Telechelic PEG-polymers end-capped with chromophores: Using as cationic reactive dyes and salt-free dyeing properties on cotton fabrics

In this article, telechelic polymers containing polyethylene glycol (PEG) moieties as space groups were combined with chromophores to synthesize cationic reactive dyes (BCD-R, BCD-Y, and BCD-B). The salt-free dyeing performance of these telechelic polymeric cationic reactive dyes on cotton fabrics was evaluated. The exhaustion and fixation of the dyes in salt-free dyeing was above 89.33 and 77.22%, respectively. The color fastness of dry rubbing for the three dyes reached grade 4–5, and their color fastness to light reached grade 5–6. Their washing fastness also reached grade 4–5, except for that of BCD-Y (grade 3–4). The results showed that the dyes possessed good leveling and build-up properties and substantivity to cellulose fiber. The zeta potential (ξ-potential) of dyed fabric was estimated, and it was found that the ξ-potential of the fabrics increased after dying with telechelic polymeric cationic reactive dyes, and the more dye that was used, the greater ξ-potential increase. The exhaustion curves of dyes were also determined, and they were much different from those of anionic reactive dyes. The adsorption kinetics and isotherms of BCD-R were investigated. It was found that the pseudo-second-order kinetic model gave the best fit of the experimental data at all three tested dyeing temperatures (25, 45, and 65°C) with R² values over 0.998. Both the Langmuir and Freundlich models could be used to describe the adsorption of BCD-R onto cellulose fibers and the Langmuir model fit the experimental data better than the Freundlich model. The thermodynamic parameters (ΔG, ΔS, ΔH, and activation energy) of the dye adsorption process were researched further. The results indicated that the adsorption of BCD-R onto cotton fibers was spontaneous and exothermic and that after adsorption onto the cotton fibers, the degree of freedom of the dye decreased.     

糖基双子阳离子表面活性剂的表面活性

通过吊片法和最大泡压法测定了4种糖基双子阳离子表面活性剂(SGCS)的平衡表面张力和动态表面张力,对其表面活性进行了评价。SGCS的γcmc在30 m N/m左右,cmc均在10-4mol/L数量级,比普通阳离子表面活性剂的cmc低1~2个数量级,表明SGCS具有优良的表面活性。SGCS的lg ccmc和pc20与疏水基的碳链长度符合线性关系。随着SGCS浓度的增大,动态表面张力下降速度加快,更容易达到介平衡。随着温度的升高,动态表面张力下降速率加快,说明温度越高动态表面活性越强。     

Physicochemical principles in dyeing freshly spun polyacrylonitrile fibres and films with mixtures of cationic dyes

Conclusions Two process stages may be discerned in the technology of dyeing freshly spun PAN fibres with cationic dyes and mixtures of them, depending on the temperature. In the first stage, at 20–50°C, the dye rapidly diffuses into the freshly spun gel and is sorbed in its submicroscopic volume. The second stage — bonding of the dye with formation of heteropolar bonds — takes place during the process of drying and heat-setting the fibre. The nonequilibrium sorption of dyes in the first stage is characterized by the instantaneous values of the affinity of the freshly formed polymer for the dyeing solution, _ins ⁰ .It is possible to determine the compatibility of cationic dyes in mixtures in dyeing freshly spun PAN gels from the _ins ⁰ values. For compatible components, these figures should not exceed 0.8–1.4 kJ/mole.Freshly spun PAN fibres containing various acid groups up to 1.5% by wt., and prepared by various technologies, have practically an identical affinity for cationic dyes.Translated from Khimicheskie Volokna, No. 4, pp. 39–41, July–August, 1986.     

过硫酸盐氧化法降解水中有机物的研究进展

对过硫酸盐氧化法(persulfate,PS)的氧化机理和活化技术进行了研究。按热活化、光活化、过渡金属离子活化、活性炭活化、电化学活化、微波活化、超声波活化等活化方法分类,总结近几年PS技术应用的降解效果,讨论PS技术对废水中常见有机物的反应的最佳条件和降解过程的限制因素,以期为过硫酸盐氧化法今后的研究提供参考和借鉴作用。     

阳离子型双子表面活性剂在石油行业的应用进展

针对用于缓蚀剂、杀菌剂、驱油剂、压裂液和防腐剂这5个方面对阳离子型双子表面活性剂的合成、使用条件、应用现状进行了综述,发现存在的问题有:缓蚀剂溶解性较差、对环境有污染;在高温、高浓度前提下防腐剂性能不强;杀菌剂稳定性较差、易产生抗药性;驱油剂的吸附量不够低、在地层介质中没有较大的扩散速度;压裂液的耐温性能较差、破胶不够快速、彻底。针对上述的不足之处提出了对于驱油剂应加强其对于超高温、高盐地层的适应性;提高压裂液的降滤失能力;发展有利于环境生产、无污染或低污染的缓蚀剂;提高防腐剂在高浓度条件下的防腐效果;制备稳定性强的杀菌剂等建议。     

分子结构对阳离子双子表面活性剂性能的影响

以十六烷基二甲基叔胺、棕榈酰胺丙基二甲基胺、1,4-二氯丁烷和1,4-二溴丁烷为原料合成了四种阳离子双子表面活性剂(CG-C、CG-PC、CG-B和CG-PB)。产物结构经红外光谱和核磁共振氢谱进行确认,并通过对表面张力、油水界面张力、泡沫性和乳化性等性能的测定来阐述分子结构(疏水碳链和无机反离子)对阳离子双子表面活性剂效能的影响。结果表明,含Br^-的表面活性剂的表面活性优于含Cl-的表面活性剂的表面活性优于含Cl^-的,碳链上酰胺基团的引入导致表面活性降低;反离子对降低界面张力的能力影响不大,未带有酰胺基团的降低界面张力的能力较强;含有Cl-的,碳链上酰胺基团的引入导致表面活性降低;反离子对降低界面张力的能力影响不大,未带有酰胺基团的降低界面张力的能力较强;含有Cl^-(未带酰胺基团)的乳化性能强于含有Br-(未带酰胺基团)的乳化性能强于含有Br^-(酰胺基团)的;含Br-(酰胺基团)的;含Br^-的泡沫性能稍强于含Cl-的泡沫性能稍强于含Cl^-的,含酰胺基团的起泡能力较差,但泡沫稳定性好。     

Application of rare earth as mordant for the dyeing of ramie fabrics with natural dyes

Selecting appropriate metallic compounds as mordants is essential for dyeing with natural dyes. This paper presents the application of rare earth compounds as mordant for the dyeing of ramie fabrics with four kinds of natural dyes. The influences of pre-mordanting, simultaneous mordanting, and post-mordanting on the dyeing effect were explored. The post-mordanting was proved to give rise to the highest dye uptake. The effects of dyeing conditions including dyeing temperature and time, dyeing bath pH and the concentration of rare earth on the dye uptake were investigated systematically. The fabrics dyed with natural dyes in presence of rare earth as mordant exhibited high color shade stability in the baths with pH varying from being acidic to neutral and alkaline. Employing rare earth as mordant apparently raised the color fastness to washing, rubbing and light of the ramie fabrics dyed with the natural extracts. In comparison with the commonly used metallic salts, using rare earth chlorides as mordants can greatly reduce the ionic concentration employed in natural dyeing. This study proved that rare earth would be a kind or promising environmentally friendly mordant in natural dyeing.     

新型松香基阳离子Gemini表面活性剂的合成及分析

以松香酸、环氧氯丙烷、四甲基丙二胺为原料,通过酯化、季铵盐化反应制备了松香基阳离子双子表面活性剂,产率为70.5%,纯度为95.5%;采用FT-IR对产物结构进行确证;表面活性分析结果表明:临界胶束浓度(CMC)值为4×10-4mol/L,γcmc为37.35 mN/m,pc20为4.45,乳化性能强,泡沫密集且稳定,HLB值约为13.98,属于水包油(O/W)型乳化剂,与阴离子相溶性好。     

Reactive dyeing of cellulosic fibers: Use of cationic surfactants and their interaction with reactive dyes

Cotton fabrics were dyed with three reactive dyes, C.I Reactive Blue 263, C.I Reactive Red 269, and C.I Reactive Yellow 208, after pretreatment of the fabrics with three alkyl trimethyl‐ammonium bromides (tmabs) having 12, 14, and 16 carbon atoms in the alkyl chain. The pretreated samples were dyed with standard dyeing methods using conventional, reduced amounts of electrolyte, and no electrolyte. Pretreatment with the three cationics (tmabs) resulted in an increase in dye exhaustion with all dyes used, whereas total dye fixation was lower for both red and blue dye and equal for the yellow, when compared to the reference untreated samples dyed according to the same standard dyeing method. The interaction between dodecyl trimethyl‐ammonium bromide and the three dyes was studied and the stoichiometry of the various dye/dodecyl trimethyl‐ammonium bromide (12‐tmab) complexes formed has been deduced. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of new 5-thiazolyl azo-disperse dyes for dyeing polyester fabrics

Diazotized aryl amines were coupled with 2-aminothiazoles 1 and 2 to give the corresponding thiazolylazo dyes 3 and 4, respectively. 2-Amino-5-arylazothiazoles 5 reacted with chloroacetyl chloride to afford the chloro-acetamide derivatives 6 which further reacted with 2-mercaptobenzothiazole to furnish a new series of 5-arylazothiazolyl dyes 7. The azo structure of the dyes (rather than the tautomeric hydrazo structure) was assessed by ab initio DFT calculations at the B3LYP/6-31G* level. These dyes were applied to polyester fabric as disperse dyes and their fastness properties were evaluated.     

阳离子型Gemini表面活性剂改性膨润土的制备及结构表征

以膨润土为原料,以系列阳离子Gemini表面活性剂(Gm-n-m)为插层剂制备了有机膨润土,利用红外光谱、X射线衍射及差热-热重分析对产物结构进行了表征,并探讨了温度、时间、搅拌速率及插层剂用量对有机膨润土结构的影响。结果表明,当Gm-n-m分子进入到膨润土层间后,其疏水性增强,层间距由1.51 nm增大到3.91 nm,有机物含量达到23.53%,且层间距明显大于单链CTAB改性膨润土的层间距。适宜的制备条件为:插层剂用量为钠基膨润土的40%,70℃下水浴反应3 h,搅拌速率为205 r/min。     

非对称双子季铵盐阳离子表面活性剂的合成及性能

以十二烷基二甲基叔胺、盐酸、环氧氯丙烷为原料,合成了中间体N-(3-氯-2-羟丙基)-N,N-二甲基十二烷基氯化铵,后与3种不同烷基链长的长链烷基叔胺反应,得到3种非对称Gemini季铵盐阳离子表面活性剂(Ⅰ～Ⅲ)。通过IR光谱,1HNMR确证了中间体及目的产物的结构。测定了产物的临界胶束浓度cmc及γcmc。cmc分别为1 07×10-3mol·dm-3、1 99×10-3mol·dm-3和9 55×10-3mol·dm-3,γcmc分别为40 9mN·m-1、48 0mN·m-1和50 9mN·m-1。结果表明:所合成的非对称Gemini季铵盐阳离子表面活性剂具有较高的表面活性。     

The effect of polyhydroxyurethane on dyeing of cellulosic fabrics with direct and reactive dyes

Dye yields and fastness properties are reported for direct and reactive dyes using a modified dyeing solution with polyhydroxyurethane. Excellent dye yields and colour fastness properties were obtained without the use of electrolytes, multiple rinsing or fixation agents, which are normally employed in cotton dyeing. From the results, it was found that polyhydroxyurethane media exhibit better dyeability and fastness than the normal aqueous media. Dye adsorption in polyhydroxyurethane media was much higher than in other aqueous systems. The dyed samples showed good hot pressing and washing colour fastness properties within the color change range. The excellent solubility of these dyes in the polyhydroxyurethane aqueous solution makes them ideal for use in exhaustion dyeing.     

Effects of cationic fixing agents on the direct dyeing properties of cotton fabrics

One mono-reactive and two bis-reactive 2,3-epoxypropyl derivatives of quaternary ammonium chloride have been synthesised and characterised using different spectroscopic techniques. The effects of these compounds as fixing agents have been evaluated on the direct dyeing properties of cotton fabrics. The results indicated that pretreatment of cotton fabrics with these cationic agents enhanced the colour strength and fastness properties of direct dyeings over the untreated dyeings without using high electrolyte concentrations. However, bis-reactive derivatives have proved to be more effective than the mono-reactive derivative. Amongst bis-reactive derivatives, the compound with lower steric hindrance has shown superior results.     

Effect of metal salts on the dyeing of freshly spun polyacrylonitrile fibre with acid dyes

Conclusions The effect of the metal cations Al³⁺, Zn²⁺, and Cr³⁺ on the process of dyeing freshly spun PAN fibres with acid dyes has been studied. It has been found that the greatest amount of dye is fixed on the fibre when Al³⁺ ions are introduced into the dye bath.On the basis of analysis of the IR spectra of the dyed fibres, a mechanism has been proposed for the interaction of both the metal cations and also of the dye with PAN fibre. It has been found that the metal cation is bonded with the fibre both by an ionic bond with the—COOH groups and also by a coordination bond with >C=0 groups of the polymer substrate.Translated from Khimicheskie Volokna, No. 6, pp. 13–14, November–December, 1986.     

Pyrimidinium cationic surfactants as emulsifiers for oil-in-water emulsions

Pyrimidinium cationic surfactants with 13–17 carbon atoms in the hydrophobe were used as emulsifiers for oil-inwater (heptane/water) emulsions at concentrations near the critical micelle concentrations. Interfacial tensions of the emulsifier solutions in water against heptane were measured. Drop size distributions of the emulsions were determined at different times using microscopic techniques, and the rate of coalescence was calculated. The structure having 16 carbon atoms in the alkyl chain had coalescence rates lower than the other structures, including two conventional C-16 cationics used as controls.     

Application of chitosan/nonionic surfactant mixture in reactive dyes for dyeing wool fabrics

The feasibility of wool fabrics pretreated with a chitosan/nonionic surfactant mixture and dyed with reactive dyes was studied. The results showed that the presence of the chitosan/surfactant improved the application to wool, which greatly enhanced the color strength when dyed at 50°C but little change was observed when dyed at 80°C. The higher the concentration of chitosan/surfactant added, the greater was the color strength of the dyed wool fabrics. The amounts found to be optimum for dyeing were 0.5% chitosan and 1.0% surfactant. The washing fastness of the dyed wool fabrics was in the range of grades 4–5, the dry rubbing fastness was in the range of grades 4–5, and the wet rubbing fastness was in the range of grades 3–4. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2859–2864, 2001     

糖基双子阳离子表面活性剂与十二烷基硫酸钠复配性能研究

测定了糖基双子阳离子表面活性剂(SGCS)与十二烷基硫酸钠(K_(12))复配体系的稳定性和表面性能。由实验结果可知,在宽的复配范围内不同碳链长度的SGCS与K_(12)均有良好的复配稳定性;C_(14)-SGCS/K_(12)复配体系表现出明显的协同增效作用,当n(C_(14)-SGCS)∶n(K_(12))为3∶5时复配溶液临界胶束浓度(cmc)、cmc时的表面张力(γ_(cmc))和降低表面张力的效率(pc_(20))分别为1.1×10~(-5) mol/L、23.69 mN/m和5.48,均明显优于C_(14)-SGCS和K_(12)自身的表面性能。     

Salt-free reactive dyeing of betaine-modified cationic cotton fabrics with enhanced dye fixation

Novel cationic cotton fabrics were prepared by an efficient and simple one-step pad–dry–bake pretreatment process with betaine as cationic reagent. Ester bonds formed between cotton fibers and betaine hydrochloride were proved by Fourier transformed infrared attenuated total reflection(FTIR-ATR) spectra. Moreover, the properties of the cationic fabrics, including X-ray Diffraction(XRD), tensile strength and whiteness and yellowness index,were investigated in comparison with that of the untreated ones. The cationic fabrics were applied in salt-free dyeing of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19. Different dye fixation processes were applied and compared for untreated and cationic cotton. Dye fixation and color fastness properties of the dyes were tested, and the results presented that dye fixation on the cationic fabrics in the absence of salt was improved with satisfactory light fastness property and applicable wash and rub fastnesses.     

非离子型Gemini表面活性剂的性质

Gemini表面活性剂具有的优良表面活性,使之有望作为三次采油用的表面活性剂。用界面张力仪及HAAKERS600流变仪研究了非离子型Gemini表面活性剂的表面活性及流变特性。结果表明,25℃下,氧乙基数(EO数)分别为8,10,12的3种非离子型Gemini表面活性剂8-NP-8、10-NP-10及12-NP-12的临界胶束浓度(cmc)值分别为:0.99,0.15和0.032 mmol/L;非离子型Gemini表面活性剂的表面活性及cmc值受电解质的影响较小;氧乙基数为12的非离子型Gemini表面活性剂可以使亲水及亲油固体表面的接触角明显降低,水润湿性增强;非离子型Gemini表面活性剂溶液的粘度随剪切速率增加基本保持不变,呈现出牛顿流体的特性。