The Reactions of Lignins with High Temperature Hydrogen Peroxide Part 2. The Oxidation of Kraft Lignin

Holzforschung ◽  
1999 ◽  
Vol 53 (3) ◽  
pp. 277-284 ◽  
Author(s):  
J.F. Kadla ◽  
H.-m. Chang ◽  
H. Jameel
Keyword(s):  
Hydrogen Peroxide ◽  
High Temperature ◽  
Molecular Oxygen ◽  
Kraft Lignin ◽  
Phenolic Hydroxyl ◽  
Hydroxyl Groups ◽  
Peroxide Oxidation ◽  
Alkaline Hydrogen Peroxide ◽  
Phenolic Hydroxyl Groups ◽  
Increasing Temperature

Summary A technical pine kraft lignin was subjected to alkaline hydrogen peroxide oxidation in the presence of DTMPA and molecular oxygen at various temperatures. In the presence of DTMPA the lignin was found to undergo increasing levels of oxidation and degradation with increasing temperature. At 110°C over 80% of the kraft lignin was degraded. Analyses of the degraded lignins indicated that both phenolic and nonphenolic lignin moieties were degraded. At 90°C the addition of molecular oxygen resulted in further lignin demethoxylation, but did not decrease the amount of phenolic hydroxyl groups or hydrogen peroxide consumed. In the absence of DTMPA the hydrogen peroxide was rapidly degraded, and accompanied by only minimal lignin oxidation.

scholarly journals Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2131
Author(s):  
Leonardo Dalseno Antonino ◽  
Júlia Rocha Gouveia ◽  
Rogério Ramos de Sousa Júnior ◽  
Guilherme Elias Saltarelli Garcia ◽  
Luara Carneiro Gobbo ◽  
...  
Keyword(s):  
Experimental Work ◽  
Chemical Structure ◽  
31P Nmr ◽  
Kraft Lignin ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Diphenylmethane Diisocyanate ◽  
Complex Chemical ◽  
Heterogeneous Reactivity ◽  
Phenolic Hydroxyl Groups

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

Effect of High-Temperature Defibration on the Chemical Structure of Hardwood

Holzforschung ◽  
2002 ◽  
Vol 56 (1) ◽  
pp. 51-59 ◽  
Author(s):  
P. Widsten ◽  
J.E. Laine ◽  
P. Qvintus-Leino ◽  
S. Tuominen
Keyword(s):  
High Temperature ◽  
Lignin Content ◽  
Bulk Composition ◽  
Chemical Properties ◽  
Water Extract ◽  
Fiber Surface ◽  
Phenolic Hydroxyl ◽  
Hydroxyl Groups ◽  
Surface Chemical ◽  
Alkyl Aryl

Summary The present paper aims at elucidating the effect of high-temperature defibration at different temperatures on the bulk and surface chemical properties of defibrated birch, aspen and eucalypt. The results indicate that defibration of these hardwoods results in partial depolymerization of fiber lignin via (homolytic) cleavage of interunit alkyl-aryl (β-O-4) ether bonds. This increases the phenolic hydroxyl content and produces relatively stable (phenoxy) radicals. Syringyl-type lignin is more extensively depolymerized than guaiacyl-type lignin. Defibration generates water-extractable material, which is enriched in hemicellulose-derived carbohydrates and has a substantial content of aromatic compounds rich in phenolic hydroxyl groups. The amount of water-extract and the extent of lignin interunit ether bond cleavage increase with an increase in defibration temperature. The differences between various hardwood species in this respect are small. The surface chemical composition of the fibers differs considerably from their bulk composition, but is not significantly influenced by variations in defibration temperature. Lipophilic extractives cover a large portion of the fiber surface, while the lignin content of lipophilic extractives-free fiber surfaces is 2–3 times as high as the bulk lignin content of the fibers.

Methylation of Phenolic Hydroxyl Group and Demethylation of Anisoles

2009 ◽  
Vol 2009 (4) ◽  
pp. 229-230 ◽  
Author(s):  
Nobuhiro Sato ◽  
Hiroyuki Endo
Keyword(s):  
Microwave Heating ◽  
Room Temperature ◽  
Reverse Reaction ◽  
Phenolic Hydroxyl ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Phenolic Hydroxyl Groups ◽  
Phenyl Ethers ◽  
Methyl Phenyl

A mild methylation of phenolic hydroxyl groups with iodomethane was enabled in the presence of sodium bis(trimethylsilyl)amide at room temperature. The reverse reaction, namely demethylation of methyl phenyl ethers, was easily achieved by microwave heating with neat iodotrimethylsilane.

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