Quantitative Phosphorus-31 NMR Analysis of Lignins,a New Tool for the Lignin Chemist

A novel quantitative method has been developed for the determination of the various types of hydroxyl groups present in lignins. The syringyl, guaiacyl and p-hydroxyphenyl free phenolic groups, as well as the primary, and the secondary hydroxyl groups (belonging to individual erythro and threo forms of the aryl-glycerol β-O-4 ether strctures) can be quantitatively determined from a ³¹P NMR experiment. This is made possible by phosphitylating lignins with 1,3,2 dioxaphospholanyl chloride, followed by ³¹P NMR spectroscopy, in the presence of a relaxation reagent (chromium acetylacetonate) and an internal standard. The various aspects leading to the development of this technique are discussed together with relevant statistical information pertaining to the reproducibility and quantitative validity of the method. This simple and novel form of spectroscopy may become a valuable resource to the lignin chemist, because it can supply detailed quantitative information about the structure of a soluble lignin sample.     

Characteristics of Dioxane Lignins Isolated at Different Ages of Nalita Wood (Trema orientalis)

Abstract

Nalita (Trema orientalis) is one of the fastest growing trees in the tropical countries. The structural characteristics of lignin isolated at different ages of Nalita wood (Trema orientalis) by acidolytic dioxane method were examined by UV, FTIR, ¹H‐NMR and ¹³C‐NMR spectroscopy, alkaline nitrobenzene oxidation, molecular weight determination, elemental and methoxyl analysis. The data were compared with aspen lignin. The structural analysis revealed that Nalita wood lignin is syringyl‐guaiacyl type. The methoxyl content in Nalita wood lignin was lower than aspen lignin. The C₉ formulas for 30‐months‐old Nalita was C₉H_9.31O_3.13(OCH₃)_1.27, whereas that of aspen was C₉H_8.94O_3.15(OCH₃)_1.47. The weight average molecular weight of Nalita wood lignin was decreased from 36,500 to 25,500 with increasing tree age from 12 to 30 months, whereas weight average molecular weight of aspen was 20,000. Both alcoholic and phenolic hydroxyl group in Nalita wood lignin is lower than aspen lignin.     

Lignins as macromonomers for polyurethane synthesis: A comparative study on hydroxyl group determination

The hydroxyl group contents of four technical lignins [Indulin AT (Meadwestvaco), Alcell (Repap), Curan 27‐11P (Borregaard LignoTech), and Sarkanda (Granit SA)] were investigated in view of their valorization as polyols in polyurethane synthesis. The different hydroxyl group contents were determined by the following methods: titration and ¹H‐NMR, ¹³C‐NMR, and ³¹P‐NMR spectroscopy. The titration method chosen was on the basis of a standard method commonly used to characterize commercial polyols for polyurethanes synthesis. The values of the total and phenolic hydroxyl contents determined by the different techniques were found to be in good agreement. For the total hydroxyl contents, coefficients of variation of 5.6% (Alcell), 3.2% (Indulin AT), 2.3% (Sarkanda), and 6.2% (Curan 27‐11P) were established. For the phenolic hydroxyl contents, a good correlation was observed between data obtained from ³¹P‐NMR and ¹³C‐NMR for all lignin samples, except for the Sarkanda lignin, for which a relatively high coefficient of variation (12.6%) was found. For softwood lignins (Indulin AT and Curan 27‐11P), the phenolic hydroxyl content determined by ¹H‐NMR was always lower than that deduced from ³¹P‐NMR and ¹³C‐NMR spectroscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structural Characterization of the Lignins from the Green and Yellow Bamboo of Bamboo Culm (Phyllostachys pubescens)

Milled wood lignins were isolated from green and yellow bamboo (Phyllostachys pubescens), termed MWLg and MWLy, respectively. The structural features of the lignin preparations and the remaining LCC were characterized by quantitative ¹³C nuclear magnetic resonance (¹³C NMR) spectroscopy and two-dimensional heteronuclear signal quantum coherence NMR (2D HSQC NMR) spectroscopy. The results indicated that the main substructures in MWLg and MWLy were β-O-4 alkyl-aryl ether, resinol, phenylcoumaran, spirodienone, and α,β-diaryl ether, and their abundances per 100 Ar units were 38.2 and 39.8, 6.9 and 6.3, 3.8 and 2.9, 1.7 and 2.1, 0.4 and 0.3, respectively. The S:G:H ratios of MWLg and MWLy were estimated to be 40:54:6 and 51:44:5, respectively. The γ-acylation of green bamboo lignin was 17.22%, lower than that of yellow bamboo lignin (21.12%). Moreover, a flavonoid compound (tricin) was also detected in the MWLg and MWLy. Some carbohydrates remained in the purified MWL preparations, which were considered as the lignin-carbohydrate complexes (LCC).     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 2: Structural Characterization

Extraction of ground spruce sapwood with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min resulted in isolation of galactoglucomannans and aromatic substances, including lignin. The isolated lignin preparations were characterized by spectrometric (UV, FT-IR, ¹H NMR, liquid and solid-state ¹³C NMR), chromatographic (RP-HPLC, HP-SEC, GC-FID, and GC-MS), conventional pyrolysis, thermally assisted hydrolysis, and methylation techniques in tandem with GC-MS, and classical wet chemistry (methoxyl groups, total and phenolic hydroxyl groups, derivatization followed by reductive cleavage—DFRC). The content of β-O-4 bonds in isolated lignins was similar to that in MWL and their proportion decreased with extraction time. The oxidation of isolated lignins and content of total hydroxyl groups were significantly increased with extraction time. The lignin structure underwent condensation and demethylation reactions during hot-water extraction. The induction of new phenylcoumaran substructures was proposed in isolated lignins.     

The Characteristics and Reactivity of Acid-Labile Aryl Ether Units in Wood Lignin

Wood lignin contains significant amounts of acid-labile aryl ether units, which play a significant role in lignin modification or delignification processes. We have evaluated the rate and reaction kinetics on the acid-catalyzed cleavages of aryl ether structures for wood lignin in situ based on the formation of phenolic hydroxyl groups. The content of acid-labile aryl ether units was quite uniform for a variety of softwood wood lignins (～4% per C₉ unit) and it varied appreciably among hardwood species, ranging from 4% for aspen to 9% for beech wood lignin. These variations, however, appear to be related to the content of syringyl units in wood lignin. The reactivity of these reactive aryl ether structures was noticeably higher for the spruce than for the aspen wood lignin. This difference in reactivity, based on the behavior of lignin model compound reactions, can be attributed to the influence of syringyl moieties in aspen wood lignin. It appears that most of the acid-labile aryl ether units in hardwood were associated with the syringy moiety being present as a benzyl unit, which is much less reactive than the corresponding guaiacyl moiety.     

Structural Aspects of Lignins From Eucalyptus Regnans Wood Steam Exploded By the Iotech and Siropulper Processes

Abstract

The lignins extractable by acetone from Eucalyptus regnans wood after steam explosion treatment by either the Canadian Iotech Process¹ or the Australian Siropulper Process² have been examined by ¹³c NMR spectroscopy. Comparison with MWL showed structural changes which are discussed, compared for the two processes and compared with those for another hardwood (aspen) and a softwood (Pinus radiata). IR, MW and elemental analysis data are also discussed.

The structural changes resulting from the two processes are quite similar and dominated by 8-ether cleavage. The modified structures found in E. regnans lignin differ from those found in the lignins from P. radiata and aspen in the amount and variety of reduced side-chain groups and in the amount of demethylation of aromatic moieties. Structural changes include elimination of hydroxy-groups and formation of carbonyl groups, α,β-unsaturation and carbon-carbon linkages.     

Chemical Structure of Residual Lignin from Kraft Pulp

Structural characteristics of wood lignin and residual lignin in conventional and modified kraft pulps were examined employing elemental and methoxyl analysis and ¹³C, ¹H, and ³¹P-NMR. The structural analysis revealed that kraft residual lignin differs significantly from wood lignin while differences between residual lignins in conventional and EMCC® pulps have similar structural characteristics at kappa numbers corresponding to the point where the selectivity of the cook becomes poor. NMR analysis suggested that residual lignin, compared to the wood lignin, is much less reactive towards pulping chemicals due to the low content of aryl ether linkages and the prevalence of condensed type structures.     

The Influence of Pulping Conditions on the Structure of Acetosolv Eucalyptus Lignins

Acetosolv lignins obtained under a variety of pulping conditions as regards acetic acid concentration, catalyst concentration, temperature and pulping time were characterized structurally by elemental analysis, FTIR and ¹H and ¹³C NMR spectroscopy, and determination of methoxyl group content. Increasing catalyst concentration and pulping time favours both the dissolution of lignin (by cleavage of α and β-O-4 bonds) and the occurrence of condensation reactions. Increasing temperature favours the degradation of syringyl units more than of guaiacyl units.     

How Well Do MWL and CEL Preparations Represent the Whole Hardwood Lignin?

Hardwood lignin preparations were isolated using classical milled wood lignin (MWL) and cellulolytic enzyme lignin (CEL) protocols. Furthermore, we managed to produce a lignin preparation of a very high yield, above 90%, with high purity and minimal structural degradation. This was achieved by dissolution and regeneration of milled wood prior to enzymatic hydrolysis, along with the use of 80% dioxane for lignin extraction. This preparation (RCEL-80) yield was about 4.5 and 2.5 times higher than the yields of the traditional MWL and CEL preparations, correspondingly, at the same milling time. The preparations obtained were comprehensively analyzed with state-of-the-art quantitative NMR techniques and wet chemistry methods. CELs were representative preparations for hardwood lignins as the S/G ratios in the CELs were equivalent to those in lignin in situ. Degradation of the main lignin subunits was very low. Importantly, the structures of CELs were independent of the preparation yield and were very similar to the structure of the high-yield lignin, RCEL-80. In contrast, the structures of MWLs were noticeably dependent on the preparation yield, especially when the yield was below 15–20% of total wood lignin. In particular, the S/G ratio increased with increasing MWL yield, but was still lower than the S/G ratios of the whole lignins in situ, even at high MWL yields. The amounts of β-O-4 lignin units in MWL were lower than those in the corresponding CEL preparations. It has been concluded that CEL preparations were representative of the whole wood lignin whereas MWLs represent a fraction with a lower S/G ratio.     

乙酰溴法对小兴安岭碱法杨木黑液提取物成分的研究

衍生化后的还原裂解(DFRC)法作为木质素结构解析的新方法,可以对碱法杨木黑液提取物中大分子结构的β-O-4醚键和α芳基醚键实施选择性的高效断裂.实验采用DFRC法对碱法萃取的杨木木质素进行降解,通过GC及GC-MS,分析研究了小兴安岭碱法杨木黑液提取物的成分和结构.结果表明:碱法杨木黑液提取物中主要包括4类化合物:B...     

Characterization of Lignins Isolated from Alkali Treated Prehydrolysate of Corn Stover

Lignins were isolated and purified from alkali treated prehydrolysate of corn stover. The paper presents the structural features of lignins in a series purification processes. Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy and proton nuclear magnetic resonance spectroscopy were used to analyze the chemical structure. Thermogravimetric analysis was applied to follow the thermal degradation, and wet chemical method was used to determine the sugar content. The results showed that the crude lignin from the prehydrolysate of corn stover was a heterogeneous material of syringyl, guaiacyl and p-hydroxyphenyl units, containing associated polysaccharides, lipids, and melted salts. Some of the crude lignin was chemically linked to hemicelluloses （mainly xylan）. The lipids in crude lignin were probably composed of saturated and/or unsaturated long carbon chains, fatty acids, tdterpenols, waxes, and derivatives of aromatic. The sugar content of purified lignin was less than 2.11%, mainly composed of guaiacyl units. DTGmax of purified lignin was 359 ℃. The majority of the hydroxyl groups were phenolic hydroxyl groups. The main type of linkages in purified lignin was β-O-4. Other types of linkages included β-5, β-β and α-O-4.     

The Lignin of the Diffuse Porous Angiosperm Tree Triplochyton scleroxylon K. Schum with Low Syringyl Content

“Milled wood lignin” was isolated from Triplochyton scleroxylon tree (wawa MWL) and subjected to elemental analysis before and after acid treatment, and to analytical pyrolysis. Both FT-IR and ¹H NMR spectra were recorded. For comparison, lignins from spruce and beech isolated by the MWL, dioxane/HCl (DIL), and Cuene (CUL) techniques were also characterized. The residual carbohydrate content of the lignins was estimated. Wawa MWL is a GS lignin with 88% G and 12% S content. The utility of analytical pyrolysis and FT-IR for lignin classification is discussed. FT-IR spectroscopy, calibrated with data of 50 MWLs (PLS approach), gives reliable results with a minimum of experimental work. The yields of S phenols obtained by pyrolysis has to be multiplied with a factor around 0.5 for correction if the S content of a lignin is low. The cross-linking indices and OH_phen/OH_aliph ratios of lignins increase in the order MWL < DIL < CUL. ¹H NMR spectroscopy is also helpful to recognize the S/G ratio of a lignin.     

Fractionation and Characterization of Water-soluble Hemicelluloses and Lignin from Steam-exploded Birchwood

Abstract

Two crude hemicellulosic fractions, obtained by extraction of steam-exploded birchwood with hot water, were treated with 8% NaOH at 20[ddot]C for 1 and 4h, and subsequently sub-fractionated into four lignin and four hemicellulosic fractions. Acid hydrolysis, alkaline nitrobenzene oxidation, ultraviolet (UV), gel-permeation chromatography (GPC), Fourier transform infrared (FT-IR), and carbon-13 nuclear magnetic resonance (NMR) spectroscopies were used to investigate the chemical compositions and structural features of the fractionated hemicelluloses and lignins. The sugar analyses indicated that xylose was the predominant sugar component in the four hemicellulosic fractions. Due to the autohydrolysis at elevated temperature and lower in acidity during the steam treatment processes, all the four hemicellulosic fractions showed a low degree of polymerization (DP, 38–41), with molecular-average weights between 5620 and 6160. Assignments of all the signals in the NMR spectrum led to the conclusion that the four lignin fractions, which differ from the organosolv lignins obtained from steam-exploded aspen wood meals, are still mainly composed of β—O—4 ether bonds, together with small amounts of less common β—β and β—1 carbon-carbon linkages between the lignin structural units. The weight-average molecular weights were found to be 2250–2620 with the polydispersity of 1.5.     

Effect of Lignin Carbohydrate Complexes of Hardwood Hybrids on the Kraft Pulping Process

Lignin-carbohydrates complexes influence many chemical properties in the wood, such as difficult-to-remove lignin from Kraft pulps at the end of pulping due to the occurrence of lignin carbohydrates bonds. Therefore, this study aimed to study the influence of lignin-carbohydrate complexes on eucalyptus Kraft pulping. Spectroscopic techniques (¹³C NMR and HSQC-2D) were applied for the determination and quantification of lignin-carbohydrate complex (LCC) structures, and then evaluated the effect of LCC on Kraft pulping of eucalyptus hybrids. The analytical tools allowed the identification and quantification of the benzyl ether, γ-ester, and phenyl glucoside linkages of the lignin-carbohydrate complexes in eucalyptus hybrid wood. The glycosidic phenyl and γ-ester linkages are, respectively, more and less significant from the quantitative point of view. Analysis of ¹³C NMR of the samples showed that the eucalyptus hybrid GxGL contained high β-O-4 linkages content and also higher pulping yield than the other samples, suggesting that the linkages between lignin are more important than LCC linkages in pulping.     

Carbon-13 NMR Spectra of Lignins, 10.1 Comparison of Structural Units in Spruce and Beech Lignin

90.7 MHz Carbon-13 NMR spectra of spruce and beech milled wood lignins (MWLs) and comparison with the spectra of their acetates as well as acetylated dehydrogenation polymer (DHP) from coniferyl alcohol reveals detailed information on the constitution of the two lignins. The signals indicative of β-0-4 units are split, due to the occurrence of erythro and threo isomers. In beech lignin erythro β-0-syringyl ethers by far prevail in the β-0-4-linkages. The spectra also provide unequivocal evidence for the occurrence of β-5 and β-β linkages in both spruce and beech lignins, while some anomalies remain in the case of β-1 and α,β-bis-0-4 units. Two-dimensional ¹³C-J(¹H)-NMR spectra of acetylated DHP corroborate the assignment of signals in the spectra of acetylated MWLs.     

Gordon Research Conference on Chemicals and Materials From Renewable Resources

Abstract

This Conference will be held July 2-6, 1984 at Brewster Academy, Wolfeboro, New Hampshire. Among the topics to be discussed are the following: solid state ^iJC NMR spectra of celluloses, ultrastructure ofcellulose fibers - some new aspects, plant cell wall polysaccharides, 13 structural C NMR studies of lignin and lignin-like materials from flash utohydrolyzed wood, isolation of lignins from wood, electron transfer reactions in lignin and pulping chemistry, and structural inhomogeneity of lignin in wood cell walls.     

Effects of Solvation and Ionization on 13C NMR Spectra of Lignin Model Compounds,Spruce Milled Wood Lignin and Kraft Lignin

The effects of alkali and polar aprotic solvent on the aromatic carbons signals in ¹³C NMR (Carbon-13 nuclear magnetic resonance) spectra of lignin model compounds and spruce milled wood lignin (MWL) were studied. It was found that in 1 M aqueous NaOH signal shifts of C-1 and C-4 carbon atoms in the aromatic ring were the most noticeable in lignin models with free phenolic hydroxyl groups, which are ionized under the conditions. A similar effect in the spectra of the studied model compounds was observed in 0.5 M aqueous NaOD-deuterated dimethyl sulfoxide (DMSO) mixture (DMSO: water ratio 3:7 v/v). The model data help explaining changes in the ¹³C NMR spectra of MWL and lignin in situ dissolved in spruce kraft black liquor caused by ionization. In the ¹³C NMR spectra of spruce black liquor the signals of phenolic and non-phenolic lignin units are clearly separated and do not overlap with the signals of the carbon atoms of carbohydrates and other aliphatic products of wood degradation. The data obtained are useful in understanding the important role of solvation and ionization processes leading to lignin solubilization.     

Enhancing water resistance of welded dowel wood joints by acetylated lignin

Low molecular mass acetylated organosolv lignin from wheat straw and from depolymerised low sulphur organosolv wood lignin have been shown to markedly improve both the water resistance and the mechanical performance of welded dowel wood joints. The acetylated oligomers distribution and extent of acetylation of the two lignins were determined by Matrix assisted laser desorption ionization-time-of-flight mass spectrometry. Extensive acetylation was confirmed by CP-MAS ¹³C NMR spectrometry. Force–displacement measurements on welded dowel joints to which acetylated wood lignins were added showed a ductile behaviour. This is due to the interpenetration of the elastic acetylated lignin network into the more rigid composite network of the welded interphase.     

Investigation of oil palm based Kraft and auto-catalyzed organosolv lignin susceptibility as a green wood adhesives

The aim of this study is to highlight the application and potentiality of oil palm based lignins in the synthesis of green phenolic resins. The delignification processes were conducted using Kraft and auto-catalyzed ethanol–water pulping processes. The extracted lignins were characterized using elemental analysis, Fourier transform-infrared, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, molecular weight distribution (M_n, M_w and polydispersity), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained FTIR results revealed that the Kraft lignin contained substantial amounts of guaiacyl units with smaller amounts of syringyl units. The molecular weight of Kraft lignin was 1564 g mol⁻¹ which is higher than organosolv lignin at 1231 g mol⁻¹. The activated free ring position (2.99%) of Kraft lignin was comparatively higher than that of organosolv lignin (2.06%) which was measured using Mannich reactivity analysis. Thermal analysis of Kraft lignin showed higher thermal stability compared to organosolv lignin. The structural and thermal characteristics implied that Kraft lignin had higher potential for the production of green phenolic resins when compared with organosolv lignin.