1，8-萘酰亚胺类荧光染料的合成与应用

【作者】 郭璞；

【导师】 樊君；

【作者基本信息】 西北大学 ， 化学工程， 2009， 硕士

【摘要】 本文主要研究荧光染料在汽车空调系统荧光检漏中的应用,寻找或合成出可以应用于汽车空调系统荧光检漏的荧光染料。主要从两个方面进行实验研究,一方面是从已在市场上有销售的荧光染料中筛选出适合的荧光染料;另一方面是自行设计合成出适合的荧光染料。本文研究了国内外市售的多种荧光染料在汽车空调系统R-134a制冷剂所对应的润滑油(PAG)中的溶解性能,并以此为标准进行筛选。最终选出三种有明显的黄绿色荧光并在润滑油中有一定溶解度的荧光染料:荧光黄8GF-1、荧光黄571及荧光黄R(Solvent Yellow 43)。其溶解度分别为0.2mg/ml、0.3mg/ml、0.8mg/ml,但按规定稀释后荧光剂的粘度、荧光强度等都达不到荧光检漏可检的要求。实验进一步尝试将有机胺类表面活性剂加入荧光染料的润滑油溶液中以增大荧光染料的溶解度。并测定了荧光黄8GF-1、荧光黄571及荧光黄R(SolventYellow 43)三种物质的紫外全波长扫描谱图及荧光光谱,为下一步的合成实验提供了参考和实验依据。本文以前述应用实验及大量的参考文献为指导,研究了以4-溴-1,8-萘酐为原料经过亚胺化合成了中间产物4-溴-N-十八烷基-1,8-萘酰亚胺。并以产率和熔程为指标对该化合物的合成工艺进行了单因素实验及正交实验,得到了优化的反应条件。即未经纯化的4-溴-1,8-萘酐和十八胺一次性加料,其配料比为1:1.08,60℃水浴加热至回流,降温至50℃,反应3h,反应液静置过夜,其产率可达到81.6%。实验测定了该中间产物的红外谱图,其结果符合实验设计要求。还测定了该物质的荧光光谱。本文进一步经取代反应以中间产物4-溴-N-十八烷基-1,8-萘酰亚胺以及醇类化合物为原料,在碱性条件与表面活性剂存在的条件下,80℃水浴加热,反应6h得到了黄色或桔黄色目标产物4-烷(苯)氧基-N-十八烷基-1,8-萘酰亚胺类化合物。测定了其在润滑油中的溶解性及其相应的荧光光谱、紫外全波长扫描谱图及红外谱图。结果表明,这类物质符合设计的要求;其溶解度均大于50mg/ml(以聚乙二醇为原料的除外);在波长490～550nm之间均有明显的发射峰;与前述应用实验筛选出的荧光染料相一致,但荧光强度与之相比较弱;其中以聚乙二醇为原料合成得到的物质荧光强度很强但该类化合物不溶于润滑油中。本文还进一步探索研究了其他可行物质的合成。以4-溴-1,8-萘酐及4,4’-二氨基二苯醚为原料反应得到中间产物4-溴-N-(4-对氨基苯氧基苯基)-1,8-萘酰亚胺。以产率和熔程为指标对该化合物的合成工艺进行了单因素实验,得到较优的合成工艺。即未经纯化的4-溴-1,8-萘酐和4,4-二氨基二苯醚一次性加料,其配料比为1:1.3,80℃水浴加热,反应6h,反应液静置过夜,其产率可达到89.2%。更多还原

【Abstract】 In this research,the study of fluorescent dyes is in the automotive air-conditioning system in the application of fluorescence leak detection.It is,search or synthetic fluorescent dyes which can be applied to fluorescent leak detection in the vehicles air-conditioning system.There are mainly from two aspects of the experimental study.On the one hand,selected suitable fluorescent dyes which are taken from the market.On the other hand,synthetic suitable fluorescent dyes by research.The research bought various fluorescent dyes from home and abroad.And studied the solubility of them in lubricant(PAG) which was applicable to automotive air-conditioning system with the type of R-134a refrigerant.Selected suitable fluorescent dyes that the choice standard was the solubility.Finally Selected three fluorescent dyes with obviously yellow-green fluorescence under UV irradiation and solubility in lubricant.These were Solvent Yellow 8GF-1,Solvent yellow 571 and Solvent Yellow 43.Their solubility were 0.2mg/ml,0.3mg/ml,0.8mg/ml.However, the viscosity,fluorescence intensity of the fluorescent agents could not reach the fluorescent leak detection requirements when were diluted.The study tried to add some organic amines into the fluorescent agents which aim to increased the solubility of the suitable fluorescent dyes.But the result was unsatisfactory.The study detected the UV wavelength scan the whole map and fluorescence spectrometry of the three suitable fluorescent dyes.And these spectrums could be as the reference and experimental evidence for the next phase of the synthesis experiment.Use the application of the foregoing tests and many references as a guide,the study synthesized the intermediate product 4-bromo-N-octadecyl-1,8-naphthalimide used 4-bromo-1,8-naphthalene dianhydride as raw materials through the imidization reaction.To yield and margin of melting point as indicators optimized the imidization process through single-factor test and orthogonal test,that was 4-bromo-1,8-naphthalene dianhydride Without purified and Octadecylamine were one-time fed and their ingredient ratio was 1:1.08.The reaction temperature was heated to 60℃then cooled down to 50℃.The reaction time was 3h.The reaction deposit overnight then filtrated it.The yield of the intermediate product 4-bromine-N-18 alkyl-1,8-naphthalimide was up to 81.6%.Detected infrared spectra of the intermediate product,and it meet the requirement of the design.The study also measured fluorescence spectrometry of the intermediate product.The study synthesized yellow or orange goal products 4-alkoxy(phenoxy)-N -octadecyl-1,8-naphthalimide through the substitution reaction which used product last step and alcohols as raw materials in alkaline conditions and the existence of surfactant.The conditions of synthesis was 80℃water-bath heating.The reaction time was 6h.The study detected the solubility of the goal products in lubricants,their fluorescence spectrometry,UV wavelength scan the whole map and infrared spectra. The result showed that:the goal products meet the requirement of the design.Their solubility was more than 50mg/ml(except polyethylene glycol as raw material).They had obviously emission peak between 490～550nm.The results were consistent on the fluorescent dyes which were selected in application of the experimental mentioned. But the fluorescence intensity were weaker than before.One of the goal products had stronger fluorescence intensity which used polyethylene glycol as raw material.But the compound did not dissolve in lubricants.The study also explored the synthesis of other suitable substances.The study synthesized the other intermediate product 4-bromo-N-(4-p-phenoxy-phenyl)-1, 8-naphthalimide which used 4-bromo-1,8-naphthalene dianhydride and 4,4’-diamino diphenyl ether as the raw material.To yield and margin of melting point as indicators optimized the process through single-factor test.that was 4-bromo-1,8-naphthalene dianhydride Without purified and 4,4’-diamino diphenyl ether were one-time fed and their ingredient ratio was 1:1.3.The reaction temperature was 80℃.The reaction time was 6h.The reaction deposited overnight then filtrated it.The yield of the intermediate product 4-bromo-N-(4-p-phenoxy-phenyl)-1,8-naphthalimide was up to 89.2%.更多还原