Lignin reactivity

It is well known from very early studies on lignin reactivity that hydrogen bond formation and other secondary valence forces strongly affect the... 

Resource and manufacturing processes affect the chemical composition and reactivity as well as the geometry of the fibres in plant fibres. Lignin, reactive substances like tannins, resins and tanning agents as well as reactive wood polyoses or smooth surfaces of the elements significantly influence the quality of the bonding and, hence, the later product properties. Furthermore, particle size and slenderness ratio play a role. 

Two laboratories have been involved more recently in the synthesis and characterization of PUs based on unmodified lignins. In both approaches, the trick aimed at enhancing the lignins reactivity consisted in using a diol as third monomer, preferably capable of dissolving the lignin. 

A. Kovalcik, M. Machovsky, Z. Kozakova, M. Koller, Designing packaging materials with viscoelastic and gas barrier properties by optimized processing of poly(3-hydroxybutyr-ate-co-3-hydroxyvalerate) with lignin. Reactive and Functional Polymers, ISSN 1381-5148 94 (September 2015) 25-34. http //dx.doi.Org/10.1016/j.reactfunctpolym.2015.07.001. 

Conversion of Aromatic Rings to Nonaromatic Cyclic Structures. On treatment with oxidants such as chlorine, hypochlorite anion, chlorine dioxide, oxygen, hydrogen peroxide, and peroxy acids, the aromatic nuclei in lignin typically ate converted to o- and -quinoid stmctures and oxinane derivatives of quinols. Because of thein relatively high reactivity, these stmctures often appear as transient intermediates rather than as end products. Further reactions of the intermediates lead to the formation of catechol, hydroquinone, and mono- and dicarboxyhc acids. 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

Chemical Properties. Lignin is subject to oxidation, reduction, discoloration, hydrolysis, and other chemical and enzymatic reactions. Many ate briefly described elsewhere (51). Key to these reactions is the ability of the phenolic hydroxyl groups of lignin to participate in the formation of reactive intermediates, eg, phenoxy radical (4), quinonemethide (5), and phenoxy anion (6) ... 

The aromatic ring of a phenoxy anion is the site of electrophilic addition, eg, in methylolation with formaldehyde (qv). The phenoxy anion is highly reactive to many oxidants such as oxygen, hydrogen peroxide, ozone, and peroxyacetic acid. Many of the chemical modification reactions of lignin utilizing its aromatic and phenoHc nature have been reviewed elsewhere (53). 

Phenols. The first stable ozone oxidation product of phenol in water is ds ds-raucomc acid, which requires - 2 mol O /mol phenol. In practice, larger dosage levels of ozone are required because other ozone-reactive substances are present in most wastes. Ozone oxidation of phenoHc effluents is employed in paper mills, coke mills, oil refineries, and thermoplastic resin manufacture, producing effluents that are safe to freshwater biota (122,123) (see Lignin Pulp). 

Supercritical fluid solvents have been tested for reactive extractions of liquid and gaseous fuels from heavy oils, coal, oil shale, and biomass. In some cases the solvent participates in the reactions, as in the hydrolysis of coal and heavy oils with water. Related applications include conversion of cellulose to glucose in water, dehgnincation of wood with ammonia, and liquefaction of lignin in water. 

The application of lignin as an adhesive is possible in principle. The first attempt needed very long press times due to the low reactivity (Pedersen process) [161]. This process was based on lignin polycondensation under strong acidic conditions, which led to considerable corrosion problems in the plant [161]. The particles had been sprayed with spent sulfite liquor (pH = 3-4) and pressed at 180°C. After this step, the boards were tempered in an autoclave under pressure at 170-200°C, whereby the sulfite liquor became insoluble after splitting off water and SO2. 

Quinone methides have been shown to be important intermediates in chemical synthesis,1 2 in lignin biosynthesis,3 and in the activity of antitumor and antibiotic agents.4 They react with many biologically relevant nucleophiles including alcohols,1 thiols,5-7 nucleic acids,8-10 proteins,6 11 and phosphodiesters.12 The reaction of nucleophiles with ortho- and /iara-quinone methides is pH dependent and can occur via either acid-catalyzed or uncatalyzed pathways.13-17 The electron transfer chemistry that is typical of the related quinones does not appear to play a role in the nucleophilic reactivity of QMs.18... 

Zanarotti, A. Synthesis and reactivity of lignin model quinone methides. J. Org. Chem. 1983, 50, 941-945. 

Leary, G. Miller, I. J. Thomas, W. Woolbouse, A. D. The chemistry of reactive lignin intermediates. Part 5. Rates of reactions of quinone methides with water, alcohols, and carboxylic acids. J. Chem. Soc., Perkin Trans. 1977, 2, 1737-1739. 

---