新型对称双偶氮苯化合物的合成及光学性能

以联苯二胺为原料,通过重氮化、偶联和Williamson醚合成反应,设计合成了一系列新型的对称性不同端基的双偶氮类化合物,考察了溶剂、不同取代基对偶氮化合物紫外吸收影响。以4,4’-二(4-辛氧基-苯偶氮基)-联苯(Azo3)为例,在365 nm紫外光照射下发生反-顺光异构化,光照10 min后达到光稳定态,具有良好的光致变色性。     

含氟取代基的不对称变色酸双偶氮试剂与金属离子显色反应性能的研究

系统研究了４种（膦类、胂类、羧类、羟类）共１１个含氟取代基的不对称变色酸双偶氮类试剂与３６个金属离子显色反应的性能。考察了反应酸度、配合物的最大吸收峰的位置和反应灵敏度等。探讨了金属离子的种类、性质及试剂分子结构与显色反应性能之间的关系。     

单偶氮及双偶氮苯咔唑类化合物的合成与表征

以对硝基重氮盐与N-羟基烷基咔唑作原料,用相转移催化剂十二烷基苯磺酸钠(NaDBS),通过重氮偶联反应合成了单偶氮和具有对称结构的双偶氮化合物。单偶氮:3-(4-硝基苯基偶氮基)-N-(6-羟己基)咔唑(收率28.8%)、3-(4-硝基苯基偶氮基)-N-(10-羟癸基)咔唑(收率14.2%);双偶氮:3,3-′2(4-硝基苯基偶氮基)-N-(6-羟己基)咔唑(收率25%)、3,3-′2(4-硝基苯基偶氮基)-N-(10-羟癸基)咔唑(收率11.9%)。并用红外光谱、核磁共振光谱对该4种化合物的结构进行了表征。红外谱图表明生成的产物中含有N N和NO2;核磁共振谱图中,只存在4种氢:化学位移7.1~8.8的咔唑环和苯环氢,化学位移4.3附近的—CH2—O—的氢,化学位移3.61附近的—CH2—N—的氢,以及化学位移在1.2~1.9的脂肪链上的氢。红外谱图中的特征峰及核磁共振谱图中质子的化学位移和数目证明了这4种化合物的结构。     

含异双活性基活性染料的合成工艺

综述了含异双活性基的活性染料的品种和合成工艺，提示了若干尚未公开的活性染料的化学结构，合成工艺涉及单、双偶氮类、蒽醌类、酞菁类、甲脂类和三苯二噁嗪类染料，色谱从黄到黑，从单一结构到拼色染料品种，其化学反应涉及了重氮化、偶合、各种缩合及金属络合等．详细阐述了各类反应的工艺条件和特点。含氟活性基和溴代丙烯酰胺活性基的染料将成为开发热点。有16篇参考文献。     

含异双活性基活性染料的合成工艺

综述了含异双活性基的活性染料的品种和合成工艺，提示了若干尚未公开的活性染料的化学结构合成工艺涉及单、双偶氮类、蒽醌类、酞菁类、甲脂类和三苯二噁嗪类染料，色谱从黄到黑，从单一结构到拼色染料品种，其化学反应涉及了重氯化、偶合、各种缩合及金属络合等。详细阐述了各类反应的工艺条件和特点。含氟活性基和溴代丙烯酰胺活性基的染料将成为开发热点。有16篇参考文献。     

新不对称含膦(胂)酸基变色酸双偶氮衍生物的合成及其与稀土元素显色反应的研究

通过将各种取代基引至变色酸双偶氮衍生物不含成盐基团一侧的偶氮苯的邻、间或对位上,合成了一系列新的不对称含膦(胂)酸基变色酸双偶氮衍生物。这些化合物是偶氮胂 DBM、偶氮胂DBEO、偶氮氯膦 DBM 和对三氟甲基偶氮氯膦等。单取代的试剂与稀土的配合物具有两个吸收峰,分别在610～620 nm 和660～670 nm,而多取代试剂与稀土配合物的吸收峰是630～645 nm。配合物摩尔吸收系数大于或等于10(?)。     

KN型双偶氮活性蓝色染料的制备及其染色性能研究

以对硝基苯胺重氮盐与1-氨基-8-萘酚-3,6-二磺酸(H酸)在酸性条件下偶合首先制备了红色单偶氮染料,接着与对(β-硫酸酯乙基砜)苯胺重氮盐在中性条件下与单偶氮红色染料偶合制备了KN型双偶氮活性蓝色染料,通过红外、紫外-可见吸收光谱和质谱对产物结构进行了表征。通过浸染工艺,将该KN型双偶氮活性蓝色染料用于棉纤维的染色研究,结果表明染色棉纤维的干/湿摩擦牢度分别为4和3～4级,日晒牢度4级,水洗牢度4～5级。     

偶氮化合物的光电导性能的研究

本文合成了五种双偶氮颜料 ,它们是以芴酮为桥基 ,以含有五种不同取代基的色酚为偶合剂的化合物 .测定了这些化合物的吸收光谱和X射线衍射光谱 ;分别以这五种偶氮颜料为电荷产生材料制备了功能分离型双层光电导体 ,并对它们的光电导性能进行了研究 .     

吡啶酮系偶氮型分散染料结构与性能的研究──Ⅰ．吡啶酮系偶氮型分散染料结构与光谱性能的关系

本文合成了６８个吡啶酮偶氮型分散染料及Ｃ．Ｉ．分散黄１１９，研究了重氮组份及偶合组份上取代基与染料光谱性能的关系。吡啶酮系偶氮染料光谱性能规律和一般苯系偶氮染料光谱规律不同，并且脱氰基吡啶酮分散染料较含氰基吡啶酮分散染料有好的耐酸、碱变色性。     

吡啶酮系偶氮型分散染料结构与性能的研究：Ⅰ.吡啶酮系偶氮型分散染料结…

本文合成了６８个吡啶酮偶氮型分散染料Ｃ．Ｉ．分散黄１１９，研究了重氮组份及偶合组份上取代基与染料光谱性能的关系。吡啶酮系偶氮染料光谱性能规律和一般苯系偶氮染料光谱规律不同，并且脱氰基吡啶酮分散染料较含氰基吡啶啶酮分杂料有好的耐酸，碱变色性。     

Synthesis and Electronic Spectra of some 4–Aminoazobenzenes

The synthesis of a range of monoazo disperse dyes prepared from monosubstituted anilines as the diazo components is reported The absorption maxima of the dyes are recorded, and shifts resulting from the effect of different substituents in both the diazo component and the coupling component are correlated with the nature of the substituent. The use of monosubstituted aniline; as diazo components, coupled to different TV–substituted anilines, can result in dyes with λD_max differing by about 100 nm.     

Novel azo dyes derived from phthalimide. Part 2: Dyeing properties and colour fastness on polyester fibres†

The coloration and fastness properties of 18 carbocyclic monoazo disperse dyes bearing a phthalimide ring fused to the aromatic ring of their diazo components have been investigated. In each case, the phthalimidyl nitrogen atom was substituted with either a butyl, sec‐butyl or isopropyl group, while the adjoined phenyl ring bore a substitution pattern typical of commercial colorants. Dye uptake and build‐up onto both conventional and microfibre polyester through exhaustion dyeing were examined: while the expected tendency of greater exhaustion on microfibre was noted, there were few clear trends with respect to dye structure. The nature of the N‐alkyl group made no consistent difference to dye uptake. Attempts to explain the observed percentage exhaustion values by mapping them to calculated partition coefficient or solubility parameter values were unsuccessful. Wash fastness tended to be best for blue dicyano‐substituted derivatives, which may be as a result in part of these substituents promoting hydrolysis of the adjacent phthalimide ring to give more soluble phthalate species. In contrast, the dicyano dyes had relatively poor photostability compared with their unsubstituted analogues.     

Dichroic and spectral properties of anthraquinone-based azo dyes for PVA polarizing film

Dichroic dyes with broad absorption bands are advantageous for the production of neutral gray polarizing films. For this purpose, anthraquinone-based azo dyes were synthesized to have a conjugated bichromophore design and this was applied to PVA polarizing films. The spectral and dichroic properties of the polarizing films were examined and compared to the films produced with a general disazo dichroic dye. The polarizing films with anthraquinone-based azo dyes had wider absorption bands, but lower dichroic ratios compared to the films with a general disazo dichroic dye. It was found that the alignment between the transition moments of the anthraquinone and azo chromophores is an important factor for the dichroic properties of anthraquinone-based azo dyes.     

Substituent Effects on the Colour,Dyeing and Fastness Properties of Trisubstituted 4–N–β–Hydroxyethyl–N–β–Cyanoethylaminoazobenzenes

School of Chemistry and Chemical Technology University of Bradford Bradford West Yorkshire BD7 1DP The synthesis of a series of 2′, 4′, 6′-trisubstituted derivatives of 4–N–β–hydroxyethyl–4– N–β–cyanoeth ylaminoazobenzene is reported, and the effect of the nature of the substituents on the colour, dyeing and fastness properties of these dyes is described. The dyes coloured synthetic–polymer fibres well, with the exception of those containing a methylsulphonyl group, which gave weaker dyeings on polyester. Dyes substituted by 2′-nitro groups tended to have poor light fastness, and reasons for the variations in the light fastness of monoazo dyes of this type are discussed.     

WATER SOLUBLE DISPERSE DYES CONTAINING CARBOXY-METHYL-SULFONYL GROUP

Water soluble disperse dyes of either monoazo or anthraquinone types containing the carboxymethylsulfonylgroup(-SO_2CH_2COOH)were synthesized.Ammonium salts of this type of dyes are more soluble thanother salts.These dyes are suitable for pad dyeing or printing on polyester fiber and polyester/cottonblends in either weak acid,neutral or weak alkali medium without a dispersing agent.The formation of-SO_2CH_3 group from -SO_2CH_2COOH group after fixing on the fiber was proved.     

Structure—wet fastness relationships of some blue disperse dyes for polyester

A range of monoazo blue disperse dyes has been synthesised by coupling benzenoid and heterocyclic diazo components to aniline derivatives containing ester functions. The colour properties and wet fastness of the dyes on polyester at 1/1 standard depth have been examined and rationalised in terms of dye structure. Styryl dyes have also been prepared in order to compare their wet fastness properties to those of the azo dyes.     

Substituent effects on the photofading of disperse azo dyes on poly(ethylene terephthalate) substrate

The relationships between the chemical structures and oxidative fading of the disperse azo dyes, p‐nitrophenylazo‐ and benzothiazoleazo‐anilines, on poly(ethylene terephthalate) substrate are discussed in terms of the parameters k_0,i (rate constants of reaction towards ¹O₂) and f_i (photosensitivity), the molecular parameters of molecular orbital theory and substituents in the diazo and coupling components, on the assumption that the initial rates of oxidative fading are proportional to the product of k_0,i and f_i. 2‐Methoxy‐5‐acetylamino‐N‐substituted aniline couplers exhibited large f_i values. 2‐Chloro and 4‐nitro substituents of aniline diazo components exhibited small f_i values or high quantum yields of internal conversion, while 4‐nitro substituent did not. A close correlation between N‐substituents and light fastness, proposed by Müller and supplemented by Dawson, demonstrates the applicability of frontier orbital theory, through the highest occupied molecular orbital (HOMO) energy of the dyes, to the analysis of oxidative fading. Dyes with N‐2‐cyanoethyl substituents, which gave a lower HOMO energy, also exhibited superior light fastness compared with N‐2‐hydroxyethyl substituents.     

含羧甲磺酰基水溶性分散染料的研究

本文提出一类含有羧甲磺酰基（—SO_2CH_2COOH）的新的水溶性分散染料。利用应用时的高温,它转变为不溶性的分散染料。因此,在成品加工时不必进行砂磨,不需要扩散剂。它在弱酸、中性和碱性中都可使用,并适用于纯涤纶和涤/棉织物的印花和轧染。     

Synthesis of temporarily solubilised azo disperse dyes containing a β‐sulphatoethylsulphonyl group and dispersant‐free dyeing of polyethylene terephthalate fabric

Disperse dyes containing a β‐sulphatoethylsulphonyl group have temporary solubility and can be applied for dispersant‐free dyeing of hydrophobic fibre. Six novel temporarily solubilised azo disperse dyes having a β‐sulphatoethylsulphonyl group in their structures were synthesised, and their dyeing properties on polyester were investigated. As a dye intermediate, a diazo component having dibromo groups was prepared, and 4‐diethylamino‐4′‐(2‐sulphatoethylsulphonyl‐4,6‐dibromo)azobenzene dyes were prepared by a diazo‐coupling reaction. Then, the dyes containing dicyano groups were prepared by cyanation of corresponding dyes with dibromo groups. The absorption maxima of the dyes were affected by the substituents in the diazo and coupling component rings and varied from 434 to 616 nm in dimethylformamide. Polyethylene terephthalate woven fabric could be dyed with the synthesised temporarily solubilised dyes without using any dispersants. Dyebath pH affected the K/S value at maximum absorption as well as percentage exhaustion on polyethylene terephthalate fabric, and the optimum pH was 5. The dyes gave brownish orange, red, purple, and greenish blue hues on polyethylene terephthalate fabrics, and colour build‐up was good. Wash fastness was good to excellent, rubbing fastness was moderate to excellent, and light fastness was poor to moderate.     

Photostability of Anthraquinone and Azo Dyes in N-Ethylacetamide (Nylon Model)

Measurements of the quantum yields of photodegradation of anthraquinone and azo dyes in N-ethylacetamide (nylon model) and triplet sensitisation of dye fading showed that the photochemical reactions are initiated by an upper excited n-π* triplet state. The primary photochemical reaction with both anthraquinone and azo dyes involves hydrogen abstraction from the amide so/vent. In some cases oxygen retards dye fading by reoxidation of the reduced structures. In other cases oxygen accelerates the photochemical reaction via free-radical initiated oxidation reactions. The quantum yields of dye fading are strongly wavelength dependent. On exposure to a simulated sunlight spectrum photodegradation is mostly caused by radiation in the region 300–400 nm. While unsubstituted anthraquinone is very photoreactive, amino-substituted anthraquinones are much more photostable in N-ethylacetam/de. Photostability of mono- and di-substituted anthraquinone derivatives increases with the electron-donating power of substituent groups. Azo dyes with increased conjugation such as diazo and naphthazo structures are more photostable than simple azobenzene derivatives. Certain electron-withdrawing substituents, which do not affect dye colour, improve the ‘oxidative’ photostability of both anthraquinone and azo dyes. A cobalt premetallised azo dye (C.I. Acid Red 182) is very photostable in N-ethylacetamide, showing the effect of metal chelates on photostability. The low values of quantum yields for the dye solutions are comparable with those of acid and disperse dyes in nylon films, indicating that N-ethylacetamide is a suitable nylon model for mechanistic studies of dye fading.