Prog. Polym. Sci.

26 (2001) 1763±1837
www.elsevier.com/locate/ppolysci

The chemistry of side reactions and byproduct formation in the system NMMO/cellulose (Lyocell process)
Thomas Rosenau a,*, Antje Potthast a, Herbert Sixta b,1, Paul Kosma a
a

Christian Doppler Laboratory for Pulp Reactivity, Institute of Chemistry, University of Agricultural Sciences Vienna, Muthgasse 18, A-1190 Vienna, Austria b R&D Lenzing AG, A-4860 Lenzing, Austria Received 27 November 2000; revised 12 June 2001; accepted 20 June 2001

Abstract N-Methylmorpholine-N-oxide monohydrate (NMMO) is used as a solvent for direct dissolution of cellulose in industrial ®ber-making (Lyocell process). Ideally, Lyocell ®ber production per se should be an entirely physical process that does not cause chemical changes in pulp or solvent. However, there are several side reactions and considerable byproduct formation in the system cellulose/NMMO/water which can cause detrimental effects, such as degradation of cellulose, temporary or permanent discoloration of the resulting ®bers, decreased product performance, pronounced decomposition of NMMO, increased consumption of stabilizers, or even thermal runaway reactions. The present paper will focus on chemical aspects of the system NMMO/cellulose. After a short section on Lyocell ®ber production, the analytical techniques to monitor side reactions in the Lyocell system will be discussed. In the main part, the side reactions of NMMO in the Lyocell process have been divided into homolytic (radical) and heterolytic (non-radical) processes in a systematic investigation. In all homolytic reactions of NMMO, cleavage of the N±O bond with formation of an aminium (aminyl) radical is the ®rst step. Formation, properties and subsequent reactions of this primary radical species will be summarized. In the absence of oxygen, the radical undergoes disproportionation or other redox processes that ®nally produce N-methylmorpholine, or morpholine and HCHO, respectively. In contrast, reactions of C-centered tautomers of the radical with dioxygen dominate in the presence of oxygen. Also the effects of transition metal ions, which are potent inducers of homolytic reactions of NMMO, are described. Heterolytic reactions in the Lyocell system proceed according to three major pathways. First, reductive deoxygenation of NMMO produces N-methylmorpholine with concomitant oxidation of available reductants, e.g. cellulose or carbohydrate model compounds. Second, Polonowski type reactions, which are intramolecular redox processes, ®nally generate morpholine and formaldehyde. In a third pathway, an autocatalytic process induced by carbonium±iminium ions can cause quantitative decomposition of NMMO. The formation and
* Corresponding author. Fax: 143-1-36006-6059. E-mail addresses: trosenau@edv2.boku.ac.at (T. Rosenau), h.sixta@lenzing.com (H. Sixta). 1 Fax: 143-7672-7013542. 0079-6700/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 0 7 9 - 6 7 0 0 ( 0 1 ) 0 0 02 3 - 5

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T. Rosenau et al. / Prog. Polym. Sci. 26 (2001) 1763±1837

determination of reactive intermediates and heterolytic degradation products as well as their role in the system is analyzed. Furthermore, thermal degradation reactions under controlled conditions or under conditions leading to uncontrolled thermal degradation, i.e. explosions or `exothermic events', are considered. Especially the latter processes are important from the viewpoint of system safety since they can be induced by several of the discussed radical and non-radical reactions. The homolytic, heterolytic and thermal degradation reactions in the system cellulose/NMMO/water have been reviewed in terms of reaction mechanisms, byproduct formation, and negative effects on the Lyocell system. Precise knowledge of reaction mechanisms as well as the role of harmful intermediates and products allows for the safe and economical production of Lyocell ®bers, and a rational design of chemical stabilizers for the Lyocell system. q 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Lyocell; Cellulose; Cellulosic ®bers; N-Methylmorpholine-N-oxide; Decomposition; Homolytic processes; Heterolytic processes; Thermal degradation

Contents 1. General aspects of the system NMMO/water/cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1765 1.1. The Lyocell process Ð a (very) brief history . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1765 1.2. Fundamentals of the Lyocell process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1766 1.3. NMMO Ð a cellulose solvent and much more . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1767 1.4. Side reactions and byproduct formation in the Lyocell process . . . . . . . . . . . . . . . . . . . . . . . . .1774 2. Analysis of NMMO and its degradation products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1777 2.1. Analysis of NMMO by traditional methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1777 2.2. Determination of NMMO by instrumental analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . .1778 2.3. Analysis of NMM and M as main NMMO degradation products . . . . . . . . . . . . . . . . . . . . . . . .1778 2.4. Simultaneous determination of NMMO, NMM and M . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1778 2.5. Determination of other degradation products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1780 3. Side reactions in the NMMO/cellulose system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1783 3.1. Degradation of NMMO Ð homolytic versus heterolytic processes . . . . . . . . . . . . . . . . . . . . . .1784 3.2. Homolytic reactions in the system NMMO/cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1786 3.2.1. Formation of primary radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1786 3.2.2. The in¯uence of metal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1793 3.2.3. The in¯uence of oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1796 3.2.4. Summary: homolytic reactions in the system NMMO/cellulose . . . . . . . . . . . . . . . . . . .1800 3.3. Heterolytic reactions in the system NMMO/cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1801 3.3.1. Heterolytic deoxygenation of NMMO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1801 3.3.2. Polonowski type reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1807 3.3.3. The role of formaldehyde in the Lyocell system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1811 3.3.4. Autocatalytic decomposition of NMMO by carbonium±iminium ions . . . . . . . . . . . . . .1812 3.3.5. Summary: heterolytic reactions in the system NMMO/cellulose . . . . . . . . . . . . . . . . . . .1820 3.4. Thermal degradation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1821 3.4.1. Controlled thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1821 3.4.2. Uncontrolled thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1823 4. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1827 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1829 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1830

T. Rosenau et al. / Prog. Polym. Sci. 26 (2001) 1763±1837

1765

1. General aspects of the system NMMO/water/cellulose 1.1. The Lyocell process Ð a (very) brief history Utilization of cellulose is an extremely old topic, already the ancient Egypt civilizations had obtained apparel, garment and delicate artwork from cotton as well as papyrus from ®brous material of the `Egyptian paper plant'. Only since 1884, when Duke Chardonnet invented arti®cial silk, also cellulose from wood became a raw material for transformation into ®bers. This was the birth of the utilization of wood cellulose as one of the most important textile raw materials. Cellulose is produced by green plants on a 100±150 billion ton scale each year, albeit only a small percentage of this huge amount is further utilized. Being fully biocompatible and compostable, cellulosic products, such as ®bers, possess a great advantage as compared to synthetic polymer counterparts. Also their origin Ð cellulose is a renewable, natural resource Ð is a decisive plus. The demand for apparel ®bers has been steadily growing in the past century and will most likely continue to do so in the nearer future. As possibilities to expand cotton ®ber production are limited, there is considerable potential for a further increase in the production of `cellulosics', especially viscose (rayon) ®ber. However, conducting the viscose process in a way that is fully compatible with even the most stringent environmental regulations is most demanding, which explains that the search for alternative processes to generate cellulosic ®bers has continued over time. The most promising of these approaches with potentially bright future prospects is the amine oxide procedure which uses the monohydrate of N-methylmorpholine-N-oxide (NMMO, 1) Ð or more generally a mixture of NMMO and water Ð to directly dissolve pulp without prior derivatization of the cellulose. The generic term `Lyocell' is commonly used to designate the industrial process, the ®bers produced therein, and NMMO/cellulose mixtures. Lyocell ®bers are thus cellulosic ®bers produced by an `organic solvent spinning process', they are classi®ed as separate category within the group of cellulosic man-made ®bers [1]. The ®rst patent on a procedure to dissolve cellulose in different tertiary amine oxides was issued to È Granacher and Sallmann in 1936 and 1939 [2,3]. About 30 years later, Johnson et al. ®led patents describing solutions of different synthetic and natural polymers in different cyclic tertiary amine oxides [4±6]. At the beginning of the 1980s, intensive research on approaches to produce cellulosic ®bers from amine oxide/cellulose solutions had been carried out by AEC (American Enka Corporation, United States) [7±9], ARLO (Akzo Research Laboratory Obernburg, Federal Republic of Germany) [10], and at the University of Grenoble, France. The work of Chanzy et al. [11,12] is today widely regarded as the basis for the developments that later resulted in the Lyocell process. Among several amine oxides tried, most promising results were obtained for N-methylmorpholine-N-oxide as the cellulose solvent. While the studies at ENKA were largely terminated due to cotton prices temporarily going down, investigations were continued at Courtaulds (UK), Lenzing AG (Austria), TITK Rudolstadt (Germany) and after brief intermission at AKZO Nobel (The Netherlands). The prosperous development in this period, especially in the ®eld of process technology, spinning technology, ®ber properties and solvent recycling, was re¯ected in booming research activities and frighteningly high numbers of patents issued. At the same time research groups at different companies came up with different brand names for their products: Tencel (Courtaulds), Lyocell by Lenzing (Lenzing), Alceru (TITK Rudolstadt) and Newcell (Akzo Nobel). All these labels designate essentially similar products, namely Lyocell ®bers, which are cellulosic ®bers spun from cellulose solutions in NMMO.

000 and 20. and in the idealized case. even though problems with spinability may be encountered in some cases. Sci. certain substances can be added to the solution to tune speci®c properties of the ®bers. in relation to the traditional viscose production. which is also an important economic factor. As shown in Fig. it is certainly justi®ed to regard Lyocell as a well-established and important new member in the family of high-tech. cotton. e. respectively. are currently developed or are already commercially produced [15±19]. high-quality textile ®bers. 26 (2001) 1763±1837 Fig. either in production and further handling. paper grade pulp. This is mainly due to the low toxicity of NMMO. As in the viscose process. such as ®lms. NMMO and water are completely recycled. Polym. Several pilot plants exist. The ¯exibility of the process in terms of the cellulosic raw materials is another major advantage. no derivatization. is required [20]. membranes and ®laments. Production lines for cellulosic ®bers from NMMO solutions on pilot plant scale and ®nally on larger industrial scale have been established in the last decade of the 20th century [13. In commercial large-scale systems. some general features are brie¯y outlined in the following. such as alkalization and xanthation in the case of rayon ®bers. FCFC (Taiwan). for instance at TITK (Germany). Thus. beads. NMMO recovery is greater than 99%. Very few process chemicals are applied. Rosenau et al. Lyocell ®bers.2.g. However. Cellulose ®bers are directly obtained from the cellulose solution in NMMO. 1. the Lyocell process pertains a signi®cantly lower speci®c environmental challenge [21]. 80.1766 T. also other cellulosic products. the Lyocell process comprises a comparatively low number of process steps.000 ton. Lyocell ®bers consist of regenerated cellulose (cellulose II). In comparison with cotton and viscose. 1. to provide a general understanding of the Lyocell process and to place it in relation with other approaches for cellulosic ®ber generation. Today. Hanil (Korea) and Grassim (India). and its biodegradability [22]. Theoretically. unbleached chemical pulp. Acordis and Lenzing produce annually approx. 1. / Prog.14]. The Lyocell process in general. The Lyocell process in general. Fundamentals of the Lyocell process Technical aspects and process technology of Lyocell ®ber production as well as the physicochemical processes during cellulose dissolution and the structure of the dissolved cellulose are not within the scope of this review. They are distinguished by . Based on the Lyocell technology. rayon ®bers or even waste paper can be employed as raw materials for Lyocell ®ber production.

26 (2001) 1763±1837 1767 high crystallinity. the remaining aliphatic group and the oxygen as substituents. details of the dissolution process and the interactions between cellulose hydroxyl groups and NMMO remain largely unclear in both time and spatial dimension. tertiary amine oxides. NMMO Ð a cellulose solvent and much more N-Methylmorpholine-N-oxide (1) belongs to the family of cyclic. such as dielectric relaxation spectroscopy [47] and quantum-mechanical computations [48±51].44]. This inherent feature. resulting in a very high dry and wet tensile strength. laser diffraction [46]. The most prominent feature of NMMO is the highly polar N±O group with a dipole moment of 4. thermal instability and discoloration. the latter referring to structures wherein the tertiary nitrogen is a part of the aromatic ring system.65] and X-ray methods [66±68] have been applied to probe the structure of the dissolved cellulose. donor±acceptor. but also by less conventional techniques. and thus. long crystallites.55]. proving that NMMO was unable to generate molecular-disperse cellulose solutions.e. Cellulose dissolution in NMMO. The term `cyclic' points out that the nitrogen is incorporated into an alicyclic ring system.33]. so that Roder et al. but also other ®ber properties. Product properties and marketing potential of Lyocell ®bers have been the topic of several previous reviews [39±42]. The potential structures were pinned down to shapes between soft spheres and homogeneously branched particles. The physicochemical process of the cellulose dissolution and the structure of the dissolved cellulose have been intensively investigated. Polym. Various scienti®c efforts have concentrated on elucidating the dissolution process. A characteristic of Lyocell ®bers is their tendency towards ®brillation (pilling) [27±31].38 mD [72]. The highest electron density is located at the oxygen. interactions ®nally leading to a far-reaching restructuring of the hydrogen bond network [54. aliphatic.T. especially by ®nishing conditions [34±38]. rheology [45]. Progress has been made when the combined force of static and dynamic light scattering and other È methods was applied. Thus.3. the necessity of working at elevated temperatures. [69±71] were able to demonstrate the occurrence of large cellulose aggregates. Sci. The nature of the N±O group is best described . oblate rotational ellipsoids (fringed micelles) were proposed as a model for cellulose dissolved in NMMO. and can even be used to achieve special optical effects and wear properties. However. Lyocell ®bers can be advantageously utilized in hetero-yarns. a high wet modulus and high loop tenacity [24±26]. / Prog. light-scattering techniques [64. can be in¯uenced by process and spinning parameters [32. The `chemical' processes during dissolution are thus merely acid±base. The term `aliphatic' is used to distinguish this class of compounds from aromatic (heteroaromatic) amine oxides. Mainly rheology [59±63]. such as pronounced self-structuring and a high viscosity. Rosenau et al. high degree of orientation. all of which generally pose dif®culties to a smooth characterization. and well-oriented amorphous regions [23]. so that the nitrogen carries this ring structure. such as a `peach-skin' look. but are still far from being comprehensively understood. State of solution of cellulose in NMMO. The nitrogen can thus be described by sp 3-hybrid molecular orbitals resulting in tetrahedral geometry. employing thermoanalytical methods [43. and nonwoven fabrics with speci®c properties. i. speciality textiles. investigations are generally hampered by inherent properties of the solvent.53]. However. The statement about limited knowledge equally applies to the solution state of cellulose in NMMO [56±58]. Today it is commonly agreed upon that the solvation power of NMMO originates in its ability to disrupt the hydrogen-bond network of cellulose and to form solvent complexes by establishing new hydrogen bonds between the macromolecule and the solvent [52. 1.

and a very high hygroscopicity. 26 (2001) 1763±1837 Fig. with a positive charge at the nitrogen and a negative charge at the oxygen. several abbreviations for N-methylmorpholine-N-oxide. The N±O bond must be regarded as rather energy-rich. 3). 2) and morpholine (M. MMNO or NMO are used. Rosenau et al. which is approved by IUPAC and will also be used throughout this paper. by a coordinate-covalent bond. Amine oxides. Due to the high polarity of the N±O bond. NMMO is a compound with very high hydrophilicity. / Prog. or as a simple single bond. with no indication of its special character.e. the cellulose solvent N-methylmorpholine-N-oxide (NMMO) and main degradation products of NMMO. such as NMMNO. 2) or morpholine (M. NMMO is a weakly basic compound …pKB ˆ 9:25†. and is very sensitive towards all types of catalysts that induce N±O bond cleavage. as donative. 2. N-methylmorpholine (NMM. In formula schemes. 3) . the increased use in organic synthesis has helped to establish `NMMO' as a short. the negatively charged exo oxygen acts as the proton acceptor. General properties. especially in the older literature. see Fig. Three important properties result from that feature: NMMO is a strong oxidant. it can thus be readily broken and releases the relatively large energy of 222 kJ/mol upon cleavage. 2. is thermally labile. Its basicity is much lower than that of N-methylmorpholine (NMM. Polym. Even though. resulting in extremely high solubility in water.1768 T. Sci. with an arrow pointing at the oxygen. i. the bond is either written as ionic. a pronounced tendency to form hydrogen bonds. complete miscibility.

and recrystallization from an appropriate organic solvent [12]. UK. Germany. P21/c a ˆ 12:803. The high polarity of the N±O bond Ð with its ability to form hydrogen bonds Ð and the weakness of the N±O bond are the basis of the two main applications of NMMO today. 78 and 398C. Germany.28 White. Generation requires azeotropic drying from organic solutions followed by crystallization [75. P21/m a ˆ 9:886. gives the anhydrous material that is exclusively used for synthetic purposes. The disesquihydrate itself can be synthesized by addition of appropriate amounts water to anhydrous NMMO or monohydrate. all three forms exhibit hygroscopicity so that atmospheric moisture is easily taken up. P21/c a ˆ 25:481. [78] with kind permission of the International Union of Crystallography Parameter Formula M (g/mol) Density (g/cm 3) Color. It is also obtained by dehydration of the disesquihydrate. c ˆ 21:913. respectively. crystalline 39 Monoclinic. respectively. Sci. b ˆ 6:621. the monohydrate NMMO pH2O and the disesquihydrate NMMO p2. Anhydrous NMMO cannot be obtained simply by heating the monohydrate or the disesquihydrate. Commercial production. NMMO forms two stable hydrates. the use as cellulose solvent and the application in synthesis. Hydrate forms of NMMO. or vacuum sublimation [77].74] and is not suf®cient to give a positive phenolphthalein test.5H2O C10H32N2O9 324. b ˆ 110:548 Unlimited 7529-22-8 507437 NMMO pH2O C5H13NO3 135. but fails to provide neat anhydrous material. NMMO is produced by oxidation of NMM (2) with aqueous hydrogen peroxide and is primarily obtained as concentrated. the monohydrate NMMO pH2O with 13. which was assigned to solid±solid phase transition of the NMMO crystals [12]. crystalline 76±78 Monoclinic. b ˆ 6:04. Polym. The disesquihydrate has not found utilization so far. Azeotropic drying.T. c ˆ 5:112. Thermograms of anhydrous NMMO show an endothermic transition at 1108C in addition to the melting at 1848C.33 White. crystalline 184 Monoclinic.1 1. According to . appearance Mp (8C) Crystal form Ê Unit cell dimensions (A) Solubility in water CAS number Beilstein registry NMMO C5H11NO2 117. / Prog. Adapted from Ref.5H2O are listed in Table 1. mostly 50 wt%. The physicochemical data for NMMO. 26 (2001) 1763±1837 1769 Table 1 Physical and chemical data of NMMO and its hydrates. NMMO in lab-scale quantities is commercially available from most of the common chemical distributors. and Texaco. Simple evaporation of water in vacuo at temperatures above the melting point of the monohydrate is possible. Rosenau et al. b ˆ 109:998 Unlimited 80913-65-1 5449450 [73. b ˆ 6:50. Melting of anhydrous NMMO is immediately followed by decomposition. The phase diagram of the NMMO/NMMO pH2O system cannot be classi®ed as simply eutectic. BASF AG.25 White.3% (w/w) H2O and the disesquihydrate NMMO p2. The melting points are thus lowered with increasing hydrate water content. NMMO monohydrate is the product of evaporation of aqueous NMMO solutions. b ˆ 99:888 Unlimited 70187-32-5 5449441 NMMO p2.76]. Main producers are Degussa.2 1. Differential scanning calorimetry (DSC) heating curves of the three forms of NMMO clearly show the melting points at about 184. c ˆ 9:186. Evaporation of water gives the monohydrate that is used as cellulose solvent and in organic synthesis. in turn.4 1. aqueous solution.5H2O with 28% (w/w) H2O.

In the monohydrate. dashed lines indicate hydrogen bonds. / Prog. However. In anhydrous NMMO. 3).79]. the morpholine ring adopts a chair conformation with an axial N±O bond. Chanzy et al. 26 (2001) 1763±1837 Fig. (A) Anhydrous N-methylmorpholine-N-oxide: packing in the crystal. The phase diagram of the binary system NMMO pH2O and NMMO p2. the most frequent application in organic synthesis is their use as oxidants [82]. [12] the system represents a borderline case between a eutectic system with the eutectic point on the axis of the lower-melting constituent and a part of a peritectic system with incongruent melting of the monohydrate. Crystal structures have been reported for NMMO and its monohydrate [78.5H2O is of simple eutectic type. (B) N-methylmorpholine-N-oxide monohydrate: projection down the b axis.1770 T. Tertiary amine oxides are frequently occurring natural products. Sci. 3. Rosenau et al. NMMO in organic synthesis. In both structures. Polym.81]. leading to a polymer-like self-structure (Fig. NMMO (1) is the most frequently applied tertiary amine oxide in . water molecules link the N±O groups of NMMO through an extensive hydrogen bond network. Adapted from [78] with kind permission of the International Union of Crystallography. and have thus been the targets of synthetic efforts [80. the N±O bonds of neighboring molecules are arranged in antiparallel orientation.

N. In most cases. most importantly.N.T. Sci. This approach is used for the oxidation of primary and secondary alcohols into aldehydes and ketones. Rosenau et al.87]). respectively [84. for the cis-dihydroxylation of ole®nes by stereospeci®c syn-addition (for a review on oxidations with OsO4 see Refs. 26 (2001) 1763±1837 1771 Fig. NMMO ®nds multiple uses in the oxidation of main group . oxidizes the organic coreactant and is re-oxidized in situ by the NMMO present. Applications of NMMO in organic synthesis. / Prog.85] and. NMMO can be used for the direct oxidation of primary alkyl. [86. The mediator. 4. osmium tetroxide being most frequently used for this purpose. benzyl or allyl halides to the corresponding aldehydes [83].N-dimethylamine-Noxide (BEDMO) are less important. however. Polym. synthetic applications. the amine oxide is stoichiometrically applied together with catalytic amounts of osmium or ruthenium compounds as redox mediators that act as the actual oxidants.N-trimethylamine-N-oxide (TMANO) and N-benzyl-N.

Polym. NMMO up to a water content of 17% (w/w). especially in the oxidation of alkylboranes to borinates. see Table 2. A conversion of high importance is the reaction with metal carbonyls. / Prog. 4. at water concentrations below 4%. Also transition-group organometallics are oxidized. at higher water contents mixtures are obtained that precipitate cellulose.g. Adapted from Ref. NMMO as cellulose solvent. The oxygen of the N±O bond in NMMO is able to form one or two hydrogen bonds with two partners containing hydroxyl groups. [12] with kind permission of Wiley Solvent Cellulose concentration (% w/w) 0 NMMO 1 4% H2O (w/w) (8C) NMMO 1 17% H2O (w/w) (8C) 170 75 5 159 68 10 144 65 organometallics. Rosenau et al. a mild method to `activate' the complex towards the substitution of a carbonyl with another ligand [89. with water as in the monohydrate [78] or with alcohols [91]. Phase diagram of the ternary system NMMO/water/cellulose. is not able to dissolve cellulose. Depending on the water content and the characteristics of the pulp. the dissolution temperatures come close to the decomposition point of NMMO. 26 (2001) 1763±1837 Table 2 Depression of the melting point of NMMO by cellulose. boranates and ®nally alkyl borates [88]. its hydrate and their mixture are strongly depressed in the presence of cellulose. Similar hydrogen bonding is believed to occur with cellulose and to be the cause for cellulose dissolution. Water and cellulose exhibit competitive behavior as to hydrogen bond formation with NMMO. e. with water being evidently preferred. corresponding to a `1. Sci. The range for the water content in NMMO which allows dissolving cellulose is thus reasonably set between 4 and 17%. 5. so that this value is generally taken as the lower limit for cellulose solutions. The different uses of NMMO in organic synthesis are summarized in Fig. is able to dissolve cellulose.1772 T. This explains why the disesquihydrate. Adapted from Ref. in which both positions available for hydrogen are already blocked by water. The melting points of NMMO. Process steps and approximate solubility range of cellulose are indicated. Fig.2 hydrate'. . [144] with kind permission of Wiley-VCH. However.90].

up to 21% in the temperature interval 72±1208C. equilibrium between an isotropic and an anisotropic phase is observed. temperature. cellulose is introduced into a mixture of NMMO and water to give a slurry which should be as homogeneous as possible. Stabilizers are added at this point. the latter dominates if the cellulose concentration is further increased. up to 29%. approx. excess water is evaporated. Specially designed reaction vessels allow on-line control of all the important parameters. thus enabling a more rapid and gentle dissolution. The large effect of mechanical force during dissolution is thought to originate from breaking of intermolecular hydrogen bonds in cellulose and formation of bonds between the solvent and solute. The viscosity of the resulting cellulose solution is strongly dependent on both the cellulose concentration and the molecular weight of the cellulose. The transition temperature for the phase transition isotropic± anisotropic is dependent on the cellulose concentration and on the DP of the cellulose sample [92]. Typical compositions are 50±60% NMMO. Dissolving cellulose in NMMO pH2O produces isotropic solutions at lower concentrations. 10% water. 20±30% water and 10±15% pulp. 6. which are summarized in Fig. such as concentrations. Sci. . 5. The solution is extruded at temperatures between 100 and 1208C. possibly under reduced pressure. cellulose solutions up to approx. Polym. At higher cellulose concentrations. Thorough mixing and input of mechanical energy help to achieve short dissolution/reaction times and a uniform product at a temperature as low as possible. 76% NMMO. Factors in¯uencing dissolution of cellulose in NMMO/water. 30% can be produced. Generally. / Prog. The use of the aqueous NMMO solution favors intimate mixing.T. Shear stress causes not only a signi®cant decrease in the apparent viscosity of the solution. but it is also a crucial factor in accelerating the dissolution process and to accomplish a smooth dissolution. the occurrence and velocity of cellulose dissolution is in¯uenced by ®ve parameters. pressure and shear stress during the dissolution procedure. Subsequently. 26 (2001) 1763±1837 1773 Fig. The phase diagram of the ternary system NMMO/water/cellulose is given in Fig. Rosenau et al. at a preset temperature until the region in the phase diagram NMMO/water/ cellulose is reached in which dissolution of the cellulose occurs. approx. A typical composition of the dope is 14% cellulose. 6. In most industrial and pilot-plant Lyocell processes.

which is not only a cellulose solvent. some of which have been mentioned above. would be involved. the negative properties of NMMO. In fact. With the observation of blasts and explosions in laboratory scale and pilot-scale trials with Lyocell mixtures. it was not fully recognized for some time that the chemistry of NMMO/cellulose solutions is far from being trivial. a severe discoloration of the solution due to chromophore formation has been observed. whereas the physical and technological dif®culties of the Lyocell process had already been solved with great success. processes that cause permanent chemical modi®cations either on the solvent NMMO or on the solute cellulose.e. 2) and morpholine (M. Studies on degradation reactions Ð the second phase. which might be seen as a second phase in the investigation of decomposition processes in Lyocell mixtures. respectively. Many of the stabilizers used to prevent aging of synthetic polymers. both solvent and cellulose undergo degradation reactions. / Prog. Sci. initiated by metal ions present and catalyzed by decomposition products of NMMO. Apart from this. Polym. fundamental research work was carried . however. The decrease in the degree of polymerization (DP) of cellulose and the loss in NMMO were always taken as measure for decomposition or stabilization. Due to the seemingly negligible chemical side of the process. but also a relatively labile compound and a strong oxidant.100]. albeit with different success. No `chemical' reactions. it were the chemical problems in the NMMO/cellulose system that remained as obstacles to pilot-plant or industrial production in the 1980s. often denoted with the euphemistic terms `fast exothermic process' or `thermal runaway reaction'. Most important. sterically hindered phenols [96] or mild reductants [97]. were the observations that cellulose in 1 undergoes severe degradation at the elevated process temperatures used. and that NMMO/cellulose mixtures may become unstable. the question of the chemical stability of the system suddenly entered a new dimension [98]. In this period. bases [95]. This phenomenon found its parallel in irregularities in the course of reactions that used NMMO as the oxidant in organic synthesis. the corresponding research in the 1970s and 1980s focused almost exclusively on process development. Here the instability of reaction mixtures and the occurrence of unpredictable thermal runaway reactions had also been reported [99. N-Methylmorpholine (NMM. such as phosphonates [94]. Side reactions and byproduct formation in the Lyocell process From a theoretical point of view. have also been proposed for the Lyocell process.1774 T. degradation reactions were mainly regarded as radical processes. 3) have been early recognized as the two main degradation products of NMMO (1). After the ®rst patent describing the bene®cial effect of propyl gallate as antioxidant in the system was issued in 1980 [93]. i. In this ®rst phase of research on degradation reactions in NMMO/cellulose. Rosenau et al. so that the more conventional means of stabilization with antioxidants and complexing agents were thought to be suf®cient. were commonly welcomed.4. 26 (2001) 1763±1837 1. Lyocell ®ber generation should be an entirely `physical' process. whereas the chemical aspect of the process was not adequately developed. a series of publications ensued in the following few years. which covered in detail different means to stabilize cellulose/NMMO mixtures. It became clear that adequate means to stabilize Lyocell solutions have to encompass especially the solvent and have to focus on avoiding those exothermic reactions. Studies on degradation reactions Ð the ®rst phase. had been underestimated. technological problems and testing of ®ber and textile properties. Evidently. Although the high potential of NMMO as cellulose solvent and the numerous advantages of Lyocell processing and technology. As soon as NMMO was suggested as a solvent for cellulose it was also suspected that the image of Lyocell ®ber production as a merely physical procedure would mean a misleading oversimpli®cation: in NMMO/cellulose mixtures.

to avoid their detrimental effects. it was the incentive of the work to minimize side reactions. Increased chromophore formation does not only result in problems in the recycling of the NMMO and process water. of different measures to stabilize Lyocell solutions. Driven by economical considerations and increasing demands for Lyocell ®bers of highest quality. it can also cause discoloration of the spun ®bers. a more comprehensive understanding of the effects of degradation processes in the Lyocell system and of the requirements for an effective stabilization was accrued. Rosenau et al. The empirical search for optimized stabilizers. A classi®cation into ®ve categories appears advantageous. Losses in NMMO are not only important from an economical point of view. starting from a slight yellow tint of the initially colorless solution up to a dark brown discoloration at elevated reaction times. ² Third. provided a systematic view of side reactions and byproduct formation by a division into homolytic (radical) and heterolytic (non-radical) processes [105±107]. Sci. but also the primary decomposition products have been recognized as inducers of further decomposition. may be regarded as a third phase in research on NMMO/cellulose degradation reactions. secondary reactions of these compounds are the reason for the whole spectrum of undesired effects in the system. the focus of interest shifted towards the underlying chemical mechanisms of the degradation reactions in the Lyocell system. A few key articles by Buijtenhuis et al. Rosenau et al. This fact alone would hardly be suf®cient to justify the scienti®c efforts to study their mechanisms and the economic interest in their avoidance. As the knowledge about suitable stabilizers and their mode of action was acquired on an empirical and largely unsystematic basis. Polym. chromophore formation is accompanied by a degradation of the pulp. the effects of those side reactions can be most detrimental. ² An increased consumption of stabilizers is another facet of side reactions. / Prog. Phenolic antioxidants. form highly .T. Firgo et al. The reactions of the solvent are thus the basis of an understanding of side reactions in the Lyocell process. However. i. [102] and Lang et al. This element of side reactions is most critical as it directly in¯uences the ®ber quality. Negatively affected tensile properties and rheological irregularities at the spinning machine are possible results. which can still be regarded as milestones in the ®eld of degradation reactions in NMMO/cellulose and stabilization. a progressing DP loss of the cellulose employed. ² The ®rst harmful effect of side reactions in the Lyocell system is a gradual decomposition of the solvent NMMO (1). Moreover. and to allow a well-aimed use of stabilizers. ² The second aspect and most prominent result of side reactions is a progressing formation of chromophores. [101]. and of the negative in¯uences known so far that cause these side reactions.e. which is also re¯ected in a high number of patents. Studies on degradation reactions Ð the third phase. a classi®cation which is also the basis for the present overview. Taeger et al. This period. Negative effects of side reactions in the Lyocell process. [104] succeeded in a systematization of those negative effects of side reactions. ®nally resulted in safe and secure industrial production processes for Lyocell ®bers. [103] were published in that time. Side reactions in the system NMMO/ cellulose naturally cause the formation of byproducts. This discoloration can be as severe as to cause persistent brightness loss with permanently reduced bleachability. 26 (2001) 1763±1837 1775 out to come closer to an understanding of these detrimental processes. for instance. With increasing process experience. starting approximately at the beginning of the last decade. Subsequent efforts were mainly located in different industrial companies. The reaction products of stabilizers are potentially harmful compounds.

cause more side reactions to occur. in turn. 7. The complex interactions in the system of side reactions. thus preventing the occurrence of the initial step of side reactions and consequently eliminating any other secondary undesired effects.1776 T. which means compensation of the harmful secondary effects of NMMO degradation. stabilizers are limited to intervention in later stages of the causality chain. This circulus vitiosus can only be overcome by generally minimizing side reactions so that high stabilizer charges can be avoided from the beginning. due to the above-discussed lability of NMMO and because of its oxidizing properties. and reductants may cause additional consumption of the oxidant NMMO. absorbent quinoid chromophores. Such a stabilization of the Lyocell reaction mixture does not only comprise addition of suitable . or Ð in real-world systems Ð at least minimized to an acceptable level. cellulose degradation or exothermic events. blasts and explosions. 26 (2001) 1763±1837 Fig. The ideal stabilizer would completely avoid decomposition of NMMO. A higher load of stabilizers thus means more byproducts. Rosenau et al. reduce formation of chromophores/to remove chromophores after formation. if measures to stabilize Lyocell solutions are to be effective. the mechanical integrity of the whole production line might be affected. such as chromophore formation. Polym. Potentially detrimental results of side reactions and byproduct formation in the Lyocell system. Consequently. Unlike the four aforementioned points. make understandable that an effective stabilization of the NMMO/water/cellulose system is not trivial. 7: ² ² ² ² ² to to to to to avoid/minimize decomposition of NMMO. remove harmful degradation products and intermediates from the system. The tasks that an optimum stabilization has to ful®l follow directly from the possibilities of adverse incidents given in Fig. / Prog. which. This is certainly the most detrimental of the possible effects as it concerns aspects of work safety. all of the above ®ve effects of side reactions must be completely avoided in the idealized case. where only the quality of the NMMO/cellulose mixture is in¯uenced. Sci. prevent uncontrollable reactions. However. as shown in Fig. and perhaps most important result of side reactions in the Lyocell system is the occurrence of exothermic reactions. 7. stabilize cellulose against degradation/to ensure constant rheological properties. ² The ®fth.

but also means to include all physical and technological measures that aim at keeping down degradation reactions. the unknown sample is titrated by HCI in isopropanol with potentiometric detection [108. NMMO is converted into the stronger base NMM (2). A rough determination of the amine oxide content is nevertheless possible. Analysis of NMMO and its degradation products 2. but yields rather inaccurate results. which is subsequently titrated with strong acids to a pH of about 4 [110]. Solutions of NMMO exhibit very low conductivity. Usually.1. Different approaches to stabilize Lyocell solutions. however. / Prog. Dif®culties mainly arise from the incomplete reduction of NMMO and from side reactions in this step. Titanium (III) chloride has proved to be an advantageous reductant [111. 26 (2001) 1763±1837 1777 Fig. Austria. [104] with kind permission of Lenzing AG. However. Chemical determination. NMMO is very labile in its protonated form so that it is hardly possible to limit decomposition to an acceptable level. substances. Sci. Precipitation of NMMO as the picrate and subsequent gravimetric quanti®cation is also possible. Sulfuric acid was used as titrant [110]. have been proposed. Adapted from Ref.109]. Apart from chemical determination.112]. approaches based on physical properties of water/NMMO mixtures dominate. most of them working in aqueous media. Furthermore. conductometric determination of NMMO was reported to become feasible after increasing the background conductivity by the addition of a conducting salt. but they are well suited to provide a quick value of the NMMO content in solutions of NMMO with small amounts of impurities. 8. Analysis of NMMO by traditional methods Several simple methods for the quanti®cation of NMMO (1). Polym. 2.T. . The different possible measures against side reactions and their negative effects from the viewpoint of a large-scale pilot plant or industrial production are given in Fig. Most procedures fail in the presence of larger amounts of degradation products or chromophores due to disturbing side reactions or interference with the measurement. 8. Direct acidimetric determination of NMMO by titration with strong acids is dif®cult due to its low basicity. Higher accuracy is provided by the reductometric method. the resulting picrate is highly labile as dry material and tends to decompose spontaneously. Rosenau et al.

Both techniques are also capable of simultaneously analyzing thermal degradation products [114.3. however. HPLC is well suited as the quanti®cation method for a limited number of samples containing NMMO.114]. the refractive index at 508C was used as reference.1778 T. GC is especially suitable if also volatile products are produced [116]. NMMO is a rather labile compound with appreciable oxidative power. The method. leaving the amine oxide in the aqueous phase. is not able to provide results better than rough approximations. NMM and M The main degradation products of 1 are N-methylmorpholine (2) and morpholine (3). The content of NMMO in aqueous solutions can be estimated by density measurements. In general. 2. Detection by GC. as these applications require a quick and robust method with large sample throughput. such as HPLC or GC. Due to the problems discussed above. Far-reaching limitations as to the applicability of instrumental analytical methods result from these properties. and its thermal lability imposes intense oxidative stress on the column ®llings.4. 2. Due to the entirely aliphatic bond system in NMMO. For the NMMO content in the binary system with water the following equation was obtained [110]: NMMO…%† ˆ …n50 2 1:336†=0:168: mix 2.2. only the rather complicated reductive mode can be used. NMM and M is dif®cult. In order to expand the applicability of the method also to higher-melting mixtures having lower water contents. however. and UV-detection requires wavelengths below 195 nm. especially for kinetic investigations or in industrial process control. nearly colorless solutions of NMMO in water with only small contents of impurities. / Prog. This. The application of the traditional HPLC or GC conditions requires separation of the amine products from the excess NMMO. in turn. Rosenau et al. Determination of NMMO by HPLC has been the only available instrumental method until the late 1980s. Analysis of NMM and M as main NMMO degradation products The analysis of NMM (2) and M (3) in the absence of NMMO predominately relies on established techniques. Polym. means rather high requirements for solvent purity. As discussed above. This procedure. utilization as a general analytical approach is limited. and a suitable mode of detection has to be found [113. high requirements on instrumental set-up and analytical approach as well as maintenance. a simultaneous determination and quanti®cation of NMMO.115]. Due to the rather tedious analytical protocol. Simultaneous determination of NMMO. ¯uorescence detection is ruled out. 26 (2001) 1763±1837 Physical determination. In transparent. Determination of NMMO by instrumental analytical methods Handling of the strong oxidant NMMO in analytical procedures has to cope with some inherent troublesome features of the analyte. This can be achieved by liquid±liquid extraction with an organic solvent. for instance. It poses. is again erroneous so that the method of choice is a simultaneous determination of the amines together with NMMO. In most cases only byproducts can be quanti®ed. regardless of the scale of the application. however. . Sci. NMMO cannot be vaporized without decomposition. To use HPLC. Electrochemical detection in the oxidative mode is not feasible. two dif®culties have to be overcome: the column material has to be suf®ciently inert to tolerate the oxidant NMMO. is very dif®cult. a reliable determination is possible by refractometry.

00 19. A distinct progress was made by the application of capillary isotachophoresis with conductometric detection [117]. At a pH of 3.56 70. but could not be quanti®ed. Polym.5. frequently occurring problems with conventional hydrostatic sampling in the analysis of dark-colored . Rosenau et al. First. 26 (2001) 1763±1837 Table 3 Percentage of protonated amine compounds at different pH values in 1 M solutions Compound NMMO-H 1 …pKA ˆ 4:75† NMM-H 1 …pKA ˆ 7:38† M-H 1 …pKA ˆ 8:33† pH 3. On the other hand. NMM and M in the corresponding reaction mixtures was based on HPLC [114]. with the system 4-methylbenzylamine/2-hydroxy-2-methylpropanoic acid (hydroxyisobutyric acid.58 99. pH optimization showed a neutral value …pH ˆ 7† to give best separation results. a simultaneous measurement and quanti®cation of the three compounds is rather dif®cult. An early attempt to tackle the analytical problem of the quanti®cation of NMMO. Capillary electrophoresis (CE) with indirect UV detection at 254 nm in a chromate buffer was also used as the analytical method [118]. This electrolyte makes indirect UV detection at 214 nm possible and allows reliable performance down to a pH of 2. Only nearly complete protonation ensures that the compound can be detected and reliably quanti®ed.53 pH 7. Potassium morpholinopropanesulfonate was used as the leading electrolyte. NMM and M were not separated at this lower pH value.90 99. cf.32 96. although elaborate methods exist for the determination of either NMMO alone or the amine decomposition products alone. In addition.0 84. NMM and M were separated at pH values above 6. Capillary electrophoresis. Table 3. appears to negatively affect the separability of NMM and M [118]. NMM and M can be separated and accurately quanti®ed even in a 1000fold excess of NMMO. tetrabutylammonium perchlorate as the terminating electrolyte. To analyze all of the nitrogen-containing compounds Ð NMMO included Ð in the electrophoretically mobile protonated form.00 pH 4. calculated according to the well-known Henderson±Hasselbalch equation [119]. However.53 1779 pH 8.25 100. This problem was solved by replacing conventionally used background electrolytes.35 68.95 pH 6. / Prog. a rather low pH of the electrolyte is required. Application of capillary electrophoretic techniques have additional practical advantages. no additional component which might interfere with the electrolyte balance was introduced into the system. lowering the pH is an intricate task because of the increasing corrosiveness of the chromate electrolyte.00 100. Thus. In addition. which is positive in terms of complete protonation. NMMO was detected at pH 5. One disadvantage of the method is the failure to quantify NMMO that is not protonated at the conditions applied and therefore does not migrate electrophoretically. which are based on chromate or imidazole.0 98. A reliable quanti®cation of NMM and M even in a large excess of NMMO was achieved and tested on Lyocell process samples. one gradient even nonlinear. HPLC and capillary isotachophoresis.58 95.13 but cannot be detected together with NMMO and vice versa.0 35. Thus.00 pH 5. A typical separation is shown in Fig.0 0.T.0 0.3.95 100. the pH was adjusted to a low value by hydroxyisobutyric acid. HIBA)/18-crown-6. Sci.5 [121]. which gives the percentage of protonated compounds at the respective pH values.99 99. 9. This is shown in Table 3. but merely the concentration of one component of the background electrolyte was increased [120]. the limitations introduced above apply: the method requires a complicated procedure including application of two HPLC systems with gradient elution.00 99.0 5. a decreasing pH value.

the chemical shifts of the individual components and the concentration dependence of the chemical shifts in the respective deuterated solvent must be known. Minor constituents with a content of less than about 5% cannot be reliably detected. Polym. Separation of NMMO. a high sample throughput is no longer a problem thanks to short analysis times. In order to apply NMR to study the decomposition of reaction mixtures of NMMO. are well-suited. 26 (2001) 1763±1837 Fig.1780 T.5. Determination of other degradation products Investigation into the degradation reactions in the system NMMO/water/cellulose must often deal . Rough quanti®cation is done by evaluation of the integral curves in 1H spectra. Rosenau et al. Austria. / Prog. molar ratio 1:3. [121] with kind permission of Lenzing AG. the scope. and from Ref. no sample preparation apart from dilution of the sample to a concentration within the calibrated range is necessary. Second. [120] with kind permission of Walter de Gruyter and Co. Nuclear magnetic resonance (NMR).5:1. 9. This applies especially to reactions in the ®eld of organic synthesis. the latter for mixtures with a water content higher than in NMMO monohydrate. it limited to less complex mixtures containing not more than three to four major components. At present. Table 4 presents the 1H chemical shifts of NMMO and of some of its typical degradation products in deuterated chloroform as the solvent. Adapted from Ref. 10 an illustrative proton spectrum of a reaction mixture containing NMM (2).. 75:1:1) at different pH values of the electrolyte.5 is shown [122]. Both CDCl3 and D2O. Even though conventional NMR spectroscopy does not really have a reputation for being helpful in the analysis of mixtures. NMM and M (molar ratio approx. however. Third. The ratio of the different components can be easily determined from the integral curves. The value of the method lies in its rapidity and broad availability. so that monitoring of reaction kinetics with large sample numbers becomes viable. Sci. capillary electrophoresis can be regarded as the method of choice to separate and quantify NMMO and its degradation products NMM and M simultaneously. it can indeed be used as a quick means to unravel the composition of reaction mixtures involving NMMO. samples due to disturbance of the UV detection by chromophores in the analyte can be almost completely overcome by electromigrative sampling. in Fig. 2. morpholine (3) and 4-formylmorpholine in the approx.

is a rather intricate task since the concentration of individual compounds is extremely low. O±CH2.50 (t. 1H.60 (s. OH) 2. 2H. NH. ±CHO) 2. O±CH2.44 (s. NH. with the determination and identi®cation of decomposition products in very low concentrations.69 (t.90 (s.41 (m. 2H.68 (m. NH) 2. J ˆ 5:3 Hz) 3. 3H.6 Hz) 3. b. Analytical approaches are mostly adapted from methods .66 (t. OH) 3. J ˆ 11. O±CH2.6 Hz) 4. 4H.73 (s. J ˆ 3:6 Hz) 3.11 (dd. O±CH2. 3.21 (s.43 (dt. 2H. O±CH2.4 0 -Dimorpholinomethane Aminoethanol (29) N-methylaminoethanol (30) a 300 MHz. J ˆ 4:6 Hz) 2. N±CH2. important advances will be described in connection with the respective degradation reaction. O±CH2) 8. Rosenau et al.4. J ˆ 11. N±CH2. Sci.4 Hz) 3.78 (dd. 2H. absorption (column) chromatography or ion exchange chromatography. 4H. 1. J ˆ 5:4 Hz) 2.T. such as organic acids derived from 1. N±CH2. J ˆ 0:8 Hz) 3. N±CH3) 2.29 (s.70 (t. J ˆ 4:7 Hz) 3. e. TMS. N±CH2. 2H. J ˆ 4:6 Hz) 2. Chromophores. 3H. J ˆ 3:6 Hz) 1. 1. 2H. / Prog. N±CH2) 3.58 (t. As the analytical approaches cannot be generalized.7. 3.g.79 (t. N±CH3) 3. 4H. in the case of highly hydrophilic material. J ˆ 11. Low-molecular weight compounds. N±CH3) 2. 3H. The determination of low-molecular weight degradation products of NMMO mainly relies on HPLC and GC methods in combination with different detection modes. d values (ppm) in CDCl3 vs. J ˆ 4:7 Hz) 3. N±CH2.71 (t. N±CH2-N.26 (s. J ˆ 5:4 Hz) 3.87 (m.06 (s. b. J ˆ 11. 2H. N±CH2. 2H. 2H.57 (m. and the composition of the reaction mixture might be very complex. In most cases. O±CH2. The analysis of chromophores. 2H. 4H. 2H. N±CH2) 3.4 Hz) 2. 2H. 8H. 4H.4. This can be readily accomplished by extraction in the case of organic-soluble matter. 26 (2001) 1763±1837 Table 4 1 H NMR data of NMMO and major NMMO degradation products Compound NMMO (1) 1 1781 H resonances a 3. 8H.68 (m.40 (t. or by chromatographic techniques. 3H. N±CH2. Polym. O±CH2.38 (dt. 1H. in terms of the structure elucidation.7. and only general references and remarks are given here. J ˆ 5:3 Hz) NMM (2) M (3) 4-Formylmorpholine 4. a separation from excess NMMO will be required.

the harmful effect of decomposition inducers as well as the ef®cacy of stabilizers can readily be evaluated. Sci. / Prog. the approaches will be presented in combination with the discussion of the respective reactive species. A simple example for the application of UV spectroscopy in studies of NMMO degradation reactions is shown in Fig. 10. The most prominent technique.126]. 1H NMR spectrum of a NMMO reaction mixture. CE [127]. and HPLC. some general . This might be accomplished by means of a temperature-controlled UV-cell holder. 11. Many techniques have proved to be useful: IR [124]. However. The chromophore formation in the reaction of NMMO monohydrate with different coreactants at 1208C after 30 min reaction times is investigated: the spectra show differences in the reactivity and a small bathochromic shift of the products with increasing size of the coreactants [122]. Intermediates. which were developed for the analysis of Maillard processes [123]. Rosenau et al. GC-MS [125. No general procedure can be given for the determination of reactive intermediates. Furthermore. In the following.1782 T. cuvettes must be provided with heating and temperature regulation since reaction temperatures from 70 up to 1508C are required. UV spectroscopy is the method of choice to follow kinetics of the `reaction' NMMO 1 coreactant ! NMMO product 1 chromophore. 26 (2001) 1763±1837 Fig. Polym. To apply UV measurements to the NMMO system. which has found the widest applicability thus far. either by speci®c trapping reactions or by analytical techniques. which well illustrates the usefulness despite the simplicity of the method and the possibly oversimplifying assumptions in terms of the underlying reactions. Similarly. on the general understanding that the formation of chromophores is a direct measure of side reactions in the system. However. due to the fact that NMMO reaction mixtures develop a deep color with resulting high absorbance even in short reaction times. Those cuvettes will have to be replaced by1 mm-cuvettes in most cases. where the coreactant can be cellulose or an appropriate model compound. is UV spectroscopy even though it can only provide very limited structural information. the light path in conventional cuvettes with 1 cm thickness might be too long.

rules. ² Presence in suf®ciently high concentrations to ensure a quick reaction with the intermediate. 11. ² Formation of a stable and readily separable trapping product. ² A selective reaction with the intermediate. addition of the trap to the NMMO prior to dissolution of the pulp another one. investigations into the degradation reactions of NMMO. A good trapping agent for reactive intermediates must exhibit the following features. 3. This is additionally complicated by the fact that reactivities at the prevailing elevated temperatures are generally high. Polym. Chromophore formation during reactions of NMMO with coreactants as seen by UV spectroscopy.T. . and formation of chromophores. their mechanisms and products in the Lyocell process will be summarized. which can be extracted from the reaction mixture by organic solvents after dilution with water. Sci. Rosenau et al. As distribution of reagents by mixing is rather ineffective. 26 (2001) 1763±1837 1783 Fig. Side reactions in the NMMO/cellulose system In the present paper. despite of the dif®cult environment. formation of byproducts. The separability can be increased by utilization of less hydrophilic reagents. / Prog. no stabilizing agents were used throughout the experiments mentioned. The terms `reaction' and `reaction mixture' will consequently refer to the system NMMO monohydrate/cellulose or NMMO monohydrate/model compound and to all the chemical processes in this system that cause decomposition of NMMO. must be observed for trapping reactions of short-lived intermediates under the prevailing conditions. application of an inert solvent to dilute the medium and to lower the viscosity might be one solution. This is only possible to a limited degree since the viscosity of the medium strongly restricts transport of reagents. If not stated otherwise. which arise from the peculiar conditions within the Lyocell dope. ² Suf®cient stability under the elevated reaction temperatures and in the presence of the oxidant NMMO.

Hence. Rosenau et al. reveals substantial differences. Relative to the direct cleavage. transfer of two electrons causes heterolytic processes with formation of N-methylmorpholine and hydroxyl ions (Fig. Sci. . the activation actually `prepares' the bond for the subsequent breakage. the electron density at the exo oxygen is lowered. Polym. so that a general classi®cation into homolytic and heterolytic processes appears justi®ed. heterolytic). by protonation. 1. and cleavage with two-electron transfer to the N±O bond (pathway III. 87 kJ/mol for course II. lengthens the N±O bond from about 1.122]. the homolytic cleavage is favored by about 130 kJ/mol. Also a comparison of the activation energies DE # for the elementary step of the cleavage.38 A [48]. With a DE # of 315 kJ/mol for pathway I. 3. Primary steps in the degradation of NMMO: homolytic and heterolytic pathways. with the heterolytic reaction being slightly favored. and 68 kJ/mol for course III. differences in the free reaction enthalpies DRG of the three pathways are signi®cant. see Fig. Thus. the homolytic and the heterolytic pathway differ only insigni®cantly. Protonation at the terminal oxygen. The two latter pathways are the basis of all reactions of NMMO. Protonation weakens the N±O bond which explains the general observation of acidic conditions being detrimental to the stability of NMMO. Through the activation step.6 times as high as that of the homolytic bond ®ssion.36 to approx. This is understandable since this group is the most labile structure in the molecule.1.1784 T. occurrence of the direct decay of protonated NMMO into aminyl radical 4 and a hydroxyl radical is energetically extremely unlikely. for instance by complex formation with metals. / Prog. the N±O bond energy is decreased. homolytic). for Ê instance. In terms of activation energy. 26 (2001) 1763±1837 Fig. by O-acylation or O-alkylation or. and 4. catalyzed by transition metals or reducing agents. 12). cleavage with one-electron transfer to the N±O bond (pathway II. Any degradation reaction of NMMO. starts with cleavage of the N±O bond as the primary step. Such activation process occurs in all transition-metal catalyzed oxidations with NMMO as the oxidant. most common. Degradation of NMMO Ð homolytic versus heterolytic processes The primary degradation step. Cleavage can only occur after `activation' of the terminal oxygen. 12. 12. no matter whether thermally induced. Fission of the activated N±O bond can in principle occur according to three different pathways: direct cleavage (pathway I).6 times as high as that of the heterolytic one. which constitutes a reductive process. and the N±O bond distance is increased. As shown by quantum-chemical computations on the semi-empirical and the ab initio level [51. Cleavage of the N±O bond is always accompanied by a ¯ow of one or two electrons towards NMMO. the activation barrier of the direct bond ®ssion is 3. the heterolytic one by approx. which is largely independent of coreactants. Transfer of one electron initiates the homolytic pathway with the production of 4 besides hydroxyl ions. 480 kJ/ mol.

T. Rosenau et al. / Prog. Polym. Sci. 26 (2001) 1763±1837

1785

Fig. 13. Determination of the occurrence of both homolytic and heterolytic processes in the system NMMO/cellulose by means of a-tocopherol as a probe molecule.

Proof of the simultaneous occurrence of radical and non-radical processes. The reaction steps as shown in Fig. 12 are the initial stages in any decomposition reaction of NMMO. The homolytic cleavage will give rise to subsequent radical reactions whereas the heterolytic cleavage can induce a cascade of non-radical conversions. Of course, the system of subsequent reactions is very complex, so that a homolytic reaction may cause non-radical reactions to follow and vice versa. The classi®cation into two reaction types applies to the primary step of degradation reactions, but also to the whole spectrum of side reactions in the system at a given point of time, which can be regarded as a superposition of radical and non-radical processes. A classi®cation into homolytic and heterolytic side reactions of NMMO is certainly valuable as a systematic approach, but also the practical value became evident when a method to monitor the course of heterolytic and homolytic reactions in the Lyocell system was developed [128]. According to this approach, determination of the ratio between homolytic and heterolytic reactions in the system is accomplished by means of tocopherol derivatives as molecular probes. The application of this method requires several precautions [129] if a quantitation is attempted, but provides a rough estimation in any case. It allows either to take a `snap shot' of the ratio between heterolytic and homolytic processes in the reaction mixture at a given time, or to follow the course of the reactions over time. The procedure is based on the fact that a-tocopherol (vitamin E, 5) is oxidized both homolytically and heterolytically in a selective manner, affording easily distinguishable products at comparable reaction rates: one-electron oxidation produces ®nally para-tocopheryl quinone (7) (for preparation see Ref. [130], detailed NMR data are given in Ref. [131]) via the tocopheroxyl radical (6), whereas two-electron oxidation gives the spiro-dimer of a-tocopherol (9) [132] via an ortho-quinone methide intermediate (8), as shown in Fig. 13. Monitoring the occurrence of both homolytic and heterolytic oxidation processes in the system NMMO/cellulose showed that the total amount of side reactions in the system increased with reaction time, as expected. However, contrary to traditional assumptions, this increase is not mainly due to radical processes, but must be attributed to heterolytic reactions. The amount of radical reactions

1786

T. Rosenau et al. / Prog. Polym. Sci. 26 (2001) 1763±1837

Fig. 14. Homolytic vs. heterolytic side reactions in the system NMMO/cellulose: total amount and ratio.

keeps rather constant throughout the reaction, and the ratio of homolytic to heterolytic reactions decreases. A typical example is shown in Fig. 14: the amount of side reactions in NMMO monohydrate/cellulose (13 wt%) at 1208C over a reaction time of 40 min [133].

3.2. Homolytic reactions in the system NMMO/cellulose 3.2.1. Formation of primary radicals Radical reactions of NMMO are initiated by the homolytic cleavage of the N±O bond with concomitant transfer of one electron. The product of this process is an aminyl radical (N-methylmorpholinyl, 4) which must be considered the primary radical intermediate in homolytic reactions of NMMO. In principle, any one-electron reductant can act as the electron-donating coreactant. In the Lyocell system, the reducing agents are in particular transition-metal ions, see Section 3.2.2. The primary aminyl radical Ð tautomeric forms. Theoretical considerations predict the aminyl radical to occur in an N-centered form 4 and two C-centered tautomers (4a and 4b). The proton loss leading to the formation of 4c or 4d is extremely fast. It is an energetically favored process since deprotonation and resonance stabilization of the radical are superimposed. According to quantum mechanical computations, the stability of the nitrogen-centered radical 4 is almost equal to that of the exo-centered radical 4b, but much greater than that of the ring-centered radical 4a. The C-centered radicals 4c and 4d are much more stable than 4a and 4b, respectively, from which they are obtained by deprotonation. The stability of 4d is by far the highest of the different radical species [122,134] (Fig. 15). Disproportionation. The most prominent reaction of the primary aminyl radical is its disproportionation that yields N-methylmorpholine (2) and N-(methylene)morpholinium cation (10). The latter immediately produces morpholine (3) and formaldehyde (11) upon reaction with water, so that the overall disproportionation reaction is the formation of NMM, M and HCHO from two equivalents of aminyl radical and water. The disproportionation as the main reaction of the aminyl radical was experimentally con®rmed for aqueous and organic solutions of NMMO [122]. The reaction can also be assumed to proceed in Lyocell solutions as soon as the radical has formed. However, it is impossible to conclude

T. Rosenau et al. / Prog. Polym. Sci. 26 (2001) 1763±1837

1787

Fig. 15. The primary aminyl radical: formation and tautomeric forms.

from the products that the disproportionation reaction actually had occurred, since numerous other processes are also generating NMM and M (Fig. 16). Disproportionation of aminyl radicals is usually the result of a dissymmetric radical coupling, i.e. coupling of two different radical tautomers. A symmetric radical coupling of the N-centered aminyl radicals does not occur [135]. This is also true for the NMMO-derived aminyl radical, where recombination of the two most stable tautomers of the aminyl radical, namely 4 and 4d, leads to the formation of the observed non-radical products 2, 3 and 11. However, symmetric radical coupling of the C-centered tautomer 4d was observed, albeit at low temperatures in organic solution [133]. The product of this reaction is 1,2-di(4-morpholino)-ethane (12), a new C±C bond is formed upon this radical recombination. For the ring-centered radical tautomer 4a neither products of dissymmetric coupling nor products of symmetric recombination were found, which is an indication that the species is apparently energetically disfavored. Thus, it will not be formed, or at least its equilibrium concentration will be rather low.

Fig. 16. Disproportionation and recombination of primary aminyl radicals derived from NMMO.

for eclipsing of the p-orbital axis at the nitrogen with the C±H b bond (0 or 1808) hyperconjugation reaches its maximum. but fails to report their exact chemical structure. Using spin traps as an alternative approach was dif®cult insofar as most of the common spin traps have been developed for application under physiological or less harsh conditions. 26 (2001) 1763±1837 Fig.1788 T. EPR spectroscopy is able to con®rm the production of radicals in NMMO/cellulose. see Fig. A de®nite proof of the occurrence of 4 was provided by speci®c trapping reactions with vitamin E derivatives [133. Interaction of g-tocopherol (13) with radicals generates an intermediate g-tocopheroxyl radical. Formulae of spin traps and EPR spectrum of a NMMO/cellulose reaction mixture. Observing the aminyl radical experimentally is very challenging since the species is extremely reactive and thus short-lived. . To con®rm the occurrence of 4 under Lyocell conditions. Sci. 17 [106. Trapping reactions. Direct EPR investigation at ambient conditions is impossible. NMMO was heated to process conditions of about 1008C or above. could not be resolved into its hyper®ne structure due to the effect of the readily solidifying matrix. Thus. which is nearly true for the axial H b in the aminyl radical 4.138]. Trapped 4 and trapped 4a have been observed in small amounts only. With this compound. Consequently. an EPR signal was obtained which. but no EPR signals could be obtained due to the lability of the primary aminyl radical. trapping product 14 is formed by interaction of the trap with the aminyl radical tautomers 4b or 4d.107]. studies require low temperatures (77 K) and generation by g-irradiation of NMM [136]. so that they are unstable under Lyocell conditions. The spin coupling with the axial protons is due to hyperconjugation which actually means p. no hyperconjugation occurs. The low temperature EPR spectra are not well resolved and exhibit a coupling constant of ab ˆ 2:9 mT for H the three methyl protons and a coupling constant of ab ˆ 3:8 mT for two b-standing methylene protons H [137].5-dimethyll-pyrroline-N-oxide (DMPO) and N-tert-butyl-phenylnitrone (PBN). A radical trap that is stable under the reaction conditions and does not decompose is 2. Only the axial b-protons of the methylene groups exhibit coupling.s-spin delocalization from the p-orbital at the nitrogen atom to a pseudo-p orbital formed by the 1s atomic orbitals of the H b atoms. to the widely used spin traps 5. 17. equatorial protons are not re¯ected in the spectrum. which might be due to sterical hindrance of the recombination reaction. While the O-centered form of the g-tocopheroxyl radical has low af®nity towards other radicals. the tautomer with the radical centered at C-5 readily recombines with other radicals present in the mixture. Polym. the C±H b bond lies in the nodal plane of the p-orbital. heated to 1008C with 1% DTBMP. however. For an angle of nearly 908 as is the case for the equatorial methylene protons. This applies.6-di-tert-butyl-4-methyl-phenol (DTBMP). Rosenau et al. and the protons give no coupling in the spectrum. In organic NMMO solutions. Observation by EPR. for instance. / Prog.

and not only in organic solutions of NMMO. Sci. Coupling of the corresponding aminyl radical 4b-D3 produces the bisdeuterated coupling product 14-D2 which ®nally gives the tetradeuterated dimer 9-D4 (Fig. In addition. reduction of the aminyl radical produces NMM (2). The primary aminyl radical 4. oxidation of the aminyl radical . 19). Polym. see Fig. redox processes with coreactants other than the different tautomeric forms can occur. Interestingly. The presence of competitive heterolytic processes was again excluded by using O-methylated trapping agent. This was demonstrated by applying NMMO selectively deuterated at the methyl group (1-D3) as the starting material [139]. In the trapping product 14 as well as in 8 and 9 the additional carbon originates from the exo-CH2 group of the aminyl radicals 4b or 4d. Proof of the occurrence of the primary aminyl radical in organic solutions of NMMO by selective trapping. Since the deuterium can only arise from the methyl group in the starting material NMMO. However. 18. the procedure must be modi®ed since trapping product 14 is thermally unstable above 608C and eliminates morpholine to produce the ortho-quinone methide 8 which in turn dimerizes to the spiro-dimer 9. The fact that no trapping products were found in this case demonstrated unambiguously that the formation of 14 is indeed caused by homolytic reactions involving 4d. but not homolytically. Also the dominating reaction. / Prog. 16. is in fact an intermolecular redox process. In general. is a highly reactive species that immediately undergoes stabilization reactions. disproportionation. the occurrence of the labeled product is a proof of 4b and 4d as intermediates.T. both 8 and 9 are typical products in the chemistry of a-tocopherol (5) which differs from the employed trapping reagent g-tocopherol by an additional methyl group in position 5. O-methylated 13 was employed which would react by electrophilic substitution. 18). but not by competitive heterolytic processes (Fig. with its tautomers 4a and 4b. Rosenau et al. To exclude the possibility that the trapping product 14 was formed by electrophilic substitution involving the carbonium±iminium ion 10 and not by radical coupling. which are all redox processes. The trapping reaction with g-tocopherol (13) is also suitable to proof the occurrence of the primary aminyl radical directly in the Lyocell dope. Redox reactions of the aminyl radical. 26 (2001) 1763±1837 1789 Fig.

if it is assumed that the oxidation potentials of aminyl radical and other oxygen radical species undergo a similar shift upon transfer from neutral aqueous solution to molten NMMO: with 1. the reduction potential of 4 is too low to cause a reaction with NMMO. Sci. 2. A comparison of the standard reduction potential vs. In contrast to its high reactivity towards metal ions.1790 T. The reduction of the aminyl radical 4 is possible by disproportionation as mentioned. 20. Polym.44 in water pH 0). yields the carbonium±iminium ion intermediate 10. NMMO was shown to be largely inert towards different free radicals [104. NHE Ð which is measured in water Ð can provide relative reactivities also for NMMO solutions. NMMO. all oxidations of model compounds Fig. see Fig. 1. pH 7) the redox potential of 4 is larger than that of the superoxide anion radical (0. but smaller than that of the hydroxyl radical (2.31 V in water pH 7. Hence. A reaction of the aminyl radical with the only other available oxidant in the system. which is subsequently hydrolyzed to morpholine (3) and formaldehyde (11). 26 (2001) 1763±1837 Fig. Rosenau et al. but also by involvement of coreactants which are oxidized in turn. can be excluded.47 V (water.142]. Redox reactions of the primary aminyl radical. 20.140]. Evidently.89 V in water pH 7. The oxidation process probably occurs exclusively by disproportionation of 4. such as model compounds or cellulose. / Prog. 19.72 in water pH 0) [141. Proof of the occurrence of the primary aminyl radical under Lyocell conditions by selective trapping (selectively deuterated NMMO as the starting material). .

as very well-known from bleaching chemistry [143±146]. thus. 21. Generation of trace amounts of formic acid in the Lyocell system has been described. can readily be accomplished also by aminyl radical 4. ®nally leading to chain cleavage by b-elimination and thus. Sci. This observation strongly supports the hypothesis that the actual rate-determining step of the cellulose chain cleavage is a b-alkoxy elimination which has an activation energy of 67±72 kJ/mol [51. It is a direct consequence of homolytic reactions. Cellulose chain scission with resulting DP loss is the most important effect of the action of the aminyl radical in the Lyocell system. However.4. or from 570 to 185 during 2 h at 908C [148].52]. and cellulose by hydroperoxyl radicals and the superoxide anion radical. since it is the result of the random attack of the aminyl radical at the cellulose chain. and with aldoses to furnish 2-ketoaldoses [135]. see Fig. Polym. The radical 4 is a strongly electron-de®cient species which. result of the action of the aminyl radical is the formation of formic acid (15) from primary carbohydrate reaction products. but not directly at the keto or aldehyde group. The reaction between morpholine (3) and HCHO (11) was proposed to be another pathway to generate 15 [102]. will react with electron-rich positions in cellulose or model compounds. / Prog. Another. trialkylaminyl radicals react with a-hydroxyacids to give a-ketoacids. analogous to hydroperoxyl radicals. 21. 26 (2001) 1763±1837 1791 Fig. Such a cellulose degradation in NMMO solutions has been most frequently reported [101±104]. it was experimentally con®rmed later that oxidation of formaldehyde by NMMO to either formic acid or carbon dioxide does not proceed [122]. In analogy. albeit indirect. see Section 1. Cellulose chain scission as a consequence of homolytic reactions. to counteract this process is one main task of stabilizers. Typical values given in the literature for solutions without stabilizers added are DP losses from 472 to 177 during 6 h at 1058C [147]. the main result of the action of 4 on pulp will be the random introduction of keto groups into the 2-position of the anhydroglucose repeating units of cellulose. It will. The chain cleavage by elimination occurs statistically. Rosenau et al. Reactions of the aminyl radical with pulp. The activation energy for the cellulose chain cleavage in NMMO at temperatures above 1158C has been determined to be about 69 kJ/mol. a decreased DP. react at the CH-acidic groups in a-position to carbonyl functions. but was attributed to the oxidizing effect of NMMO on HCHO [44].T. For instance. the reduction of the . However.

1792 T. intermediate N-hydroxymethylmorpholine to NMM by formaldehyde in the classical Eschweiler reaction requires high formaldehyde concentrations and elevated temperatures from 130 to 1608C [149]. producing formic acid besides the d-arabino homologue. but not generate it. Generation of formic acid as a result of homolytic primary reactions: formation of HCOOH from NMM and from oxidized cellulosic structures. 22.3. generates acidic groups and thus leads to additional destabilization of the Lyocell mixture. 21). Apart from degradation of NMMO at very high . The formation of formic acid in trace amounts can easily be explained by subsequent reactions of 2-keto structures in cellulose as the primary products of the oxidizing action of 4. Polym. 26 (2001) 1763±1837 Fig. While 2-keto groups along the chain give rise to cellulose chain breakage by b-elimination (see Fig. Sci.2. see Fig. those at the reducing end undergo disproportionation which exhibits some similarities to Cannizzaro-type reactions. The only reaction that would convert larger amounts of N-hydroxymethylmorpholine reductively into NMM under Lyocell conditions is the reduction by formic acid itself in a classical Eschweiler±Clarke reaction which would consume HCOOH. and that a disproportionation of formaldehyde under the process conditions proceeds very slowly. see Section 3. Benzilic acid rearrangement is another reaction of the 2-keto-sugar which. Rosenau et al. Experiments demonstrated that under the process conditions at temperatures up to 1208C formaldehyde is largely inert towards N-hydroxymethylmorpholine. 47 [150]. / Prog. like the generation of 15.

However. / Prog. Sci.2.158±161] and will not be further stressed here (Fig. Table 6 In¯uence of different Fe and Cu concentrations on the starting temperature for the exothermic decomposition. [101] with kind permission of ZELLCHEMING. The formation and reactions of 2-keto-sugar structures. Especially transition metal ions were of concern due to their ready valency changes and the resulting ability to participate in redox processes. NMMO as the oxidant. [104] with kind permission of Lenzing AG. The effect of iron and copper on the stability of NMMO has been studied in greater detail.T. The adverse effect of different metal ions on NMMO stability upon heating for 2 h to 1508C is demonstrated in Table 5. Polym. 26 (2001) 1763±1837 Table 5 In¯uence of metal ions on the stability of NMMO. 3.2. including generation of 15. see Table 6. and from Ref. and that stabilization with antioxidants and complexing agents was an appropriate countermeasure [93±97]. since it is of special importance with regard to their use as construction materials and their corrosive properties. The in¯uence of metal ions The majority of investigations on the chemistry of Lyocell solutions focussed on the effects of metal ions in the system. see Table 7. the ion acts as the reductant. [101] with kind permission of ZELLCHEMING Metal (300 ppm) Ni Ag Cr Co Fe Cu a 1793 NMMO recovery (%) a 90 88 83 79 37 0 Heated for 2 h at 1508C. but mainly due to subsequent reactions of oxidized carbohydrate structures. Adapted from Ref. Rosenau et al. Also the in¯uence of iron traces in the solution on cellulose degradation has been demonstrated. temperatures.4. have been comprehensively studied in the chemistry of pulp bleaching [143±145. Increased concentration of iron or copper drastically decreases the onset temperature of exothermic runaway reactions. already traces of Fe(II) lead to a progressing decomposition in which more Fe(II) is formed. Adapted from Ref. In the reaction of metal ions with NMMO. Hence. This was con®rmed when it was shown that extremely pure Fe(III) had no effect on NMMO [140]. It was realized soon that the subsequent chemistry of transition-metal ions is mainly radical in nature. proving the radical nature of the underlying reactions. Austria Fe (ppm) 0 10 30 60 Tonset (8C) 160 149 144 138 Cu (ppm) 0 3 30 300 900 Tonset (8C) 178 172 157 130 112 . Chapter 3. 22). cf. formation of HCOOH in Lyocell solutions under process conditions is generally not a direct result of NMMO decomposition.

000 62. the reaction of Fe(II) with NMMO has been postulated to generate NMM and `activated oxygen species' [44] or `nascent oxygen' [151] as radical species with appreciable oxidative potential.000 Mz 500.000 Mw/Mn 5. 26 (2001) 1763±1837 Table 7 Effect of Fe on the degradation of cellulose.000 173. .000 23.000 38.000 97. it had been unambiguously established experimentally [140.2 reports on the catalytic action of Fe (III) might be based on materials that contained traces of two-valent iron which initiated the decomposition reactions. [101] with kind permission of ZELLCHEMING Cellulose sample Starting material 16 h/1208C 16 h/1208C/300 ppm Fe Mn 30.000 Mw 165.5 2. Adapted from Ref. In some references. Polym.000 17. Reactions in the system Fe/NMMO. Sci. / Prog. Effect of iron.7 2.152] and Fig. Rosenau et al. 23. However.1794 T.

The catastrophic action of copper on the stability of NMMO Ð it is by far more severe than iron Ð [101] results from the presence of small amounts of Cu (I). but the NMMO-derived radical 4. Polym.3. Sci. and also the ®nal products obtained should be the same. The reactions between NMMO and the iron ion couple even provide an indirect proof of the structure of 4: if the primary radical intermediate in radical reactions of NMMO is species 4. Reactions in the system Cu/NMMO. see also Fig. then both the reduction of NMMO with Fe(II) and the oxidation of NMM with Fe(III) should afford the radical. Rosenau et al. In subsequent reactions.52.140.2. The postulate that the decomposing action of iron originates exclusively in its interaction with dioxygen and the establishment of Fenton. 23. Weiss or Udenfriend cycles [153] can be dismissed since the degrading action of iron is not diminished in the absence of dioxygen. the strong oxidant produced is not an `activated oxygen species'. 24. Effect of copper. Consequently. see Fig. However. see Section 3. Exactly this was observed in experiments [122. or is further oxidized to an carbonium±iminium ion intermediate 10. although oxygen does not in¯uence the primary reaction step between Fe (II) and NMMO. the aminyl radical can either be reduced to NMM (2) by Fe(II).152].122] that the action of Fe(II) in NMMO produces aminyl radicals and releases the oxygen from the N±O bond as hydroxyl ions or water. such as NMMO or acetonitrile.T. which ®nally affords morpholine (3) and formaldehyde (11) after hydrolysis. The driving force is the high hydration enthalpy of Cu (II) with 2123 kJ/mol as compared to that of Cu (I) with only 582 kJ/ mol. 23. theoretically [51. 26 (2001) 1763±1837 1795 Fig. / Prog. This situation changes completely in non-aqueous media. As the . Cu (I) is highly unstable in aqueous solution and undergoes immediate disproportionation into Cu and Cu (II). The initial reaction between Fe(II) and NMMO produces 4 and Fe(III). it may alter the course of subsequent reactions of the aminyl radical.

for instance: [154]).3). hydration enthalpy cannot be provided by the system. The resulting aminyl radical reacts either in a reduction step with excess lowervalent ions.3. or by symproportionation of Cu with Cu(II). which easily undergo changes in valency. 25. The in¯uence of oxygen The concentration of oxygen in the Lyocell dope is rather low. Initial traces of Cu(I) in the NMMO system are produced by reduction of two-valent copper ions by carbohydrates present. The aminyl radical can be oxidized by Cu(II) generating new Cu(I) which again attacks NMMO. In lab-scale Lyocell solutions the oxygen available in the dope corresponds to the rather small amount of physically dissolved gas. Thus copper would be an exception among transition metals insofar as it could react with amine oxides also in the highest-valent state. if indeed a participation of Cu(III) is assumed. the oxygen concentration . or in an oxidation with the higher-valent species produced. However. see Fig. Reactions of lower-valent (M x1) and higher-valent transition metal ions (M (x11)1) with NMMO. whereas no reaction occurs with the metal in the highest oxidation state. and disproportionation does not occur (see textbooks of inorganic chemistry. In the technical process. As these processes are radical in nature. It was also proposed that Cu(II) is capable of directly reacting with NMMO.2. such as degradation of cellulose (see above) or reactions with oxygen present (see Section 3. Cu(I) becomes the more stable species in organic solution. 26 (2001) 1763±1837 Fig. see Fig.157] and the stability of the formed copper (II) amine complexes. However. In general.2. only their rate and the product ratio is affected by the respective metal. it must be considerably smaller than in oxidative bleaching stages of pulping processes where an optimum contact between the pulp and oxygen is required. multiple side-reactions result. Rosenau et al. see Fig. 24. Sci. / Prog. 24. The lower-valent metal ion reacts with NMMO in the primary step. Copper metal is not inert under Lyocell conditions and is slowly oxidized to Cu (II) which undergoes symproportionation with excess metal so that a mixture of Cu(I) and Cu(II) is ®nally obtained. or the oxidation of Mn(II) to manganese dioxide. it should be mentioned that also heterolytic reactions of NMMO with metals are possible Ð albeit less important in the Lyocell system Ð for instance the synthetically widely used reaction with OsO3 to give OsO4 [84±87]. 3. Essentially the same decomposition reactions proceed in all cases. all transition-metal ions. leading to its decomposition into morpholine and HCHO [155]. Obviously. also copper would follow the rule that only lower-valent oxidation stages react with amine oxides.1796 T. Possible reasons for this behavior are resonance stabilization of the oxy-intermediate involving a trivalent state [156. affect the stability of NMMO. Polym. 25.

N-methyl-ethanolamine. N-formyl-dehydromorpholine and 3-oxa-pentanedioic acid. 3-hydroxy-4-formylmorpholine (16) and smaller amounts of hydroxyacetic acid (17) were found as minor products. usually almost unnoticeable processes must be enforced. The latter two must be attributed to reactions with oxygen since they are not formed in its absence. Several other products. seemed to be formed from the major reaction products in subsequent hydrolysis or elimination processes. 26 (2001) 1763±1837 1797 Fig. 26 [122]. which were expected to be oxygenized. low-molecular weight. Contact with atmospheric oxygen is rather unlikely in a largely closed system. The product distribution indicated that the degradation processes which proceed in the absence of . the respective. Sci. This was achieved by working with increased oxygen pressure under otherwise unchanged conditions. excess water is evaporated under reduced pressure.T. 26. Even though the starting concentration in technical Lyocell dopes must be regarded to be very low and though the diffusion coef®cient is rather small in the highly viscous system. Reaction products with oxygen. is even lower: to achieve cellulose dissolution starting from pulp and concentrated aqueous solutions of NMMO. Product 16 as well as its elimination product N-formyl-dehydromorpholine are strongly prone to condensation reactions. Polym. among them ethanolamine. This causes an additional degassing of the dope with consequently lower concentrations of oxygen. see Fig. / Prog. and are therefore a likely source of chromophoric products. Homolytic reactions in the Lyocell system involving dioxygen: experimental approach to analysis and main products identi®ed. Side reactions in the system NMMO involving dioxygen will thus not be dominant. were isolated by extraction and were separated by chromatographic techniques. oxygen has a high reactivity at the elevated process temperature. it is restricted to surface regions. Rosenau et al. The reaction products. hydrophilic compounds. Besides NMM (2) and M (3) as the two main reaction products. and were obtained only in trace amounts. To study reactions with participation of O2 in greater detail. but cannot be neglected. if it occurs.

because oxygen reacts with the positions of the highest spin density available. . Polym. These are the carbons adjacent to the nitrogen in the tautomers 4c and 4d (Fig. Abstraction of a hydrogen at a-positions to the ring oxygen followed by formation of a `classical' ether peroxide would require much higher energy than the reaction with those carbons. which can be regarded as a biradical itself. Rosenau et al. whereas the C-centered tautomers 4c and 4d react with O2 to form the hydroperoxyl radicals 16a and 17a. 27). 27. The reason for this peculiar reactivity is again related to the occurrence of the aminyl radical 4 as the primary intermediate formed upon homolytic cleavage of the N±O bond in NMMO. This is contrary to the conventional behavior of cyclic ethers which are notorious for ready formation of peroxides at a-positions to the ether oxygen. Homolytic reactions in the Lyocell system involving dioxygen: formation of oxygenated degradation products from NMMO. is reasonable. which already carry a radical function. The regioselectivity in the reaction of dioxygen. Sci. Only N-CH2 or N-CH3 groups were oxidized whereas methylene groups in a-position to the ring oxygen remained unaffected. However. Incorporation of oxygen Ð reaction mechanism. all oxidized NMMO products had undergone oxidation at positions adjacent to the ring nitrogen quite regioselectively. reactions with O2 became more prominent. As seen in 16 and 17 and in the trace byproducts.1798 T. The N-centered form of radical 4 is unable to react with dioxygen. / Prog. 26 (2001) 1763±1837 Fig. because mainly NMM and M were formed. oxygen also remain dominant in the presence of O2.

for instance. These spontaneous radical stabilizations are known as Barton-type II reactions in the literature. accounts for the larger amounts of 16 compared to 17. The a-(hydroperoxyl)amines 16a and 17a undergo immediate stabilization in concerted reactions consisting of a sequence of g-proton abstraction.e. In general. 27. Rosenau et al.) The observed products 16 and 17 were formed from 16a and 17a according to this mechanism. 28. which was also found in the above-described trapping experiments. The higher stability of 4d as compared to 4c. These oxidative. i. involvement of oxygen in homolytic reactions in the system NMMO/cellulose will cause generation of `ring-oxygenized' products. In general. / Prog. homolytic processes are accompanied by hydrolytic . is converted into the stable 3-methoxy-4-formylmorpholine upon chromatography with methanol-containing eluents or forms N-formyl-dehydromorpholine by elimination. redox process and rearrangement (Fig. Possible autoxidation products derived from cellulose.T. Polym. ethanolamine and hydroxyacetic acid (17) upon acidic or thermal hydrolysis. 26 (2001) 1763±1837 1799 Fig. 16. 17b produces formaldehyde. Sci. The N-(hydroxyalkyl)-amides 16 and 17b easily undergo subsequent hydrolysis reactions. N-(a-peroxylalkyl)-amines are converted into N-(a 0 -hydroxyalkyl)-amides: prior to the reaction one of two methylene groups adjacent to a nitrogen carries a peroxyl radical function. upon reaction the N-(a-peroxylalkyl) group is converted into an amide structure and a hydroxyl group is concomitantly introduced at the second N-methylene group. compounds which have been oxidized at carbon atoms belonging to the morpholine ring.

g. Rosenau et al. Some major possible pathways are given in Fig. These reactions will also attack carbohydrate moieties present in a manner wellknown from oxygen bleaching chemistry [158±161]. are thus indicative of reactions involving dioxygen. 26 (2001) 1763±1837 Fig. Occurrence of oxidation and fragmentation products of the morpholine ring. the start of typical autoxidation processes is possible. / Prog. ² The main pathway for stabilization of the primary aminyl radical is its disproportionation which ®nally leads to equivalent amounts of N-methylmorpholine.4. ² Homolytic bond cleavage produces the primary aminyl radical N-methylmorpholinyl (4) which exists also in the form of two tautomeric C-centered radicals 4a and 4b. it must be kept in mind that the concentration of dioxygen in the Lyocell system is rather low and that its reaction with the C-centered forms of the primary aminyl radical is by far the most favored reaction path. Summary: homolytic reactions in the system NMMO/cellulose. see Fig. such as hydroxyacids or substituted ethanolamines. are autoxidation processes involving cellulose. Sci. by protonation or by complexation with metal ions. 29: ² Homolytic cleavage of the N±O bond in NMMO requires an `activation'.2. 3. A reaction of peroxyl radicals with the solvent NMMO does not occur [140]. With the generation of peroxyl radicals in the system. 29. which readily undergo changes in valency. steps that cause cleavage of the oxidized heterocycle. Polym.1800 T. ² Transition-metal ions. However. Summary: homolytic reactions in the system NMMO/cellulose The homolytic reactions in the system NMMO monohydrate/cellulose are brie¯y summarized in the following. Autoxidation. morpholine and formaldehyde. apart from the reaction with the aminyl radical. so that the only alternative processes consuming oxygen. 28. which will suppress the occurrence of competitive processes involving dioxygen. catalyze the decomposition of . e.

not metal-catalyzed. i. / Prog. 3. which is cellulose in the Lyocell process or an appropriate model compound in lab-scale experiments. other neat conversions with organic materials have not been found. tetrathiomolybdate [165]. There are three basic mechanisms which cause heterolytic decomposition of NMMO in the Lyocell process: deoxygenation reactions. Pathway III in Fig. such as phosphorous reagents [162]. As mentioned in Chapter 3. but less frequently as deoxygenation of amine oxides. Upon reduction the formal oxidation number of nitrogen changes from -1 in NMMO to -3 in the product. quantitative deoxygenation of NMMO is also effected by organic compounds. Sci. the differences to the homolytic pathway are rather small. The initial step is the reaction of NMMO with the lower-valent metal ion to give the aminyl radical that subsequently can react with both the lower-valent and the higher-valent metal ion. Also autoxidation processes involving carbohydrate structures present might be initiated at higher oxygen concentrations. Polonowski type reactions and autocatalytic decomposition by Mannich intermediates. 12. and hydride reagents [166] or hydrogen [167]. also coreactants. a tendency that comes from organic synthesis. At the same time.1. sodium hydrogen telluride [163]. ² The C-centered tautomers of the aminyl radical react with dioxygen to produce peroxyl radicals that undergo subsequent stabilization to ring-oxygenated products. it became clear that a direct. Rosenau et al. 26 (2001) 1763±1837 1801 NMMO into the aforementioned decomposition products. All of them use inorganic compounds which are good two-electron reductants that are readily oxidized from oxidation stage n to (n 1 2).1. A neat direct reaction of NMMO with organic compounds. it was established that NMMO in organic . All three processes affect not only NMMO alone. are either directly involved in the reaction. trialkylamine±SO2 complexes [164]. Such redox processes are usually seen as oxidations of organic compounds by amine oxides. Deoxygenation of NMMO.3. a coreactant is oxidized. was only observed for special halides and activated alcohols [83±85]. the results are introduction of 2-keto structures into cellulose and random chain scission.T. Heterolytic deoxygenation of NMMO Heterolytic deoxygenations are reductions that cause formation of NMM. Polym.e. requires simultaneous transfer of two electrons onto that bond. without transition-metal catalysts. However. such as acetic formic anhydride [168] or formic pivalic anhydride [169]. This might explain why in early years of Lyocell research a direct heterolytic interaction between NMMO and cellulose was considered unlikely. heterolytic cleavage is the most favored pathway for N±O bond scission in NMMO in terms of both reaction enthalpy and activation energy. Heterolytic reactions in the system NMMO/cellulose Heterolytic cleavage of the N±O bond in NMMO. cf. Later on. the latter case would constitute an intramolecular redox process. The source of these electrons can be a coreacting reductant or another part of the NMMO molecule. With the ®nding of special organic reagents. or they consume reaction products. and why all side reactions occurring in Lyocell solutions were consequently thought to be radical processes. such as cellulose or model compounds. 3. ² The aminyl radical can be reduced to NMM by homolytically oxidizing carbohydrate structures present.3. Several well-established methods for the reduction of NMMO or other tertiary aliphatic amine oxides to the corresponding amines exist.

To achieve a neat heterolytic reduction of NMMO. Heterolytic deoxygenations of amine oxides to the corresponding amines have two steps in common. Rosenau et al.106. 30. the initial reaction with the reductant should . 30. 26 (2001) 1763±1837 Fig. such as those described in Sections 3. a-hydroxy acids to a-ketoacids. solutions and NMMO melts could be used to oxidize aldehydes to the corresponding carboxylic acids. keto-acids and aldaric acids was observed as non-radical side reaction [81. Heterolytic deoxygenation (reduction) of NMMO by different reductants. the formation of minor amounts of alduronic acids. Reduction mechanism and selectivity of NMMO.3. Sci. with glucose as representative of aldoses and lactic acid as example of a-hydroxyacids. The formation of byproducts mainly arises from competing reactions. independent of the huge variety of agents and conditions used.2 and 3.107]. Polym.1802 T. The different reactions that result in a heterolytic deoxygenation of NMMO are summarized in Fig. and aldoses to the corresponding aldonic acids.3. / Prog. In the latter reaction.3. A complexation or covalent chemical modi®cation at the N±O bond is followed by the actual transfer of two electrons to NMMO with concomitant N±O bond cleavage [169].

This step proceeds according to a concerted twoelectron mechanism. Polym. and thus decreases selectivity. the reaction will proceed quite smoothly. so that the reaction becomes less selective. a quite selective process that would not afford signi®cant byproduct formation. but can as well provoke Polonowski-type processes or autocatalytic decomposition of NMMO which give completely different reaction products. the O-conjugated NMMO undergoes reduction upon which NMM is formed and the coreactant is oxidized. With 19 or other carbohydrate reductants. the formic acid moiety is oxidized to carbon dioxide. If only one reductant is available. strong steric hindrance prevents a reaction at the pivaloyl carbonyl group accounting for the highly regioselective attack at the formyl group. attack at the `desired' carbonyl position is less favored. by NMMO with different chemoselectivity. the high reaction temperature additionally increases reactivity of NMMO. in the presence of multiple reactive sites a product mixture will result. The ®rst step of the deoxygenation reaction is the nucleophilic attack of the negatively charged oxygen in 1 at the carbonyl group of the coreactant. such as different carbonyls. carbons carrying hydroxyl groups or other readily oxidizable structures. 26 (2001) 1763±1837 1803 Fig. the actual reduction. 31. Such processes also cause deoxgenation of NMMO. formic pivalic anhydride and cellobiose. can occur. . While the former reagent yields NMM quantitatively without side reactions. In the example of formyl pivaloyl anhydride. the reaction can be forced into an unambiguous course only by the reductant.T. whereas cellobiose is mainly converted into cellobionic acid. superimposed by side reactions at different positions. Sci. Under Lyocell conditions. In 18. This is well illustrated by the reaction of molten NMMO with formic pivalic anhydride (18) [169] and cellobiose (19). as the reductants. see Fig. 31. the carbohydrate model compound reacts less selectively. Rosenau et al. / Prog. Since NMMO exhibits very low chemoselectivity. respectively. In the second step. The different outcome of NMMO deoxygenations depending on the reducing coreactants is thus caused by a different course in the ®rst step of the two-step mechanism. proceed as straightforward as possible to limit the number of positions at which the second reaction step. Oxidation of two different reagents.

g. cellobiose. Oxidation of 3-(5-tocopheryl)-3-hydroxypropanal by NMMO. as side reactions are minimized and only the oxidation of the aldehyde remains dominant. Polym. which might mathematically result from superposition of at least two competing reactions with different kinetic rate-laws [171].1804 T. such as glucose or xylose. the kinetic . Rosenau et al.107]. with good accuracy at lower temperatures and less agreement towards the upper temperature limit [147]. 32. the reaction approaches a ®rst-order kinetics. The overall reaction of pulp with NMMO is described by ®rst-order kinetics over the whole temperature range from 70 to 1308C. The fact that the kinetics does not change substantially with increasing temperature. see Fig. indicates. are converted into the aldonic acids according to ®rst-order kinetics for the model compounds [106. as for instance in the case of cellobiose. Sci. illustrating the low selectivity of NMMO in heterolytic oxidations under Lyocell conditions. / Prog. Oxidation under Lyocell conditions afforded a mixture of products oxidized at all three positions. an aliphatic aldehyde structure. Hence. At temperatures below 1008C. Homolytic competitive processes during the reaction did not occur. The low selectivity of NMMO towards different oxidizable structures was well illustrated with 3-(5-tocopheryl)-3-hydroxypropanal (20) as the coreactant. 32. and a hydroquinone moiety. so that the latter remains a minor pathway even at elevated temperatures. Reactive aldoses. In the case of carbohydrate models with multiple reactive centers. The oxidation of reducing end groups in pulp as measured by the increase in the carboxyl group content was also shown to follow a ®rst-order reaction rate. 26 (2001) 1763±1837 Fig. The compound possesses three readily oxidizable positions. Deoxygenation of NMMO by carbohydrate structures Ð kinetics. even though the reaction rate was different [170]. a benzylic hydroxyl group. e. that the heterolytic oxidation of reducing end groups in pulp is largely favored over heterolytic oxidation of other structures. the consumption at higher temperatures above 1008C obeys zero-order or mixed-order kinetics.

10. to the corresponding carboxylic acids. ®rst First First results. the prominent heterolytic reaction is the oxidation of aldehyde functions. . summarized in Table 8. e. 31. are excluded [7. and the oxidized species. It was demonstrated that the deoxygenation of NMMO to NMM was directly dependent on the DP of the cellulose. Rosenau et al. and thus on the number of reducing moieties [103]. Deoxygenation of NMMO by carbohydrate structures. if other competitive processes. see the analytical chapter 2. by CE or NMR. The same overall equation applies for the heterolytic reaction of NMMO with pulp.g. or titration. The concentration of NMMO decreases according to ®rst-order kinetics for glucose. Such a relation was also found for Fig.1008C) Higher (. by HPLC. especially homolytic reactions. In cellulose. Sci. e.1008C) Lower (. 26 (2001) 1763±1837 Table 8 Comparison of kinetic orders for the consumption of model compounds and NMMO upon mutual heterolytic reaction Kinetic order Consumption of coreactant Consumption of NMMO Temperature Lower (. ion chromatography. The formation of chromophores cannot be taken as a general measure for heterolytic reactions: discoloration is a result of both homolytic and heterolytic processes and can only be directly related to heterolytic reactions if radical processes can be largely suppressed or completely excluded. of reducing end groups.T. as discussed above and shown in Fig.1008C) Simple aldoses First First First First Cellobiose First Mixed First Mixed 1805 Pulp (cellulose) First Approx. and cellulose throughout the relevant temperature range. con®rm the occurrence of the observed reactions. / Prog. 33.e. Linear dependence of NMMO consumption on the number of reducing end groups per molecule in the reaction with carbohydrate model compounds [122]. It should be noted that the determination of reaction rates and kinetics must rely on the exact monitoring of the consumed species. For cellobiose the rate law changes from ®rst order at temperatures up to 1008C to mixed-order at higher temperatures.1008C) Higher (. Polym.g.153]. xylose. The net reaction of heterolytic deoxygenations of 1 by aldehydes or aldoses can be described: NMMO 1 R-CHO ! NMM 1 R-COOH. The consumption of carbohydrate models is paralleled by the consumption of NMMO. i.

33 [106. / Prog. . Generally. the reaction rate is directly proportional to the amount of reducing end groups present. 34. Heterolytic oxidation of cellulose by NMMO: different reaction sites and pathways. 34. If the reacting position is C-2 of anhydroglucose (AHG) units. The heterolytic reduction of NMMO to NMM is the main reaction in the Lyocell system. low-molecular weight compounds up to tetraoses. Slow heterolytic oxidation of carbons carrying hydroxyl groups was also shown by slow conversion and cleavage of cyclodextrins [122]. Polym. 21 for the mechanism. the result is an introduction of a keto group at this position and. Rosenau et al. also hydroxyl groups of cellulose are heterolytically converted into carbonyls to a minor extent. This is proven by the fact that DP loss in the complete absence of homolytic reactions Ð achieved by a large excess of radical quenchers Ð is rendered extremely slow. is the same as in homolytic oxidations by the aminyl radical. Beside this main reaction type.1806 T. 26 (2001) 1763±1837 Fig.170]. additional cellulose chain cleavage by b-elimination may result. This corresponds to the ®nding of NMM as the major degradation product in both technical and laboratory processes. However. but not completely prevented. As a consequence. thus. see Fig. Sci.107. see Fig. the extent of cellulose chain cleavage because of heterolytic oxidations is negligible in comparison to chain scission by homolytic oxidations. see Fig.

thionyl chloride (SOCl2) sulfuryl chloride (SO2Cl2) or sulfur dioxide [177. The absence of radical processes during Polonowski reactions has been demonstrated [173]. Even optimized variants exist. followed by addition of nucleophiles to the resulting iminium ion. acetic anhydride. mostly tri¯uoroacetic acid or its anhydride are used as inducing agents.T. Polonowski reactions are extremely exothermic processes. and an iminium ion is generated. Polym. elimination of a b-proton gives enamines. Even though not tested with cellulose or pulp so far. acetate. The action of NMMO on the hydroxyl groups of cellulose would thus eventually cause formation of 2. see path A in Fig.g. e. but also carboxylic acids themselves and inorganic acid anhydrides and halides. It was shown that NMMO oxidized a-hydroxyketones and a-hydroxyacids to the corresponding 1. so-called modi®ed Polonowski reactions or Polonowski±Potier reactions. cf. a-substituted tertiary amines are obtained. in the course of which the nitrogen is reduced from the formal oxidation stage 21 to 23 and an a-carbon is oxidized from 22 to ^0. 35 [179. Acylation at the exogenous oxygen lowers the electron density along the N±O bond. which allow to conduct the reaction in a more de®ned manner with satisfying product yields [175.3. With the ®nding of more selective inducers. path B in Fig. the synthetic applicability was very limited since the commonly used inducing agent.3-diketo structures rather than only monooxidation at C-2 or C-3. 3. Polonowski type reactions Polonowski reactions have been known for some 70 years [172]. with the broken bond being arranged antiperiplanar to the N±O bond.2-dicarbonyl compounds [82] more rapidly than simple alcohols. Not only carboxylic acid anhydrides and halides as very potent acylating agents can be employed. and facilitates proton abstraction in a-position to the nitrogen. In these modi®cations. The reaction proceeds further with the loss of the respective acid anion. In this step the N±O bond is cleaved. Polonowski reactions are induced by O-acylation of the amine oxides. 35. In the overall process. the resulting a-substituted tertiary amines represent semi-aminals which are labile and decompose into secondary amine and carbonyl compound. Alternatively. In the presence of other nucleophiles. / Prog. The conversions are thus heterolytic `self-oxidations' which do not require external oxidants. hence. and the a-position of the cleaved alkyl substituent is oxidized to a keto function. considerably high bonding energies are released since the labile N±O bond is cleaved and a very stable CyO keto structure is . the amine oxide is dealkylated. Early studies had mainly focussed on elucidation of the mechanisms. Polonowski reactions are intramolecular redox reactions in tertiary aliphatic N-oxides. see Fig. Addition of excess carboxylate in a-position with subsequent N±C bond ®ssion produces the secondary amines or their corresponding amides.176].174]. Upon reaction. Sci. produced a very complex reaction mixture [173.180]. 35.2. Polonowski reactions found some applications in organic synthesis. Rosenau et al. 26 (2001) 1763±1837 1807 Subsequent oxidation of the respective neighboring hydroxyl group is a more prominent result of the introduction of a keto group at C-2 or C-3 in cellulose than chain scission. The high yields in Polonowski±Potier reactions are due to the use of the weakly nucleophilic and weakly basic tri¯uoroacetate which fails to ef®ciently abstract a-protons so that other elimination reactions become dominant.178]. such as phosphoroxychloride (POCl3). With water or hydroxyl ions as the nucleophile. and simultaneous deprotonation from the a-position in a trans-elimination process. weakens this structure. These competitive processes are especially Ca ±Cb cleavages. introduction of a carbonyl in C-2 would accelerate oxidation at C-3 and vice versa. and the term Polonowski type reaction refers to all processes that are inducible by acylation or esteri®cation of the amine oxide oxygen. Reaction mechanism.

such as hydroxyl ions. The a-carbons in the morpholine ring. Rosenau et al. also the second main degradation product of NMMO under Lyocell conditions besides NMM. as one possible heterolytic degradation pathway of NMMO. is consequently: NMMO ! M 1 HCHO. which is ®nally converted into formaldehyde. In the case of NMMO. possessing properties of both a vinyl ether and an enamine. water. Different pathways and products in Polonowski reactions. Thus. While these addition products are stable in organic solutions of NMMO at ambient temperatures. or it adds nucleophiles. or alcohols.3. formed. The reason for the regioselectivity of the reaction in NMMO is still unclear. . 35. Polonowski type processes cause largely selective oxidation of the N-methyl group. the resulting ring-centered carbonium±iminium ion 21 forms dehydro-NMM (22) by proton release. for which a reactivity similar to that of the N-CH3 group should be expected. In contrast to the deoxygenation reactions described in Section 3. / Prog. both oxygen and N-methyl group are detached from the nitrogen in Polonowski type reactions. Reaction with NMMO. can be generated via non-radical pathways. to form 3-hydroxy or 3-alkoxy substituted NMM. path A. 26 (2001) 1763±1837 Fig. Ef®cient cooling and working in diluted non-aqueous solutions are absolute requirements to ensure usability in synthesis. they eliminate the substituent to generate 22 at the elevated temperatures of the Lyocell process.1808 T. Polym. path B). Dehydro-NMM (22). Sci. If the a-carbons in the morpholine ring are affected by Polonowski type reactions (Fig. is strongly prone to condensation reactions and thus possibly a major source of chromophores. The net reaction of such processes. namely morpholine. 36. are less affected. see Fig.1 where only the oxygen is removed. 36. and to avoid an explosion-like course with complete charring of the reaction mixture.

HCOOH/M since these compounds are present under Lyocell conditions. In contrast to the behavior of the monohydrate. if occurring under the conditions used. In organic solutions of non-hydrated NMMO Polonowski type reactions can be induced by any acid halide or acid anhydride. Salt formation between amine and acid. no reaction occurs with NMMO p2. Sci. 36. also carboxylic acids in combination with amines Ð but not the acids alone Ð are able to induce Polonowski processes. Even less reactive anhydrides. Therefore. and gluconic acid …pKS ˆ 3:6† [122] can act as inducer of Polonowski type reactions in molten NMMO. the situation is quite different.T. the reactions proceeds slower. such as phthalic anhydride or benzoic anhydride. pivalic acid …pKS ˆ 5:0†. the inhibiting action of the water should not be due to hydrolysis of the acylating agent. N-methylmorpholine (2) N-ethyl-N. but there is no more acylating agent needed than for the non-hydrated amine oxide. the effect of the only weakly acylating acid is strongly enforced through the amine which acts as a base deprotonating the a-carbon. does not prevent the induction of NMMO degradation. Apparently. Also carboxylic groups in pulp are able to induce Polonowski-type reactions in the presence of 2 or 3. / Prog. even the respective ammonium salts can be employed as inducers. In the case of NMMO monohydrate. The reaction with acid halides and reactive anhydrides is extremely fast and very dif®cult to control due to the limited heat exchange. but due to the blocking of the amine oxide oxygen by hydrogen bonds that results in hindrance of the acylation step. This is especially interesting for combinations of gluconic acid/NMM. Interestingly. Small amounts below 1 wt% are suf®cient to start the reactions. benzoic acid …pKS ˆ 4:2† [173]. which do not induce Polonowski reactions in organic solution. The strength of the acid is apparently not a crucial factor for the Polonowski-inducing activity. This . cause a fast and almost immediate decomposition. Polym. formic acid …pKS ˆ 3:7†. For instance. oxalic acid …pKS1 ˆ 1:3†. With solid NMMO monohydrate. Rosenau et al. Polonowski type reactions in NMMO. any binary acid±amine combination out of the three bases È morpholine (3).5H2O or in the presence of even larger amounts of water. especially at elevated temperatures in the molten state. 26 (2001) 1763±1837 1809 Fig.N-diisopropylamine (Hunig's base) and the acidic components acetic acid …pKS ˆ 4:75†. The reaction proceeds only when such large amounts of acylating agent are added that the excess water is eventually consumed by hydrolysis. gluconic acid/M and HCOOH/NMM.

The ®rst reaction step. is thus a good means to prevent Polonowski type reaction from the beginning. The different means to induce Polonowski type reactions under Lyocell conditions are summarized in Fig. 37. / Prog. gradual . 22. with increasing pH of the mixture. or usage of the respective alkali carboxylates instead of the acids. Rosenau et al. completely prevents the occurrence of Polonowski reactions. regarding the harmful effects of acid generation in the Lyocell system.g. 26 (2001) 1763±1837 Fig. which commence immediately and mostly become uncontrollable. Potential possibilities for both generation of low-molecular acids and acidic groups in pulp exist under Lyocell conditions. Neutralization of the acid by alkali in the system. Different inducers of Polonowski type reactions under Lyocell conditions. 27. 21. As a good example for the destabilization caused by acids it was demonstrated that sulfur-containing radical stabilizers with acid groups adversely affect stability. 28. In contrast to the reactions with acid halides or anhydrides. 37. Neutralization of the acids in the system by suf®ciently strong bases. acylation at the amine oxide oxygen by the acid. Sci. but also the ability of acids to act as inducers of Polonowski type reactions in the presence of amines. Polym. Different pathways for the homolytic and heterolytic formation of acids are discussed above and shown in Figs. the overall stability of NMMO is enhanced because the destabilizing protonation of the N±O bond is prevented. was demonstrated by the effect of a mixture of polyglucuronic acid (1%) [181] and NMM (1%) which rapidly decomposed NMMO under Lyocell conditions [182]. Polonowski processes of NMMO induced by acids normally proceed rather slowly. whereas the corresponding esters have the desired protective effect [147]. by aqueous alkali. not only the increasing acidity in the system which leads to a weakening of the N±O bonds must be considered. Avoiding the input of acidic groups into the Lyocell system is also one reason for the application of propyl gallate Ð instead of free gallic acid Ð as a stabilizer. In addition. so that the reaction products morpholine (3) and HCHO (11) are also released in a slow. is prevented. Hence. e. 31 and 34.1810 T.

Due to its high carbonyl reactivity. trapping as water-insoluble hydroxymethanesul®nic acid. The role of formaldehyde in the Lyocell system Possible formation pathways. 26 (2001) 1763±1837 1811 manner. Occurrence of trace amounts of HCHO was merely conceded for the spinning bath and other aqueous ef¯uents because of subsequent hydrolytic processes.5-dimethylcyclohexa-1. see next chapter. Taeger et al. This appears plausible since the occurrence of formaldehyde must have been assumed to be highly unlikely in Lyocell processes as the compound is extremely reactive under the prevailing conditions and would undergo immediate consumption by reaction with carbohydrate structures present [183]. the autocatalytic decomposition of NMMO. these products have to be removed from the system if the `pure' Polonowski process are to be studied without superimposed competitive reactions. 22). such as the formation of hydrazones.3. 22 [143±145. Apart from its generation from oxidized carbohydrate moieties (cf. 23) was applied in a two-phase system with o-dichlorobenzene as the organic phase and the Lyocell dope as the `aqueous' phase. but merely show its occurrence in the aqueous extract. As indicated above. Polym. NMM (2) and M (3). Fig. cf.158±161]. The direct detection of HCHO in the reaction mixture NMMO/water/ cellulose Ð to verify the presence of formaldehyde under Lyocell conditions Ð proved to be rather dif®cult. 38 [184]. While morpholine originates in the heterocyclic ring structure of NMMO. This approach could thus not eliminate the possibility that HCHO originates from hydrolytic reactions in subsequent steps. Addition of dimedone into the system resulted in the formation of the dimedone-formaldehyde adduct bis(2-oxo-hydroxy-5. were the ®rst to postulate the reaction between formaldehyde and morpholine to N-hydroxymethylmorpholine and its subsequent reduction by excess HCHO to proceed under Lyocell conditions [92. However. the role of formaldehyde as a crucial degradation product and intermediate has been somewhat neglected. formaldehyde in the Lyocell dope has not been considered.3-dione (dimedone. Sci. / Prog. it will immediately react with nucleophiles present. were able to prove the occurrence of HCHO Ð albeit in trace amounts only Ð in solutions of cellulose in NMMO monohydrate. the formaldehyde produced in the system will immediately undergo subsequent reactions. cf. Potthast et al. because the trapping reagents are either unstable under Lyocell conditions or they react with the carbohydrate moieties present in the system. the parallelism in the production of 3 and 11 is independent of the reaction type by homolytic or heterolytic pathways. Fig. becomes dominant very rapidly. the formaldehyde represents the `remains' of the N-methyl group after cleavage and oxidation. Also dilution of the system with water and determination of formaldehyde in the resulting aqueous mixture is not viable. since it would not prove the presence of HCHO in the dope. Apart from these rather rare cases. Virtually all commonly applied reactions to determine aldehydes. 39. in most cases the further course of the reaction is rather dif®cult to study since a competitive process. Rosenau et al. Fig. In contrast.102]. As this reaction is catalyzed by the products of Polonowski processes. semicarbazones or oximes. see Fig.3.5-dimethylcyclohexenyl)-methane (24) [185. has been known since the early stages of Lyocell research. Interestingly. This is shown in Fig. 3. Proof by trapping reactions. 23. The trapping agent 5. are not suitable here. The formation of the two major degradation products of NMMO in the Lyocell process.T. and also the formation of HCHO as the consequence of oxidative degradation of carbohydrate structures had been known from pulp bleaching.186]. the production of formaldehyde (11) always parallels the production of morpholine (3) in the Lyocell system. or reaction with chromotropic acid. which was readily extracted into the inert organic solvent. . The formation of HCHO as one major product of the action of transition metals on organic solutions of N-methylamine oxides was demonstrated [140].

it cannot be excluded that condensation reactions or formation of intermolecular bridges occur at the elevated temperatures during processing. N-(Methylene)morpholinium cations (10) and other carbonium±iminium ions represent highly reactive electrophiles that immediately undergo subsequent stabilization reactions by the addition of nucleophiles. decomposes into the starting compounds so that a chemical equilibrium is established. Reaction of HCHO with the simultaneously formed morpholine produces N-hydroxymethylmorpholine (25) which. 3. Sci.189]. 40. Due to their occurrence in the classical Mannich reaction. In addition to decomposition into morpholine and HCHO. 38.e. / Prog.4. Reaction with the pulp mainly causes hydroxymethylation of hydroxyl groups [187] and generation of methylene bridges. respectively. At higher temperatures. Autocatalytic decomposition of NMMO by carbonium±iminium ions Formation and general reactions of Mannich intermediates.1812 T. However. at the methylene carbon produces N-hydroxymethylmorpholine (25) which will decompose into morpholine and HCHO. This reaction requires protonation beforehand to convert the hydroxyl structure into a better leaving group. Trapping of in situ-generated HCHO in the Lyocell system with dimedone. i. [184] with kind permission of Walter de Gruyter and Co. the addition compound becomes less stable. formation of formaldehyde semiacetals and acetals.3. carbonium±iminium ions are commonly called Mannich intermediates [190]. N-hydroxymethylmorpholine (25) undergoes elimination of water at higher temperatures to form N-(methylene)morpholinium cations (10). respectively [188. transient species. or . a (negatively charged) nucleophile can only react with the C-terminus of the N-methylene structure. and the equilibrium is shifted to the side of the starting material. with the positive charge being centered either at the nitrogen (iminium ion) or the carbon atom (carbonium ion). see Fig. Adapted from Ref. in turn. attack at the nitrogen would produce an ammonium ylide which cannot exist under protic conditions. The N-(methylene)morpholinium cation belongs to the class of carbonium±iminium ions which are resonancestabilized. The concentration of 25 under Lyocell conditions will thus be rather low. Polym. Addition of water or hydroxyl ions. However. Rosenau et al. 26 (2001) 1763±1837 Fig.

The result of this process is thus an aminomethylation of the attacking carbon nucleophile. Reaction of 10 with nitrogen-based nucleophiles yields formaldehyde aminals which are also labile and prone to fragment into 10 and amine. produces stable intermediates. Polym. 26 (2001) 1763±1837 1813 Fig. eliminate water after protonation to regenerate 10. the carbonium±iminium ion 10 can not only be generated by elimination from N-hydroxymethylmorpholine (25). as for instance in the Mannich reaction. Fig. 39. Sci. After formation of a stable C±C bond. the nucleophile cannot be eliminated in a reversal of the addition reaction. but may actually be formed by a variety of different homolytic and heterolytic reactions.T. cf. 40. . In fact. Reaction of 10 with carbon nucleophiles. however. 39. the N-(methylene)morpholinium cation (10) can occur as a precursor in every process which ®nally yields morpholine and formaldehyde. / Prog. In the Lyocell system. Different ways for the generation of HCHO (11) and N-(methylene)morpholinium ions (10) in the Lyocell system. Rosenau et al. see Fig.

Under Lyocell conditions. Both the addition of water to the Mannich intermediate. the absolute concentration of N-(methylene)morpholinium cations (10) in the Lyocell system must be expected to be very low. Carbonium±iminium ions: formation by reaction of HCHO with morpholine. . / Prog. this compound is rather labile and tends to decompose in a reversal of the formation reaction. which consumes the precursor for 10. and reaction with different nucleophiles. 26 (2001) 1763±1837 Fig. and the fragmentation of N-hydroxymethylmorpholine (25) into morpholine and HCHO. 40. Reaction of 10 with morpholine produces dimorpholinomethane. Polym.1814 T. and then ®nally morpholine and HCHO. despite the high number of possible generation reactions. resonance stabilization. consuming 10 itself. Sci. are extremely fast reactions. The preferred reaction path of 10 in the NMMO/cellulose system is the addition of water or hydroxyl ions which yields N-hydroxymethylmorpholine (25). Therefore. Rosenau et al.

a major dif®culty is the selection of the trapping reagent which must be stable under the applied reaction conditions. This represented a problem since Mannich bases readily eliminate the secondary amine group at elevated temperatures to form a. carbonium±iminium ions present in the NMMO reaction mixture will react rather unselectively with all nucleophiles present due to their high reactivity. As mentioned above. Polym. Multiple condensations of the reactive products lead to higher-molecular weight products and deeply colored compounds. 41. also in carbohydrates. Moreover. [184]. e. Reaction of carbonium±iminium ions with carbohydrate structures. making the product range even more complicated. / Prog. might ¯uctuate via enediole intermediates (Lobry de Bruyn± van Ekenstein rearrangement in carbohydrates). 26 (2001) 1763±1837 1815 Fig. This requirement eliminated the application of aliphatic aldehydes as trapping reagents because they react with NMMO (cf.b-unsaturated carbonyl compounds. The yields are rather low since the highly reactive 1. Trapping. temperatures above 1008C and the presence of NMMO as a relatively strong oxidant. among them aldoses or ketoses. Trapping of carbonium±iminium ions in the Lyocell system with 2-acetonaphthone. The dif®culty was overcome by the application of 2-acetonaphthone (26) which reacts with N-(methylene)morpholinium cations (10) to 3-(4-morpholino)propionaphthone (27). Answering the question whether intermediate 10 is indeed present in the system NMMO/ cellulose poses the same problems as the detection of HCHO. aldol condensation or enamine formation. Besides the major pathway of the reaction with water (hydroxyl ions). and a-hydroxyaldehydes.3-dicarbonyl compounds. which is the most abundant good nucleophile present. Fig. The strongly electrophilic carbonium±iminium ion is able to attack CH-acidic positions neighboring a keto. The latter process is important as it causes a chemical modi®cation of the pulp that may ®nally result in nitrogen-containing heterocycles as potent chromophores. and thus the position of the electrophilic attack. in a-hydroxyketones. the reaction with nucleophilic carbohydrate structures will also proceed.192]. the composition of the product mixture is very complex so that the Mannich reaction with a-hydroxycarbonyl compounds is of little value for synthetic purposes. the position of the carbonyl structure. . 42 [193].3-dicarbonyl compound will immediately undergo subsequent reactions. 41. which gives rise to additional byproduct formation [194. This way. The trapping product is stable up to temperatures of 1108C and can be easily separated by extraction into organic media due to the lipophilic naphthene structure. [184] with kind permission of Walter do Gruyter and Co. which constitutes the classical Mannich reaction [191. Sci. i. With a-hydroxy-carbonyl compounds. i. see Fig. the actual mechanism can be explained either as attack at a carbanion or as addition to an enol/enolate. Mannich intermediates react according to a multi-step sequence which formally exchanges the hydroxyl group by a formyl group to produce 1. see Fig.g. As another requirement. Adapted from Ref.195]. the products of the reaction must also be stable and easily isolable. acetal or enamine structure. In most cases.e. Depending on the reaction conditions. With a Mannich reaction as the method of choice to trap the carbonium±iminium ion.e. the occurrence of the carbonium±iminium ions N-(methylene)morpholinium (10) directly in the Lyocell dope could be demonstrated by Potthast et al. Rosenau et al.T. repeated Mannich addition. 30) and tend to undergo self-condensation.

de®nite products have not been identi®ed so far. For 2-keto-structures. 42. It is obvious that the product structures will immediately undergo further condensation reactions. the same pathway. / Prog. Fig. 43. 21. The pathway. However. assumes that cellulose behaves similar to low-molecular weight carbohydrate model compounds. Rosenau et al. Fig.1816 T. because a-carbons in ketones are attacked more readily by carbonium±iminium ions than a-carbons in acetals. 43. Reactions of carbonium±iminium ions (Mannich intermediates) with a-hydroxycarbonyl compounds. as shown in Fig. For the reaction with cellulose. namely attack of N-(methylene)morpholinium cations (10) at C-2. . Incorporation into aromatic structures Ð which means anchoring of chromophores onto the cellulose chain Ð formation of inter-chain links and fragmentation reactions possibly causing chain cleavage are plausible pathways. Sci. the attack of 10 at the neighboring C-3 would occur at a higher rate than the attack at C-2 in genuine cellulose. 26 (2001) 1763±1837 Fig. such as those produced by the oxidative action of the aminyl radical. Polym. Proposed reactions of N-(methylene)morpholinium cations (10) with cellulose and oxidized structures in cellulose. leading to introduction of a one-carbon fragment at C-2. must be supposed. cf.

While Polonowski processes start with O-acylation. The reaction mechanism and the kinetics of the autocatalytic decomposition of NMMO are shown in Figs. 26 (2001) 1763±1837 1817 Fig. In solution the reaction can be controlled by cooling. Reaction mechanism and kinetics. could show that carbonium±iminium ions are even able to quantitatively decompose NMMO into morpholine (3) and HCHO (11) [196. 44. The cationic intermediate resulting from the alkylation step is cleaved in a concerted mechanism. the decomposition is an autocatalytic. The initial step consists of O-alkylation of NMMO (1) by the N-(methylene)morpholinium cation (10) in its C-centered resonance form. and will extremely quickly advance in the following. For .N-dimethyliminium iodide (Eschenmoser's salt) [198].197]. Rosenau et al. the reaction starts immediately. the decomposition of NMMO by carbonium±iminium ions is initiated by an O-alkylation step. and N-hydroxymethylmorpholine (25) is produced. General pathway of the autocatalytic decomposition of NMMO. In every catalytic cycle the labile N±O bond is broken and the very stable CyO bond in formaldehyde is formed. Since morpholine and formaldehyde will regenerate N-(methylene)morpholinium cations (10). An induction of the reaction by stable Mannich intermediates. If suitable precautions are taken. heterolytic process. / Prog. it ful®ls the function of both an initiator and a catalyst. see Fig. and no induction period is observed. Autocatalytic decomposition of NMMO. In 1999 it was demonstrated that Mannich intermediates in the Lyocell system do not exclusively react with water or carbohydrate structures as the nucleophiles. Rosenau et al. The initiation of the reactions thus shows an interesting similarity to Polonowski reactions. The reaction will commence as soon as N-(methylene)morpholinium cations have formed during a short induction period. so that the process becomes highly exothermic. the `alkylating agent' N-(methylene)morpholinium (10) is regenerated. Sci. is also possible. but also with the solvent NMMO which is present in a large excess. In this case. during which the N±O bond is broken and a proton is abstracted from the N-methyl group.T. such as N-methylene-N. The autocatalytic decomposition of NMMO in organic solution or melt can easily be triggered by the addition of a mixture of morpholine and formaldehyde at elevated temperatures. similar to Polonowski type reactions. 44. but is well controllable in organic solution. 45 and 46. The role of the carbonium±iminium ion 10 in the reaction is somewhat dif®cult to de®ne. Through the autocatalytic nature of the reaction. The decomposition reaction can easily adapt an explosion-like course in molten NMMO. but might also generate additional carbonium±iminium ions. only minute amounts of carbonium±iminium ions are required to decompose large quantities of NMMO. As a result of the fragmentation. the latter can form morpholine and formaldehyde. Polym. The former starts a new catalytic cycle by alkylating NMMO. in the melt this is very dif®cult so that in most cases the reaction will become uncontrollable. it can even be used for high-yield conversions in synthetic organic chemistry as it accomplishes a neat and selective deoxygenation and demethylation of NMMO or other N-methylamine-N-oxides.

/ Prog. 45. Large amounts of base.1818 T.1% tri¯uoroacetic acid. instance. (A) NMMO. Rosenau et al. (C) NMMO.4. addition of 0. 1 wt% of Eschenmoser's salt is able to completely decompose NMMO into morpholine and formaldehyde in less than 1 h. inhibit the formation of carbonium±iminium ions from N-hydroxymethylmorpholine (25) by preventing Fig. 26 (2001) 1763±1837 Fig. no additives.1% 1. addition of 0. however. induced and catalyzed by carbonium±iminium ion 10. Sci. Reaction mechanism of the autocatalytic decomposition of NMMO. Small amounts of base accelerate the reaction by supporting proton abstraction from the N-methyl group in the fragmentation step. Polym. 46. Reaction kinetics of the autocatalytic decomposition of NMMO into morpholine and HCHO by 1% Eschenmoser's salt.8-diazabicyclo[5. no additives. . (B) NMMO pH2O. (D) NMMO.0]undec-7-ene (DBU).

Due to the high exothermicity of the reaction. After all. and probably lead to complete decomposition of the reaction mixture. but highly sensitive towards metal ions which quickly generate N-(methylene)morpholinium (10) ions by redox processes. Lyocell dopes can be handled safely and are even used on an industrial scale. see Fig. 45. So the question arises why solutions of cellulose in NMMO are usually stable and not subjected to immediate decomposition as might be expected from the experimental results with carbonium±iminium ions in NMMO melts. Even though the decomposition can be the consequence of numerous different processes Ð all reactions that generate carbonium±iminium ions Ð. the reaction rate for non-hydrated NMMO and NMMO monohydrate are comparable. the autocatalytic decomposition is always a heterolytic process (see Fig. Also with these different inducing agents. The answer is given by the much lower nucleophilicity of NMMO as compared to hydroxyl ions (O-nucleophiles). so that M and HCHO are the main products. A higher water content suppresses the reaction by acting in a way similar to that of larger amounts of bases. with formic acid as the reductant. Effect of the reaction in the Lyocell system. which forms 21 by protonation. In Lyocell solutions. It must be mentioned that in NMMO melts or Lyocell dopes the autocatalytic decomposition by carbonium±iminium ions can only be observed in its initial stages. see Section 3. are able to induce the autocatalytic decomposition of NMMO. Another reaction of carbonium±iminium ions is their reduction to amines. the catalytic cycle continues as shown in Fig. amines or cellulose cannot compensate for its production any more. From the current state of knowledge it seems convincing that the instabilities of Lyocell solutions sometimes observed are only different facets of the same basic mechanism. seems to constitute a contradiction.4. the actual degradation mechanism is the same. both formic acid and N-(methylene)morpholinium ions (10) are present so that their reaction will produce NMM (2). Similar to Polonowski processes. such as when carbohydrate structures are present. Only if the local concentration of 10 reaches such a high level that the consumption by water. and both compounds can undergo multiple faster conversions. . The reaction is a very illustrative example of the close interrelationship between homolytic and heterolytic processes in the Lyocell system. will take over and cover up the heterolytic autocatalytic decomposition. 47. 39). The fact that carbonium±iminium ions are de®nitely present in NMMO/cellulose reaction mixtures on the one hand and exhibit such adverse effects on NMMO on the other hand. the concentration of both reactants is extremely low. will the reaction with NMMO commence. This also explains the observation that NMMO is largely inert towards organic radicals [104. Sci. 45). and consume carbonium±iminium ions by competitive nucleophilic addition. Rosenau et al. However. 26 (2001) 1763±1837 1819 protonation. / Prog. as Leuckardt±Wallach reaction. Therefore. independent of how the carbonium±iminium ions have been formed in the system. Both the ring-centered carbonium-iminium ion 21 and dehydro-NMM (22). even though the inducer/catalyst might have been formed according to homolytic pathways (see Fig. albeit at a much slower rate than the carbonium-iminium ion 10 or Eschenmoser's salt. Polym. amines (N-nucleophiles) or carbanions/enolates (C-nucleophiles). so that occurrence of a reduction of 10 by formic acid in the Lyocell system is by no means a major pathway. This process is known in organic synthesis as reductive amination or. The small amounts of free N-(methylene)morpholinium ions (10) generated will be immediately consumed by the reaction with those good nucleophiles.T. after short time an uncontrolled thermal decomposition.122] Ð which fail to cause formation of 10 Ð. which normally leads to complete charring of the reaction mixture.

5. O-acylation or O-alkylation. 3. low-molecular weight acids. also Fig. Sci. such as polyglucuronic acid. such as gluconic acid or formic acid. Summary: heterolytic reactions in the system NMMO/cellulose. The reactions requires Oacylation and deprotonation of the N-methyl group. e. Fig. cause degradation of NMMO. Under Lyocell conditions. Rosenau et al.g. 26 (2001) 1763±1837 Fig. 48. as well as high-molecular weight acids. can induce Polonowski reaction in the presence of small amounts of bases. ² Polonowski type reactions. Summary: heterolytic reactions in the system NMMO/cellulose The heterolytic reactions in the Lyocell system will be brie¯y summarized in the following.1820 T. mainly into morpholine and formaldehyde. by protonation. cf. 48. besides minor amounts of dehydro-NMM. intramolecular redox processes. Reduction of carbonium±iminium ions by formic acid. 47. but less favored. introduction of keto structures along the chain is also possible. / Prog. ² Heterolytic cleavage of the N±O bond in NMMO requires an `activation step'. Reducing end groups are readily oxidized to carboxylic acids. . Polym. ² Heterolytic deoxygenation (reduction) of NMMO produces NMM with concomitant oxidation of cellulose.3.

which are normally favored over the reaction with the weakly nucleophilic NMMO. might provoke uncontrollable decomposition of the reaction mixture which will produce complete charring. even though the catalyst. in turn. albeit at higher rates.4. the reaction temperature should be kept as . Degradation of NMMO by Mannich intermediates is a non-radical process. which.1. 120 up to 1508C. On the other hand. N-(Methylene)morpholinium ions are highly reactive intermediates that quickly react with nucleophiles. ² The autocatalytic decomposition of NMMO is a highly exothermic process. autocatalytic process. From the present knowledge it is obvious that those reactions are not thermally induced processes. although the concentrations are very low. causing complete decomposition of the reaction mixture (charring).101]. can be described as thermal explosions. in terms of kinetics. In the pertinent literature the term `thermal degradation' of NMMO mixtures is unfortunately not clearly de®ned. ² Both formaldehyde and N-(methylene)morpholinium ions have been shown to be present in the Lyocell dope. Controlled thermal degradation Especially in early years of Lyocell research. 3. Within this temperature interval the degradation reaction of NMMO will be accelerated. Thermal runaway reactions in the Lyocell system are thus the direct consequence of a highly exothermic heterolytic reaction. However. it is suggested to introduce the terms `controlled thermal degradation' for the decomposition at elevated temperature and `uncontrolled thermal degradation' for the explosion-like reactions. but has not yet got out of control. In order to minimize degradation. `thermal degradation' refers to the `exothermic events' which. if highly exothermic. can be produced by both heterolytic and homolytic pathways. is insuf®cient to immediately trap all Mannich intermediates that are generated in the system. The degradation proceeds according to the above discussed homolytic and heterolytic mechanisms. Sci. The reaction starts only if the consumption of carbonium±iminium ions by competitive processes. / Prog. ² N-(Methylene)morpholinium ions and other carbonium±iminium ions decompose NMMO into morpholine and HCHO in a heterolytic. To avoid confusion between the two sides of thermal degradations. 26 (2001) 1763±1837 1821 ² Reaction of formaldehyde and morpholine can yield N-(methylene)morpholinium ions (Mannich intermediates). These carbonium±iminium ions can also be produced by several other homolytic and heterolytic reactions. but a sum of homolytic and heterolytic reactions. any process leading to degradation of NMMO was regarded as a thermal decomposition reaction since the reaction system was a melt and the system temperature was relatively high.2 and 3. On the one hand. Thermal degradation processes The reactions described in the previous chapters have in common that they are more or less `regular' processes that lead from a rather small number of starting materials to a limited number of reaction products via distinct and discernible pathways. Polym. it refers to the degradation of NMMO at elevated process temperatures in the range of approx. which were presented in the chapters 3. so that the reaction quickly becomes explosion-like. 3. it was also indicated that these reactions. can originate in both heterolytic and homolytic processes.4.T. The latter cases have been described as `exothermic events' or `thermal runaway reactions' [98. Rosenau et al. such as water or carbohydrate structures present.3. carbonium±iminium ions.

With the homologous .1822 T. In that reaction.N-disubstituted hydroxylamine and an alkene in a b-elimination process.4). 3NMMO ! 2NMM 1 M 1 CO2 1 H2O [103]. In addition. it has been frequently proposed in discussions that NMMO should undergo a Cope elimination which is a typical reaction of aliphatic amine N-oxides [199. Thus. is only feasible to some extent. First. and also HCOOH is generated in the system as a consequence of oxidative modi®cations. Traces of acids. Polym. the release of CO2. would strongly increase production of morpholine (by Polonowski type reactions and subsequent autocatalytic decomposition by carbonium±iminium ions. Rosenau et al. controlled thermal degradation in the NMMO system should rather be seen as a complex of different homolytic and heterolytic parallel reactions. the Cope reaction is a thermal syn-elimination which requires the molecule to adopt a ®vemembered planar transition state. such as the concentrations of the numerous potential catalysts. However. Therefore. consequently. is rather small. It may be furthermore considered that pulp with high amounts of reducing end groups or oxidizable groups along the chain would favor production of NMM (by heterolytic deoxygenation.3. In general. the evolution of carbon dioxide seems to be largely overestimated for the average degradation of NMMO in the Lyocell process. Hence. describing overall degradation of NMMO into two parts of NMM and one part of morpholine and carbon dioxide. as a consequence of the reduction of carbonium±iminium ions by HCOOH. wherein their ratio is determined by the reaction temperature and the presence of speci®c promoters or catalysts. in contrast.g. the ratio of different degradation pathways.3: the solubility of cellulose and the viscosity of the resulting mixture are among the main limiting factors. see chapter 1.. for instance homolytic reactions or Polonowski reactions. This. Sci.200].1. cf. Fig. the amine oxide is cleaved into an N. with increasing temperature the rate of reactions with higher activation energy will be more profoundly increased than the rate of processes with lower activation energy. 47. see Section 3. is thus only valid for one speci®c case and can only be seen as a rough estimation for the Lyocell system in general. As a summary. six-membered heterocyclic amine N-oxides. however. see Section 3. and thus the spectrum of products.2 and 3. The strong temperature dependence of the reactions and their sensitivity towards even minute amounts of catalysts makes it almost impossible to give an overall reaction equation for the controlled thermal decomposition. depend on the presence of metal ions. it becomes obvious that even a rough approximative overall equation for the NMMO degradation in Lyocell systems is problematic because the reaction system is too complex and depends on too many parameters. Furthermore. This will better support the understanding of the system than overall reaction equations that are inevitably rather in¯exible. however. 26 (2001) 1763±1837 low as possible. does not take place and the results of this work. see Fig. In fact. The reaction given by Lang et al. The N-methyl group is mainly cleaved as HCHO. individual processes. degradation of NMMO solutions can be regarded as a system of parallel reactions. will change with increasing temperature.1). such as N-methylpiperidine-N-oxide or N-methylmorpholine-N-oxide.3. 49. In a crude simpli®cation which neglects the interrelationship of the reactions and participation of individual species in multiple reactions. Therefore. have not been reproduced. e. This reaction. it is extremely dif®cult to generate equal starting conditions for the `parallel reactions' without favoring (disfavoring) one of them by higher (lower) amounts of the respective catalyst. One reference erroneously stated the decomposition of NMMO into NMM and oxygen starting at 778C without other competitive reactions [44].2. / Prog. do not undergo Cope eliminations since they cannot adopt the required transition state geometry.3. A syn-elimination process can thus be excluded as a pathway for the thermal decomposition of NMMO. see Sections 3. acids or other intermediates which act as catalysts.

Both 4a and 22 are subjected to ring cleavage and oxidation of the resulting secondary amine to give N-methyl-N-hydroxy-ethanolamine structures. Uncontrolled thermal degradation Uncontrolled thermal degradation of NMMO or Lyocell solutions occurs if the energy produced by Fig. the radical species must be a different one. while coupling with the equatorial b-protons of the methylene groups does not occur. three equivalent protons and two equivalent protons interacting with the lone electron. During thermal treatment of NMMO in the presence of oxygen (air) and traces of transition metal ions.4. From the present knowledge. Similar NvO radicals are resonancestabilized and are much more stable than. the planar con®guration of the transition state can be attained more readily.T. Section 3.202]. 49. The EPR spectrum indicated the presence of a nitrogen atom. . seven.2. after thermal treatment of NMMO in the presence of iron ions and air (without pulp). 50. and the reaction may proceed [201]. 50. This would in principle agree with the spectrum of the primary aminyl radical 4 which shows couplings with the protons of the methyl group and the two axial b-protons. However. aminyl radicals. or by subsequent reactions of dehydro-NMM (22). radicals have been detected by EPR in several instances [44. cf. in contrast. for instance.2. which then are oxidized to nitroxyl radicals. 26 (2001) 1763±1837 1823 Fig.1.and eight-membered ring systems. Rosenau et al. Possible mechanism for the formation of EPR-detectable radical 28 in trace amounts. sterically hindered nitroxyl radicals are even persistent and widely used as spin labels [203]. since the primary aminyl radical derived by NMMO cannot be detected directly by EPR under ambient conditions or even elevated temperatures due to its instability. General mechanism of the Cope elimination of tertiary aliphatic amine oxides. it appears convincing that the EPR spectrum is caused by radical species 28 which is formed either by subsequent reactions of the C-centered form of the primary aminyl radical (4a). for a possible pathway see Fig. / Prog. Sci. 3. Polym.

The ®rst task was accomplished by thermal treatment of NMMO as a ®ne. such as DTA.1824 T. the monitored reaction kinetics will describe a superposition of various reactions between NMMO and different impurities. respectively. it was demonstrated that the initial step of the thermal degradation of pure NMMO follows second-order kinetics [120]. produce even more heat. The second problem was solved by removal of NMM. [120] with kind permission of Walter de Gruyter and Co. which act as a means of heat exchange and of lowering the concentration of NMMO. Inset: test for second-order kinetics by linear regression of the equation 1=‰AŠ ˆ 1=‰A0 Š 1 unukt: Adapted from Ref. The resulting increase of the system temperature causes acceleration of the reactions that. Sci. see Table 6 [101. Rosenau et al. In the presence of even small amounts of byproducts. Polym. From the thermodynamic point of view the state of a thermal explosion is reached. continuous removal of reaction products). can easily be determined by calorimetric methods. such as NMM or M. which indicates a bimolecular reaction between two molecules of NMMO. p-dibromobenzene as inert reaction medium. the exothermic reactions cannot be compensated by the heat uptake of coolant and system. and preventing the reaction between NMMO and degradation products already formed. M and formaldehyde from the reaction mixture immediately after its formation by ¯ushing the reaction mixture with nitrogen. The temperature `Tonset' where the exothermic evolvement of heat and thus the uncontrolled thermal degradation starts. A second-order reaction is consequently obtained only if NMMO `®nds' no other coreactants than itself. but not exclusively the initial degradation step in the decomposition of NMMO [120]. 51. see Fig. The initial step. There are two inherent problems in studying this initial elementary step: decreasing the rate of the reaction to make monitoring of the kinetics feasible. . thoroughly stirred solution or suspension. A low Tonset means a decreased stability of the mixture. in turn. in inert solvents. the reaction proceeds according to a ®rst-order rate law for NMMO. Hence. The initial step of the thermal degradation of pure NMMO proved to be hard to study. Kinetics of the thermal decomposition of pure NMMO at 1808C …‰A0 Š ˆ 1 mol l21 . unless the presence of those species can be excluded. Tonset has been used as a measure to characterize the stability of NMMO solutions. the effectivity of stabilizers and the decomposing activity of metal ions and other species. 26 (2001) 1763±1837 Fig. so that a reaction between NMMO and the impurities must be assumed as initial step in that case.104]. 51. / Prog. This way.

acids or other catalytically active species as . oxygen. The remaining two-thirds undergo complete degradation. Sci.T. Rosenau et al. amorphous solid [170]. The analysis of the reaction products of uncontrolled thermal degradations of NMMO was intricate because of the extremely complex composition. Polym. morpholine (3) and formaldehyde (11) accounted for roughly one-third of the starting material. The black amorphous remainder is completely charred material. Experimental setup for the degradation and analytical approach towards identi®cation of the products are given in Fig. The major components of the gaseous phase are formaldehyde and carbon dioxide. Analysis of reaction products of the uncontrolled thermal degradation of NMMO. was relatively small. a nearly colorless liquid.e. but is completely miscible with water. 52. mainly into charred remainder. morpholine (3) and two-carbon organic acids. the effect of metal ions. N-methyl-ethanolamine (30). The formation of de®ned products such as ethanolamine (29). Elemental analysis shows a very high carbon ratio with very low hydrogen and oxygen contents. Experimental setup and analytical approach. Product analysis. / Prog. four phases are obtained upon decomposition under normal atmosphere: a malodorous gas phase. besides N-methylmorpholine (2). viscous oil. The different products of the uncontrolled thermal degradation of NMMO are summarized in Fig. a brown. N-methylmorpholine (2). The colorless liquid phase is immiscible with the brown liquid phase and has a lower density. 26 (2001) 1763±1837 1825 Fig. Several minor constituents and other trace products have been identi®ed. The major components are ethanolamine. The brown `organic phase' contains also 2 and 3 besides numerous other compounds. among them nitrogen-containing aromatic heterocycles and a large part of condensation products with higher molecular weight. air or inert gas. i. water and carbon dioxide. In general. and a black. Although the in¯uence of the working atmosphere. 53. 52. N-methyl-ethanolamine and water.

Uncontrolled thermal decomposition of NMMO: in situ-trapping of vinyl ether structures. / Prog. 53. well as the presence of pulp is supposed to be appreciably larger. undergoes immediate elimination and decarbonylative aromatization to a highly condensed Fig. Rosenau et al. The mechanism of the uncontrolled decomposition is extremely complex. Polym. at the high temperatures present. . 54.1826 T. The trapping reagent reacts with vinyl ethers in a Diels±Alder reaction to a primary addition product which. 26 (2001) 1763±1837 Fig. The only species whose intermediacy was shown for the uncontrolled thermal decomposition of Lyocell mixtures are vinyl structures. Trapping of vinyl intermediates. The in¯uence of those factors should be the subject of further studies. Sci. Main products of the uncontrolled thermal decomposition of NMMO. With the trapping agents phencyclone (31) and tetracyclone (32) vinyl ether type structures were trapped in situ in the reaction mixture.

see Fig. aromatic system. Polym. the main byproducts in the Lyocell system are arranged according to their major possible formation pathways in Table 9. The origin of the vinyl ether structures is dif®cult to assess. the method is quite selective for vinyl ethers. / Prog. the trapping product 34a is obtained which undergoes transacetalization with the solvent ethanol to the ®nal product 34. 4. see Fig. It is likely that the high temperatures during the uncontrolled degradation allow also those decomposition processes to proceed. The presence of 34 proves the occurrence of low-molecular weight vinyl ethers in the gas phase of uncontrolled degradation reactions of NMMO. For this reason. 54.T. The local heating by the gas causes local formation of the ortho-quinone methide 8 as the actual trapping reagent. it was not possible by this approach to identify the second ether moiety that was eliminated in the rearomatization step. 55. 55. In the absence of vinyl type structures. reactions in the Lyocell system have been divided into two classes: homolytic (radical) and heterolytic (non-radical) pathways. 26 (2001) 1763±1837 1827 Fig. With the knowledge about different processes in the . Since enamine type structures do not react in a similar way and substituted ole®nes do not undergo rearomatization. Sci. which are thermodynamically strongly disfavored under the usual process conditions. As a summary of the different possible reactions. the hot reaction gases were introduced into an ethanolic solution of 5a-bromo-a-tocopherol (33). Another conclusion is presented in Table 10. However. Vinyl ether structures have also been identi®ed in the gaseous phase. If vinyl ethers are present. Uncontrolled thermal decomposition of NMMO: in situ-trapping of vinyl ether structures in the gas phase. Conclusions and future perspectives Within this review. dimerization to the spiro-dimer 9 occurs. Rosenau et al.

Polym. 23) X Heterolytic by Polonowski type reactions (intramolecular redox reaction of NMMO) (Figs. 40) X Minor product of Polonowsi reactions (Fig. it became clearer which reactions in the Lyocell process must be prevented in order to achieve minimum side reactions and byproduct formation. Thus. the outcome of a more comprehensive understanding of the modes of action that a good stabilizer must exhibit is a better rational design of new. 22) X Parallel to the formation of morpholine and HCHO (Fig. Main degradation products in the Lyocell process related to their different formation pathways Byproduct N-methylmorpholine (NMM. . 2) Formation pathways X Heterolytic by deoxygenation of NMMO. followed by subsequent reactions X Homolytic by oxygen species in autoxidation processes (Fig. more effective agents. 16 and 20) X Homolytic by action of metal ions (Fig. 21) X As a consequence of non-selective heterolytic oxidation X From oxidized carbohydrate structures (Fig. 22) X Release from oxidized carbohydrate structures X Reduction of carbonium±iminium ions by HCOOH (Fig. carbohydrates Chain scission Formic acid CO2 system that cause degradation of NMMO and possible chemical modi®cation of the pulp. 3) HCHO (11) Carbonium±iminium ions (10) N-Hydroxymethylmorpholine (25) Dehydro-NMM (22) Ring-oxidized products Oxidation of coreactants. 27) X Heterolytic by deoxygenation of NMMO (Figs. 44 and 45) X Homolytic by oxidation of the primary aminyl radical (Figs. 47) Morpholine (M. 36) X Reaction between M and HCHO X Reaction of water and carbonium±iminium ions (Fig. 39) X Release from oxidized carbohydrate structures (Fig. 40) X From ring-oxygenized products by elimination X Homolytic by reaction of the C-centered tautomers of the primary aminyl radical with oxygen (Fig. 44 and 45) X Intermediate in Polonowski reactions (Fig.1828 T. Even though side reactions are certainly troublesome inherent features of the system. concomitant oxidation of coreactants X Homolytic by reduction of the primary aminyl radical (Figs. / Prog. 16 and 20) X Homolytic by action of metal ions (Fig. 29) X As a consequence of homolytic attack by aminyl radicals (Fig. 23) X Parallel formation to morpholine (Fig. Sci. 39) X Formation from N-hydroxymethylmorpholine (Fig. 35 and 36) X Heterolytic by hydrolysis of carbonium±iminium ions via Nhydroxymethylmorpholine X Heterolytic by autocatalytic degradation of NMMO catalyzed by carbonium± iminium ions (Figs. when the advantages of the current technology are taken into consideration. 40) X Heterolytic by autocatalytic degradation of NMMO (Figs. 30±32 and 34) X Homolytic by aminyl radicals. 22) X Oxidation of formaldehyde (Fig. they represent a tolerable drawback only. 26 (2001) 1763±1837 Table 9 Conclusions. Rosenau et al.

Why stabilize Lyocell solutions and against which species and reactions? Stabilization against Transition metal ions Oxygen radicals Homolytic reactions in general Acids Formaldehyde Carbonium±iminium ions Heterolytic reactions in general a 1829 Why? Decomposition of NMMO. oxidative modi®cation of pulp. for the recording numerous NMR spectra. radical scavengers Antioxidants. formation of carbonium±iminium ions Possible stabilizer a Complexing agents (bases) Antioxidants. chain scission Autoxidation. Ho®nger. radical scavengers Bases (Formaldehyde quenchers) Good C-nucleophiles (Removal of reductants) Compounds in parentheses will be of limited effectivity only. see Table 10. As a concluding remark. Institute of Chemistry at the University of Agricultural Sciences Vienna. the Lyocell process certainly has brightest future perspectives. Applied research will mainly have to focus on three topics: ² ®brillation tendency of Lyocell ®bers. ² yellowing of Lyocell ®bers caused by chromophores during the production process. radical formation. Despite the need for further studies. including means of prevention or utilization. Rosenau et al. Fig. e. and DI J. modi®cation of pulp Polonowski reactions. oxidative modi®cation of pulp. 26 (2001) 1763±1837 Table 10 Conclusions. / Prog. ² rational design of stabilizers that act in multiple ways. without giving further details: ² identi®cation of the exact structure of chromophores. Sci. Polym.g. material management and chemical additives. as well as . condensation with pulp Autocatalytic decompostion of NMMO. Acknowledgements È The authors would like to thank Dr A. it might be valuable to point out major current problems in the basic chemistry of side reactions that will be tackled by future investigations. ox. cf. by optimized technical measures. ² identi®cation and quanti®cation of oxidative modi®cations along the cellulose chain which are caused by NMMO and its derivatives in the process. chromophore formation Degradation of NMMO. Side reactions will be controlled in the future even better than now. 8. Rohrling. and Lyocell ®ber production can be expected to advance soon to a major source of man-made cellulosic material. ² identi®cation of the structures in which residual nitrogen is incorporated into the ®bers.T. weakening of the N±O-bond Formation of carbonium±iminium ions. both in the reaction mixture and in the ®ber material. chain scission Degradation of NMMO.

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