非硫光气法合成一些难合成的芳基异硫氰酸酯

在三乙烯二胺存在下，芳胺与二硫化碳反应先生成芳胺基二硫代甲酸盐，然后与双(三氯甲基)碳酸酯(BTC)反应，可用于制备苯环上连接了硝基、三氟甲基或者两个以上卤素等吸电子基团的难合成芳基异硫氰酸酯，收率达到71％～95％。     

芳磺酰异硫氰酸酯的合成工艺研究

报道了以芳磺酰胺为起始原料,与氢氧化钾在N,N-二甲基甲酰胺中混合,滴加二硫化碳,在氮气保护下于45°C反应7.5 h,析出棕黄色二硫代芳磺酰亚胺钾盐。过滤,真空干燥,将所得化合物悬浮于无水二氯乙烷中,滴加二(三氯甲基)碳酸酯二氯乙烷溶液,1.5 h加毕,在45°C下持续反应15 h,得芳磺酰异硫氰酸酯,产率61%~75%。     

异硫氰酸酯的制备及应用

异硫氰酸酯作为一类重要的有机合成中间体,其制备及应用受到广泛关注。笔者综述了异硫氰酸酯的多种制备方法及其在化合物合成、生物技术方面的应用,并对糖基异硫氰酸酯这类特殊的异硫氰酸酯的应用作了较详尽的阐述。     

三氯甲基碳酸酯替代光气的应用

本文介绍了三氯甲基碳酸酯（BTC）的制备和在精细化工领域替代光气的应用。     

异硫氰酸酯的制备及应用

本文综述了异硫氰酸酯的实验室制备方法,并介绍了其在杂环化合物合成及生物技术等方面的应用。     

2,4-二氯苯异氰酸酯的清洁工艺合成研究

以双(三氯甲基)碳酸酯为原料制备2,4-二氯苯基异氰酸酯,研究了反应时间、温度、物料配比、催化剂用量对2,4-二氯苯基异氰酸酯产率的影响,并以反应温度、反应时间、物料配比为考察因素,采用RSM响应面分析法,确定了2,4-二氯苯基异氰酸酯制备的最佳工艺参数,即反应时间为2.76h、反应温度为67.41℃、物料配比n(2,4-二氯苯胺)∶n(双(三氯甲基)碳酸酯)为0.14∶1。在此优化工艺下2,4-二氯苯基异氰酸酯产率预测值为39.07%,验证实验中实际测得2,4-二氯苯基异氰酸酯产率为38.01%,预测值与实际值无显著差异。     

双三氯甲基碳酸酯的合成与应用

介绍了双三氯甲基碳酸酯的性能,制备和应用。     

非异氰酸酯聚氨酯材料的制备技术及应用研究进展

介绍了非异氰酸酯聚氨酯(NIPU)的发展概况,讨论了NIPU的主要制备技术,并综述了NIPU在涂料、胶粘剂和泡沫等方面的应用研究进展。     

三氯甲基碳酸酯的生产和应用

三氯甲基碳酸酯是一种可以代替光气和双光气的新型化工原料,用途广泛。本文介绍了三氯甲基碳酸酯的性质,制备方法及其在医药,农药和高分子材料等方面的应用。     

4-异氰酸酯基苯乙酸乙酯的合成工艺研究

介绍了以对氨基苯乙酸乙酯和三光气为原料合成其异氰酸酯的研究.重点讨论了溶剂、原料配比、反应时间、反应温度和滴加顺序等对合成工艺的影响.研究表明:以1,2-二氯乙烷为溶剂,反应回流时间为4-5 h,物质的量比n二(三-氯甲基)碳酸酯(BTC):n对氨基苯乙酸乙酯=1:2,收率可达97%.     

Dimeric isocyanates in polyurethane powder coatings

Internally-blocked polyurethane crosslinkers based on the uretdione of isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) will be introduced. The principal structures and the performance properties of different products will be described. Besides the use in conventional high-gloss coatings, the possibilities will also be pointed out for special uretdione adducts for coatings with greater chemical resistance, specifically solvent resistance, or in the preparation of matte surfaces.     

绿色化学在异氰酸酯合成中的应用

介绍了近十年来异氰酸酯在绿色合成中的研究进展。分析了绿色原料、反血工艺、催化剂及友好溶剂四方面的优点及不足,阐述了其反应机理,并对非光气法合成异氰酸酯的前景做了展望。同时,分别介绍了脱水剂选择和摧化剂选用的研究进展。最后,指出发展绿色合成异氰酸酯的可行性和重要性。     

有机异氰酸酯生产技术进展

对近年世界有机异氰酸酯的生产技术发展状况、液相光气化混合反应技术、气相光气化混合反应技术、非光气法制异氰酸酯研究与技术进展等进行总结,并对其发展趋势进行展望。     

有机异氰酸酯的生产及市场消费状况

对近年国内外有机异氰酸酯生产及市场消费状况进行了全面介绍,并对未来的生产消费趋势进行了展望。     

固体光气和氯代苯胺合成氯代苯异氰酸酯反应的量子化学研究

对反应物氯代苯胺的异氰化进行了量子化计算研究.通过构型优化、热力学分析、电荷分布分析等模拟计算,从理论上确定了氯代苯胺进行异氰化反应的难易程度为对氯苯胺＞间氯苯胺＞邻氯苯胺.通过对合成氯代苯异氰酸酯的反应进行研究可知,邻、间、对氯苯基单异氰酸酯的收率分别达84.7％、86.2％、89.0％,实验结果与理论计算结果相符.     

13C NMR investigation of the reaction in water of UF resins with blocked emulsifiable isocyanates

A solid state ¹³C NMR study of hardened networks obtained by the reaction of blocked and nonblocked isocyanates (pMDI) with urea‐formaldehyde (UF) resins in water showed different results according to the temperature of the reaction. At high temperature, in water, both a nonblocked or an emulsifiable, blocked isocyanate, appear to crosslink with UF resins through the formation both of traditional methylene bridges connecting urea to urea and of urethane bridges. The latter have been confirmed by ¹³C NMR to form in water by reaction of the isocyanate ? N?C?O group with the hydroxymethyl groups of the UF resin. At ambient temperature, UF/pMDI resins where the pMDI is a emulsifiable blocked isocyanate, do not appear to form urethanes to any great extent but rather to crosslink through the usual UF resin urea to urea methylene bridges. Even in this case, when urethane bridges appear to be absent, evidence of crosslinking in water through reaction of the isocyanate with the ? NH₂ and ? NH? amide of the UF resin has not been observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 589–596, 2006     

封闭型异氰酸酯胶粘剂的研制

以聚乙二醇（PEG）、甲苯-2,4-二异氰酸酯（TDI）等为原料制得阳离子水性聚氨酯,异氰酸酯用丁二酮肟进行封闭制备封闭型异氰酸酯胶粘剂,探讨了阳离子水性聚氨酯溶液的固含量、TDI的封闭,解封以及封闭型异氰酸酯的用量对产品性能的影响.结果表明：30%的阳离子水性聚氨酯溶液加入溶液质量15%左右的封闭型异氰酸酯的胶粘剂对金属的粘接效果较好.     

Detailed study of distribution patterns of polycyclic aromatic hydrocarbons and isocyanates under different fire conditions

This study has examined the distribution patterns between gas phase and particle phase of some chemical compounds produced in fires. It has also addressed the question of the distribution of individual particle‐associated species between the different size‐ranges of particles. The chemical compounds studied and discussed in this paper are polycyclic aromatic hydrocarbons (PAHs), and isocyanates. The steady‐state tube furnace, ISO/TS 19700, was chosen as the physical fire model in order to study the production of particles from different types of fire exposure, that is, oxidative pyrolysis, well‐ventilated flaming fires and under‐ventilated flaming post‐flashover fires. Two materials were chosen for investigation, a polyvinyl chloride ( PVC) carpet and a wood board. The particle production from the two materials investigated varied concerning both the amounts produced and the particle size distributions. The analysis of PAHs showed that volatile PAHs were generally dominant. However, when the toxicity of the individual species was taken into account, the relative importance between volatile and particle‐associated PAHs shifted the dominance to particle‐bound PAH for both materials. The substantial degradation in the tests of the low polyurethane content of the PVC carpet, and the (4,4′‐methylenediphenyl diisocyanate)‐based binder in the wood board resulted in no or very small amount of quantifiable diisocyanates. Copyright © 2013 John Wiley & Sons, Ltd.     

封端异氰酸酯合成聚酰亚胺及其性能

以苯甲醇封端的甲苯二异氰酸酯、苯甲醇封端的二苯甲烷二异氰酸酯和3,3',4,4'-二苯酮四酸二酐为原料制备聚酰亚胺,并在高温条件下进一步热处理提高其相对分子质量。采用傅里叶变换红外光谱、热重分析、差示扫描量热法等研究了其结构和性能。结果表明:在250℃处理5 h,然后350℃处理2 h后,成功制备了具有较好热性能和较高相对分子质量且具有良好溶解性能的聚酰亚胺。     

Structure–property relationship of blocked diisocyanates: synthesis of polyimides using imidazole‐blocked isocyanates

Imidazole, 2‐methylimidazole and benzimidazole‐blocked aromatic and aliphatic diisocyanates have been prepared and polymerized with pyromellitic dianhydride in the presence of a basic catalyst. The polymers are characterized with FTIR, ¹H NMR and ¹³C NMR spectroscopy and GPC, DSC and TGA. The structure–property relationship of blocked diisocyanates are discussed in terms of molecular weight of the polyimides obtained. Considering the blocking agent, GPC results show that the benzimidazole blocked adduct yields higher molecular weight polymer than the 2‐methylimidazole‐blocked adduct which, in turn, yields higher molecular weight polymer than the imidazole‐blocked adduct. Considering the structure of the isocyanate, the molecular weight of polymer increases from isophorone diisocyanate to hexamethylene diisocyanate and to toluene diisocyanate (TDI). DSC traces of the polymers derived from TDI show glass transitions (T_g) in the temperature range 152–180 °C and the values increase from the polymer based on imidazole‐blocked TDI to 2‐methylimidazole‐blocked TDI and to benzimidazole‐blocked TDI. © 2000 Society of Chemical Industry