A 13C NMR study of the methylol derivatives of 2,4′‐ and 4,4′‐dihydroxydiphenylmethanes found in resol phenol–formaldehyde resins

A total of 13 of the 16 possible methylol derivatives of 2,4′‐ and 4,4′‐dihydroxydiphenylmethane have been synthesized, isolated, and identified. These compounds are found as intermediates in the cure process of resol phenol–formaldehyde (PF) resins. Analysis of the ¹³C NMR spectra (in acetone‐d₆) of these compounds provided a way to evaluate the seven methylolphenol ring types (methylol derivatives of 2‐hydroxyphenyl and 4‐hydroxyphenyl rings) found in typical resol PF resins using the ipso carbon region from 150 to 160 ppm. A simple diagnostic test was developed using the chemical shift values of the methylol methylene carbon atoms to identify the presence of intermediates containing either a 2‐hydroxyphenyl or a 4‐hydroxyphenyl ring. Using these data it is now possible to analyze the major components in extracted prepreg PF resins. Copyright © 2002 John Wiley & Sons, Ltd.     

Demonstration of methylene-ether bridge formation in melamine-formaldehyde resins

¹H and ¹³C NMR have been used for the quantitative determination of methylene-ether bridges in melamine-formaldehyde (MF) resins. The amount of methylene-ether bridges was determined by ¹³C NMR from the number of monomethylolated amino groups consumed in the condensation reactions and is in agreement with that calculated from the condensation water contents. This latter method, which involves a combination of ¹H and ¹³C NMR, is based on the amount of condensation water released during the formation of both methylene and methylene-ether bridges. © 1995 John Wiley & Sons, Inc.     

酚醛树脂热（裂）解产物的X射线衍射研究

用X射线衍射方法研究了酚醛树脂及对甲基酚醛树脂热解产物本征态及碘掺杂结构,结果表明,不加ZnCl_2的酚醛树酯热解产物具有多晶结构,且随T_p升高层间距如值逐渐减小,加入一定比例ZnCl_2起着增大比表面积和孔径的作用,掺杂碘后如值比本征态有所增加,对甲基酚醛树脂热解产物虽具有无定形结构,但如值基本上不随T_p变化。     

空气中甲醛的乙酰丙酮分光光度快速测定方法

对乙酰丙酮分光光度法测定甲醛的实验条件进行了改进。方法的检出限为0.024μg mL,线性范围为0.05～2.0μg mL,相关系数为0.9996,测定空气中甲醛的最低质量密度为0.008mg m3。改进后的方法可用于空气中微量甲醛的快速检测。     

钙钛矿型La0.2Pb0.4Sr0.4FeO3的制备及其气敏性

采用溶胶-凝胶法首次制备出平均粒径为22.3 nm的La0.2Pb0.4Sr0.4FeO3的晶体,这种复合晶体是正交的钙钛矿型结构.通过对其导电性和气敏性的研究,发现La0.2Pb0.4Sr0.4FeO3材料是一种p型半导体材料,并且在175℃下对甲醛具有很好的气敏性.     

Sensitive Solid Reagent For Formaldehyde,And A New Formaldehyde Generator

Abstract

A solid reagent of Purpald®-acetone aminal on sodium or potassium bicarbonate responds to formaldehyde in the sub-ppm concentration range. A purple color (λ=560 nm) is developed proportional to concentration of formaldehyde and time of exposure after wetting with a 90% acetone-10% water solution. The reagent should be of value as a semi-quantitative warning device for the presence of formaldehyde. A device is described which generates formaldehyde in air in the sub-ppm concentration range at room temperature with desired relative humidity. This generator could be used in the same manner to generate low concentrations of other substances of low volatility.     

A study of condensation of trithiane hexaoxide with formaldehyde

The title reaction catalyzed by NaOH in aqueous media was studied. The oligomeric products formed are characterized in terms of their yield, structure, etc. The effects of reaction parameters and media are also discussed. The reaction mechanism is proposed. © 1993 John Wiley & Sons, Inc.     

室内空气中微量甲醛光催化降解研究进展

综述了甲醛的室内空气污染的研究现状及其对人体健康的影响,阐述了光催化降解的基本原理,分析了液相和气相条件下甲醛降解的途径和影响因素,以及光催化降解甲醛的催化剂的发展情况,讨论了甲醛光催化降解进一步研究的方向和应用前景.     

分光光度法测定甲醛

重点论述了各种测定甲醛的分光光度法的现状及其改进,目前存在的不足之处及面临问题,同时展望了该法的前景。     

甲醛测定方法的进展概述

甲醛是一种重要的化工原料,因其价格低、用途广、易制备等原因被广泛应用到化工、建材、食品、材料、纺织等行业。但甲醛毒性较高,对人体健康、空气质量都有着严重的影响,其污染问题愈来愈受到人们的关注。因此,甲醛的及时准确检测显得尤为重要。该文综述了几种常用的甲醛测定方法。     

Kinetics of heptene-I interaction with formaldehyde in trifluoroacetic acid

A mechanism for formation of hydrogenated furans in the reaction of α-olefins with formaldehyde is suggested. Based on kinetic data, it involves the equilibrium addition of protonated formaldehyde to the olefin.     

乙酰丙酮法测定甲醛反应的产物

探讨了乙酰丙酮与甲醛反应的机理 ,并利用质谱及核磁共振波谱研究了该产物的结构 ,提出了关于乙酰丙酮分光光度法测定甲醛反应产物的新的描述 ,证实该产物为 2 ,6 二甲基 3 ,5 二乙酰基 1 ,4 二氢吡啶。对产物进行了水溶液中的紫外可见光谱研究。该产物在 4 1 3nm处的摩尔吸光系数为 6 63 9× 1 0 3L·mol- 1 ·cm- 1 。     

甲醛去除方法的研究进展

甲醛存在于我们的衣、食、住、行,无处不在,因其毒性大,对人身体危害大,是生活中的隐形杀手,因此甲醛的去除显得尤为重要。综述了几种常用的甲醛去除方法。     

分光光度法测定纺织品中的甲醛含量

针对国家标准“GB/T 2912.1-1998《纺织品甲醛的测定》中第1部分:游离水解的甲醛(水萃取法)”之测定方法中的主要操作条件进行多次试验,分析了分光光度法测定甲醛会产生影响的几个主要操作条件,为执行该标准提供了一个较严谨、较准确的补充方法。     

Assembled Organoruthenium(II) for Formaldehyde Decomposition and Hydrogen Production

Formaldehyde decomposition is not only an attractive method for hydrogen production, but also a potential approach for gaseous formaldehyde removal. In this research, we prepare some assembled organoruthenium through coordination reaction between Ru(p-Cymene)Cl₂ and bridge-linking ligands. It is a creative approach for Ru(p-Cymene)Cl₂ conversion into heterogeneous particles. The rigidity of bridge-linking ligand enables assembled organoruthenium to have highly ordered crystalline structure, even show clear crystal lattice with spacing of 0.19 nm. XPS shows the N−Ru bond are formed between bridge-linking ligand and Ru(p-Cymene)Cl₂. The assembled organoruthenium has high abundant active sites for formaldehyde decomposition at low temperature. The reaction rate could increase linearly with temperature and formaldehyde concentration, with a TOF of 2420 h⁻¹ at 90 °C. It is promising for gaseous formaldehyde decomposition in wet air or nitrogen. Formaldehyde conversion is up to 95 % over Ru-DAPM is 4,4′-diaminodiphenylmethane at 90 °C in air. Gaseous formaldehyde decomposition is a two-steps process under oxygen-free condition. Firstly, formaldehyde dissolve in water, and be converted into hydrogen and formic acid through formaldehyde-water shift reaction. Then intermediate formic acid will further decompose into hydrogen and carbon dioxide. We also find formaldehyde decomposition is a synergetic catalysis process of oxygen and water in moist air. Oxygen is conducive to formic acid desorption and decomposition on the active sites, so assembled organoruthenium exhibit slightly higher conversion for formaldehyde decomposition in moist air. This work proposes a distinctive method for gaseous formaldehyde decomposition in the air, which is entirely different from formaldehyde photocatalysis or thermocatalysis oxidation.     

柱前衍生-萃取阻断反应-高效液相色谱法测定化妆品中游离甲醛

建立了柱前衍生化-萃取阻断反应-高效液相色谱(HPLC)测定化妆品中甲醛的方法。化妆品中甲醛检测的难点是: 甲醛缓释剂类防腐剂在衍生过程中释放甲醛,影响游离甲醛的准确测定。以2,4-二硝基苯肼(DNPH)乙腈溶液-磷酸盐缓冲液(pH 2)(1:1, v/v)为提取溶液,于室温下快速衍生2 min后,立即加入二氯甲烷萃取,阻断衍生反应,经乙腈稀释后进行HPLC测定。以Agilent C18柱(250 mm×4.6 mm, 5 μm)为分离柱,乙腈-水(60:40, v/v)为流动相,流速为1.0 mL/min,于355 nm波长下检测。在洗发水、乳液、膏霜、洗手液、牙膏、指甲油、粉饼中分别添加50、100、500、1000 μg/g 4个浓度水平的甲醛,其回收率为81%～106%,相对标准偏差(n=6)＜5.0%。方法的定量限(以信噪比(S/N)＞10计)为50 μg/g。该方法快速、简便、重现性好,且可以有效避免甲醛缓释剂类防腐剂分解释放甲醛,适用于化妆品中游离甲醛的测定。     

MBTH法测定织物中的微量甲醛

研究了MBTH法测定织物中微量甲醛的原理及条件．甲醛与MBTH反应形成嗪，嗪与MBTH的氧化产物反应生成青蓝色化合物，该青蓝色化合物在635nm处有最大吸收，在最佳条件下甲醛的检出限为0．00l8μg／mL.利用此法测定织物中甲醛的含量，相对标准偏差为0％-2.5％，回收率为96％-105％，结果满意．     

快淬法制备La_(0.8)Ce_(0.2)Fe_(11.4)Si_(1.6)合金的磁熵变研究

为了探求La系磁熵变材料的短时退火工艺,利用两种方法制备了磁制冷材料La0.8Ce0.2Fe11.4Si1.6合金,其一为将电弧熔炼合金退火5天(样品A),其二为将合金利用铜模铸造方法得到快淬样品,再退火2 h(样品B)。X射线衍射表明,样品A和B主相为NaZn13相结构。通过对比发现,尽管样品A的最大磁熵变值大于样品B的,但样品B在制冷温区和制冷能力方面优于样品A。因此,快淬加短时间热处理可以大大节省时间和能量,是一种制备La0.8Ce0.2Fe11.4Si1.6磁制冷材料的高效且性能优越的方法。     

氯酸钾-甲基红体系动力学光度法测定甲醛

在H2 SO4 介质中 ,利用甲醛催化氯酸钾氧化甲基红的褪色反应 ,建立了催化光度法测定痕量甲醛的新方法。方法的线性范围 0 0 4～ 0 80 μg·mL- 1,检出限 1 74× 1 0 - 9g·mL- 1。本法应用于化妆品中甲醛的测定 ,结果满意     

4-溴吲哚-3-甲醛的合成

以2-甲基-3-硝基苯胺为原料,经重氮化反应先合成2-溴-6-硝基甲苯(1),1与N,N-二甲基甲酰胺二甲基缩醛经L-B吲哚合成法制得4-溴吲哚(3),3与N,N-二甲基甲酰胺和三氯氧磷起Vilsmeier-Hacck反应得4-溴吲哚-3-甲醛,总收率62．0％。其结构经^1H NMR和IR确证。