苯甲酰异氰酸酯合成路线及反应条件研究

综述了苯甲酰异氰酸酯的合成路线，并探讨了利用苯甲酰胺与草酰氯制备苯甲酰异氰酸酯的最佳反应条件。     

苯甲酰基脲类杀虫剂伏虫隆的合成

伏虫隆是一种新苯甲酰脲类杀虫剂,尤其对有机磷、拟除虫菊酯、氨基甲酸酯三类杀虫剂已产生抗性的害虫防治效果更佳。采用2,4-二氟硝基苯经氯化、还原合成巾间体3,5-二氯-2,4-二氟苯胺,2,6-二氟苯甲酰胺与二(三氯甲基)碳酸酯酰化合成另一中间体2,6-二氟苯甲酰异氰酸酯,2,6-二氟苯甲酰异氰酸酯与3,5-二氯-2,4-二氟苯胺加成得到杀虫剂伏虫隆,总收率为79．3％。该工艺具有原料易得、异构体少、反应步骤短等特点。     

除虫脲合成研究

以２，６－二氟苯甲酰基异氰酸酯和对氯苯胺为原料，对除虫脲的合成工艺作了研究，为进一步开发苯甲酰脲类农药提供了重要依据。     

含邻氨基苯甲酸结构的苯甲酰脲类化合物的合成及杀虫活性

以取代的邻氨基苯甲酸为原料,经固体光气合环再经取代胺或醇开环制得邻氨基苯甲酸类中间体,然后与2,6-二氟苯甲酰异氰酸酯反应合成了12个具有邻氨基苯甲酸结构的苯甲酰脲类化合物.目标化合物的结构经1H NMR进行了确证.室内生测结果表明化合物Ⅲ-2、Ⅲ-4在100 mg/L时对甜菜夜蛾具有较好的防治效果.     

杀虫剂伏虫隆的合成

以 1,2 ,4 三氯苯为原料 ,经硝化、氯化、氟化和还原等步骤合成了 5 二氯 2 ,4 二氟苯胺 ,产率为 72 % ;以 2 ,6 二氯苯腈为原料 ,经氟化和水解制得 2 ,6 二氟苯甲酰胺 ,产率为92 % ;将 2 ,6 二氟苯甲酰胺先用二 (三氯甲基 )碳酸酯酰化后制得 2 ,6 二氟苯甲酰异氰酸酯 ,再与 3,5 二氯 2 ,4 二氟苯胺加成得到苯甲酰脲类杀虫剂伏虫隆 ,产率为 93%     

苯甲酰丙烯酸乙酯中主要杂质的定性分析与转化

顺丁烯二酸酐与苯在三氯化铝的存在下,经傅-克反应生成苯甲酰丙烯酸,在强酸性水介质中,若温度高于35℃,则部分发生与水的加成反应生成苯甲酰乳酸。含苯甲酰乳酸的苯甲酰丙烯酸在浓硫酸的存在下与无水乙醇反应,可分别生成苯甲酰丙烯酸乙酯和苯甲酰乳酸乙酯。而苯甲酰乳酸乙酯在二甲苯中回流可脱去一分子水而转变为苯甲酰丙烯酸乙酯,从而使苯甲酰丙烯酸乙酯的纯度从85%提高到93%。     

苯甲酰甲酸及其酯的合成

本文报道了高锰酸钾氧化苯乙烯制备苯甲酰甲酸和固体超强酸催化苯甲酰甲酸酯化制备苯甲酰甲酸甲酯、乙酯的方法。     

苯甲酰甲酸甲酯的合成

研究了苯甲酰甲酸甲酯的制备方法。以苯乙酮为原料,亚硝酸氧化生成苯甲酰甲酸,强酸性阳离子交换树脂催化酯化合成苯甲酰甲酸甲酯,总收率为65.85%。产物结构经核磁共振氢谱、质谱确证。     

二苯甲酰甲烷酮式-烯醇式互变异构的研究

本文研究了甲醇钠用量,酸化条件,水洗温度和结晶溶剂的种类等后处理因素对二苯甲酰甲烷酮式-烯醇式互变异构的影响,并对二苯甲酰甲烷的稳定性进行了分析。实验中发现烯醇式结构的含量与二苯甲酰甲烷的热稳定性的关系．对二苯甲酰甲烷作为高分子材料的辅助稳定剂的应用具有重要的意义．     

手性拆分剂L-二苯甲酰酒石酸和L-二乙酰酒石酸的合成工艺研究

研究了手性拆分剂L-二苯甲酰酒石酸和L-二乙酰酒石酸的合成工艺及各种反应条件对收率和产物旋光纯度的影响。在路易斯酸催化下,L-酒石酸与苯甲酰氯及二氯亚砜作用生成L-二苯甲酰酒石酸酐,然后L-二苯甲酰酒石酸酐再水解成L-二苯甲酰酒石酸,二步总收率86%,旋光纯度大于99%;在硫酸催化下,L-酒石酸与乙酐作用生成L-二乙酰酒石酸酐,再水解成L-二乙酰酒石酸,二步总收率为75%,旋光纯度大于99%。     

Mechanical and thermal properties of bisphenol A-based cyanate ester and diallyl phthalate blends

Cyanate ester resins are a high performance class of compounds. They have excellent mechanical properties, dielectric properties and thermal properties; however, their major drawback is their brittleness. An attempt was made to improve the impact strength of the cyanate ester resin. In the present study a commonly used cyanate resin, bisphenol A dicyanate (BADCy), was modified by the addition of diallyl phthalate (DAP) and was cured with benzoyl peroxide. The properties of the blends such as thermal and mechanical properties were investigated in detail by scanning electron microscope, dynamic mechanical analysis, thermogravimetric analysis, and mechanical measurement. The results indicate that the addition of the appropriate amount of DAP can effectively improve the impact toughness and the flexural strength while sacrificing the thermal properties of the blends. The maximum impact strength and flexural strength were observed on addition of 15 phr DAP content. However, the thermal stability of the blends was found to be lower than that of the unmodified BADCy resin.     

氰酸酯树脂及其胶粘剂

介绍了高性能氰酸酯树脂的品种、主要性能、商业产品和氰酸酯树脂固化反应的原理和特点;评述了氰酸酯树脂与环氧树脂、双马来酰亚胺树脂和热塑性树脂共混体系的物理－机械性能。     

Synthesis and characterization of novel low‐dielectric cyanate esters. II

A novel cyanate ester, 2,6‐dimethyl phenol dipentene cyanate ester (DPCY), was successfully synthesized from cyanogen bromide with 2,6‐dimethyl phenol dipentene novolac, which was synthesized from dipentene and 2,6‐dimethyl phenol. For the purpose of increasing the mobility of residual DPCY during the final stage of curing and achieving a complete reaction of cyanate groups, a small quantity of a monofunctional cyanate ester, 4‐tert‐butyl phenol cyanate ester, was added to DPCY to form a cyanate ester copolymer. The thermal properties of the cured cyanate ester resins were studied by dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those of the commercial bisphenol A cyanate ester system. The cured modified cyanate ester exhibited a dielectric constant of 2.59–2.50, a dissipation factor of 0.0055–0.0089, and moisture absorption of 0.91–1.17%; these values were all lower than those of the as‐cured bisphenol A dicyanate system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 369–379, 2005     

Effect of cyanate ester on the cure behavior and thermal stability of epoxy resin

Epoxy resin (diglycidyl ether of bisphenol A, DGEBA)/cyanate ester mixtures were cured with a curing agent, 4,4′-diaminodiphenylsulfone, and the effect of cyanate ester resin on the cure behavior and thermal stability in the epoxy resin was investigated with a Fourier transform infrared spectrometer, a rheometer, a dynamic mechanical analyzer, and a thermogravimetric analyzer. Cure reactions in the epoxy/cyanate ester mixture were faster than that of the neat epoxy system. The cure reaction was accelerated by increasing the cyanate ester resin component. Glass transition temperature and thermal stability in the cured resins were increased with increasing cyanate ester resin component. This may be caused by the increase of crosslinking density due to the polycyclotrimerization of the cyanate ester monomer to form triazine rings and the reaction of cyanate ester resin with the epoxy network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 85–90, 1997     

热塑性树脂增韧氰酸酯树脂的研究进展

阐述了目前热塑性树脂如聚醚酰亚胺、聚苯醚、聚砜和芳香聚酯类对氰酸酯树脂增韧的研究,分析了影响增韧效果的因素.结果表明,在使用热塑性树脂改性氰酸酯时,须综合考虑热塑性树脂对氰酸酯韧性、耐热性和工艺性能的影响,以获得综合性能相对较佳的体系.     

低溴环氧/氰酸酯树脂共固化反应及其层压板性能的研究

用差示扫描量热仪(DSC)、傅立叶交换红外光谱(FT-IR)对不同配比的低溴环氧／氰酸酯树脂的共固化反应机理以及固化物的结构特征进行了研究,同时测定和讨论了其层压板的耐热性和介电性能等。研究结果表明,在低溴环氧／氰酸酯树脂的固化体系中,氰酸酯和环氧树脂通过两种途径反应最终生成噁唑烷酮结构：固化反应温度与体系的组成有关,体系中低溴环氧树脂减少固化反应温度降低：加入催化剂能明显促进体系共固化反应,同时也降低了层压板的耐热性和介电性能。在性能方面,低溴环氧树脂中加入氰酸酯使共固化物耐热性增加、Tg升高,但氰酸酯用量增加到一定范围后,低溴环氧树脂／氰酸酯配比对Tg影响不大;低溴环氧树脂／氰酸酯层压板的耐热性和介电性能在一定实验范围内随着氰酸酯用量的增加明显提高。     

氰酸酯树脂体系介电性能研究新进展

综述了近年来国内外氰酸酯树脂体系介电性能研究的新进展,主要包括催化剂体系、两相体系及新型氰酸酯树脂单体等对氰酸酯树脂介电性能的影响,并对提升氰酸酯树脂介电性能值得关注的发展方向作了展望.     

氰酸酯树脂及其胶粘剂（续）

５　改性氰酸酯树脂氰酸酯树脂与其他热固性树脂相比虽然具有较好的韧性,但如作为结构用复合材料和胶粘剂的基体,仍然较脆。与其他热固性树脂的增韧相似,它可采用热塑性塑料（ＴＰ）和橡胶增韧。这类增韧改性氰酸酯树脂许多已商品化。另一类是氰酸酯分别与环氧、ＢＭＩ共混改性,以达到取长补短的目的。这２种共混树脂也已商品化。５．１　ＴＰ增韧氰酸酯氰酸酯树脂可与许多无定形的ＴＰ共混。固化后形成半互穿网络（Ｓｅｍｉ－ＩＰＮ）［１５,１６］。所用ＴＰ主要有：聚砜（ＰＳＵ）、聚醚砜（ＰＥＳ）、聚醚砜亚胺（ＰＥＩ）和聚碳酸…     

Fabrication of Bioactive Material-Reinforced Caprolactam-Based Cyanate Ester Composite for Coating Applications

The nanocomposite material consisting of bioactive amine-terminated cyclotriphosphazene and functionalized titanium dioxide nanoparticle-reinforced caprolactam-based cyanate ester composites (amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam) was developed for coating applications. The structural characterization and coating properties of amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam composites coated on MS plates were studied by Fourier transform infrared spectroscopy, scanning electron microscope, contact angle, and electrochemical measurements. The antibacterial studies of amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam were also performed by disk diffusion method. Hence, the results conclude that the amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam nanocomposites have improved hydrophobic, thermal properties, enhanced antimicrobial, and corrosion resistance properties due to the incorporation of amine-terminated cyclotriphosphazene and functionalized titanium dioxide nanoparticles.     

氰酸酯树脂/环氧树脂共混物的化学和性能

氰酸酯 (CE)树脂 /环氧 (EP)树脂是一类具有特殊反应活性的树脂混合物。CE/EP的固化物由于自身独特的结构特征 ,是一类性能优异的树脂共混物。重点介绍了CE/EP的反应机理和主要性能。