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。     

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%.     

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.     

Factors affecting the resinification of liquefied phenolated wood

Wood of Chinese fir and poplar were liquefied in phenol at 150℃ and atmospheric pressure. The liquefied wood were reacted with formaldehyde to synthesize the liquefied wood-based resin. The factors affecting the resinification and the properties of new resin were investigated. The results show that the formaldehyde/liquefied wood molar ratio, reaction temperature, reaction time and sodium hydroxide/liquefied wood molar ratio have important influence on the resin characteristics. With the increase of formaldehyde/liquefied wood molar ratio, the yield of resin increases, and the flee phenol content of resins decreases, showing that the resinification of liquefied wood is more complete at higher formaldehyde/liquefied wood molar ratios. The reaction temperature on the viscosity of the liquefied resin has considerable effect; the viscosity of resin increased with increasing reaction temperature, and the amount of liquefied poplar resin increased more quickly than that of liquefied Chinese fir resin. The resinification time also has obvious influence on the viscosity of resin; the viscosity of liquefied poplar resin is more sensitive to resinification time compared with that of liquefied Chinese fir. The amount of sodium hydroxide can improve the water miscibility of liquefied wood resin. The optimum sodium hydroxide/liquefied wood molar ratio for preparation of liquefied wood-based resins exceeds 0.4.     

木束条尺寸对杉木积成材性能的影响研究

为了探索较佳的木束条尺寸,以提高杉木积成材的质量,研究了不同尺寸的杉木木束条对杉木积成材性能的影响规律,结果表明:木束条的长度对杉木积成材的纵向静曲强度、弹性模量、24h吸水厚度膨胀率有较大的影响;木束条的厚度对杉木积成材纵向静曲强度、弹性模量的影响不大,但对24h吸水厚度膨胀率、内结合强度有较大的影响;木束条的宽度对杉木积成材的物理力学性能影响极小,不存在统计意义上的影响;木束条的较佳尺寸为:长度120 mm,宽度4mm,厚度2.5 mm.     

Effect of Wood Variables on the Properties of Wood Fiber-Polypropylene Composites

The effect of wood species (Chinese fir and Poplar), wood fiber content (10%, 25%, 40%) and wood fiber sizes (16 to 32 mesh, 32-65 mesh, above 65 mesh) on the properties of the wood fiber-Polypropylene composites were studied in this paper. The results indicate that the effect of wood fiber content and size in composite were more important than that of chosen wood species. Compared with polypropylene without wood fiber, the flexural strength of the composites increased when adding wood fiber into polypropylene, but the tensile and unnotched charpy impact strength decreased. And the above strength decreased with the wood fiber content increasing. When the wood fiber size becoming smaller (in higher mesh), the strength increased. In the comparison of wood species, the properties of composite using Chinese fir wood were better than that of Poplar, but not significant. The dynamic mechanical properties of the composites and PP were also tested and analyzed in this paper.     

人工林珍贵树种柚木和楸木的热解特性及动力学

木材阻燃体系的选择应考虑其热解特性，选取人工林珍贵树种柚木、楸木和速生材杉木、辐射松为研究对象，通过化学成分和热重（TG）分析试验，研究热解特性、热解动力学模型和参数，为阻燃体系选择提供理论依据。结果表明：四种木材的热解过程均可分为失水、过渡、剧烈降解和成炭等四个阶段；柚木、楸木的最大热解速率温度、活化能和活化因子均低于杉木和辐射松，适用于热解温度相对较低的阻燃体系。     

超临界甲醇液化杉木工艺的探讨

采用超临界流体技术液化杉木，考察了溶木比、温度、压力及时间对液化率及分子特征的影响，并使用FTIR和XRD对液化产物及其残渣进行了分析。结果表明，当溶木比为12：1，温度为270℃，压力为12MPa，时间为60min时，有较高的液化率，且液化产物的分子量分布均匀。FTIR和XRD的分析结果显示，杉木超临界液化产物中含有大量的具有反应活性的芳核衍生物，同时也仍然有一些微晶结构存在。     

杉木木材性质研究进展

文中重点对杉木的木材解剖性质、物理力学性质、化学性质的研究现状进行了归纳和分析, 并针对影响杉木木材性质变异规律的生长因子进行了总结, 最后就杉木木材性质的研究方法、趋势提出了几点建议。     

杉木/钙基蒙脱土插层复合材的结构表征

为了对杉木/钙基蒙脱土插层复合材的结构进行表征,笔者通过色差计测定其颜色,通过扫描电镜(SEM)和X射线衍射仪(XRD)测定了其微观结构.研究结果表明:1.通过色差计可见,杉木/钙基蒙脱土插层复合材的颜色比未处理杉木深,但杉木的天然纹理并没有被改变.2.通过SEM可见,钙基蒙脱土全部或基本充实整个细胞腔和纹孔腔,且填充完整连续,与细胞壁紧密接触.但杉木的填充存在不均匀性,单个细胞和纹孔中,其填充程度也有差异.3.XRD证明,杉木/钙基蒙脱土捕层复合板材中水溶性酚醛树脂插入到钙基蒙脱土层间,为插层型复合材料.蒙脱土和酚醛树脂在一定程度上撑大了杉木的无定区域.     

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.     

Properties of Wood/Montmorillonite Nanocomposites

INTRODUCTIONWood possesses many special properties, such asbeautiful grain, natural color, high strength-to-weightratio, good electricity and heat insulation; and it can beeasily processed, glued or dyed. It is biodegradable,recyclable and environmental-friendly (Wang Tianminet al. 2002). But as a biomaterial, it also has intrinsicdefects as easy decaying, burning and deforming,which largely limits its usage. Nano science andtechnology opens a completely new way to developwood composites…     

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.     

杉木短轮伐期工业材物理力学性质预测模型的研究

以应用正交试验设计方法对不同林龄、不同立地条件和不同林分密度下人工杉木林木材物理力学性质变异规律的研究为基础,采用多元线性回归方法,建立了用林龄、林分密度、地位指数 ３ 因子预测杉木短轮伐期工业林木材物理力学性质指标的一系列回归方程,并经回归显著性检验,这些方程的复相关关系均显著     

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.     

无机物填充改性复合木材的制备及性能研究

为改善速生杉木木材的性质,试验中先后用硫酸铝和水玻璃等溶液对其进行处理,浸入木材的铝离子与硅酸根离子结合,在木材微纤丝间隙和管胞(或纤维)的胞腔中生成硫酸铝沉淀,从而使木材中填充了大量的无机物,得到杉木无机复合木材.无机复合木材的尺寸稳定性显著提高,在最优化工艺下,复合木材的抗收缩系数可达34.21,稳定系数在80%以上.同时,复合木材除抗冲击韧性略有下降外,其余如抗弯强度、抗弯弹性模量、顺纹抗压强度及硬度等主要力学性能指标均有明显提高.     

支持向量机结合近红外光谱法测定杉木木质素的含量

采用支持向量机(SVM)结合近红外光谱(NIR)技术建立测定杉木中木质素的定量分析模型。以47个杉木样品作为实验材料,用常规方法测定了样品中木质素的含量,用近红外光谱仪采集相应的光谱,对光谱数据进行平滑、求导、小波压缩以及归一化,结合支持向量机,以径向基(RBF)作为核函数,建立了测定杉木中木质素含量的模型。校正相对误差的平方和为0.007433,预测相对误差的平方和为0.001219。结果表明,该方法测量比较准确,可以用于杉木中木质素含量的预测。     

超临界CO_2流体处理工艺对木材渗透性的影响

以苯—乙醇为夹带剂,研究超临界CO2流体不同处理压力、温度、时间对福建产杉木、马尾松、檫木木材渗透性的影响。结果表明,在35 MPa内,处理压力的增大有利于3种木材渗透性的提高;杉木在处理温度为40℃时,渗透性的变化率达到最大,为493%,马尾松和檫木在处理温度为45℃时,渗透性的变化率达到最大,分别为479%和349%;较佳的处理时间为30 min。     

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     

Use of Near Infrared Spectroscopy to Measure Mechanical Properties of Solid Wood

The visible and near infrared （NIR） （350-2500 nm） spectra and the MOE of 438 small clear wood samples from Chinese fir, eucalyptus and poplar 72 were measured. Using partial least-square （PLS） modeling, the NIR spectra could be used to predict MOE and MOR of the clear-wood samples from Chinese fir and eucalyptus solid wood. NIR spectra could only be used to Predict MOE but not MOR of poplar clear-wood samples. With the exception of MoR of poplar clear-wood samples, the correlations between NIR and the mechanical properties are very strong, and the calibration and test correlation coefficients are both above 0.80.