Reaction behavior of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

Reaction of Japanese beech (Fagus crenata) in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which can dissolve cellulose, was investigated. Although both lignin and polysaccharides such as cellulose and hemicelluloses can be liquefied at a treatment temperature of around 100°C, the liquefaction of polysaccharides mainly occurs at the beginning of the treatment with [C2mim][Cl]. Cellulose crystallinity in the wood was gradually broken down as the treatment continued. The solubilized polymers were depolymerized to low molecular weight compounds. The results indicate that [C2mim][Cl] is an effective solvent and reagent for the liquefaction of wood components and subsequent depolymerization of them. Part of this report was presented at the 58th Annual Meeting of the Japan Wood Research Society, Tsukuba, April 2008     

Morphological changes in sugi (Cryptomeria japonica) wood after treatment with the ionic liquid, 1-ethyl-3-methylimidazolium chloride

We investigated morphological changes in wood tissues of sugi (Cryptomeria japonica) resulting from treatment with the ionic liquid 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which dissolves cellulose. Treatment with [C2mim][Cl] caused dissociation and distortion of tracheids in latewood, but not in earlywood. This difference was due to the difference in swelling behavior of the cell wall between earlywood and latewood. Many pit membranes in bordered pits were broken by treatment with [C2mim][Cl]. In addition, some chemical changes in wood components, such as cellulose and lignin, occurred before significant disruption or destruction of the cell wall. Our results show that the reaction of wood liquefaction by [C2mim][Cl] treatment is not homogeneous, both from chemical and morphological viewpoints.     

Reaction behavior of cellulose in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

We investigated the reaction behavior of cellulose in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which can dissolve cellulose. The cellulose samples were treated with [C2mim][Cl] at 100, 120 and 140 °C. At the beginning of the treatment, the solubilized cellulose in [C2mim][Cl] is depolymerized into various low molecular weight compounds such as cellobiose, cellobiosan, glucose, levoglucosan and 5-hydroxymethylfurfural. As the treatment continued, some of the low molecular weight compounds reacted with the ionic liquid to form new polymers, which were black and contained nitrogen. [C2mim][Cl] is, therefore, not only a solvent for cellulose, but also a reagent for both depolymerization to produce various low molecular weight compounds, and subsequent polymerization of those compounds.     

Morphological changes of Japanese beech treated with the ionic liquid, 1-ethyl-3-methylimidazolium chloride

The morphological changes in wood tissues of Japanese beech (Fagus crenata) upon treatment with the ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which can dissolve cellulose, were investigated. Treatment with [C2mim][Cl] induced significant swelling of all wood tissues. However, the swelling behavior of wood fibers was different from that of vessels. Intervascular pits were occluded, and pit membranes in ray-vessel pits were broken after treatment with [C2mim][Cl]. No significant differences in swelling behavior were found between latewood and earlywood, although different morphological changes for latewood and earlywood during [C2mim][Cl] treatment were seen in our previous studies on sugi (Cryptomeria japonica). We have found that the effects of [C2mim][Cl] on Japanese beech tissues are inhomogeneous and different from those found for other wood species.     

Comparative study of morphological changes in hardwoods treated with the ionic liquid, 1-ethyl-3-methylimidazolium chloride

Three hardwoods of varying vessel arrangement were treated with the ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which can dissolve cellulose, to investigate its influence on wood tissue morphology. Characterization was carried out by light and scanning electron microscopy. The wood fibers of all species swelled significantly during [C2mim][Cl] treatment. The swelling behavior varied according to wood species and differed from other cell types such as ray parenchyma cells. Morphological changes of the pits also varied between wood species. Treatment with [C2mim][Cl] affects wood tissues differently depending on wood species and cell type. These differences are not due to the vessel arrangement and its presence, but possibly from the chemical component and the microfibril angle of various wood tissues.     

Ionic liquids as formaldehyde-free wood adhesives

Several ionic liquids promote depolymerization of wood components, i.e., polysaccharides and lignin, into low molecular weight compounds, some of which further re-polymerize into resin-like compounds. In this study, the depolymerization/re-polymerization of wood components in ionic liquids was applied to preparation of plywoods from Japanese cedar (Cryptomeria japonica) veneers by employing ionic liquids as adhesives. The adhesive solution was prepared by mixing an ionic liquid (pyridine hydrochloride ([Py][Cl]), imidazole hydrochloride ([IM][Cl]), or 1-ethylpyridinium chloride ([EtPy][Cl])) with water and d-glucose in various weight ratios. Tensile shear test of the three-ply plywoods prepared from the veneers and the adhesive solution through hot-pressing indicated that the plywood bonded with the [IM][Cl]-based solution ([IM][Cl]/water/glucose ratio: 9/3/2) exhibited the highest strength. Scanning electron microscope observation on the plywoods suggested that the ionic liquids softened the cell walls of the probably plywood through the depolymerization/re-polymerization reactions and the cell walls were compressed during the hot-pressing process. Entwining of the compressed cell walls and van der Waals force enhanced by the compression were considered to be origins of the adhesion of the veneers.     

在酸催化下不同形态木材液化的研究

对粉状、纤维状和刨花状等形态木材,在不同酸催化下的液化效果进行的研究发现,木材液化率几乎不受木材颗粒粒度的影响,木液比和催化剂的种类是影响液化反应的重要因素,对液化率的影响较大.     

Effects of phosphoric acid on liquefaction of wood in phenol and optimum liquefaction processing parameters

To clarify the influencing factors of liquefaction of wood in phenol using phosphoric acid as a catalyst and get its liquefaction technology, a study on the liquefaction technology of Chinese fir (Cunninghamia lanceolata) and poplar (triploid Populus tomentosa Carr) under different conditions was conducted. The results indicate that the residue rate decreases with the increase of liquefaction temperature, liquefaction time, catalyst content or liquid ratio. It is also found that the optimum condition of liquefaction for poplar is estimated as: the reaction temperature of 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio)of 4.5 and catalyst content of 8%, and 4.2% residue rate could be obtained. Under the processing parameters of temperature 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio) of 4 and catalyst content of 10%, the residue rate of Chinese fir can reach 5.6%.     

Preparation of synthetic wood composites using ionic liquids

Synthetic wood composite films containing cellulose, hemicelluloses, and lignin, the three major components of natural wood, were prepared in a room temperature ionic liquid solvent, 1-ethyl-3-methylimidazolium acetate, [EMIM][Ac]. Various synthetic wood composites were obtained by dissolution of individual wood components together with additives, including polyethylene glycol (PEG), chitosan, and multi-wall carbon nanotubes (MWNTs) in [EMIM][Ac]. The addition of water affords a gel that was dried in either a low humidity environment or under vacuum. Synthetic wood films showed smoother surface textures, higher water resistance, and higher tensile strengths than cellulose films formed by the same methods. Tailor-made synthetic wood composites were also prepared having a variety of desirable properties, including antimicrobial activities, controlled hydro-phobicity/philicity, high relative dielectric constant, and a high degree of cohesiveness.     

Preparation and Characterization of the Phenolated Wood Using Sulfuric Acid as a Catalyst Ⅱ. FT-IR and GPC Characterization

By means of gel permeation chromatography analysis, the molecular weight of liquefied wood under different reaction conditions was investigated to trace the change in the structural characteristics of the liquefied wood. The insoluble residues were analyzed by Fourier transform infrared to investigate the liquefaction order of three main wood components. The results indicate that both reaction temperature and reaction time could affect the molecular characteristics of the liquefied wood obtained. The molecular weight of liquefied Chinese Fir wood is higher than that of liquefied Poplar wood under most of reaction conditions. During wood liquefaction, lignin is liquefied firstly. Hemicellulose is liquefied in the middle stage and cellulose is the most difficult to be liquefied.     

Liquefaction of wood (Metasequoia glyptostroboides) in allyl alkyl imidazolium ionic liquids

The results of wood liquefaction by allyl alkyl imidazolium ionic liquids indicated that wood (Metasequoia glyptostroboides) without any pretreatment is liquefied in ionic liquids at temperatures below 100°C within 40 min. Acidic ionic liquids show low residue even at 70°C and 30 min. The liquid/wood ratio of the reactants affects the reaction course. After the reaction is over, ionic liquids can be separated from the products and recycled at least five times maintaining good liquefaction activity. The suitability of the ionic liquids for wood liquefaction is ascribed to the functional groups of the ionic liquids. Influencing factors of wood liquefaction are discussed in relation to the ionic composition of the ionic liquids.     

Analysis on residue formation during wood liquefaction with polyhydric alcohol

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     

思茅松的苯酚液化及树脂化研究

研究了硫酸催化条件下，将恩茅松在苯酚中液化用于制备酚醛树脂的技术工艺，分析了各工艺参数对思茅松液化效率的影响，测定了由液化产物制备的液化木基酚醛树脂的物理化学性质和胶合强度。结论如下：1）．液比、反应温度、时间和木粉目数是影响液化反应效率的重要因素，液化产物的残渣率均随上述工艺参数值的升高而降低。2）．残渣含量对树脂物化性质和胶合强度均有影响，残渣含量降低，树脂粘度减小，聚合时间缩短，游离酚含量降低，胶合强度升高。3）．甲醛／苯酚摩尔比对树脂的物化性质和胶合强度也有影响，甲醛／苯酚摩尔比增加，树脂粘度增加，聚合时间减少，游离酚含量减低，胶合强度升高。     

磷酸/离子液体复合体系催化合成乙酸松油酯的研究

将3种磷酸与离子液体组成的复合体系用于催化合成乙酸松油酯的反应,其中,H3PO4/[C4m im]BF4和H3PO4/[C8m im]BF4均显示出很高的催化活性;以H3PO4/[C4m im]BF4为代表,详细考察了反应的影响因素;得出最佳工艺条件:n(松油醇)∶n(乙酸酐)为1∶1.5,松油醇0.03 mol,磷酸0.03 g,反应温度40℃,反应时间10 h,离子液体[C4m im]BF45 g,此条件下所得粗产物中未反应松油醇质量分数仅为0.9%,松油醇的质量分数86.5%,松油烯11.0%。H3PO4/[C4m im]BF4复合体系重复使用7次后,适当补加H3PO4可使催化活性与新催化体系相当。     

Effect of ozone treatment of wood on its liquefaction

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     

木材保护用笼型倍半硅氧烷的合成

木材作为一种重要的建筑材料,本身含有丰富的纤维组织、微孔和导管,由毛细作用吸收空气中的水分。由于受自然环境(如光照、湿度和温度等)的影响,木材易发生湿胀干缩而导致开裂、形变,从而影响其观赏和使用价值,缩短其使用寿命。笔者以使木材表面具有疏水功能为出发点,以硅溶胶和甲基三乙氧基硅烷(MTES)为原料,采用一步法聚合反应得到笼型倍半硅氧烷低聚体(MS)。通过扫描电子显微镜、傅里叶红外光谱、X射线衍射对各合成条件下所得MS的形貌和结构进行了分析,得到的MS颗粒为表面带有羟基基团的微米级、光滑的立方晶体,其最佳合成条件是把1.2 g MTES和0.2 g硅溶胶置于30 mL无水乙醇中,加入20 mL碱催化剂(0.1 mol/L NaOH),室温下超声反应2.5 h。经聚合得到的MS溶液处理后的木材表面构建起微米级粗糙结构,且MS颗粒填充在木材起吸收水分的细胞腔、导管、纹孔等结构中。通过接触角测试得到用MS溶液处理后的木材具有良好的疏水性,接触角达到141.5°。反应所得溶液可直接使用,合成工艺简单,具有良好的应用前景。     

杉木粉液化与液化产物树脂化的研究

以硫酸为催化剂、苯酚为液化剂采用溶剂热法对杉木粉进行液化,用杉木粉液化产物制备出酚醛树脂;考察了反应温度、反应时间、液比(苯酚-木粉的质量比)和催化剂用量对杉木粉液化效率的影响,并初步探讨了液化产物残渣率对所制酚醛树脂性能的影响。实验结果表明,杉木粉液化的最佳工艺条件是:反应温度160℃,液化时间12 h,液比值3,催化剂用量3%,在此条件下残渣率约为10%。液化产物残渣率的测定表明,升高反应温度、延长反应时间、增加液比和催化剂用量可以降低残渣率,提高液化效率;液比值为0.5~1.5时残渣率随液比增加而显著降低,催化剂用量为0.5%~2%时液化效率的变化明显。红外光谱结果表明,由液化产物所合成的酚醛树脂中羟甲基含量较高。液化产物残渣率低时制备的酚醛树脂残碳率较高。     

Preparation and Characterization of Phenolated Wood Using Sulfuric Acid as a Catalyst I: Liquefaction Behavior of Plantation Wood

Chinese fir (Cunninghamia lanceolata) and poplar (Populus spp.) wood meal were phenolated in the presence of sulfuric acid used as a catalyst. The effects of reaction time and reaction temperature on the wood liquefaction were investigated. The results showed that the reaction temperature had the greater influence on the residue content than reaction time. Additionally, the liquefaction curve for the Chinese fir and Poplar were similar in general.     

Characterisation of the curing of liquefied wood by rheometry, DEA and DSC

Liquefied wood is a naturally based product which has the potential to be used as an adhesive. The bonding of wood with liquefied wood requires a high enough temperature to cure the liquid polymers and achieve bond strength. Dielectric analysis, rheometry and differential scanning calorimetry were used to analyse the curing process of low solvent liquefied wood. For the liquefaction, ethylene glycol was used as a solvent and sulphuric acid was used as a catalyst. The dielectric analysis was used for in situ measurements of the curing of liquefied wood during the bonding of wood. It was found that curing started after a temperature of 100 °C had been reached in the bond. This is correlated with the water evaporation and the diffusion of water and ethylene glycol from the liquefied wood into the wood substrate. Rheological measurements proved the influence of the substrate on the curing of the liquefied wood during bonding. Differential scanning calorimetry showed that the curing of liquefied wood occurs in two parts: first, the initial elimination of water and ethylene glycol from the liquefied wood, and then the chemical reaction of the liquefied wood at higher temperatures.     

Reaction behavior of wood in an ionic liquid, 1-ethylpyridinium bromide

The reactions of Japanese cedar and Japanese beech in a pyridinium-based ionic liquid, 1-ethylpyridinium bromide ([EtPy][Br]) were studied. Japanese beech was more easily liquefied than Japanese cedar. Hemicellulose is liquefied rapidly, lignin more slowly, while cellulose is partially liquefied. X-ray diffraction analyses on the [EtPy][Br]-insoluble residues revealed that the crystalline structure of cellulose is maintained even after treatment. The difference in liquefaction can be explained by chemical structural differences between softwood and hardwood lignins and hemicelluloses.