落叶松树皮栲胶废渣各组分及其磺化产物的表面活性对比研究

分析了兴安落叶松树皮栲胶废渣的主要化学组分及各组分的磺化产物对木质素磺酸盐的表面活性的作用,发现树皮栲胶废渣制备的木质素磺酸盐表面活性、分散性能和净浆流动度较木材木质素磺酸盐高。表面活性和分散性能好的主要原因是栲胶废渣中可溶单宁和红粉的存在,而具有更好的净浆流动度是因为可溶单宁和酚酸的存在。     

尼罗河荆树树皮红粉及其亚硫酸化

天然产生的聚合酚类红粉是用二甲替甲酰胺从尼罗河荆树(AcaciaNilotica)树皮中分离出来的。将树皮物料直接亚硫酸化能陡单宁浸出物增加到31.0%。纯粹的红粉试样在亚硫酸盐浸提中很易溶解,而用沸水预先处理红粉后再进行亚硫酸化使试样的35.0%成为可溶。这证明了通过亚硫酸化能增加得率。用脱灰山羊皮进行鞣革试验,制成的皮革后经过化学分析。值得提到的是,用亚硫酸浸提液以及用二甲替甲酰胺浸提液中的水溶物所鞣制的皮革质量是优良的。     

单宁物质的化学和利用

本文讨论了单宁在分析测定和结构分析中存在的问题,并叙述了树皮和单宁在各种生物工艺上的利用。例如,分别用沸水或1％的氢氧化钠水溶液在95～100℃浸提云杉树皮30小时,其浸出物得率分别为27％和50％左右(以绝干树皮计),然而碱浸出物主要是单宁以外的化合物。用绿色木霉中的纤维素酶水解纤维素的水解作用能被云杉树皮中的粗单宁所抑制,而纯单宁却不影响纤维素酶的水解活性。     

橡椀栲胶简介

一、橡椀栲胶生产概况: 栲胶是林业化工产品,是从含有单宁的树皮、根、茎、叶、果实或果壳做原料,经过浸提浓缩、干燥等工序加工制成的。橡椀栲胶是用麻栎、栓皮栎(俗名又叫橡树)的果壳(又叫橡椀)为原料加工制成的。我国栲胶资源极为丰富,有几十种植物可以浸提栲胶,主要有落叶松树皮、橡椀、化香果、红根、解树皮、木麻黄树皮、杨梅树皮、余柑树皮、板栗壳和黑荆树皮等,在     

国产落叶松栲膠的鞣革性能

我国第一座栲膠厂正在大兴安嶺牙克石兴建,今年将大量生产落叶松栲膠,供給全国各制革厂使用。落叶松学名Larix gmelini,pilg,树皮内含一种品质优良的植物鞣料,属儿茶类鞣质(单宁),含量約8～12%,純度約62%;落叶松栲膠即自树皮中提出,故又名落叶松树皮栲膠。国产落叶松栲膠的化学成分,如以含水分为20%計,其中含鞣质41%,不溶物14%。关于它的糅革性能,分别简述如次: 一、收敛性与pH值(酸碱值):收斂性不大,     

麦草碱木质素的过氧化氢氧化氨解 Ⅲ.过渡金属对氧化氨解反应的影响

探讨了过渡金属对麦草碱木质素过氧化氢氧化氨解的影响。结果表明 ,加入Mn2 + 和Cu2 + 导致过氧化氢无效分解 ,使氧化氨解产物的氮含量下降 ;而添加Fe2 + 作催化剂 ,在 5× 1 0 - 6 ～ 2 5× 1 0 - 6 (质量分数 )浓度范围内可有效地促进产物氮含量的提高。当Fe2 + 的添加量为 2 5× 1 0 - 6(质量分数 )时 ,氧化氨解木质素的总氮和有效氮含量分别提高 34 %和39% ,甲氧基含量进一步下降 ,羧基含量增加 ,并且在 50℃时反应时间可缩短至 60min。     

兴安落叶松木素化学结构特性的研究

从兴安落叶松的边材、心材和经0．1mol／NaOH抽提过的心材中分离出二氧六环木素，用化学分析和光谱分析研究了分离木素的化学结构特性．结果表明兴安落叶松的边材和心材术素都是典型的针叶材木素，三种分离木素的元素组成、官能团含量和光谱性质没有显著差异，心材多酚类化合你又少与木素存在化学连接，只是心材木素的缩合程度略高，分子量低于边材术素．兴安落叶松边材、心材和经0．lmol／NaOH抽提的心材的二氧六环木素C9单元式分别为C9H8.80O3.06（OCH3）0.96C9H8.80O3.14（OCH3）0.93和C9H8.55O3.03（OCH3）0.96，与马尾松二氧六环木素十分相似。     

桉树皮单宁分析

对广西高峰林场桃源分厂4年生的大叶桉和尾叶桉树皮的单宁含量进行了分析,并分别进行了栲胶的试制。分析结果表明:大叶桉和尾叶桉树皮单宁属于缩合类单宁,树皮单宁含量分别为7.6%和7.8%,纯度分别为67.9%和70.3%;大叶桉树皮栲胶单宁含量为65.4%,尾叶桉树皮栲胶单宁含量为63.3%。桉树皮可作为新品种栲胶原料,其栲胶值得推广应用。     

泰妥拉唑的合成及表征

以2-氯甲基-4-甲氧基-3,5-二甲基吡啶盐酸盐(Ⅱ)和2-巯基-5-甲氧基咪唑并[4,5-b]吡啶(Ⅲ)为原料,在氢氧化钠水溶液中于30℃反应生成2-[2-(4-甲氧基-3,5-二甲基)吡啶甲硫基]-5-甲氧基咪唑[4,5-b]吡啶(Ⅳ),收率90.1%。随后用质量分数为30%的过氧化氢氧化制得泰妥拉唑(Ⅰ),收率86.3%,两步总收率为77.8%。产物结构经IR、1HNMR确证。     

树皮酚类制备油田钻井液添加剂的研究

研究了兴安落叶松树皮经碱性磺化浸提 (15 0～ 180℃ ,3～ 6h)后 ,所得酚类磺化物再经络合(70～ 90℃ ,30～ 10 0min)、偶合 (70～ 10 0℃ ,1～ 5h)、缩合 (70～ 10 0℃ ,1～ 6h)、交联 (5 0～ 6 0℃ ,30～ 90min)多步化学改性 ,制备聚合物钻井液添加剂的新方法。所得添加剂中相对分子质量在5 0 0 0以上级分的摩尔分数 >80 % ,其分子上含有 3种亲水基团 :w(—SO3H) =13.4% ,w(—COOH)=8.2 6 % ,w(Ph—OH) =0 .96 % ;该添加剂在黏土颗粒表面发生吸附包被的摩尔分数为 93.9% ,在聚合物钻井液中的添加量为 0 .0 1kg/m3 时 ,降黏率和降滤失率分别为 6 5 .8%和 42 .9%。     

A new source of natural adhesive: Acacia mangium bark extracts co-polymerized with phenol-formaldehyde (PF) for bonding Mempisang (Annonaceae spp.) veneers

Acacia mangium is a fast-growing dicotyledonous tree species and has become the dominating plantation in Malaysia. It was grown particularly as a raw material for veneer, pulp, and paper industries. The chemical properties test in this study showed that the A. mangium tree bark contains higher extractive content as compared to the wood portion (sapwood). Tannin extracts from A. mangium tree bark were found to be rich in phenolic compounds and had the potential to replace conventional phenol-formaldehyde (PF) adhesive used in the plywood manufacturing industry. Tannin adhesive (tannin-paraformaldehyde) prepared from A. mangium bark tannin by cross-linking with paraformaldehyde were used for bonding of Mempisang (Annonaceae spp.) plywood board. However, the resulting bonding strength using tannin adhesive was found to be only suitable for interior grade application. Further extension of its application for interior and exterior grade plywood could be achieved with addition of PF (co-polymerization with resol) during the production process. The optimized formulation of tannin adhesive consists of A. mangium solid extracts (90 parts), commercial PF (10 parts), and paraformaldehyde (3%). Results have shown that the plywood shear strength complies with the requirement for European norms EN 314-1 and EN 314-2:1993, which includes the dry test, cold water test, and the boiling test.     

有机酸水溶液提取玉米芯木质素及其性质

以甲酸/乙酸水溶液为溶剂提取玉米芯木质素。利用响应面法考察了甲酸浓度、提取温度和反应时间等因素对木质素产率的影响。结果表明,最优的反应条件为:V(甲酸)∶V(乙酸)=4∶5,提取温度为91℃,反应时间4 h,在该条件下木质素产率的预测值为67.91%,实验验证值为70.16%。利用紫外光谱法和化学滴定法研究了木质素的纯度、酚羟基和羧基含量,测定了木质素在不同溶剂中的溶解性,通过红外、紫外、核磁共振及热重等方法对所提取的木质素的结构和性质进行了表征。结果显示,有机酸水溶液提取的木质素同时含有紫丁香单元(S)、愈创木基单元(G)和对-羟基苯丙烷单元(H),而且与碱木质素结构相似。热重分析表明,该木质素具有更好的热稳定性,600℃时热解残余物的质量分数为42%。有机酸水溶液处理法是提取高纯度玉米芯木质素的有效方法。     

Rapid Hydrothermolysis of Poplar Wood: Comparison of Sapwood,Heartwood, Bark,and Isolated Lignin

Abstract

Rapid hydrothermolysis at 350°C of poplar sapwood, heartwood and bark, as well as the lignin extracted from the sapwood and heartwood, gives oil and water soluble fractions whose chemical analysis is correlated with the nature of the feed stock. Results from cellulose and Douglas fir are included, and the poplar bark and heartwood lignin are shown to give an ether soluble oil that consists mainly of guaiacyl units while the sapwood product is mainly syringyl. However, the chloroform soluble oil from both sapwood and heartwood was mainly syringyl with the additional presence of carbohydrate derived material in the heartwood oil. The acetone-only soluble residue from sapwood was shown by pyrolysis mass spectrometry to be mainly cellulose derived while that from heartwood was mainly from lignin. Thus there is a fundamental difference in the behaviour of the poplar sapwood and heartwood that may arise from different distributions of the guaiacyl and syringyl units, and of the binding to the cellulose. The origin of the rapid hydrothermolysis products with respect to the major wood components is discussed. An empirical approach to the calculation of the lignin content based on the rapid hydrothermolysis fractions is presented.     

Insights into depolymerization pathways and mechanism of alkali lignin over a Ni1.2–ZrO2/WO3/γ-Al2O3 catalyst

This study performed catalytic depolymerization of alkali lignin over Ni-based catalysts. Effects of different promoters (Zr and W), Ni loadings, reaction temperatures, and the addition of formic acid and catalyst on lignin conversion and products distribution were all investigated. The result showed that the highest oil yield (40.1% (mass)) was obtained at 240?℃ over Ni_1.2/γ-Al₂O₃ promoted by Zr and W species. Quantitative analysis indicates that Zr and W species prefer to lignin depolymerization while Ni active phase prefer to hydrodeoxygenation and hydrogenation. The interconversion of products derived from lignin depolymerization was determined by gas chromatography-mass spectrometer, which demonstrated that phenolic compounds were dominant products in all lignin derived bio-oils, wherein the proportion of vanillin was highest (65.7%) at 180?℃, while that of alkyl guaiacols increased with the increase of temperature (from 12.45% at 180?℃ to 66.67% at 240?℃). Residual lignin obtained after lignin depolymerization was also investigated for detecting differences on functional groups, wherein the disappearing peaks at 1511?cm^?1 (stretching of aromatic rings), 1267, 1215 and 1035?cm^?1 (vibrations of guaiacyl and syringyl units) were detected by Fourier transform infrared spectrometry. Additionally, the higher O/C ratio measured by elemental analysis also confirmed that alkali lignin was depolymerized effectively under mild conditions.     

Synthesis and characterization of phenolic novolacs modified by chestnut and mimosa tannin extracts

The possibility of reacting chestnut and mimosa tannins with the intermediates of the synthesis reaction for phenolic novolacs under acid conditions has been proved using differential scanning calorimetry (DSC). The amount of intermediate compounds and the percentage of free phenol and formaldehyde in the reaction mixture is decisive for the determination of the stage in which the addition of tannin is suitable. Synthesis of novolac resins modified with 14 wt % mimosa tannin extract or with several percentages (until 40 wt %) of chestnut tannin have been performed. The reaction pathways have been investigated by DSC, fourier transformed infrared spectroscopy and gel permeation chromatography. Ester groups of chestnut tannin result in a reaction pathway different from the one for mimosa‐modified resins and nonmodified resins. Preliminary studies of curing reactions of synthesized resins with hexamethylenetetramine indicate that the cure of modified‐resins is even more favorable than the one for nonmodified resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4412–4419, 2006     

毛泡桐(原变种)内桐皮的化学成分

对玄参科(Scrophulariaceae)泡桐属(Paulownia)植物毛泡桐(原变种)(Paulownia tomentosa(Thunb.)Steud.var.tomentosa)内桐皮的化学成分进行了研究。采用Sephadex LH-20柱色谱及薄层色谱等方法进行反复纯化分离及制备,从其70%丙酮提取物乙酸乙酯萃取相中分离到5种化合物,经理化性质和波谱解析化合物分别鉴定为:对香豆酸(ρ-coumaric acid,Ⅰ)、咖啡酸(caffeic acid,Ⅱ)、毛蕊花糖苷(verbascoside,Ⅲ)、异毛蕊花糖苷(isoverbascoside,Ⅳ)和肉苁蓉甙F(cistanoside F,Ⅴ)。化合物Ⅰ和Ⅱ为酚酸类化合物,Ⅲ～Ⅴ为差向立构苯丙素苷类化合物,Ⅰ、Ⅱ和Ⅴ首次从该植物中分离得到。     

Performances of larch (larix gmelini) tannin modified urea–formaldehyde (TUF) resin and plywood bonded by TUF resin

Tannin from larch (Larix gmelini) bark extracts, as a natural renewable resource, was used to prepare tannin–urea–formaldehyde (TUF) resin. The chemical structures of larch tannin and TUF resin were characterized by matrix‐assisted laser desorption/ionization‐time of flight mass spectrometry and ¹³C nuclear magnetic resonance. The thermal behaviors of TUF resin were evaluated by differential scanning calorimetry (DSC) and thermomechanical analysis (TMA). The performances of TUF resin were investigated by measuring the bond strength and formaldehyde emission of its bonded plywood. It was clearly shown that larch tannin is mainly composed of prodelphinidin repeating units. Phenolic groups were introduced into TUF resin mainly linked by methylene bond. Larch tannin has an adverse effect on the resin curing. However, it promoted the rigidity and flexibility of the glued system and upgraded the properties of plywood. Therefore, larch tannin could be applied in the modification of urea–formaldehyde resin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41064.     

Studies on the Reactions of Phenolic and Non-Phenolic Lignin Model Compounds with Chlorine Dioxide

The reaction between chlorine dioxide and four different lignin model compounds (phenolic and non-phenolic, with or without an α-hydroxyl group) are studied. The key difference with previous studies is the effective elimination of hypochlorous acid by sulfamic acid during chlorine dioxide treatment. The elimination of hypochlorous acid, an important intermediate formed during chlorine dioxide bleaching, makes it possible to study the consumption of the lignin model compounds solely as a result of the action of chlorine dioxide.

Based on almost closed mass balances for the substrate and atomic chlorine it is found that the reaction between ClO₂ and lignin model compounds is generally characterized by three independent parallel reactions:

1) demethylation, 2) formation of 2-methoxy-p-quinone and 3) formation of muconic acid monomethyl ester and/or its derivatives. Although, the importance of each reaction depends on the functional groups of the substrate, the demethylation reaction is the most important. It is shown that non-phenolic lignin model compounds do react with ClO₂ when ClO₂ is supplied in large excess. However at conditions representative of industrial ClO₂ application levels, only the phenolic substrates react with chlorine dioxide when both phenolic and non-phenolic lignin model compounds are present. Contrary to the previous model compound studies done without effective elimination of hypochlorous acid, no chloroaromatic material is detected in the present investigation. This supports the view that the reaction intermediate hypochlorous acid (or chlorine) is solely responsible for the formation of chloro organic material during chlorine dioxide bleaching. Reaction mechanisms of the degradation of phenolic and non-phenolic lignin model compounds by CI0₂ are also discussed.     

Formation rate of benzyl cation intermediate from p-Hydroxyphenyl,guaiacyl, or syringyl nucleus in acidolysis of lignin

The benzyl cation intermediate is believed to be primarily formed in the acid-catalyzed reaction of lignin, and the reaction route of the intermediate determines which reaction products are afforded and whether lignin undergoes depolymerization or condensation. This study aimed to examine the formation rate of the benzyl cation intermediate from phenolic (P) or non-phenolic (N) lignin model compounds with different types of aromatic nuclei, namely p-hydroxyphenyl (H), guaiacyl (G), or syringyl (S). The rate was in the order of H > G > S for both P- and N-type model compounds and of P > N for all H-, G-, and S- type model compounds. The orders were successfully explained by the electron-donating or electron-withdrawing properties of the hydroxy and methoxy groups at the para- and meta- of the benzyl position, which is the reaction center in the formation of the benzyl cation intermediate.