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1.
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   

2.
Factors influencing the rate of acetylation were examined based on the swelling of wood in the reaction solution and the dimensions of the wood sample. The activation energy of acetylation was also estimated. In a swelling test, it was found that wood swells thoroughly in acetic anhydride even without pyridine above 60°C. Therefore, pyridine may facilitate the acetylation process as a catalyst and not as a swelling agent. The weight gain, x (%), attained at reaction time t (h), for various compositions of acetylation solution or dimensions of wood sample were analyzed by applying an original rate equation [x = a × (1 – e–kt )1/n ], where a is the ultimate weight gain (%), k is the rate constant (h–1), and n is a measure of the hindrance against the diffusion of reagent. The optimum volume fraction of pyridine in the pyridine-catalyzed acetylation was about 0.2. Accompanied by a rise in pyridine content, the reaction showed increased diffusion-controlled behavior. The rate constant, which is not affected by the dimensions of the wood sample, was estimated from which an activation energy of about 130kJ/mol was calculated.  相似文献   

3.
To clarify the non-uniform reaction of wood during vapor-phase acetylation, spruce wood blocks were exposed to acetic anhydride vapor at 120°C. Weight percent gain (WPG) due to the acetylation was estimated from the equilibrium moisture content at 25°C and 60% relative humidity. The diffusion of reagent vapor was much faster along the longitudinal direction than along the tangential direction. When the end surface was exposed to the reagent vapor for 48?h, 20% WPG, which was known to have sufficient stability and durability, was achieved to a depth of 42.5?mm. However, this depth was only 6.5?mm when the straight-grain surface was exposed. The reaction profiles were successfully approximated using reaction time (t), reaction rate (k′), delay time (t d′), and a parameter n reflecting the diffusion-controlled reaction. The t d′ value increased almost linearly as the depth increased from the surface. The k′ value ranged from 0.02 to 0.03?h?1, regardless of the depth and direction of diffusion. The n value decreased with an increase in the depth and approached 1–2. These values enabled the prediction of the degree of acetylation at any reaction time and positions of wood during vapor-phase acetylation.  相似文献   

4.
Influences of moisture content on the catalysis of sulfur dioxide and physical properties of reaction products were examined for a vapor-phase treatment of spruce wood with formaldehyde. The reaction rate was strongly dependent on the amounts of water and sulfur dioxide in the reaction system, and this was consistent with a proposal that the hydroxymethylsulfonic acid (HOCH2SO3H) formed from sulfur dioxide, water, and formaldehyde acts as a catalyst for the reaction. However, not all water molecules contributed to the formation of HOCH2SO3H, because some were adsorbed by the wood components. When the initial moisture content was high, polymeric cross-linking was likely because the ultimate weight gain was much greater than the value estimated based on monomeric cross-links. The lower values of antiswelling efficiency and higher equilibrium moisture content at a specific level of weight gain also suggested the existence of polymeric cross-links. However, the difference in the length of cross-links did not significantly influence the mechanical properties.Part of this research was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003  相似文献   

5.
Spruce wood blocks were acetylated in the presence of potassium acetate (KAc) at 20, 40, 60, 80 and 120°C. At 20°C, the weight percent gain (WPG) due to the KAc-catalyzed acetylation reached 20% in 18 days, whereas that due to pyridine-catalyzed acetylation did not exceed 8%. The hygroscopicity and dimensional stability of the KAc-acetylated wood were the same as those of conventionally acetylated wood at the same WPG, irrespective of reaction temperature. These facts suggest that the KAc enables simplified acetylation of wood at room temperature. The activation energy (E a) of the KAc-acetylation in the lower temperature range (20–40°C, 121–131 kJ/mol) was comparable to that of the acetylation of wood meal (140–146 kJ/mol). It was speculated that diffusion became a minor factor at reduced reaction rates in the lower temperature range, thus requiring a greater E a.  相似文献   

6.
Summary It has been found that the lignin in a middle lamella fraction isolated by a sieving technique has the same reactivity to bromine as the whole wood lignin. A plataue value of 1 mole bromine/mole C9-unit was obtained for both samples. The lignin in compression wood had a considerably lower reactivity to bromine than the normal wood lignin. A plataue value of 0.68 mole bromine/mol C9-unit was obtained with such lignin. The discrepancy between this and earlier results from the bromination of middle lamella and the implication of the results for lignin determination by the SEM- and TEM-EDXA technique are discussed.  相似文献   

7.
Sugi heartwood was acetylated with acetic anhydride in supercritical carbon dioxide (CO2) (120°C or 130°C, 10–12 MPa). As a result, the weight percent gain increased with increasing acetylation time up to 16%–20% at 1 h and 24%–28% at 24 h. The antiswelling efficiency of the acetylated specimens reached 75%–80% at 3–4 h of acetylation. It is supposed that the acetylation in supercritical CO2 has a high bulking effect compared with liquid-phase and vapor-phase acetylation with uncatalyzed acetic anhydride. The results showed that the acetylation progressed rapidly because supercritical CO2 and acetic anhydride formed a single phase at more than 90°C, and the acetic anhydride reached the reaction sites in the wood quickly.  相似文献   

8.
Summary The lignin distribution between the middle lamella and the cell wall of spruce fibers has been determined by a new technique based on a mercurization of the lignin and a concomitant determination of mercury by the SEM-EDXA technique. The ratio of lignin in the middle lamella at the cell corners to the lignin in the secondary wall was 2.5±0.6 for latewood and 2.4±0.6 for earlywood. This gives a lignin content of 55–58% in the true middle lamella in the cell corners. The reactivity to mercuric acetate of different wood elements was determined in separate experiments. Fractions enriched in ray cells, middle lamella, and compression wood all reacted at the same rate as the whole wood; about one mole of mercury was incorporated per mole of lignin (C9-unit).  相似文献   

9.
 The chemical conversion of phenolized sulfuric acid lignin (P-SAL), prepared from sulfuric acid lignin (SAL) by phenolation with sulfuric acid catalyst, to novel cationic surfactant was investigated. To elucidate the chemical reactivity of the P-SAL to a Mannich reaction, 1-guaiacyl-1-p-hydroxyphenylethane (I) as a simple phenolized sulfuric acid lignin model compound was reacted with dimethylamine and formaldehyde. Quantitative analysis of the products by gas-liquid chromatography suggested that the p-hydroxyphenyl nucleus was more reactive than the guaiacyl nucleus. The Mannich reaction of SAL with dimethylamine did not yield a soluble cationic surfactant, but P-SAL produced water-soluble cationic surfactant in a quantitative yield. The Mannich reaction products (MP-SAL) of P-SAL had 1,3-dimethylaminomethyl groups/C9-C6. The results of the surface tension measurements showed that the decrease in surface tension of MP-SAL was much larger than that of lignosulfonate as a commercial surfactant from lignin.  相似文献   

10.
Ezomatsu wood blocks were impregnated with potassium acetate (KAc) and then exposed to acetic anhydride vapor at 25°C and 120°C. The KAc-impregnated wood was rapidly acetylated at 120°C, and only 6 min was needed to achieve 20% weight percent gain (WPG). The WPG increased with increasing catalyst loading (CL), but it turned to decrease above 20% CL probably because the diffusion of acetic anhydride vapor was hindered by excess KAc depositing in the cell lumina. Thus, careful control of CL is necessary in the vapor-phase acetylation. KAc was also effective in catalyzing the vapor-phase acetylation at 25°C: the KAc-impregnated wood attained 20% WPG within 7 days, whereas the WPG did not exceed 10% even after 1 month in the uncatalyzed system. Irrespective of treatment methods, the hygroscopicity of wood was reduced and its dimensional stability was improved with an increase of WPG. These results confirm that the use of KAc simplifies the acetylation process at room temperature with minimal loss of acetic anhydride.  相似文献   

11.
The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.Part of this report was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003  相似文献   

12.
Common hornbeam (Carpinus betulus L.) is a highly underused wood species despite its great hardness, strength, wear-resistance and toughness. It is mainly used as firewood in Hungary because of its wood defects, irregular shape and low-dimensional stability. These wood defects and small breast height diameter result in a low yield. It is non-durable outdoors as it tends to turn grey, crack and be attacked by wood-decaying organisms. Indoors it lasts for hundreds of years. One technology that could improve the stability and durability properties is acetylation. Hornbeam was acetylated with the Accoya® method under industrial conditions. The aim of this research was the assessment of acetylation affecting the chemical properties of hornbeam wood and how these are related to the change in physical and mechanical properties. Main wood constituents (cellulose, hemicellulose, Klason lignin, extractives and ash content) were determined and compared. Chemical parameters related to the degradation of structural polymers were also evaluated (total phenolic and soluble carbohydrate contents, pH and buffering capacity, furfural, levulinic acid, formic acid, acetic acid). Structural changes in acetylated wood and in the Klason lignin fraction were also assessed using FTIR spectroscopy.  相似文献   

13.
The objective of this study was to characterize the decay of acetylated wood due to brown-rot and white-rot fungi by analysis of chemical composition, X-ray measurements, and13C-NMR spectroscopy. The decay by brown-rot fungus became inhibited at a weight percent gain (WPG) due to acetylation of more than 10%, and the mass loss (LOSS) due to decay became zero at a WPG of about 20%. The LOSS due to white-rot fungus decreased slowly with the increase in WPG, reaching zero at a WPG of about 12%. The losses of lignin by brown-rot decay increased initially with the decrease in LOSS owing to the progressing acetylation and then decreased at a LOSS of less than 60%. Polysaccharides were more easily decomposed than lignin during the decay of acetylated wood due to brown-rot fungus. The losses of both components due to white-rot decay decreased as the LOSS decreased with progressing acetylation. The white-rot fungus tended to preferentially decompose the lignin during the decay of acetylated wood. The brown-rot fungus decomposed the cellulose in the crystalline region to a large degree when the LOSS was more than 40%, whereas the white-rot fungus decomposed the crystalline region and the noncrystalline region in acetylated wood to the same degree. The brown-rot fungus preferentially decomposed unsubstituted xylose units in acetylated wood and partly decomposed the mono-substituted xylose units. It was suggested that the mono- and disubstituted cellulose were partly decomposed by brown-rot fungus.This paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society at Kumamoto and Kochi in April 1996 and April 1997, respectively  相似文献   

14.
Summary A sieving technique has been developed for the separation of middle-lamella fragments. The middle-lamella fraction as well as the whole wood and compression wood from Picea abies have been analysed by nitrobenzene oxidation and acidolysis in order to determine the content of p-hydroxyphenylpropane units in the middle-lamella lignin. These analyses revealed only traces of p-hydroxyphenylpropane units in the whole wood and in the middle-lamella fraction but considerable amounts were found in compression-wood lignin. This points to the fact that middle-lamella lignin is of guaiacyl nature and that earlier results reporting high proportions of p-hydroxyphenylpropane units in the middle lamella-lignin may be due to the inclusion of compression wood in the fraction studied. The acidolysis experiments further indicate that the middle-lamella lignin has fewer uncondensed -0-4 aryl ether structures than the whole wood lignin.The skilful technical assistance of Mrs. Britta Samuelsson and Mr. Johan Lindberg is highly appreciated. The author also thanks Dr. Knut Lundquist for supplying some of the reference compounds, and Dr. Hanne-Lise Hardell for help with the microscopic pictures  相似文献   

15.
Analysis on residue formation during wood liquefaction with polyhydric alcohol   总被引：12，自引：0，他引：12  
Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002  相似文献   

16.
The vibrational property of hematoxylinimpregnated wood was investigated from the aspect of moisture content dependence. The specific dynamic Young's modulus (E/) and loss tangent (tan) of hematoxylin-impregnated wood were determined in the relative humidity (RH) range of 0%–97%, and were compared with those of the untreated and some conventional chemically treated woods. The changes in theE/ and tan of wood with increasing RH were suppressed by acetylation and formaldehyde treatment because of a marked reduction in the hygroscopicity of the wood. Although the hematoxylin impregnation did not significantly affect the hygroscopicity of the wood, its influence onE/ and tan were similar to that of formaldehyde treatment at low RH and of acetylation at medium RH. It was supposed that at low to medium RH hematoxylin restrains the molecular motion of amorphous substances in the cell wall because of its bulkiness and rigidity. On the other hand, at high RH it seems to work as a plasticizer with adsorbed water molecules.  相似文献   

17.
Strobilurus ohshimae is an edible mushroom, and it specifically forms its fruiting bodies on buried sugi (Cryptomeria japonica) twigs. In this research, we studied lignindegrading activity of S. ohshimae. We isolated 18 strains of S. ohshimae from various regions of Japan, and determined their lignin degradation rates on sugi wood meal medium. All the strains of S. ohshimae degraded approximately 6%–12% of sugi lignin in 30 days, and these lignin degradation rates were 1.5–3 times higher than those of Trametes versicolor, which is a typical lignin-degrading fungus. Among the three main lignin-degrading enzymes, activity of lignin peroxidase and manganese peroxidase was not observed, while 4340U/g of laccase was produced in 30 days. To investigate the effect of wood species on lignin degradation by S. ohshimae, the lignin degradation rate and laccase productivity on sugi wood meal medium were compared with those on beech (Fagus crenata). In T. versicolor, both lignin degradation rate and laccase productivity were higher on beech than on sugi. Conversely, in S. ohshimae, lignin degradation rate and laccase productivity were higher on sugi than on beech. Therefore, it was suggested that coniferous lignin is not always difficult to degrade for the fungi that inhabit softwood. Part of this article presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004  相似文献   

18.
Summary To elucidate biochemical features leading to p-hydroxyphenyl-rich lignin in gymnosperm reaction wood the activities of the following five enzymes involved in the biosynthesis of p-hydroxyphenyl lignin were compared in reaction and opposite woods: phenylalanine ammonialyase (EC 4.3.1.5), cinnamate 4-hydroxylase (EC 1.14.13.11), p-hydroxycinnamate: CoA ligase (EC 6.2.1.12), cinnamyl alcohol dehydrogenase (EC 1.1.1.-) and peroxidase (EC 1.11.1.7). The enzyme activities in the reaction woods of Thuja orientalis and Metasequoia glyptostroboides were remarkably higher than those in the opposite woods, reflecting the higher contents of p-hydroxyphenyl lignin in reaction wood.This work was partly supported by the Grant-in-Aid for Scientific Research (548047) from the Ministry of Education, Science and Culture of Japan. We thank the Ministry of Education for the support  相似文献   

19.
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   

20.
To utilize acid hydrolysis lignin effectively, chemical conversion to anion-exchange resin was investigated by two methods. Sulfuric acid lignin (SAL) was selected as a typical acid hydrolysis lignin in this experiment. Because it is less reactive, SAL was phenolated with sulfuric acid catalyst to yield reactive phenolized SAL (P-SAL) with p-hydroxyphenyl nuclei. One method was the restricted resinification of P-SAL followed by the Mannich reaction with formaldehyde and dimethylamine to yield a weakly basic anion-exchange resin with an ion-exchange capacity of 2.4mEq/g. Another method was to react resinified P-SAL with glycidyltrimethylammonium chloride to yield a strongly basic anion-exchange resin with an ion-exchange capacity of 2.0mEq/g. The reaction of a simple P-SAL model compound with an epoxide suggested that the phenolic hydroxyl group of the p-hydroxyphenyl nucleus had slightly higher reactivity than that of the guaiacyl nucleus.Part of this report was presented at the 47th Lignin Symposium, Fukuoka, October 2002  相似文献   

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