【作者】 于宁；

【导师】 张淑芬；

【作者基本信息】 大连理工大学 ， 应用化学， 2019， 博士

【摘要】 有机硅橡胶具有耐高低温性、耐老化、耐油及耐化学试剂等特性,广泛用于医疗卫生、航空及宇航、电线电缆、电子电器和汽车机械等领域。在医疗卫生和电子电器等领域,需对有机硅橡胶进行着色。有机硅橡胶采用的着色剂主要有无机颜料和有机颜料。无机颜料着色剂主要为金属氧化物,色调范围窄,不鲜艳,成本较高,且部分无机颜料含有重金属,重金属具有生态环境和人体相容性的风险;有机颜料着色剂色彩鲜明、着色力强,但两种颜料着色都是以颗粒形式分散在有机硅橡胶中。针对上述问题,论文设计合成含硅活性分散染料新结构,用于有机硅橡胶着色。设计分别以对硝基苯胺和2,4-二硝基-6-溴苯胺为重氮组分,三聚氯氰、1-苯基-3-甲基-5-吡唑啉酮和间氨基-N,N-二乙基苯胺的一缩物为偶合组分,以3-氨丙基甲氧基二甲基硅烷、3-氨丙基二甲氧基甲基硅烷和3-氨丙基三甲氧基硅烷为含硅氧烷活性基组分,合成了一类新型黄、红和紫色含硅活性分散染料。通过UV-Vis、FT-IR、1H NMR、13C NMR以及MS等分析测试手段对染料进行了表征。建立了预测含硅染料溶解度的方法,分析该系列染料的溶解特性并总结规律,得出适于该类染料的溶剂种类,为该类染料的工业应用奠定基础。建立了热力学组成模型,利用已知溶剂中的溶解度关联和预测染料在其它单一或混合溶剂中的溶解度,以获得含硅染料在单一及混合溶剂中的溶解性能。运用COSMO-SAC和NRTL-SAC两种模型对两种有机硅染料分子在多种溶剂中的溶解度进行了理论计算;COSMO-SAC仅利用分子结构,即可实现对溶剂的选择进行定性分析;NRTL-SAC在对有限数据进行分析拟合后实现了对多种溶剂的溶解度较为准确的预测。探索了使用热力学模型预测含硅染料分子在混合溶剂中溶解度的方法,并以实验验证了混合溶剂比纯溶剂更利于染料溶解。该方法对难溶含硅活性分散染料合成及使用中的溶剂选择具有指导意义。将合成的染料用于有机硅橡胶着色,着色后的有机硅橡胶色泽鲜艳饱满,着色橡胶的干、湿摩擦牢度和耐洗牢度均达到了 4～5级,升华牢度在4级以上,呈现出优异的牢度性能,物理机械性能保持不变。含有三个甲氧基硅氧烷的染料着色的有机硅橡胶撕裂强度好。从原料成本考虑,合成含有三个甲氧基硅氧烷的染料(DY3、DR3和DP3)的原料3-氨丙基三甲氧基硅烷的价格要远低于3-氨丙基甲氧基二甲基硅烷和3-氨丙基二甲氧基甲基硅烷的价格。综合上述因素,在未来有机硅染料的工业应用中,含有三个甲氧基硅氧烷的有机硅活性分散染料具有更大的优势。更多还原

【Abstract】 Silicone rubbers have been extensively used in medicine,aviation and aerospace fields,electric wires and cables,electronics and electric appliances,and automobiles and machines due to their high and low temperature-resistance,aging resistance,oil resistivity and chemical resistance.Silicone rubbers should be colored in healthcare and electric wires and cables fields.Silicone rubbers’ colorants include inorganic pigments and organic pigments.Inorganic pigments are mainly metal oxides.But their tone ranges are narrow,they are not bright,and the costs of inorganic pigments are expensive.Some inorganic pigments contain heavy metals.Heavy metals have the risk of ecological environment and human compatibility.Organic pigments have bright colors and strong dyeing power,but both pigments are dispersed in the form of particles in silicone rubbers.For solving above problems,this paper designed and synthesized reactive disperse silicon-containing dyes for coloring of silicone rubbers.Novel yellow,red and purple reactive disperse silicon-containing dyes were designed and synthesized using p-nitroaniline and 2,4-dinitro-6-bromo-aniline as diazonium components,the first condensation product of cyanuric chloride,1-phenyl-3-methyl-5-pyrazolone and 3-(N,N-diethyl)amino aniline as coupling component,and 3-aminopropylmethoxydimethylsilane,3-aminopropylmethyldimet-hoxysilane,and 3-aminopropyltrimethoxysilane as silicone reactive agents.These dyes were characterized by UV-Vis,FT-IR,1H NMR,13C NMR,and MS.A method for predicting the solubility of silicon-containing dyes was established.The solubility characteristics of these dyes were analyzed and the rules were summarized.The kinds of solvents for silicon-containing dyes were obtained,which laid the foundation for the industrial application of silicon-containing dyes.For obtaining solubility of dyes in the pure and mixed solvents,this paper built a thermodynamically consistent model to correlate and predict dyes solubility in pure and mixed solvent systems based on a small initial set of measured solubility data.The solubility of the two dyes in different solvents was calculated with COSMO-SAC and NRTL-SAC models.Based only on molecular structure of the dye molecules,COSMO-SAC was able to qualitatively predict solubility,and NRTL-SAC was capable of providing accurate correlation and prediction of solubility in the pure solvents.A thermodynamic model was used to predict the solubility of silicon-containing dyes in mixed solvents.The results showed that the mixed solvents were better than pure solvents for the solubility of dyes.This method has guiding significance for the synthesis of insoluble reactive disperse silicon-containing dyes and the selection of solvents.The obtained reactive disperse silicon-containing dyes were used to color silicone rubbers and the colored silicone rubbers showed bright and rich colors.The color fastness of the dyes were evaluated,the dry/wet rubbing and washing fastness of these dyes all reached 4-5 grade and the sublimation fastness was also above 4 grade,indicating outstanding performance in terms of color fastness.Their static mechanical properties remain unchanged.The dyes with siloxane group with 3 methoxyl groups have better tear strength in the coloring silicones rubbers.Considering the cost of raw materials,the price of 3-aminopropyltrimethoxysilane(raw material of DY3,DR3 and DP3)is much lower than 3-aminopropylmethoxydimethylsil-ane and 3-aminopropylmethyldimethoxysilane.In view of the above factors,reactive disperse silicon-containing dyes with siloxane group with 3 methoxyl groups will have more advantages in the industrial application of silicon-containing dyes in the future.更多还原