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1.
2.
J. -Y. Chen Yuichi Shimizu Mitsuo Takai Jusuke Hayashi 《Wood Science and Technology》1995,29(4):295-306
Summary A new lignin isolation method has been developed. Wood and pulp were subjected to ball milling, swelled in an organic solvent, and then treated with a cellulase. The enzyme digestion time could be shortened to 1 day with this method. The lignin obtained has been named Swelled Enzyme Lignin (SEL). Swelling and enzyme digestion conditions and their effects on lignins were investigated. The SEL's from wood could be directly washed with water, while those from pulp had to be washed with aqueous acetic acid because they were water soluble. The purification of crude SEL's was accomplished by extracting them with dioxane-water, and then precipitating and washing with ethyl ether. Lignin yields were 24–67% based on the total amount of lignin present. The characteristics of the SEL's were further investigated by gel-permeation chromatography (GPC), infrared and 13C nuclear magnetic resonance (NMR) spectroscopy.Symbols SUKP
Softwood Unbleached Kraft Pulp
- BUKP
Birch Unbleached Kraft Pulp
- TD
Todomatsu (Abies sachalinensis) wood
- MWL
Milled Wood Lignin
- MWLS (BK, TD)
Milled Wood Lignin of SUKP (BUKP, TD)
- SEL-C
Swelled Enzyme Lignin (crude)
- SELS-C
SEL-C of SUKP, other materials named in the same way
- SELS-90
SEL-C of SUKP and extracted with 90% dioxane-water
- SELS-96
SEL-C of SUKP and extracted with 96% dioxane-water, other materials named in the same way 相似文献
3.
《Wood material science & engineering》2013,8(3):159-165
Abstract In this work, the lignin/polypropylene (PP) composites were prepared by lignin and PP using hyperbranched polymer lubricant (HBPL) as a compatibilizer, which was synthesized by oleic acid and amino-terminated hyperbranch (HBP-NH2) polymer in toluene solvent. The impact and flexural strength of the resulting composites were investigated. Experimental results indicated that the impact strength and flexural strength of lignin/PP composites modified with HBPL are 52.3% and 63.6% higher than that of untreated systems, respectively. HBPL treatment could also significantly improve the melt flow rate (MFR) of the lignin/PP composites. Meanwhile, the storage modulus (E′) of adding the HBPL was slightly higher than that of the uncompatibilized system. In addition, scanning electron microscope images showed that the dispersion of the lignin added with HBPL in the polymer matrix was improved. It can be inferred that the lignin and PP matrix interfacial bonding was strengthened. 相似文献
4.
After enzymic hydrolysis of polysaccharides in milled wood or pulp the unhydrolysed lignin residue becomes soluble in certain polar solvents. Extensive disintegration of the wood is necessary to obtain a sufficient accessibility toward the enzyme. For milling a porcelain rotary ball mill is recommended. A relationship has been found between the milling energy, which is proportional to the size of the mill, the milling time, and the yield of ball-milled wood lignin (BMWL). Enzymatically isolated lignin (EIL) requires a critical milling time which is shorter than that for obtaining maximum yields of BMWL. A procedure for isolation of the total lignin content from wood and pulps in the form of three fractions has been developed, giving a water soluble, low molecular carbohydrate-lignin complex by water extraction of ball-milled wood, a BMWL-carbohydrate complex by subsequent extraction with dioxane, and a EIL-carbohydrate complex by dioxane extraction of the residue after enzymic hydrolysis. 相似文献
5.
Quinone methides and the structure of lignin 总被引:1,自引:0,他引:1
G. J. Leary 《Wood Science and Technology》1980,14(1):21-34
Summary The reactions of quinone methide intermediates during the initial biosynthesis and also the subsequent aging of lignin are reviewed. The reactions during aging should lead to enhanced lignin-carbohydrate bonding and may explain the structural and analytical differences found between DHP and isolated milled wood lignins. 相似文献
6.
Masamitsu Nakajima Yuzo Furuta Yutaka Ishimaru Makoto Ohkoshi 《Journal of Wood Science》2009,55(4):258-263
To clarify the effects of lignin on the fixation of bending deformation by cooling, cooling set for delignified woods with
various lignin residues were investigated to compare with mechanical and dynamic viscoelastic properties. Bending tests showed
that steep reductions occurred in the modulus of elasticity and modulus of rupture with delignification during the initial
stage of delignification. The dynamic viscoelastic measurements revealed that the peak temperature of tan δ due to micro-Brownian
motion of lignin was reduced with delignification, and the peak disappeared in the temperature range of 5°–100°C for the specimens
that had lost more than 21% of their weight. On the other hand, no clear change in residual set was found in the range of
0%–15% of weight loss in spite of a marked reduction in lignin content. Subsequently, set decreased steeply for the specimens
delignified beyond 15% of weight loss. It was suggested that cooling set is not determined solely by lignin content but is
influenced by changes in the quality of lignin due to delignification. Lignin quality affects the balance of the elastic potential
to recover from deformation and its viscosity, which is an indication of resistance against flow.
Part of this report was presented at the 57th Annual Meeting of the Japan Wood Research Society, Hiroshima, August 2007 相似文献
7.
Summary The phenyl nucleus-exchange method (NE-method) is a procedure for the degradation of lignin which allows the C–C linkages between the side chains and the phenyl nuclei to be cleaved selectively, and the phenyl nuclei to be liberated finally as polyhydric phenols. The important characteristic of this method is to take advantage of the dealkylation in diphenylmethane type structures in the presence of boron trifluoride and excess phenol, for the degradation of lignin. The lignin building units which give phenol monomers (guaiacol and/or catechol in softwood lignin) almost quantitatively by this method are noncondensed types and diphenylmethane types, and each of these units has any of the benzyl alcohol, the benzyl ether, the conjugated double bond, the -carbonyl group and the C-aryl bond, in the side chain. The yields of phenyl nuclei are about 25–30% in softwood protolignins and about 8–13% in technical lignins. In this paper, the reaction theory and the degradation mechanism of lignins in the NE-method are outlined. 相似文献
8.
Residual wood meal after extraction of milled wood lignin (WMEM) ofEucalyptus globulus was extracted with alkali and LiCl/N,N-Dimethylacetamide (DMAc). These agents dissolve mainly hemicellulose and cellulose, respectively. The extractability of WMEM in alkali solutions was influenced by the degree of swelling of the cellulose. Under good swelling conditions, considerable amounts of cellulose and lignin were extracted with the hemicellulose. Maximum extractability was about 60% of the WMEM under optimum conditions (3 M or 5 M LiOH or 3M NaOH solution). Some portion of cellulose was extracted with LiCl/DMAc at room temperature. Thus, lignin inE. globulus WMEM was divided into three fractions: hemicellulose-lignin fraction, cellulose-lignin fraction, and insoluble-lignin fraction.Part of this work was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999; and at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000 相似文献
9.
Structural changes of residual lignin in unbleached softwood kraft pulp (SWKP) during manganese peroxidase (MnP) treatment were investigated to obtain some understanding of the biobleaching action of SWKP with MnP treatment. Alkaline-extracted lignin from darkened SWKP by MnP showed more intense color and contained moreo-quinone than that from control SWKP. However, no difference in the conjugated-carbonyl was observed between the lignins from MnP-treated and control SWKP. The nitrobenzene oxidation analysis revealed that oxidative condensation of non-condensed lignin in SWKP occurs during an early stage of MnP treatment. These observations were supported by the model experiment in which the lignin prepared from control SWKP was subjected to MnP treatments three times, and the changes of color and functional groups in the lignin were determined after each treatment. These results suggested that an increase ino-quinone and the condensation reaction of non-condensed lignin in SWKP are responsible for the characteristic darkening of SWKP during MnP treatment. It was also ascertained that darkened lignin was degraded and brightened by repeated MnP treatments. 相似文献
10.
To elucidate the formation mechanism of acidsoluble lignin (ASL) formed in the Klason lignin determination, beech wood meals were treated with sulfuric acid (SA) under various conditions, and the ASL solution was extracted with CHC13. The results indicated the following: (1) wood components yielding ASL are dissolved in 72% SA during the initial stage; (2) the quantity of ASL is highest during the initial stage, then decreases with prolonged time of 72% SA treatment and finally reaches a constant value; (3) soluble lignin prepared by 72% SA treatment and subsequent standing in 3% SA again yield insoluble Klason lignin and ASL after boiling in 3% SA; and (4) about half the amount of ASL is dissolved in CHC13. The foregoing suggest that wood components yielding ASL are dissolved in 72% SA at the beginning and finally change to ASL after being subjected to depolymerization, hydrolysis, and other reactions. ASL may thus be composed of low-molecular-weight degradation products and hydrophilic derivatives of lignin. 相似文献
11.
Summary Selective labeling of p-hydroxyphenyl-, guaiacyl-and syringylpropane moieties in protolignin was achieved by administration of corresponding 3H-labeled monolignol glucosides to differentiating xylem of pine. The growing process of the protolignin macromolecule in the specific morphological region was visualized by application of high resolution microautoradiography to the selectively labeled wood tissue.p-Hydroxyphenyl lignin is formed mainly in the compound middle lamella and cell corner in an early stage of cell wall differentiation. There are two peaks of deposition of guaiacyl lignin in the compound middle lamella at an early stage and in the secondary wall at a late stage. The content of condensed guaiacyl units is higher in the middle lamella than in the secondary wall lignin. Syringyl lignin is formed mainly in the inner layer of the secondary wall in a late stage as a minor structural moiety. During the formation of the cell wall, protolignin grows under definite biological regulations to a heterogeneous macromolecule which consists of various structural moieties arranged in a regular manner. The origin of the heterogeneous structure was explained as a result of the biogenesis of protolignin in the cell wall. 相似文献
12.
In order to examine the contribution of wood components to the acetylation of wood, we acetylated wood meal that had been
partially delignified. The results were analyzed in terms of the reaction kinetics. The first-order rate equation was successfully
adjusted to the weight gain data. The rate constant for acetylation initially increased with progress of lignin elimination
and then turned to decrease; the apparent activation energy showed the reverse tendency and ranged from about 90 to 130 kJ/mol.
These results suggest that lignin elimination brings not only separation of lignin but also drastic change of the chemical
and/or physical structure in the residual lignin, and this affects the reactivity of wood meal as a whole. The ultimate weight
gain estimated by the regression of the rate equation showed a minimum when lignin was moderately eliminated, which was explained
in terms of enhanced reactivity of lignin and lower accessibility for holocellulose than predicted. The equilibrium moisture
content had a maximum when lignin was moderately eliminated. This tendency is the opposite of that observed for the ultimate
weight gain, and suggests that the sites for acetylation do not always correspond to those for moisture adsorption.
Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004 相似文献
13.
The chemical conversion of red pine sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis lignin sample to water-soluble arylsulfonates of lignin derivation (i.e., phenolized SAL) was investigated. Treatment of phenolized SAL with chlorosulfonic acid followed by alkali hydrolysis gave water-soluble sulfonated products with a sulfonic acid group on their aromatic nuclei quantitatively. The products possess 2.0 SO3Na/C9 C6. In contrast, the content of sulfuric acid group in sulfonated SAL was only 0.33C9. Chlorosulfonation of 1-guaiacyl-l-p-hydroxyphenylethane as a phenolized guaiacyl lignin model compound revealed that the sulfonyl chloride group was introduced at thepara position of an aromatic methoxyl group, theortho position of a phenolic hydroxyl group, or both. 相似文献
14.
Seiichi Yasuda Eri Hamaguchi Yasuyuki Matsushita Hideyuki Goto Takanori Imai 《Journal of Wood Science》1998,44(2):116-124
Highly condensed lignin can be transformed by three reactions — phenolation, hydroxymethylation, and neutral sulfonation — to water-soluble lignosulfonate. To elucidate reactivities and products in the latter two reactions, simple compounds were selected as lignin model compounds. With hydroxymethylation of creosol at 60°C, the yield of a condensed-type product with the diarylmethane structure was less than 10%. Hydroxymethylation of 1-guaiacyl-1-p-hydroxy-phenylethane (compound VI) as a phenolized guaiacyl lignin model compound gave four compounds. The initial reaction introduced the hydroxymethyl group mainly in the guaiacyl nucleus, and the additional reaction created two hydroxymethyl groups in the p-hydroxyphenyl nucleus. Contrary to our estimation, treatment of the models with 13C-labeled formaldehyde (H13CIIO) did not form any diarylmethane structure. Neutral sulfite treatment of hydroxymethylated products gave corresponding sulfonates in high yields. Phenolized guaiacylglycerol--aryl ether (compound XVI) showed a reactivity similar to that of compound VI.This paper was presented at the 45th and 46th annual meetings of the Japan Wood Research Society at Tokyo and Kumamoto, April 1995 and April 1996, respectively 相似文献
15.
To analyze the structural features of lignin in the vicinity of lignin–carbohydrate linkages, water-soluble lignin–carbohydrate complex (LCC) with low lignin content was prepared from residual birch wood meal after the extraction of milled wood lignin (MWL). The molecular weight distribution of lignin in this LCC appeared together with carbohydrate in the relatively high molecular weight region of the gel permeation chromatogram. This result was consistent with our previous results obtained for the same fraction of Japanese cedar (sugi); however, after treatment with polysaccharide-degrading enzyme, the molecular weight distribution of carbohydrate and that of lignin shifted significantly to the lower region. These results demonstrated that molecular size of this LCC is determined by carbohydrates while lignin is present as a minor fragment in this fraction. The syringyl/guaiacyl (S/V) ratio of this LCC was higher than other lignin fractions. Ozonation analysis implied that this LCC has a relatively high number of β-1 structures. It is likely that lignin that exists near lignin–carbohydrate linkages has more endwise-type features than other lignin fractions.This paper was presented in part at the 48th Lignin Symposium, Fukui, Japan, October 2003 and at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003 相似文献
16.
In order to analyze the structural features of small lignin fragments that are closely associated to polysaccharides, lignin carbohydrate complex (LCC) with low lignin content was extracted with water from the residual wood meal (sugi, Cryptomeria japonica) of milled wood lignin (MWL) isolation. This LCC exhibited almost the same neutral sugar composition as those extracted by other LCC solvents (dimethylformamide, dimethylsulfoxide, and others) but the lignin content was only 5.3%, which was much lower than others. Gel filtration chromatography demonstrated that lignin in this LCC was found together with carbohydrates at the higher molecular weight region, but after the treatment with carbohydrate-degrading enzymes the apparent molecular weight of both lignin and carbo-hydrates decreased significantly. Using a mild alkaline treatment, the apparent molecular weight of lignin also decreased while that of polysaccharide was not affected. These data indicated that lignin in this LCC is present as small fragments attached to high molecular weight polysaccharide at least partly by alkali-unstable linkages. Structural analysis by ozonation method revealed that the lignin in this LCC was lower in erythro/threo ratio of -O-4 structure and relatively richer in the threo type structure carrying C-aryl linkages at -position (-5 and/or -1) than other lignin fractions present in MWL, LCCs extracted by other solvents, and their extraction residues. It was suggested that the chemical structure of lignin closely associated to carbohydrates was different from that of the main part of lignin.This paper was presented in part at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002, at the 47th Lignin Symposium, Gifu, Japan, October 2002, and at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003 相似文献
17.
Christian Lanvermann Robert Evans Uwe Schmitt Stefan Hering Peter Niemz 《Wood Science and Technology》2013,47(3):627-641
A radial core from a Norway spruce (Picea abies (L.) Karst.) estimated to be about 107 years old was cut from a board and was analyzed for density and microfibril angle (MFA). Furthermore, cell geometry, wall thickness and lignin distribution were analyzed on three selected growth rings in detail. Intra-ring differences in the density profiles are also true for cell wall thicknesses as well as radial and tangential lumen diameters. A higher MFA was found for earlywood with a slow decrease toward the latewood region. The lignin was found to remain rather constant throughout the growth rings, which suggests a constant chemical composition of the cell wall material within the growth ring. From the recorded datasets on a cellular level, it can be concluded that the main adaptation regarding structure–property relationships toward the optimization of water transport and mechanical stability is mainly achieved at the cell level. 相似文献
18.
Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin I: method and its application to lignin oxidation 总被引:1,自引:1,他引:0
Guolin Tong Tomoya Yokoyama Yuji Matsumoto Gyosuke Meshitsuka 《Journal of Wood Science》2000,46(1):32-39
A new method is applied to evaluate the progress of the oxidation reaction of lignin during oxygen-alkali treatment. This method employs the difference in permanganate consumption of the sample before and after the oxygen-alkali treatment as an indication for the lignin oxidation. When kraft lignin and residual lignin isolated from unbleached softwood kraft pulp were subjected to oxygen-alkali treatment up to 6000min, the progress of the oxidation expressed by this method was separated into clearly distinguished three phases. During the first and second phases, the progress of oxidation was well correlated to the loss of methoxyl group and to the decrease in the yield of nitrobenzene oxidation products. The addition of Mn+ to the oxygen-alkali treatment depressed oxidation during the second phase partly and that during the third phase almost completely. Calculations based on the change in the permanganate consumption revealed that the oxidation during the first phase corresponded to 4.2 electrons abstracted from one lignin structural unit on average. The oxidation process by oxygen-alkali treatment was hypothetically attributed to the direct reaction between molecular oxygen and the phenolic unit of lignin, which mainly took place during the first phase, and to the autooxidation-type oxidation during the second and third phases.Part of this paper was presented at the 9th ISWPC, Montreal, June 1997; and at the 42nd Lignin Symposium, Sapporo, October 1997 相似文献
19.
Participation of lignin in the reaction between vapor-phase formaldehyde and wood was examined by using gradually delignified
wood meal. A fi rst-order rate equation was successfully applied to the weight gain data. From the estimated reaction parameters
such as rate constant, k, and ultimate weight gain, a, the reactivity toward formaldehyde was discussed among wood components, and compared with that for acetylation. k decreased monotonously with progress of the elimination of lignin, suggesting that the reaction rate of lignin is dominant
over that of whole wood, and the decrease in the ratio of lignin retarded the reaction of wood as a whole. On the other hand,
a increased with decreasing lignin content. This may be attributable to the enhanced reactivity of the remaining lignin due
to some structural changes and to the increase in the number of reactive sites in polysaccharides as a result of their exposure
accompanying the elimination of lignin. The dependencies of k and a on the lignin content were not similar to the case for acetylation, probably because of the difference in the reaction phase.
In vapor-phase formaldehyde treatment, the remaining lignin reacts as it is, whereas in liquid-phase acetylation it would
undergo rearrangement or swelling of the structure in the reaction solution. 相似文献
20.
对新伐巴尾松剥皮或不剥皮原木喷以多种化学药剂进行了防腐、防虫试验研究、证明杀虫效果较好的有辛硫磷、倍硫磷和林丹,防腐效果较好的有6781、6782、6783、6784、FCAP、AC3B等;其中6781、6782能使剥皮尾松原木露天存放二年材质完好如新。枫香和拟赤扬剥皮原木喷药后棚内干存效果较好,但露天存放效果较差。锯材(厚板)瞬浸处理后棚内干存一年不霉不腐。 相似文献