Simulated autohydrolysis of aspen milled wood lignin in the presence of aromatic additives. Changes in molecular weight distribution

The reactions between aspen milled wood lignin (MWL) and 2-naphthol, resorcinol, and p-hydroxybenzoic acid were studied under simulated autohydrolysis conditions. The material after the reaction was separated into a dioxane-insoluble fraction (DI), a dioxane-soluble but ether-insoluble fraction (DSEI), and an ether-soluble fraction (ES). In the absence of additive, the lignin first depolymerized and remained solvent soluble, then repolymerized to become insoluble. With 2-naphthol as additive, the amount of DI lignin decreased proportionally to the amount of additive present. When more than 0.1 mole of 2-naphthol/C-9 unit was present, no DI lignin was formed, that is, all the lignin was soluble. Gel permeation chromatography studies indicated that the additive was acting effectively as a blocking agent, preventing lignin repolymerization. Small amounts of resorcinol acted as a repolymerizing agent since two or more fragments of lignin could readily condense with a molecule of the very active additive. As a result of this bridging effect, the amount of DI lignin increased. As the amount of resorcinol was increased, it behaved more like a blocking agent and a reduction in the amount of DI lignin was observed. The presence of a large excess of resorcinol resulted in the formation of soluble lignin only. The molecular weight distributions supported the proposed dual role of resorcinol as a bridging or blocking agent. The use of an excess of p-hydroxybenzoic acid prevented the formation of DI material and resulted in low molecular weight soluble lignin.     

Solution‐state NMR analysis of hydroxymethylated resorcinol cured in the presence of crude milled‐wood lignin from Acer saccharum

Resorcinol‐formaldehyde adhesives can reinforce stress fractures that appear from wood surface preparation. Researchers have found that applying the resorcinol‐formaldehyde prepolymer, hydroxymethylated resorcinol, to the surface of wood improves the bond strength of epoxy and polyurethane adhesives to wood. Hydroxymethylated resorcinol is thought to plasticize lignin components and stabilize stress fractures through reactions with lignin subunits and hemicelluloses in wood. In this study, a dilute solution of hydroxymethylated resorcinol (HMR) is cured in the presence of a crude milled‐wood lignin (cMWL) from Acer saccharum and subsequently dissolved in dimethylsulfoxide‐d₆ to delineate reactivity with lignin and O‐acetyl‐(4‐O‐methylglucurono)xylan using solution‐state NMR spectroscopy. ¹H–¹³C single‐bond correlation NMR experiments revealed that the HMR only formed 4,4′‐diarylmethane structures with itself in the presence of the cMWL; the 2‐methylols that formed remained free and did not crosslink with resorcinol. Cured HMR resin formed both 4,4′‐ and 2,4‐diarylmethane structures, confirming that the presence of lignin and O‐acetyl‐(4‐O‐methylglucurono)xylan hinders crosslinking at the C‐2 position. No evidence of reactivity between HMR and lignin subunits was found. New peaks consistent with ester linkages were observed in ¹³C‐NMR spectra of the cMWL sample treated with HMR that may be attributable to HMR moieties condensing with glucuronic acid substituents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45398.     

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.     

Dissolution of Wood with Acetyl Bromide Solutions-Reactions of Lignin Model Compounds

A Pinus radiata refiner mechanical pulp (RMP) sample and a range of lignin model compounds were treated with a solution of 25% w/w acetyl bromide (AcBr) in acetic acid to assess the reactions which take place during the dissolution of wood with the AcBr solution. The lignin model reactions were also carried out in solutions to which 4% w/w perchloric acid was added. The RMP sample gave a product which contained 9.2% bromine, and was severely degraded to low molecular weight products, the polysaccharides more so than the lignin fraction. The reactions of the lignin model compounds with AcBr included O-acetylation of phenolic and aliphatic hydroxyl groups, cleavage of β-ether bonds, C-acetylation of aromatic rings, particularly in positions para to methoxyl groups, demethylation of aromatic methoxyl groups and probable replacement of benzyl alcohol groups by bromine functions. The reactions were accelerated by perchloric acid, and the rates appeared to decrease in the order O-acetylation π bromine substitution >> β-ether cleavage π C-acetylation > demethylation. It is concluded that dissolution of wood in the AcBr solution is a consequence of depolymerisation of the polysaccharides and lignin, and acetylation to give products which would be soluble in the reaction medium.     

Quantitative Phosphorus-31 NMR Analysis of Six Soluble Lignins

By using a set of lignin samples, which have been subjected to thorough analyses by the international wood chemistry community, the recently developed quantitative method of ³¹P NMR spectroscopy was comprehensively examined. The values of total phenolic hydroxyl groups and those of total hydroxyl groups were found to favourably compare with those obtained by other laboratories, applying independent methods of analysis. Furthermore, the application of quantitative ³¹P NMR spectroscopy offered additional detailed structural information for the examined lignins which was in accord with literature accounts for similar wood species and lignin preparations. More specifically, the steam explosion lignins from aspen and yellow poplar woods and that produced by ball milling/enzyme hydrolysis of cottonwood were found to contain relatively high amounts of β-O-4 structures. In contrast, the kraft, organosolv, and the acid hydrolysis processes were found to induce significant chain scission on the resulting lignins. Ball milled cottonwood lignin contained the highest frequency of β-O-4 bonds and the lowest amount of free phenolic hydroxyls. The erythro form of β-O-4 structures were invariably predominant in the lignins from aspen, yellow poplar and cottonwood, in accord with the conclusions of previous reports on hardwood lignins. Thus, the application of quantitative ³¹P NMR spectroscopy offered the detailed chemical composition of the examined lignins.     

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.     

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.     

Methanesulfonic acid-catalyzed additions IV. Additions to methyl linoleate

Varied aromatic compounds including phenol,o-chlorophenol, 2-naphthol, resorcinol, methyl salicylate, anisole, phenetole,p-toluenethiol,p-chlorobenzenethiol and 2-napthalenethiol were added to methyl linoleate. Using methanesulfonic acid as a solvent-catalyst the additions took place as readily as to oleic acid in previous experiments. The recovery of mono-adducts, however, was complicated by the presence of di-adducts and presumably polymeric material. As observed in the earlier oleic acid studies, evidence for the formation of ether intermediates was obtained. The only identified products from arylthiol additions were thioethers. Presented at the AOCS Meeting in Minneapolis, 1963. A laboratory of the E. Utiliz. Res. & Dev. Div., ARS, USDA.     

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.     

Separation and Structural Characterization of Lignin from Hybrid Poplar Based on Complete Dissolution in DMSO/LiCl

In this paper, the physicochemical properties and structural features of six lignin preparations separated with a total dissolution of ball-milled wood in dimethyl sulfoxide and lithium chloride (DMSO/LiCl) followed by extraction with ethanol/water were investigated. These isolated lignin fractions were characterized using wet chemical analysis, FT-IR, and ¹H and¹³C-NMR techniques. Experimental results showed that separated lignin preparations were relatively free of associated polysaccharides. These lignin fractions were classified as guaiacyl-syringyl lignin type: mainly composed of guaiacyl units with noticeable amounts of syringyl units and fewer p-hydroxyphenyl units. The molar ratio of non-condensed guaiacyl units to syringyl units (G/S) decreased as the ratio of LiCl to poplar weight increased. The results also showed that these lignin preparations consisted mainly of β-O-4 ether bonds combined with small quantities of β-β′ and β-5 carbon-carbon linkages. Furthermore, considerable amounts of esterified p-hydroxybenzoic acids and minor amounts of esterified p-coumaric acid were also detected in these lignin fractions.     

Carbon-13 NMR Spectra of Lignins, 9. Spin-Lattice Relaxation Tines (T) and Determination of Interunit Linkages in Three Hardwood Lignins (Alnus Glutinosa,Corylus Auellanus and Acer Pseuooplatanus)

Abstract

The spin–lattice relaxation times (T₁) of the twelve most abundant carbon atoms in acetylated milled wood lignin (MWL) from hazelnut (Corylus avellanus) have been determined by the progressive saturation pulse Fourier transform (PSFT) technique. T₁ values below 0.5 s have been found for the aliphatic carbon atoms in the C₃ side chains, while substituted aromatic, carbonyl and CH₃ carbon atoms in methoxy and acetyl groups have T values ranging between 1 and 3 a. From these results a quantitative determination of interunit linkages in lignin may be possible from car-bon-13 spectra with pulse interval times of at least 3 s.

Furthermore, the carbon-13 NPIR spectra of three acetylated hardwood It MWLs, from black alder, hazelnut and mountain maple, have been recorded at 90.7 MHz. Five interunit linkages, β-0-4, α, β–bis-0-4, β-1, β-β and β-5, have been traced in each lignin and their frequences qualitatively compared with each other.     

Structure and formation of cellulosic chars

The formation and structure of chars produced on heating of cellulose, lignin, and wood have been investigated by FTIR and CP/MAS ¹³C-NMR, and the results have been discussed in conjunction with parallel permanganate oxidation studies reported before. These data show that when cellulose is heated for 5 min within the temperature range of 325–350°C, the IR bands associated with hydroxyl and glycosidic groups in cellulose disappear, and new bands signal the formation of unsaturation and carbonyl groups by dehydration and rearrangement. The NMR data also show the disappearance of the glycosyl carbons at 60–110 ppm and the appearance of methyl and other paraffinic carbons at 0–60 ppm, aromatic carbons at 110–170 ppm, carboxyl carbons at 170–190 ppm, and carbonyl carbons at 190–220 ppm. On heating at 400°C the IR and NMR signals for the glycosyl groups completely disappear, the signals for carbonyl and carboxyl groups diminish, and those for the aromatic and paraffinic groups expand. At this stage the char contains about 69% aromatic and 27% paraffinic carbons. At the temperature range of 400–500°C the paraffinic carbon content is reduced to 12%, and a highly aromatic (88%) char is produced. This is consistent with the permanganate oxidation studies which show the production of polycyclic aromatic structures resulting from extensive condensation and crosslinking at these temperatures. The chars produced from wood and lignin at 400°C had about the same aromatic carbon content as the corresponding cellulose char; however, the char yields were higher due to the presence of the methoxy phenyl groups that survive the heating process, as indicated by strong NMR signals at 55 and 148 ppm.     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 1: Extraction,Fractionation and Physico-Chemical Characterization

Ground spruce wood was extracted with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min. Released aromatic substances (from 2.2 to 2.5% on wood basis) were isolated on XAD-7 resin and fractionated into lignin, oligomeric aromatic substances (OAS), and compounds insoluble in methanol (IMC). The separated aromatic fractions, and the ground wood before and after extraction, were characterized by physico-chemical methods (GC, GC-MS, HPLC-SEC, TG, DSC). The major part of the aromatic substances was oligomeric aromatic substances (OAS). This fraction increased significantly with the extraction time, while the yield of dissolved lignin increased only slightly with extraction time. Isolated lignins had a lower molar mass and differed considerably from spruce milled wood lignin (MWL). The isolated lignins were more stable against oxidative thermodegradation than spruce MWL. The UV-extinction coefficients at 280 nm were lower for the isolated lignins than for MWL.     

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...     

Hydrothermal Liquefaction of Cypress: Effect of Water Amount on Structural Characteristics of the Solid Residue

Hydrothermal liquefaction of cypress was performed in an autoclave with various amounts of water. The obtained acid‐soluble and acid‐insoluble solid residues were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, sugar analysis, elemental analysis, and nuclear magnetic resonance to help understand the reaction mechanisms of this process. The characteristics of solid residues were significantly affected by the water amount. Cellulose was more stable at high water amount and hemicelluloses were much more reactive than cellulose. Comparison of nuclear magnetic resonance spectra of milled wood lignin and milled solid residues indicated a significant cleavage of the side chains. The components of milled solid residues were mainly derived from decomposition and repolymerization of lignin. The decomposition of the side chains was substantial for lignin depolymerization during hydrothermal liquefaction.     

杨木MWL和LCC制备多孔生物载体及其在人体肝细胞培养中的应用

为了比较磨木木质素（MWL）与木质素-碳水化合物复合体（LCC）与人体肝细胞的生物相容性,从杨木中提取MWL和LCC,制备水凝胶,冷冻干燥形成多孔生物载体。利用红外光谱和扫描电子显微镜对多孔生物载体的成分及表面形态进行了分析,采用多孔生物载体对人肝细胞进行体外培养,并对肝细胞形态及代谢活性进行检测。结果表明：LCC基载体中木质素含量较低而碳水化合物含量较高,因此其两亲性较MWL基载体好。以MWL和LCC制备的多孔生物载体,孔隙率达到60%左右,平均孔径约为30 μm。细胞形态、白蛋白分泌和葡萄糖代谢的分析结果显示,相比MWL基载体,LCC基多孔生物载体能更好地促进肝细胞长期生长,具有更好的生物相容性。     

Lignin Structural Changes During Liquefaction in Acidified Ethylene Glycol

Abstract

Beech (Fagus Sylvatica) milled-wood lignin was used as a model substrate in a study of lignin-catalyzed liquefaction in the presence of p-toluene sulfonic acid monohydrate (PTSA) or sulphuric acid as the catalysts. The structural changes that lignin undergoes during the treatment were studied by NMR spectroscopy, FTIR, size-exclusion chromatography, and high-performance liquid chromatography. For the sulphuric acid-catalyzed liquefaction, it was shown that the greater hydronium ion concentration in the reaction mixture induced formation of more condensed structures compared to the ones obtained after PTSA-catalyzed liquefaction. In addition, lignin during the PTSA-catalyzed liquefaction suffered degradation and was functionalized by the ethylene glycol. Gradual introduction of the ethylene glycol moieties into the lignin structure formed a condensed lignin-based polymeric material with predominant aromatic hydroxyl groups. HPLC and NMR analysis of the liquefied lignin with low-molecular mass fraction confirmed the presence of lignin monomers and further conversion of initially identified products into the aliphatic, aromatic (syringyl- and guaiacyl-based) esters and acids.     

New aspects in cationization of lignocellulose materials. V. Modification of rotten aspen wood meal with quarternary ammonium groups

Holocelluloses prepared from clear and rotten aspen wood were gradually fractionated with 2.5% NH₄OH, 4.5% NaOH, and 17.5% NaOH, respectively. A higher yield of polysaccharides (24.4%) was obtained from the rotten sample in comparison with clear wood (20.9%). Trimethyl ammonium-2-hydroxypropyl (TMAHP) derivatives of rotten aspen were prepared by the reaction of wood with 3-chlor-2-hydroxypropyltrimethylammoniumchloride (CHMAC) in alkaline medium. The quantity of TMAHP—hemicelluloses (yield 14.1%) is only slightly lower in comparison with TMAHP—hemicelluloses (yield 15.8%) obtained by modification and subsequent extraction from clear aspen wood meal. The hemicelluloses isolated from the rotten aspen wood meal are contaminated with low molecular cellulose fraction, the degradation products of cellulose attacked by fungi. The lignin component of rotten wood is less intensively attacked by fungi than the polysaccharidic one.     

Effect of Wood Welding Process on Chemical Constituents of Australian Eucalyptus

Thermochemical changes occurring during wood welding were investigated in Eucalyptus saligna and Eucalyptus pilularis. Unwelded reference wood and material from welded interface were compared via Py-GC/MS, thermogravimetric analyses, X-ray photoelectron spectroscopy, and attenuated total reflection Fourier transform infrared spectroscopy to explain differences in mechanical properties of welded wood between species. It appeared that the species originally containing more condensed substructures also provided stronger joints. The condensation index after welding allowed validating that the adhesive properties of lignin are more accessible in such species. The presence of more carbonyl functions, attributed to carbohydrate solicitation during welding process, potentially made lignin less accessible. Changes following welding were evidenced by the contribution of extractive compounds, fatty acid chains, and terpenoids, possibly reacting with hydroxyl groups and leading to adhesive properties by chemical linkage through new covalent bonds formation. Results corroborate the better mechanical properties of E. saligna, providing stronger joints possibly due to more accessible adhesive properties by esterification between lignin and fatty acid.     

Dissolved Lignin and Other Aromatic Substances in Thermomechanical Pulp Waters

Abstract

Dissolved aromatic substances in water suspensions of unbleached and peroxide‐bleached spruce thermomechanical pulp (TMP) were isolated by sorption on XAD‐8 resin and fractionated into lignin and oligomeric aromatic substances (OAS). The fractions were characterized by chromatographic (GC and HP‐SEC) and spectrometric (FT‐IR, ¹³C‐NMR, GC‐MS) methods, as well as by GC after direct on‐line pyrolysis and thermally assisted hydrolysis and methylation. The dissolved lignin in unbleached TMP water was structurally similar to spruce milled‐wood lignin (MWL), but its average molar‐mass was lower and the mass distribution more narrow. The oligomeric aromatic substances included phenolic dimers, trimers, and tetramers that were structurally different from those of MWL. After peroxide bleaching the amount of dissolved semipolar (MTBE) extractives and oligomeric aromatic substances was much lower. The amount of dissolved lignin from wood fibers was, on the contrary, much higher. The lignin released from TMP after bleaching was extensively oxidized and had a slightly higher average molar‐mass than lignin released from unbleached TMP.