尿素与甲醛加成及缩聚产物^13CNMR研究

合成并研究了几种尿素与甲醛的加成、缩聚产物结构，使用高分辨＾１３Ｃ核磁共振仪（ＤＲＸ－５００）确定了几种典型结构的化学位移并对化学位移的变化规律展开讨论他一种脲醛树脂合成中间产物及最终液体树脂的结构，指定了各吸收峰的归属；结合模型化合物研究结果并参考文献，给出了脲醛树脂各结构单元的化学位移。     

低甲醛释放量刨花板用脲醛树脂结构的研究(英文)

本文通过~(13)C NMR研究了脲醛树脂合成新工艺中不同反应阶段时的脲醛树脂的化学结构。研究结果表明脲醛树脂的化学结构主要受甲醛/尿素的摩尔比,pH值、反应温度和反应时间的影响。对脲醛树脂中主要的官能团:游离甲醛、亚甲基、亚甲基醚、Uron等相互关系也进行了研究。指出了生产低甲醛释放量,高力学性能刨花板用脲醛树脂中主要官能团的最佳含量。     

脲醛树脂研究进展

本文对脲醛树脂的甲醛释放、合成与反应机理、低摩尔比脲醛树脂的合成、树脂化学构造分析、固化机理进行了综述。并介绍了脲醛树脂合成方法与树脂化学构造的关系,以及强酸性条件下合成低摩尔比脲醛树脂固化机理的最新研究成果。     

固体核磁共振法对低甲醛释放脲醛树脂化学结构的研究

在采用液体核磁对3种低甲醛释放脲醛树脂化学构造进行分析的基础上,利用13CCP/MASNMR对脲醛树脂固化产物的化学结构进行了研究.结果表明,不同固化体系下,3种低甲醛释放脲醛树脂胶黏剂的固化历程不同,固化后树脂的结构有所差别.不添加固化剂时,脲醛树脂的固化交联反应程度低,固化产物中羟甲基含量高,甲醛释放量也随之增加.加入固化剂后,促进了羟甲基的固化交联反应,脲醛树脂固化产物中羟甲基含量普遍降低.3种固化体系下,UF-3羟甲基含量最高;在氯化铵为固化剂的条件下,UF-2羟甲基含量最低,为0.0582;不添加固化剂和复合固化体系条件下,UF-1羟甲基含量最低,分别为0.0784和0.0713.不同固化体系对不同种类脲醛树脂的固化效果不同,固化后树脂的结构不同,其力学性能和甲醛释放能力也不同.     

脲醛树脂中引入电解质作用的研究

采用FTIR、DSC等分析手段对一种可以有效降低生产成本的脲醛树脂活性剂进行研究.结果表明:活性剂的主要成分是羟甲基脲,电解质没有与脲醛衍生物产生化学结合,活性剂降低了树脂表面张力,增大了对木材的润湿性,在参与固化反应的过程中,活性剂降低了脲醛树脂固化反应的活化能,说明有更多的树脂分子参与到固化反应中来,宏观上表现出提高了脲醛树脂的粘接效率;设计了一种脲醛树脂合成工艺,在合成过程中合理引入电解质,通过压制胶合板、纸板等试验,对产物的性能进行了综合评价,结论认为由于电解质的引入,加快了反应速度,提高了粘接强度,但也导致了胶接制品的湿强度下降;从理论上对电解质发生的作用机制进行探索,为有效控制脲醛树脂的合成和应用成本提供一种可操作的方法.     

中温合成PVA缩甲醛改性脲醛树脂的研究

本文研究了饰面中密度纤维板用脲醛树脂的合成工艺，同时介绍了中温合成ＰＶＡ缩甲醛改性脲醛树脂的原理和方法。     

低甲醛释放脲醛树脂研究进展

从脲醛树脂胶粘剂的合成工艺、使用时加入添加剂、人造板的后处理等几个方面,综述了近几年来脲醛树脂及其胶接制品降低甲醛释放研究的新进展。     

木材工业用脲醛树脂的研究进展

对脲醛树脂的理论研究及其在木材工业中的实际应用进行了较全面的概括和评述。在将核磁共振应用于脲醛树脂的结构研究之后,区分了结构上的细微差别。讨论了脲醛树脂的合成过程,特别是酸性缩聚阶段的工艺条件对树脂甲醛释放量的影响。列举了脲醛树脂常用的各种改性物质及它们对脲醛树脂各种性能的改性效果。     

中温合成PVA缩甲醛改性脲醛树脂的研究

本文研究了饰面中密度纤维板用脲醛树脂的合成工艺，同时介绍了中温合成ＰＶＡ缩甲醛改性脲醛树脂的原理和方法。     

双马来海松酸酯多元醇的合成研究

利用马来海松酸中酸酐和羧基反应活性的差异，合成了两种类型的双马来海松酸酯多元醇．测试了酯化产物的分子量、聚合度、粘度、羟值和官能度等理化参数；并对各产物的耐热性和红外光谱进行了讨论．研究结果表明，所有酯化产物均可作为耐热的多元醇原料使用．     

Effects of afforestation on soil organic matter characteristics under subtropical forests with low elevation

We selected sites of natural broad-leaved forests and adjacent coniferous plantations (Cunninghamia konishii and Calocedrus formosana of 30 and 80 years old, respectively) in central Taiwan to evaluate the effects of plantations on soil organic matter (SOM) characteristics and composition. SOM was characterized by chemical analyses, solid-state ¹³C cross-polarization magic-angle nuclear magnetic resonance (CPMAS ¹³C NMR), and optical measurements. Semiquantitative analysis of CPMAS ¹³C NMR spectra showed the litter of broad-leaved forests to be less resistant to decomposition than that of coniferous forests. The humification degree of SOM was higher under broad-leaved than coniferous forests because of the relatively high percentage of aromatic C and carboxyl C in the humic acids (HAs) of A horizons under broad-leaved forests. Additionally, the E ₄/E ₆ ratio of HAs was lower in the A horizon under broad-leaved than coniferous forests, which reflected more condensation of SOM. High alkyl C content under coniferous forests could be attributed to needle litter quality, which has a high content of waxes or lipids. Afforestation with conifers induced accumulation of the litterfall layer, gradually increased SOM concentrations, and changed the composition structures of SOM in the topsoils.     

天然香豆素衍生物~（13）C－NMR化学位移研究──Ⅰ．取代基效应因子与化学位移的定量关系

通过模型化合物１３Ｃ－ＮＭＲ化学位移的经验取代基参数，对天然香豆素衍生物１３Ｃ－ＮＭＲ化学位移，进行了系统的研究．结果表明，模型化合物的取代基参数，与香豆素衍生物的化学位移具有良好的线性关系．从而提出了香豆素取代基效应因子，建立了香豆素衍生物１３Ｃ－ＮＭＲ化学位移与取代基效应因子的定量关系式．用于计算和预测香豆素的化学位移．     

Laser ablation-combustion-GC-IRMS--a new method for online analysis of intra-annual variation of delta13C in tree rings

We present a new, rapid method for high-resolution online determination of delta13C in tree rings, combining laser ablation (LA), combustion (C), gas chromatography (GC) and isotope ratio mass spectrometry (IRMS) (LA-C-GC-IRMS). Sample material was extracted every 6 min with a UV-laser from a tree core, leaving 40-microm-wide holes. Ablated wood dust was combusted to CO2 at 700 degrees C, separated from other gases on a GC column and injected into an isotope ratio mass spectrometer after removal of water vapor. The measurements were calibrated against an internal and an external standard. The tree core remained intact and could be used for subsequent dendrochronological and dendrochemical analyses. Cores from two Scots pine trees (Pinus sylvestris spp. sibirica Lebed.) from central Siberia were sampled. Inter- and intra-annual patterns of delta13C in whole-wood and lignin-extracted cores were indistinguishable apart from a constant offset, suggesting that lignin extraction is unnecessary for our method. Comparison with the conventional method (microtome slicing, elemental analysis and IRMS) indicated high accuracy of the LA-C-GC-IRMS measurements. Patterns of delta13C along three parallel ablation lines on the same core showed high congruence. A conservative estimate of the precision was +/- 0.24 per thousand. Isotopic patterns of the two Scots pine trees were broadly similar, indicating a signal related to the forest stand's climate history. The maximum variation in delta13C over 22 years was about 5 per thousand, ranging from -27 to -22.3 per thousand. The most obvious pattern was a sharp decline in delta13C during latewood formation and a rapid increase with spring early growth. We conclude that the LA-C-GC-IRMS method will be useful in elucidating short-term climate effects on the delta13C signal in tree rings.     

Determination of the surface fractal dimension from sorption isotherms of five softwoods

Summary This paper presents the determination of the surface fractal dimensions from water adsorption/desorption data of five softwood species by using three different methods. The Frenkel-Holsi-Hill model of polymolecular sorption on a fractal surface by allowing capillary condensation is shown to be the best method. Using this method, the fractal dimensions were found to be close to 2.5 and 2.4 from desorption and adsorption isotherms respectively. Moreover, they were shown to slightly vary between species, and between sapwood and heartwood for the temperature range of 30 to 60 °C, but with no clearly identifiable temperature effect. Received 13 March 1997     

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     

Simple method for synthesizing phenolicβ-O-4 dilignols

A modified synthetic method for phenolic-O-4 lignin substructure model dimers was developed involving protection of the phenolic hydroxyl group of acetophenons with benzoyl chloride, bromination with 4-dimethylaminopyridiniumbromide perbromide, condensation with phenols in the presence of 18-crown-6-ether, condensation with paraformaldehyde, reduction with NaBH₄ and debenzoylation. This method results in shorter reaction times and increasing yields without the application of strict anhydrous and drastic conditions or chloric solvents. This alternative route could be applied to the-O-4 dilignol syntheses of four combinations of guaiacyl and syringyl derivatives.     

Condensation of lignin during heating of wood

Summary The structural change of lignin during heating of wood was investigated quantitatively by a method combining nucleus exchange and nitrobenzene oxidation. Lignin modification during heating was mainly a diphenylmethane type condensation. About 40 and 75% of noncondensed units in protolignins were converted to diphenylmethane type units by heating of dry and wet wood meals up to 220 °C, respectively. On the other hand, during heating of modified lignin (dioxane lignin) various types of modifications in addition to diphenylmethane type condensation occurred. Lignin modification via the diphenylmethane type condensation was proposed as a new route for its utilization.     

Carbon isotope variation in Douglas-fir foliage: improving the delta(13)C-climate relationship

The natural abundance of stable carbon isotopes in the annual rings of forest trees is used as a tracer of environmental changes such as climate and atmospheric pollution. Although tree-ring delta(13)C varies by about 2 per thousand from year to year, variability within the foliage can be as high as 6 per thousand. Recent studies have shown that branch length affects stomatal response, which influences the integrated foliar delta(13)C signal. To improve the ability of delta(13)C to predict climate differences, we examined the relationship between branch length and foliar delta(13)C in Pseudotsuga menziesii (Mirb.) Franco from four sites across a steep climate gradient in Oregon. The transect spanned the boundary between the ranges of the coastal variety, P. menziesii var. menziesii (three sites), and the Rocky Mountain variety, P. menziesii var. glauca (one site). At the most maritime site, branch length explained 76% of within-site variation of 5 per thousand, whereas at the harshest site, branch length accounted for only 15% of this variation. We considered the possibility that cavitation in the water-conducting xylem obscures the branch length effect in the harsher climates. Cavitation, as measured by dye perfusion, was most extensive at sites where the branch length effect in the coastal variety was weakest. Trees at the site with the most substantial cavitation displayed seasonal xylem refilling. Branch length standardization significantly improved the relationship between delta(13)C and climate. With standardization to constant length, delta(13)C values were significantly related to the degree that climatic variables, as modeled with a forest growth simulation model, constrain transpiration (R(2) = 0.69, P < 0.0001). Without standardization, the R(2) was 0.27. We conclude that sampling standard length branches or tree rings from trees of similar shape and size is desirable when seeking correlations between isotopic composition and climate.     

Analysis of chemical structure of wood charcoal by X-ray photoelectron spectroscopy

Wood charcoal carbonized at various temperatures was analyzed by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffractometry to investigate the changes of chemical structures during the carbonization process. From the infrared spectra, the carbon double bonds and aromatic rings were seen to form at a carbonization temperature of about 600°C. From the XPS spectra, the ratio of aromatic carbons increased in the temperature range 800–1000°C and over 1800°C. The condensation of aromatic rings proceeded as carbonization progressed. The drastic reduction of electrical resistivity of charcoals was observed in almost the same temperature range. It was found that the condensation of aromatic rings had some relation to the decline in electrical resistivity. Wood charcoal carbonized at 1800°C was partly graphitized, a finding supported by the results of X-ray diffraction and XPS. The functional groups containing oxygen diminished with the increase in carbonization temperature.This paper was presented at the 45th Annual Meeting of the Japan Wood Research Society in Tokyo, April 1995 and at the 47th Annual Meeting of the Japan Wood Research Society in Kochi, April 1997