Formation and chemical structures of acid-soluble lignin I: sulfuric acid treatment time and acid-soluble lignin content of hardwood

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.     

麦草酶解-温和酸解木质素的化学结构特性研究

采用酶解预处理、温和酸解和溶剂提取相结合的木质素分离新技术分离得到了代表性好的麦草纤维酶解-温和酸解木质素(EAL)。采用元素分析、定量31P NMR、衍生化后还原反应(DFRC)等分析技术和实验方法,对麦草EAL木质素的官能团含量、β-芳基醚键的特性与含量、二苯并二氧桥松柏醇(DBDO)结构等特性进行了较深入的研究。     

Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

The two kinds of rigid polyurethane (PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.     

杞柳的化学成分及其木质素微区分布的研究

采用传统的化学成分测试方法和激光扫描共聚焦显微镜技术(CLSM)研究了杞柳的化学成分以及木质素在各细胞及纤维细胞各微区的分布,分析了株高不同部位化学成分的变异规律。结果表明:杞柳的1%Na OH抽提物、热水抽提物、冷水抽提物、苯醇抽提物、综纤维素、α-纤维素、酸不溶木质素、酸溶木质素、多戊糖和灰分分别为32.11%、10.85%、7.11%、3.27%、70.46%、35.50%、20.18%、4.50%、15.51%、0.90%;在不同部位,除了α-纤维素和多戊糖含量差异不显著,其余各指标均差异显著;木质素在各细胞及纤维细胞各微区分布不均一,导管细胞壁木质素浓度高于木纤维和射线,纤维细胞角隅处木质素浓度高于次生壁和复合胞间层。     

核桃壳胶粘剂化学背景的探讨

探讨漾濞泡核桃壳作木材胶粘剂原料的化学背景。化学分析结果表明:漾濞泡核桃壳中含(硝酸法)纤维素3 3 2 5 %、多戊糖2 6 72 %、木素6 0 94 %、灰分1 1 9%;核磁共振氢谱、紫外和红外光谱的分析结果表明:核桃壳木素以愈疮木基-紫丁香基木素为主,属GS型木素,且G型木素的含量大于S型木素。利用G型阔叶材木素的化学性质可以合成得到与普通酚醛树脂胶合性能相当的核桃壳木素-苯酚-甲醛共聚树脂。     

高地钩叶藤材化学成分含量分析

为构建棕榈藤材材性数据库,提升棕榈藤材高附加值加工利用水平,文章以高地钩叶藤为研究对象,对其主要化学成分含量进行测定和分析。结果表明,高地钩叶藤材综纤维素、酸不溶木质素、α-纤维素、半纤维素、苯-醇抽提物、热水抽提物、冷水抽提物、1%NaOH抽提物及灰分含量的均值分别为67.98%、16.72%、43.91%、24.38%、9.78%、18.85%、15.02%、38.60%和1.46%。径向上,综纤维素、α-纤维素、酸不溶木质素及灰分含量均为藤皮>藤中>藤芯;而半纤维素、冷水抽提物、热水抽提物、苯-醇抽提物及1%NaOH抽提物含量均为藤芯>藤中>藤皮。轴向上,综纤维素、α-纤维素、酸不溶木质素及灰分含量最大值均在中部,而半纤维素及4种抽提物含量最大值均在梢部。酸不溶木质素和α-纤维素含量最小值在梢部,综纤维素、半纤维素及灰分含量最小值在基部,冷水抽提物、苯-醇抽提物及1%NaOH抽提物含量最小值均出现在基部以上2 m处,而热水抽提物含量最小值在中部。     

The effect of hyperbranched polymer lubricant as a compatibilizer on the structure and properties of lignin/polypropylene composites

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.     

Effect of the amount of lignin on tensile properties of single wood fibers

Chemical components are the main factors affecting the mechanical properties of wood fibers. Lignin is one of the main components of wood cell walls and has a critical effect on the mechanical properties of paper pulp and wood fiber based composites. In this study, we carried out tensile tests on single mature latewood tracheids of Chinese fir (Cunninghamia lanciolata (Lamb.) Hook.), using three different delignified treatment methods to obtain different amounts of lignin. We applied single fiber tests to study the effect of the amount of lignin on mechanical tensile properties of single wood fibers at the cellular level. The results show that in their dry state, the modulus of elasticity of single fibers decreased with the reduction in the amount of lignin; even their absolute values were not high. The amount of lignin affects the tensile strength and elongation of single fibers considerably. Tensile strength and elongation of single fibers increase with a reduction in the amount of lignin.     

Phenolization of hardwood sulfuric acid lignin and comparison of the behavior of the syringyl and guaiacyl units in lignin

To study the behavior of hardwood sulfuric acid lignin (SAL) during phenolization, we compared the product yield, average molecular weight, methoxy content, and reactions of simple model compounds with those of softwood SAL, focusing on the difference between syringyl and guaiacyl units. The beech SAL reacted with phenol more readily than red pine SAL and yielded a larger soluble fraction of phenolized SAL. To investigate the difference in the phenolization activity of the syringyl and guaiacyl units in beech lignin, we prepared syringyl-nucleus-rich sulfuric acid lignin (S-rich-SAL) and guaiacyl-nucleus-rich sulfuric acid lignin (G-rich-SAL) from beech, which were subjected to phenolization. The results suggest that the syringyl unit in SAL had greater phenolization activity and its phenolized products were more soluble in acidic aqueous medium and introduced less phenol than the guaiacyl unit. Using model compounds, the study also showed that the syringyl unit had higher phenolization reactivity than the guaiacyl unit.     

Study on Chemical Components of Alkaline Nitrobenzene Oxidation from Plantation Woods

This paper deals with the chemical components and the chemical structure of lignin of Chinese fir and Poplar I-214 from plantationforest. The results revealed that the contents ofchemical component in heart wood and sapwood were almost the same except ethanol-benzene extract both in Chinese fir and in Poplar I-214, The contents of ash, holocellulose, α -cellulose, pentosan, ethanol-benzene extract and cold-water extract in Poplar I-214 were higher than that in Chinesefir, The content of lignin in Poplar I-214 was lower than that in Chinese flr. Vanillin, vanillic acid and p-hydroxybenzaldehyde were found in Chinesefir while vanillin and vanillic acid, p-hydroxybenzoic acid, syringaldehyde and syringic acid werefound in Poplar I-214 in investigation of the chemical structure of lignin by using nitrobenzene oxidization method.     

Catalytic graphitization of hardwood acetic acid lignin with nickel acetate

 Catalytic graphitization of hardwood acetic acid lignin (HAL) with nickel (II) acetate was investigated regarding the production of highly crystalline carbon. Fusibility, one of the unique characteristics of HAL, was preserved with nickel acetate additions up to 0.3% (as the weight of nickel), although the thermal mobility of HAL was depressed by the addition of nickel acetate. An obvious effect of nickel salt as a catalyst on the development of carbon crystallite from HAL was observed for more than 0.2% addition. The development was found to proceed above 850°C. All the resulting carbons had turbostratic structure, and the apparent crystallite size (L _c) was increased with increasing amounts of catalyst, as determined by X-ray diffraction. Thus, highly crystalline carbon was produced from HAL by catalytic graphitization without compromising the fusibility of HAL by adding a small amount of organic nickel salt. Received: December 17, 2001 / Accepted: March 27, 2002 Present address: Department of Wood and Paper Science, North Carolina State University, NC 27695-8005, USA Part of this paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000 Correspondence to:Y. Uraki     

纤维素乙醇炼制残渣中木质素结构的初步研究

针对燃料乙醇行业产生的大量炼制残渣所带来的资源浪费问题,采用了傅里叶红外(FTIR)、差示扫描量热法(DSC)、核磁共振(NMR)等方法,初步研究了纤维素乙醇炼制残渣中木质素的结构。研究发现,纤维素乙醇木质素有明显的酚羟基结构,相对分子质量较小,是一种潜在的重要资源。     

Chemical structure and thermal properties of lignin modified with polyethylene glycol during steam explosion

Thermoplastic processing of lignin is restricted by its high glass transition temperature (T _g). In this study, lignin was modified with polyethylene glycol (PEG) during steam explosion to improve its thermoplastic properties, and the effects of steam explosion and PEG on the chemical structure and thermal properties of lignin were investigated. Structure characterization using Fourier transform infrared spectroscopy showed that hydroxyl and ether functional groups increased and the activity of lignin was improved by steam explosion. In addition, steam explosion treatment was more effective than heat treatment for promoting the reaction of PEG with lignin. Solid-state ¹³C NMR revealed that PEG was grafted onto lignin. The T _g of raw lignin was 164.1 °C; after steam explosion, lignin exhibited more than one T _gs. The T _g of lignin was reduced when the steam explosion temperature increased and decreased further, to around 60 °C, when PEG was used to modify lignin. Therefore, this work provides an effective approach to reducing the high T _g of lignin.     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

稻壳高沸醇木质素的制备与结构分析

稻壳高沸醇木质素(RHL)是通过高沸醇溶剂法制备得到的,借助化学组分分析、红外吸收光普、氢质谱和碳质谱分析法分析其结构性质.把稻壳与70%(90%的丁二醇水溶液混合后,放入高压釜中,在一定的固液比下,加热至200(220℃,保持1.0(3.0小时.加水沉淀后,就可以得到水不溶的RHL.温度越低,木质素的得率也越低;丁二醇浓度越低,木质素得率也将越低.化学分析得到RHL分子量是1939 g(mol-1、残糖量5.12%;核磁共振得到RHL脂肪基对芳香甲氧基的相对强度分别出现在3.5-3.8 ppm和 3.8-4.0 ppm,RHL各单元主要通过β-O-4 和 β-5 碳-碳链链接.利用上述数据计算得到了经典的C9结构模型.     

杨树木质素合成酶hct基因的克隆及核苷酸序列分析

根据毛果杨全序列（AC185363.2）中唯一具有转移酶功能的保守区设计引物,以正在分化的2年生欧美杨107次生木质部总RNA为模板经RT-PCR扩增出hct基因片段,与pMD20-T载体连接,重组质粒经特异引物扩增、限制性内切酶酶切和测序鉴定。结果表明,扩增片段长度为709bp,包含一个708bp的开放阅读框,与毛果杨全序列及HCT2（EU603314）的同源性均为98%,编码的氨基酸序列与毛果杨HCT2氨基酸（ACC63883.1）的同源性为98%,断定我们克隆的cDNA为hct,属于转移酶超家族,GenBank登录号为FM202091,该重组质粒命名为pMD20-T-hct。     

绿液预处理对麦草化学成分及酶水解糖化的影响

主要探讨在不同温度、用碱量和硫化度条件下绿液预处理对麦草化学成分及酶水解效率的影响。随着预处理用碱量和硫化度的提高木质素的脱除率增加,但同时也加剧了碳水化合物的降解,导致麦草浆得率下降。绿液预处理废液的pH值小于9.5,弱碱介质可以减少碳水化合物的降解,同时避免禾草原料含量较高的硅溶解在黑液中,有利于废液的碱回收利用。预处理后浆料经过由纤维素酶、木聚糖酶和β-葡萄糖苷酶组合而成的混合酶液水解,纤维素酶用量从5 FPU/g增加到10 FPU/g时,总糖得率及转化率显著增加。在酶用量为10 FPU/g条件下经过48 h的酶水解后,温度130℃、用碱量8%、硫化度40%条件下的预处理浆料总糖得率达到最大值43%,总糖转化率为73.1%。     

青檀树皮的化学组成与细胞壁结构

为指导宣纸的生产和使用,以青植树皮为研究对象,对其化学组成、纤维形态和细胞壁结构进行研究.结果表明:青檀树皮的综纤维素含量为61.43%,木质素含量为9.03%,灰分含量为5.07%,从其化学组成来看,檀皮的木质素含量较低,容易制浆,但制浆得率比较低,檀皮中碳酸钙含量高,有利于增强宣纸的润墨性;植皮纤维的细胞壁厚,微纤丝多,其间的空隙也多,使宣纸的吸墨性很好;檀皮纤维的平均长度为2.95mm,均整性较好,平均宽度为10.99μm,长宽比为268,较一般针叶材纤维大.     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

青梅叶化学成分研究

采用正相硅胶柱、反相硅胶柱、凝胶柱等柱色谱及高效液相色谱等方法对青梅叶的化学成分进行分离纯化,并通过理化性质和核磁共振等方法鉴定化合物的结构。从青梅叶75%乙醇提取物中分离了13个化合物,分别鉴定为岩白菜素(1),1,3,4/2,5-环己五醇(2),3-(1-C-β-葡萄糖)-2,6-二羟基-5-甲氧基苯甲酸(3),木栓酮(4),木栓醇(5),羽扇豆醇(6),4-叔丁基苯甲醚(7),对甲氧基苯甲酸(8),邻苯二甲酸二异丁酯(9),邻苯二甲酸二丁酯(10),熊果酸(11),β-谷甾醇(12),β-胡萝卜苷(13)。化合物2～9均为首次从青梅属植物中分离得到,化合物1为青梅中具有保肝护肝的主要活性成分之一。