木材的液化及其在高分子材料中的应用

木材是固态的天然高分子材料，通过液化可将其转化为具有反应活性的液态分子，进一步可制备新型高分子材料如胶粘剂、注模塑料、泡沫塑料、纤维材料等，具有广泛的应用前景，是木材化学和木材利用技术新开辟的研究领域。本文综述了近二十年来木材液化技术的发展状况，内容涉及木材液化方法，液化反应机理，液化产物的开发利用。     

纳米木粉在木材工业的应用前景展望

纳米技术作为一个新突破点,在木材工业上也将产生新的技术革命.本文就纳米技术在木材工业上的发展及应用前景进行展望,预测未来纳米技术可能对木材工业产生的影响.木材变成纳米尺寸后,木材的材料特异性质、尺寸效应及其变化机理都可能发生变化.当木粉变成纳米的粒度以后,原来木材理化指标都将发生改变.在细粉状态下进行木材液化可以改变木材液化的方式和成本,使木材液化真正工业化.在复杂木雕制品的加工中,采用RPM技术利用CAD直接将纳米木粉形成各种复杂木雕制品,可能开创一种新的木材加工方法.利用纳米木基复合材料和高分子材料细胞结构重组将开创人造板科学研究的新领域.纳米木粉生产的无污染胶粘剂可代替含甲醛的有毒胶,胶粘剂的绿色革命可能从木材的纳米技术开始.木磁材料和木绝磁材料的研究将使磁材料和绝磁材料生产的成本下降,在纳米材料中,纳米木粉的成本可能是最低的.     

纳微米科学与技术在木材工业的应用前景展望

本文对纳米和微米技术在木材工业上的应用前景进行展望，预测未来纳微米技术可能对木材工业产生的影响，利用纳微米技术可能形成造纸的高得浆率方法，木材在变成纳微米尺寸后，木材的材料特异性质、尺寸效应及其变化机理，以及木材改性的显微结构关系可能使木材改性出现突破性进展。当木粉变成纳微米的粒度后，原木材理化指标发生变化，在细粉状态下进行木材液化可以改变木材液化的方式和成本，使木材液化真正工业化。在复杂木雕制品加工中，采用RPM技术利用直接CAD将纳微米木酚形成复杂木雕制品，可能开创一种新的木材加工方法。利用木材细胞的自组装方式可形成新的木基复合材料，纳米木粉生产的无污染胶粘剂可能代替含甲醛的有毒胶、胶粘剂的绿色革命可能从木材的纳微米技术开始。     

木材苯酚液化产物制备碳纤维的初步探讨

为拓宽木材液化产物的应用领域,提高木材产品的附加值,实现木材的高效利用,在研究木材苯酚液化产物特性的基础上,提出了木材苯酚液化产物碳纤维材料的制备构思和工艺路线。利用木材苯酚液化产物为前驱体,通过加入反应剂如六次甲基四胺等调制纺丝液,熔融纺丝后将纤丝在甲醛和盐酸混合溶液中加热固化形成网状交联结构,然后在惰性气体保护下高温炭化制备成碳纤维,同时对制备过程中可能存在的影响因素进行了分析。     

林产工业专业文摘

<正>竹材液化树脂发泡材料的性能与技术要求文章根据生产性试验,对竹材液化树脂发泡材料及复合发泡材料的制备工艺进行修正和完善,并对其性能和技术要求进行探讨。分析结果表明:竹材液化树脂发泡材料及复合发泡材料的制备工艺成熟,可实现重复性生产;参考或借鉴相应的国家标准测试方法,可全面测试材料的性能;产品规格尺寸能够满足装配式建筑工程要求。[刘乐群,钱华,王进,等.竹材液化树脂发泡材料的性能与技术要求.木材工业,2012,26(5):9-13.]     

木材液化的发展现状及研究前景

1 木材液化的方法 1.1 化学改性后液化法 木材化学改性主要是为了引入取代基,增加木材组织内的自由空间,加上改性反应过程中木素网络结构的断裂,引起木材体积的溶胀,降低木材组分分子间的相互作用力,降低了液化温度.木材化学改性方法包括烷基化、酰化、酯化或醚化等.依据化学处理木材不同的特性,其可在中性水、有机溶剂或者有机溶液中液化,并由此制备新的高分子材料.     

基于AFM的木质材料的纳米压痕技术

基于AFM的纳米压痕技术是微纳米尺度下研究木材及木质材料硬度和弹性模量的重要方法,介绍了AFM工作原理,以及纳米压痕技术测试木质材料硬度、弹性模量等力学性能的原理,总结了木材科研领域中原子力显微技术的应用现状,并对今后的研究方向提出了展望.     

木材的苯酚及多元醇液化反应机理研究进展

综述了国内外在木材苯酚液化及多元醇液化反应机理研究方面的进展,指出了研究木材液化反应机理的重要性,归纳了今后木材液化反应机理研究的发展趋势。深化木材液化反应机理研究可以揭示木材液化的本质,补充和完善木材液化理论研究体系,也有利于实现液化过程的绿色化、降低液化成本、建立液化工艺与产物性质之间的调控机制、加快木材液化技术应用的产业化进程。     

微观力学表征技术的发展及其在木材科学领域中的应用

微观力学表征技术是表征材料微纳米力学性能的重要技术手段,目前已被广泛用于表征材料的超微构造和解析材料的力学行为。随着材料科学研究尺度缩小,微观力学表征技术逐步从纳米向超纳米、从分子向超分子甚至粒子水平发展。按照试样信息的不同方式,微观力学表征技术主要包括纳米力学测试技术(探针技术)和超纳米力学测试技术(显微镜技术);其中,纳米力学测试技术包括准静态纳米压痕技术、动态纳米压痕技术和动态模量成像技术,超纳米力学测试技术包括原子力显微镜技术和基于原子力显微镜技术的新型微观力学表征技术。木材是一种多孔状、层次状、各向异性的非均质天然高分子复合材料,其超微结构是细胞壁由不同厚度的层次组成。细胞壁是决定木材和木质纤维材料性能的主要因素,是木材的实质承载结构;细胞壁的力学性能是由壁层结构、化学组成的分布与结合方式决定的。开展木材和改性木材细胞壁纳观尺度的力学性能、分布及影响对实现木基复合材料的高效设计具有重要意义。自Wimmer等首次将纳米压痕技术应用于天然木材细胞壁微观力学后,国内外学者主要采取准静态纳米压痕测量技术和动态纳米压痕测量技术对不同树种木材以及化学改性和生物改性木材细胞壁的硬度、弹性模量、蠕变特性与黏弹性等力学性能进行了研究。木质材料界面作为纳米级厚度的界面相或者界面层,不仅影响木质材料的强度、刚度,而且影响木质材料的断裂韧性等。界面力学是决定木基复合材料整体力学性质的关键,是引起材料变形、强度下降的主要原因。研究界面的属性和特征对于木基复合材料整体属性的评价以及结构的优化设计有一定参考价值,研究内容涉及有胶合界面、纤维增强聚合物界面以及木制品涂层的微观力学。随着研究尺度逐渐缩小,微观力学表征技术趋向高分辨率及数据定量化,如今已能在纳米级分辨率下进行力学信息成像,为木材科学领域的研究提供了方便。微观力学表征技术在木材科学领域中的应用尚具有较大潜力,但仍有较多方向尚未涉及,还应在以下3方面展开研究:一是需要开展微观力学技术在木材科学领域应用的标准化研究,规范测试过程,确保测试结果的可靠性和一致性;二是建立木质材料宏观到微观的完整力学体系,从本质上剖析木质材料的力学行为,在纳米尺度上表征木质材料的性质和失效机制;三是随着木材科学领域研究的深入,需建立微观力学与微观化学、微观物理、微观环境学的联系,丰富木材及木基复合材料在微纳尺度的研究。     

仿生光子晶体结构色在木材颜色功能性改良中的应用前景

对木材表面进行颜色功能性改良是提高木材使用价值的重要途径。文中总结传统木材染色和诱导变色工艺的发展现状及存在的问题,提出利用结构色进行颜色改良是一种清洁无污染的生态仿生着色技术,综述其在木质材料领域中的研究现状,并从木质材料表面结构色构筑及机理、木质材料表面结构色的光响应及界面机理、木质材料表面仿生结构色薄膜大规模应用技术、木质纤维素纳米晶结构色薄膜制备及其功能拓展4个方面提出研究展望。     

木材液化技术研究现状及产业化发展

扼要介绍了国内外木材液化技术研究的现状,分析了开发木材液化研究领域的重要性,并对木材液化技术的研究方向、发展趋势以及该技术在我国实现产业化应用的前景提出了建议.     

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.     

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.     

Rapid wood liquefaction by supercritical phenol

Wood was rapidly liquefied at the supercritical temperature of phenol. Under these conditions, wood was liquefied by over 90% for 0.5 min, and the combined phenol content of the obtained liquefied wood reached about 75%. The effects of various reaction conditions on liquefaction were investigated. With increases in reaction temperature, phenol/wood weight ratio, and the charged mass-to-reactor capacity (w/v) ratio, the amount of methanol-insoluble residue decreased and combined phenol content increased. The range of molecular weights and polydispersity of the products obtained after the time at which sufficient liquefaction was achieved were from 400 to 600 and from 1.5 to 2.5, respectively. Wood showed a marked decomposition to low molecular weight components early in the reaction, and then the molecular weight increased slightly with increasing reaction time. The properties of liquefied wood were investigated and compared with those obtained with conventional liquefaction methods. Combined phenol content was similar to that obtained by other liquefaction methods, except the sulfuric acid–catalyzed method, which resulted in flow properties comparable to those of other liquefaction methods. The flexural strength of moldings prepared using liquefied wood was also comparable to those prepared by other liquefaction methods.     

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 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.     

Influence of reaction atmosphere on the liquefaction and depolymerization of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

The influence of reaction atmosphere on the liquefaction and depolymerization of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), has been systematically studied. The wood samples were treated with [C2mim][Cl] at 120°C under various atmospheres such as oxygen, nitrogen, and carbon dioxide, both dried and humidified. The percentage of residue after the treatment shows that oxygen considerably accelerates the liquefaction of wood in [C2mim][Cl], and humidity hardly affects liquefaction under any atmosphere. Gel permeation chromatography (GPC) and high performance liquid chromatography (HPLC) analyses on the solubilized compounds in [C2mim][Cl] indicate that oxygen and humidity enhance the depolymerization of the wood component. Thus, the reaction atmosphere was revealed to influence, and 1be capable of controlling, the reaction of wood in [C2mim][Cl].     

Liquefaction and product identification of main chemical compositions of wood in phenol

To clarify liquefaction ratios and their construction variations of the main chemical compositions of wood in phenol using phosphoric acid as a catalyst, the chemical ingredients of wood such as holocellulose, cellulose and lignin, were measured and extracted according to GB methods. With Fourier transform infrared （FTIR）, the product identification of reactant before and after liquefaction in phenol was investigated. The molecular weights and their distributions of the liquefaction results （acetone soluble parts） were studied by gel permeation chromatography （GPC）. Results show that the molecular weights and their distributions of poplar and Chinese fir are almost the same. In poplar, the distribution of cellulose is the largest, and that ofholocellulose the smallest after liquefaction. For Chinese fir, the distribution of holocellulose is the largest, and that of cellulose the smallest. After liquefaction of poplar cellulose, the change bands of FTIR spectrum observed below 1 600 cm^-1, can be attributed to new substitute groups. The same is true for poplar lignin. For Chinese fir, the spectra of liquefaction results of all chemical compositions differ from that of wood meal. This reveals the more activity groups were produced because of the reactions between Chinese fir and phenol. The research shows that the liquefaction ratios of poplar decrease in the following order： holocellulose 〉 lignin 〉 cellulose, and those of Chinese fir in the order： lignin 〉 cellulose 〉 holocellulose.     

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