogeneous solvent for the cellulose alkalization process.

We present a method for synthesis of silver nanoparticles in N-methylmorpholine N-oxide (NMMO) and the associated mechanism, as well as their use for in situ volume modification of cellulose fibers. The synthesized particles had diameter of about 4 nm, and their colloid solution was stable for 1 year. The nanoparticles were stabilized using polyethylenimine, which apart from preventing nanoparticle agglomeration, also accelerated Ag+ ion reduction and prevented NMMO degradation. A mechanism for the nanoparticle synthesis is suggested based on the electrochemical potentials of all ions in solution, with perhydroxyl ions resulting from NMMO reducing the silver ions. We also created nanocomposites from fibers and silver nanoparticles, in which the latter showed very good dispersion in the fiber volume. Such spun fibers showed improved mechanical parameters in comparison with unmodified fibers.

In this study, the surface layer of cotton fabric was swelled with N-methylmorpholine-N-oxide with 18 % water content, washed and dried to improve its stiffness property. Finally, the finished fabric had no auxiliaries and self-stiffened. The results showed that the bending rigidity increased from 0.75 × 105 to 1.57 × 105 mN cm, the acute elastic crease recovery angle from 95.2° to 117.3°, the delayed elastic crease recovery angle from 117.6° to 146.6° and the moisture regain from 8.07 to 10.3 %. The stiffness was almost unaffected by 30 multiple washing times. The tear strength, breaking strength and whiteness properties remained excellent. Scanning electron microscopy showed that the edges of finished fibres obviously curled. According to infrared spectrum analysis, no new groups were found. X-ray diffraction analysis showed that the crystal structure of the fibre changed, with cellulose II formed disorderly in the surface layer of the cotton fibres. This mechanism permits the cotton fabric to self-stiffen in the modifying process.

International audience; The swelling and dissolution mechanisms of dry, never-dried and re-wetted Lyocell fibers were investigated using mixtures of N-methylmorpholine N-oxide and water with various contents of water (from monohydrate to 24% w/w). A radial dissolution starting from the outer layers was observed. Dissolution kinetics was dependent on the water content, the drying state and the spinning conditions. A buckling of the core of dry fibers was observed during swelling. This phenomenon was attributed to the deformation of the unswollen core to accommodate the contraction of the swollen parts of the fiber. In purely swelling conditions with no dissolution, a huge swelling of a very thin skin layer was observed in the first stage, followed then by a progressive swelling of the inside of the fiber. We postulate that this mechanism arose from the fact that this skin is much less crystalline than the core.

The syntheses of several perdeuterated substances—some of them isotopically labeled (15N) in addition—are described, which act as direct solvents of cellulose either on their own, such as N-methylmorpholine N-oxide (NMMO), 1-butyl-3-methylimidazolium acetate (BMIM-OAc), or 1-ethyl-3-methylimidazolium acetate (EMIM-OAc), or in combination with auxiliaries, such as N,N-dimethylacetamide (DMAc—for the cellulose solvent DMAc/LiCl). NMMO-d11 (9) was obtained in an eight-step approach from non-labeled diglycolic acid (1) via diethylene glycol-d8 (4) and its bis-tosylate (5), which underwent ring closure with benzylamine to N-benzylmorpholine-d8 (6). Debenzylation, methylation and oxidation completed the synthetic sequence, which was also able to provide the 15N-labeled product (9a) by usage of 15N-benzylamine. DMAc-d9 (14) was obtained from deuterated acetic acid (10) and dimethylamine-d6–carbon dioxide complex (13) in a solvent-free gas-solid reaction with acidic alumina as the catalyst. Employing the CO2-complex of 15N-dimethylamine-d6 afforded the 15N-labeled product 15N-DMAc-d9 (14a) in a similar way. The two ionic liquids EMIM-OAc (21) and BMIM-OAc (22) were obtained from imidazole in three-step sequences starting with butylation and ethylation, respectively. The resulting 1-alkyl imidazoles were purified, and subsequently methylated according to a novel protocol using dimethylcarbonate-d6. Addition of acetic acid-d4 caused traceless degradation of the methylcarbonate anions and exchange for acetate. In all syntheses, the reaction steps were optimized with non-labeled compounds towards high yields and high reproducibility before entering the “hot runs” with deuterated and otherwise isotopically labeled material.

Degradation processes of N-methylmorpholine-N-oxide monohydrate (NMMO), cellulose and cellulose/NMMO solutions were studied by high performance liquid chromatography (HPLC) and electron spin resonance (ESR) spectroscopy. Kinetics of radical accumulation processes under UV (λ = 248 nm) excimer laser flash photolysis was investigated by ESR at 77 K. Beside radical products of cellulose generated and stabilized at low temperature, radicals in NMMO and cellulose/NMMO solutions were studied for the first time in those systems and attributed to nitroxide type radicals ∼CH2–NO•–CH2∼ and/or ∼CH2–NO•–CH3∼ at the first and methyl •CH3 and formyl •CHO radicals at the second step of the photo-induced reaction. Kinetic study of radicals revealed that formation and recombination rates of radical reaction depend on cellulose concentration in cellulose/NMMO solutions and additional ingredients, e.g., Fe(II) and propyl gallate. HPLC measurements showed that the concentrations of ring degradation products, e.g., aminoethanol and acetaldehyde, are determined by the composition of the cellulose/NMMO solution. Results based on HPLC are mainly maintained by ESR that supports the assumption concerning a radical initiated ring-opening of NMMO.

The thermal stability of cellulose/N-methylmorpholine-N-oxide (NMMO) solutions were investigated using UV/VIS spectrometry with a temperature programming cuvette and caloric measurements by means of the Systag calorimeter RADEX (mini-autoclave). Both analytical methods allow to characterize the influences of stabilizers and additives. With the temporal course of the optical density, temperature and pressure thermal runaway reactions with gas evolution and accumulation of chromophoric degradation products were recognized. Kinetic model calculations compared with UV/VIS measurements demonstrate the existence of autocatalytic reactions in cellulose/NMMO solutions. Varying the heating rate autocatalysis can be proved by dynamic caloric measurements as well.

The Lyocell process is a modern ‘green’ industrial fiber-making technology, which employs N-methylmorpholine-N-oxide monohydrate (NMMO) to directly dissolve cellulose. One problem in Lyocell processing is the discoloration of the spinning dope due to chemical side reactions. Two different methods were elaborated to isolate chromophores, which are present in minute amounts only, from Lyocell fibers, the first one using hydrogen chloride in alcoholic solution, the second one employing boron trifluoride – acetic acid complex. Several chromophores were unambiguously identified by a combination of analytical techniques and comparison to authentic samples. Carbohydrate condensation products, such as catechols, were shown to dominate in early phases of chromophore formation. In later stages, these initial chromophores undergo further condensation reactions with degradation products of NMMO and NMMO itself, leading to nitrogen-containing heterocycles and quinoid products, among others. The incorporation of nitrogen into the chromophores and thus the participation of the solvent in chromophore formation were proven.

N-Methylmorpholine-N-oxide monohydrate (NMMO) is used as solvent for cellulose in the Lyocell process as a modern industrial fiber-making technology. Undesired chemical side reactions and byproduct formation in the system cellulose/NMMO/water are known to cause detrimental effects, such as chromophore formation and discoloration of the resulting fibers. A detailed kinetic study on the influence of carbonyl structures on chromophore formation in NMMO melts was carried out employing UV spectroscopy. Different sugar model compounds, such as reducing or non-reducing sugars, and sugars with additional oxidized functions, were applied. The chromophore formation rate differed widely for various reducing sugar model compounds, with pentoses generally reacting faster than hexoses, and carbohydrates with protected reducing end being largely inert. The effect of carbonyl groups on chromophore generation has been studied further using oligomers and oxidized pulps with different contents of carbonyl groups. As in the case of model compounds, also for the pulps a linear correlation between carbonyl content and chromophore formation rate was established. A distinct effect of hemicelluloses was observed.

Efficient stabilization of cellulose solutions in NMMO(1) against side reactions and their harmful effects meansprevention of both homolytic and heterolytic side reactions, which is mainlyaccomplished by trapping radicals, formaldehyde, andN-(methylene)iminium ions (5). Whileradical trapping is commonly reflected by the antioxidativeefficiency, the effectivity against heterolyticdegradationin the Lyocell dope can be expressed by the newly introduced term‘formaldehyde trapping capacity’ (FTC). Propyl gallate (PG,4), the most widely applied Lyocell stabilizer nowadays, actsas a phenolic antioxidant, and is finally oxidized to a deeply colored, highlyconjugated chromophore (11) via ellagicacid (10). It was demonstrated that 4 is alsoa quencher of formaldehyde and N-(methylene)iminium ions,both in organic solutions of NMMO and in Lyocell dope. The processes of radicaltrapping and scavenging of HCHO/5 are competitive in the caseof propyl gallate. A novel oxa-chromanol derivative, PBD (14),was designed as stabilizer for Lyocell solutions. In analogy to propyl gallate,PBD acts as a scavenger of all three dangerous species, namely HCHO,5 and radicals. Upon oxidation by radical species, PBDreleasesacetaldehyde which acts as a very efficient HCHO trap. Thus, in contrast topropyl gallate, radical trapping and HCHO trapping are not competitive. Boththeantioxidative efficiency and the capacity to trap HCHO and 5are higher for PBD as compared to propyl gallate. In preliminary stabilizertesting, mixtures of PBD and PG proved to be especially effective.

In order to gain an understanding of the process of Lyocell fiber formation, the melting and solidification behaviors, heat capacity and density of cellulose N-methylmorpholine-N-oxide monohydrate (NMMO-MH) solutions were studied by differential scanning calorimetry (DSC) and dilatometry, and the diameter development of Lyocell fibers in the air gap was measured online. It was found that the Lyocell process can be considered as both a melt–spinning process in the air gap and a wet-spinning process in the coagulation bath. Cellulose chains in the solutions hindered the crystallization of NMMO-MH, and the melting point of the solutions decreased with increasing cellulose concentration. The density of cellulose NMMO-MH solutions decreased linearly with increasing temperature in the solid or the liquid state, and it increased with increasing cellulose concentration. The heat capacity of the solutions increased slightly with increasing temperature and concentration. The development of fiber diameter, the velocity gradient, and the gradient of the filaments in the air gap were limited to a short distance from the spinneret orifice. The position at which the velocity and the tensile stress gradient reached their maximum values moved closer to the spinneret orifice with increasing take-up speed.