稀土金属络合染料的合成研究

本论文选择1-对氯苯基-3-乙基-5-吡唑酮作为偶合组分,与3-氨基-4-羟基苯磺酰胺重氮组分反应合成偶氮染料母体,合成的母体染料与稀土络合剂反应生成稀土金属络合染料。利用红外光谱、紫外可见吸收光谱对合成的金属络合染料进行了结构鉴定与分析。本论文对络合反应条件进行了详细的研究,合成1∶2偶氮金属络合染料反应体系的pH值在8.0～8.5之间,反应温度75℃,偶氮金属络合染料的收率达90%以上。     

活性黑RL染料合成工艺研究

通过实验确定活性黑RL染料的合成工艺。本文采用γ酸重氮化后,在低温酸性条件下与1-(4-磺酸基苯基)-3-羧基-5-吡唑啉酮偶合,2,5-二甲氧基对位酯重氮化后与上述产物进行第二次偶合,偶合产物经Cu络合后盐析、干燥得到活性黑RL染料成品。最佳工艺条件为:重氮反应温度控制在0～5℃、偶合反应时pH=7.5～8、Cu络合反应时温度控制在110℃、pH=6～6.2。     

环保型A1、Fe络合染料的合成及其羊毛染色

4-氨基-3-羟基-1-萘磺酸重氮化,与1-苯基-3-甲基-5-吡唑啉酮偶合,得单偶氮染料,后用Al2(SO4)3或Fe2(SO4)3在60℃～90℃进行络合反应3-5小时,得标题染料。用IR、UV对染料进行了分析和表征,Fe、Al、Cr络合染料的最大可见吸收光谱分别勾473、493、510nm,染色实验结果表明,所合成的染料在羊毛上染色有较好的应用性能。     

纸用液状C.I.直接紫51合成研究

本文介绍了C.I.直接紫51的合成及将其脱盐后制成液体纸用染料。用此方法合成的C.I.直接紫51染料溶液,在-5～40℃下保存3年未见析出。     

四-(3,4-二甲氧基苯基)硫代双烯合镍的合成与光谱性能

以中间体二-(3,4-二甲氧基苯基)乙二酮为原料,经过P2S5硫化、镍络合,合成了四-(3,4-二甲氧基苯基)硫代双烯镍络合物近红外吸收染料.利用IR和1HNMR表征了最终产物硫代双烯合镍的结构.考察了四-(3,4-二甲氧基苯基)硫代双烯合镍在不同溶剂中的最大吸收波长及其光、热稳定性.     

光谱增感菁染料自缔合作用的热力学研究——Ⅱ.3,3′-二(γ-磺酸丙基)-9-乙基-4,5,4′,5′-二苯并噻碳菁在DMF-水混合溶剂中J-聚集体生成和J-聚集热

由吸收光谱研究了3,3′-二(丁-磺酸丙基)-9-乙基-4,5,4′,5′-二苯并噻碳菁三乙胺盐(Ⅰ)在DMF-水溶液中生成J-聚集体的效应;直接测量了25℃形成J-聚集体过程的热效应,得到了J-聚集体的聚集热△Hs=—(43±1)×10~3J(表示1摩尔单分子染料连接到J-聚集体上的平均焓变化)。根据Daltrozzo等人将J-聚集体生成当作“结晶”过程的观点,求得该体系中染料I J-聚集体至少包含的染料单分子数n为6。     

改性羊毛的染色性及染料的选择

比较了氯化改性和拉伸改性羊毛的染色性。氯化改性羊毛的上色速率、上染平衡比原毛快,各项色样牢度基本相同或略高;在拉伸羊毛的拉伸率较高时,其上染率和平衡上染率会明显提高;拉伸(不)定型和染色条件对染色性能有明显影响。选择了1:1金属络合染料、1:2金属络合染料和溴代丙烯酰类毛用活性染料对改性羊毛染色,探讨了染色机理,在两种改性羊毛达到了低温染色的要求,80℃时上染速度快、上染率高,能透染。     

不对称金属络合染料C.I.酸性棕355的合成

6-硝基-1,2-重氮氧基萘-4-磺酸与乙萘酚偶合,得偶合物I;2-氨基-4-硝基苯酚-6-磺酸重氮化与1-苯基-3-甲基-5-吡唑啉酮偶合,得到偶合物II;偶合物I与铬明矾在水杨酸存在下络合,得到单络合物III;络合物III再与偶合物II在碱性条件下络合,得到不对称金属络合染料C.I.酸性棕355。     

改性羊毛的染色性及染料的选择

比较了氯化改性和拉伸改性羊毛的染色性。氯化改性羊毛的上色速率、上染平衡比原毛快,各项色样牢度基本相同或略高;在拉伸羊毛的拉伸率较高时,其上染率和平衡上染率会明显提高;拉伸(不)定型和染色条件对染色性能有明显影响。选择了1:1金属络合染料、1:2金属络合染料和溴代丙烯酰类毛用活性染料对改性羊毛染色,探讨了染色机理,在两种改性羊毛达到了低温染色的要求,80℃时上染速度快、上染率高,能透染。     

酸性金属络合染料上染锦氨织物的色牢度探讨

采用酸性金属络合染料对锦氨织物进行染色,从染料、染色工艺、助剂三个角度探讨了对染色牢度的影响。结果表明:酸性金属络合染料对锦氨织物染浅、中及中深色的牢度较好;染深色时,需通过工艺调整及助剂辅助。其优化的工艺条件为:染色温度93℃,保温时间30 min,染浴p H值在3~4,配合1.0 g/L氨纶防沾色剂,2%(omf)酸性固色剂DM-2539G及2.0 g/L增进剂CIBAFIX ECO后处理,各项牢度指标能提升到3-4级及以上。     

Characterisation of separated melamine—formaldehyde adducts (methylolmelamines) and adduct mixtures by h.p.l.c. and by n.m.r. and u.v. spectroscopy

Most of the individual methylolmelamines that occur in melamine–formaldehyde adduct mixtures have been separated by preparative high-performance liquid chromatography (h.p.l.c.) and recovered in amounts sufficient to allow their characterisation by high-field ¹H- and ¹³C-n.m.r. Particular attention has been paid to the chemical shifts of the aromatic azine carbons of the melamine nuclei. These carbon shifts are shown broadly to be in agreement with some values previously published, but additional assignments have been made. It is shown that a satisfactory quantitative analysis of the methylolmelamines in a melamine–formaldehyde adduct mixture can be carried out either by h.p.l.c. or by ¹³C-n.m.r.     

In-situ monitoring of the stabilization with hydrogen of free radicals thermally induced from coal using high pressure e.s.r., d.t.a. and p.d.a. equipment

High temperature, high pressure e.s.r. measurements of the hydrogenation reaction of Taiheiyo coal in the presence of catalysts were carried out to understand the stabilization of thermally and/or catalytically induced free radicals. A decrease in free radical concentration with increasing temperature was observed for ZnCl₂ and SnCl₂ · 2H₂O catalysts at 10MPa under hydrogen gas. High pressure modified single-cell d.t.a. and p.d.a. equipment augmented the uniquely designed high temperature, high pressure e.s.r. cell. The hydrogenation reaction was monitored under the same experimental conditions as for e.s.r. From the results of the combination of high temperature, high pressure e.s.r. with high pressure d.t.a. and p.d.a., it was established that H₂ molecules can react efficiently with free radicals from coal molecules created by the presence of ZnCl₂ and SnCl₂ · 2H₂O catalysts.     

球形壳聚糖固定化糖化酶的研究

研究了以球形壳聚糖作载体固定化糖化酶的方法，探讨了戊二醛用量，酶量，温度，pH值对固定化效果的影响。     

Two-dimensional n.m.r. characterization of cycloaliphatic epoxy resins

The cycloaliphatic epoxy resins were studied by various two-dimensional nuclear magnetic resonance (2D n.m.r.) spectroscopies. The ¹³C n.m.r. spectra of the epoxy resins were assigned by using DEPT and 2D INADEQUATE techniques and the ¹H n.m.r. spectra were assigned by using 2D ¹H---¹H and ¹H---¹³C COSY techniques. Complete characterization of the samples synthesized by the oxidation of cyclohexene derivatives not only revealed the existence of the stereochemical isomers resulting from the structural difference of the oxide rings in the samples but also provided the composition ratio of the isomers.     

Quench solvent evaluation: An e.s.r. study

An in-situ radical-quenching experiment was performed in an e.s.r. microwave cavity by using a solution flow system. Diphenylmethyl radicals produced from pyrolysis of 1,1,2,2-tetraphenylethane were quenched by several H-donor solvents. Among the solvents used, indan was the fastest in quenching, followed by hydrophenanthrene, tetralin, mesitylene and cumene in decreasing order of quenching rate.     

Evaluation of a delayed coking process by H and C n.m.r. spectroscopy: 2. Detailed interpretation of liquid n.m.r. spectra

The ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectra of a delayed coking feedstock and products, presented in a previous paper, are analysed here in detail by matching results from inspection of both nuclei. The conventional spectra of whole samples are used in combination with elemental analysis data, and substantial agreement is obtained. Differences are explored to yield valuable information. Interpretation of some band assignments is modified to account for new results. This approach results in a detailed quantitative estimation of a few key structures that contain the main functional groups that characterize these petroleum fractions.     

活性染料SEFR值与中性固色工艺研究

根据活性染料染色特征值S．E．F．R．选择适用于中性固色工艺的活性染料，结果表明，S值高和低的活性染料对碱的浓度和温度敏感，对固色率的影响较为杂乱，但在温度为80℃时，这类染料的固色率均达到峰值：染色特征值在50-60范围内的活性染料适用于中性固色、以甲酸钠为中性固色剂对活性染料进行中性固色实验，其固色率均可达到60%左右．各项牢度均达到标准。最佳工艺条件为：甲酸钠：15g／L；尿素：20g／L；双氰胺10g／L，固色温度85℃：浴比：1：20。     

E.s.r. spectra of eastern oil shales

E.s.r. spectra of several oil shales from eastern and western USA have been measured at 9 and 25 GHz. The spectra of the western shales were similar to previously reported spectra and consist of a Mn²⁺ signal and a featureless organic signal. The eastern spectra consist of a V⁴⁺ signal and a complex and unusual organic signal consisting of at least four component signals. The organic signal has been characterized in terms of g factor, line-width and saturation characteristics. The effect of oxygen on the signal has also been examined. Electron nuclear double resonance (ENDOR) signals have been obtained from the organic signals of the eastern oil shales.     

An h.p.l.e. and m.s. analysis of distillate fractions of neutral oil from hydrogenated Akabira coal to elucidate chemical structures

Akabira coal-derived neutral oil was separated into 25 narrow boiling range fractions covering 183–423 °C, and subsequently separated into compound class fractions : alkanes, monoaromatics, naphthalene-type diaromatics, fluorene-type diaromatics and tri- and/or tetraaromatics, by high performance liquid chromatography (h.p.l.c.). The compound type analyses of the distillate/h.p.l.c. fractions were performed using electron impact mass spectroscopy (e.i.m.s.) or field ionization mass spectroscopy (f.i.m.s.). Aromatic/hydroaromatic compound types and the alkyl side-chain carbon distribution of the distillate/h.p.l.c. fractions were clarified, based on the separation behaviour of h.p.l.c. and the type analyses according to Z value by m.s. By the distillation/h.p.l.c./m.s. method, coal-derived oil was characterized in terms of the distribution of the numbers of aromatic rings, naphthenic rings and carbons of alkyl groups attached to these rings. The variations in chemical structure in a compound class with distillation temperature are discussed in terms of these chemical structural factors.     

Structural characterization of Saudi Arabian heavy crude oil by n.m.r. spectroscopy

Saudi Arabian heavy crude oil was separated into six fractions, including five distillate fractions (<93, 93–204, 204–260, 260–343 and 343–454 °C) and a >454 °C distillation residue. Each fraction was analysed by ¹H and ¹³C n.m.r. spectroscopy, and combined gained information from these analyses provided reliable average structural parameters. These included estimation of aliphatic and aromatic content, average paraffinic chain length, and estimation of hydrogen, methyl and alkyl bearing aromatic carbons for each of the six fractions. The extent of branching in paraffinic chains and amount of aromatic bridgehead carbons were also calculated.