Fixation of reactive dyes using radio-frequency energy

Radio-frequency (r.f.) energy has been used to increase the fixation rate of reactive dyes on cotton fabric in pad-batch dyeing. A parallel-plate r.f. applicator was used to heat batches of fabric containing reactive dye formulations. The time required for fixation of the dyes was reduced from several hours to a few minutes by heating the fabric in the radio-frequency field. Reactive dyes incorporating three different types of reactive groups, vinylsulphone, nicotinic acid, and mixed vinylsulphone/ monochlorotriazine were studied and found to be applicable using the hot pad-batch method. The colour yield and wash fastness of dyeings with the vinylsulphone/monochlorotriazine bifunctional dyes using r.f.-assisted fixation was equal or superior to those of dyeings performed by conventional cold pad-batch dyeing methods.     

Aftertreatment of polyester fabric dyed with temporarily solubilised disperse dyes

Temporarily solubilised disperse dyes derived from aminophenyl-4-(β-sulphatoethylsulphone) are exhausted on the polyester fibre mostly in the vinylsulphone form and to a lesser extent as their hydroxyethylsulphone analogues. After dyeing, to remove the unexhausted dyes on the polyester fibre, sulphite anions were added to the dyebath. The vinylsulphone residue of the dye was attacked by the sulphite anion via an addition reaction converting the dye into a soluble derivative, which then had little affinity for the polyester fibre. The effect of sodium sulphite on the conversion of the dye was investigated using HPLC. The wash and rub fastness properties of the dyed fabric aftertreated with sodium sulphite were similar to those obtained with reduction clearing.     

The effect of reactive dyes on damage in wool dyeing

This paper demonstrates that reactive dyes exert a significant fibre–protective effect when dyeing wool fabric; this effect may be measured, in a reproducible manner, using the wet–burst strength test. The effect of dyebath pH, dye concentration, dyebath temperature and dyeing time on wool can thus be evaluated. The magnitude of the above protective effect has been compared with that achieved using commercially available fibre–protective agents. It is concluded that reactive dyes are significantly more effective than the latter agents when employed in medium to full depths. It is proposed that the unusual protective effect afforded by reactive dyes is related to the following factors. Reactive dyes readily react with sulphur nucleophiles, thus inhibiting thiol–disulphide interchange reactions and thereby significantly interfering with the level of set produced in a boiling dyebath. Reactive dyes react preferentially with non–keratinous proteins in the intercellular cement and the endocuticle thus reducing their tendency to hydrolyse and to partially dissolve in the hot aqueous dyebath.     

Synthesis of reactive dyes based on the bis-(N-carboxymethylamino)monoquaternary-triazine-bis-ethylsulphone reactive group. Part 1: Application to cotton cellulose

Reactive dyes containing the bis-( N -carboxymethylamino)monoquaternary-triazine-bis-ethylsulphone [bis-( N -CMA)-MQT-bis-ES] group and related derivatives have been synthesised. When boiled under mildly acidic conditions, such dyes are able to form two small vinylsulphone dye molecules through a process of 1,2-trans elimination. The bis-( N -CMA)-MQT-bis-ES dye was applied using different dyeing procedures (novel dyeing methods 1 and 2). The dyeing and soaping-off results of bis-( N -CMA)-MQT-bis-ES dye were compared with a model sulphatoethylsulphone dye applied using the conventional alkaline fixation method used for applying this type of reactive dye to cotton. The bis-( N -CMA)-MQT-bis-ES dye showed higher exhaustion and fixation values applied using novel dyeing method 2 compared with the sulphatoethylsulphone dye applied using the alkaline fixation method. The soaping-off efficiency for the large bis-( N -CMA)-MQT-bis-ES dye applied using novel dyeing method 2 was the same as that obtained for the sulphatoethylsulphone dye applied using the alkaline fixation method.     

A microscopical study of the pathway for diffusion of rhodamine B and octadecylrhodamine B into wool fibres*

The pathways for the diffusion of the basic dyes rhodamine B and octadecylrhodamine B into wool under aqueous and non–aqueous dyeing conditions have been investigated. The distribution of each dye within the fibre at various stages of the dyeing process was monitored by fluorescence microscopy. By judicious choice of solvent system and treatment time, the dyes could be directed into different histological components of the fibre. Intercellular diffusion, involving passage of the dye through the cell membrane complex between the cortical cells, was generally the preferred route for penetration of the fibre. The distribution patterns of the two dyes differed markedly and were strongly dependent upon the solvent composition. Whilst selective staining of the cell membrane complex occurred in an anhydrous solvent system, preferential staining of that region of the cell membrane complex associated with the orthocortex resulted when the dyes were applied from aqueous alcohol systems.     

A novel resist technique based on secondary amines for the printing of cotton with reactive dyes

In an earlier paper we have described sulphite‐based resist printing using ink‐jet procedures. This paper describes an alternative approach to sulphite inactivation of vinylsulphone dyes by using secondary amines to inactivate fluoro‐s‐triazine dyes while maintaining the reactivity of the vinylsulphone dyes. Monofluoro‐s‐triazine reactive dyes are padded onto cotton fabrics and then deactivated by ink‐jet printing with a suitable secondary amine formulation to produce a white image on a solid ground colour after appropriate fixation and soap‐off procedures have been undertaken. A coloured image can be achieved by overprinting the resist‐printed areas with a coloured ink formulation containing a β‐sulphatoethylsulphone‐type reactive dye; such dyes form a β‐bis‐alkylaminoethylsulphone dye via reaction with the secondary amine. This latter dye ‘unblocks’ during a mildly acidic steaming process to form the reactive vinylsulphone dye, and so, unlike the monofluoro‐s‐triazine dye, is not deactivated towards subsequent covalent reaction with the cotton substrate.     

Electrophoresis of polymeric dyes in macroporous polymer

Summary Macroporous poly(styrene-co-divinylbenzene), with poly(vinyl alcohol) (PVA)-coated pores, was investigated as a novel medium for thin-layer electrophoresis. The system was tested using polymeric dyes having polyelectrolyte character, which were prepared by reaction of a vinylsulphone reactive dye (CI Reactive Blue 19) with PVA. Higher molar mass samples exhibited higher mobility on electrophoresis in the macroporous medium. Received: 6 May 2002 /Revised: 2 July 2002 /Accepted: 2 July 2002     

Quaternary reactive dyes containing a thioether‐ethylsulphone group. Part 2; Application methods for the dyeing of nylon†

A member of the new series of cationic reactive dyes containing a thioether‐ethylsulphone grouping referred to in Part 1 of this series has been applied to nylon at pH 3–10. The dye is water soluble and shows excellent substantivity for nylon 6.6 when dyed at the boil at pH 8–10. Under alkaline conditions, gradual β‐elimination back to the vinylsulphone dye occurs and covalent bond formation quickly takes place with the fibre; the higher the pH the more rapidly this occurs. Dyeings carried out at pH 10 showed very good brightness and levelling, together with good wash fastness. The light fastness of dyeings at moderate depth was 4–5 on the Blue Wool scale.     

Quaternary reactive dyes containing a thioether-ethylsulphone group. Part 1; Synthesis of a trimethylammonium ethylsulphide–ethylsulphone dye

This paper describes the synthesis of a reactive dye containing a thioether-ethylsulphone group. The dye was prepared by reaction of a specially synthesised vinylsulphone dye with β-thiolethyltrimethylammonium chloride. The latter was synthesised by the reaction of choline dichloride with sodium thiosulphate; the Bunte salt thus formed was hydrolysed with aqueous hydrochloric acid to give the required thiol derivative. This reacted readily with a model vinylsulphone dye to give the desired compound.     

Behaviour of Bifunctional and Polyfunctional Reactive Dyes Applied to Cotton Cellulose

Analytical techniques, viz. electron microscopy, surface area determination, and swelling in cadoxen solvent, have been used to obtain results which provide positive evidence for the formation of crosslinks between adjacent cellulose chains in cotton dyed with different classes of bi- and poly-functional reactive dyes. Reactive dyes selected include those where either the reactive groups are present in the same nucleus (dichlorotriazinyl, monomethoxymonochlorotriazinyl, dichloroquinoxaline, trichloropyrimidinyl and difluoromonochloropyrimidinyl) or where the two reactive groups are present at different positions in the dye molecule (Procion HE (ICI) and Procion Supra (ICI)). The extent of changes observed in the morphology of cotton fibre as a result of dyeing with bi- and poly-functional reactive dyes has been found to depend on the amount of dye present in the fibre and the conditions of application.     

Modification of a vinylsulphone reactive dye using diethanolamine-O-disulphate

The β-sulphatoethylsulphone dye, Remazol Orange 3R, was converted to its vinylsulphone form and then reacted with diethanolamine- O -disulphate (DES) to produce a new type of reactive dye carrying pendent amino-di(ethyl- O -sulphate) groups. Application of the latter dye to cotton, using the pad–dry–steam process in the presence of alkali, resulted in a good level of dye–fibre covalent fixation. It had been expected that the sulphate ester would react by nucleophilic substitution to give bifunctional covalent attachment of the dye to cotton. It was shown, however, that an intermediate dye containing an aziridine residue was produced, which under hot alkaline conditions was converted by β-elimination to the vinylsulphone dye, and it was in this form that reaction with cotton took place.     

Dyeing of natural and synthetic textiles in supercritical carbon dioxide with disperse reactive dyes

Polyester, nylon, silk and wool were dyed with disperse reactive dyes in supercritical carbon dioxide (scCO₂). The dyes were substituted with either vinylsulphone or dichlorotriazine reactive groups. Since earlier research showed that water, distributed over the scCO₂ and the textile, increased the colouration, experiments were done with the vinylsulphone dye with varying amounts of water in the dyeing vessel, to investigate if there is an optimum water concentration. The amounts were such, that no liquid water was present. The maximum colouration was obtained when both the scCO₂ and the textiles were saturated with water. At the saturation point, deep colours were obtained with the vinylsulphone dye for polyester, nylon, silk and wool, with fixation percentages between 70 and 92% when the dyeing time was 2 h. The positive effect of water was due to its ability to swell fibres or due to an effect of water on the reactivity of the dye–fibre system. Also the dichlorotriazine dye showed more colouration when the scCO₂ was moist. With this dye, experiments were conducted in water-saturated scCO₂, varying the pressure from 225 to 278 bar and the temperature from 100 to 116 °C. The colouration of polyester increased with pressure, the results for silk and wool were not sensitive to pressure. Increasing the temperature had no influence on the dyeing of polyester, silk and wool. The fixations on polyester, silk and wool, being between 71 and 97%, were also independent of pressure and temperature.     

Vat dye sensitised fibre damage and dye fading by catalytic and activated peroxide bleaching

At equal levels of performance, activated (TAED) and catalytic (Mn-TMTACN) laundry bleaching can differ considerably in terms of the concomitant damage to fibres and dyes. To quantify this damage, differently dyed cotton fabrics, and a representative set of eight vat dyes and CI Reactive Brown 7 were used. It is shown that dye fading and fibre degradation are dye-specific and are both highly coupled phenomena. The interpretation of the damage data is based on dye chemistry, reflectance spectroscopy (UV/VIS and NIR) and EPR measurements. Whereas compelling evidence for a genuine catalytic cycle with the quoted manganese complex is lacking, a possible catalytic role of the dyes is proposed. The dramatic green shift resulting from the catalytic bleaching of Cl Vat Blue 4 is explained in detail. The corresponding oxidation is reversible and possibly useful as a fibre damage indicator.     

Ultrasonic‐assisted dyeing: I. Nylon dyeability with reactive dyes

The use of ultrasonic power (38.5 KHz, 350 W) to assist the dyeability of nylon‐6 fibre with reactive dyes is reported. The effects of the different factors that may affect the dyeability of nylon‐6 fibre with Reactive Red 55 were simultaneously carried out under both ultrasonic power and conventional heating conditions. The colour strength values obtained for the dyed samples using ultrasonic power were higher than those obtained using conventional heating. Also, the effect of alkaline soaping treatment on dye fixation for the dyed fabrics with different reactive dyes, at both acidic and neutral pHs, is generally better with ultrasonic than with conventional heating. The overall results indicate that the enhancing effect is mainly attributed to the de‐aggregation of dye molecules, which leads to better dye diffusion and possible assistance for dye‐fibre covalent‐bond fixation. The results of wet fastness properties of the dyed fabrics reveal improvement using ultrasonic power dyeing relative to the conventional heating method. © 2003 Society of Chemical Industry     

Structure—reactivity studies of a new polyfunctional disulphide bis(ES-MCT/SES) reactive dye applied to silk

A new polyfunctional reactive dye containing disulphidebis(ethylsulphone-monochlorotriazine/sulphatoethylsulphone) reactive system has been synthesised and applied to silk. High exhaustion/fixation results have been achieved at 90 °C and pH 9. The vinylsulphone precursor of the disulphidebis(ethylsulphone) group combined with a sulphatoethylsulphone/monochlorotriazine reactive system confers a relatively high fixation efficiency for this type of polyfunctional reactive dye when compared with that of a conventional bifunctional reactive dye containing the sulphatoethylsulphone/monochlorotriazine reactive system. The results also indicate that high fastness properties were obtained for the reactive dyes under investigation.     

The Influence of Different Substitution Levels of Guar on the Quality of Viscose Prints with VS Monoreactive Dye

Abstract

The basic problem of reactive printing on viscose with polysaccharide guar thickeners is the capability of dye molecule to react with the hydroxyl groups of cellulose (binding of the dye) as well as with the hydroxyl groups of water (the dye hydrolyzes) or the thickener (binding of the dye) (1, 2]. This latter is most clearly expressed in combination of the polysaccharide unmodified guar thickener and the bifunctional reactive dye where the bifunctional dye forms, due to the presence of two reactive groups, a bridge between the cellulose fibre and the guar thickener (3). The unmodified guar has a large number of free hydroxyl groups which cause crosslinking with cellulose and hinder the thickener to wash off, thus increasing the stiffness of the printing fabric. The further investigation has shown that this undesireous reaction with the guar molecules can be partly diminished by the suitable selection of chemically modified guar thickener or by lowering the dry substance content [4, 5].

In this paper the influence of nonsubstituted and different substitutited guar thickeners with monoreactive (vinylsulphone) dyes on the changing of fabric stiffness will be shown.     

草酸青霉Penicillium oxalicum菌体吸附活性染料的性能及微观过程

研究了草酸青霉(Penicillium oxalicum)在模拟染料废水中以边生长边吸附的方式对活性翠蓝KN-G, M-GB, K-GL,活性黑K-BR、活性艳蓝M-BR、活性红紫K-3R和活性深蓝K-R 7种水溶性活性染料的脱色性能及吸附过程. 结果显示,生长菌体对7种活性染料具有良好的脱色性能,染料初始浓度为200 mg/L时,平均脱色率可达93.0%;染料初始浓度为400 mg/L时,活性翠蓝KN-G和M-GB的脱色率仍达到了99.7%和99.9%. 上清液的紫外光谱图及染料分子中铜离子浓度的检测结果表明,染料通过吸附方式从废水中去除. 通过SEM, TEM观察发现,生长菌体在吸附过程中,菌丝发生肿胀膨大,细胞壁发生结构重组,厚度增加10~15倍. 细胞壁的结构变化是生长菌体吸附染料的重要机制,为染料吸附提供位点和进入细胞内部的通道.     

One‐bath union dyeing of a modified wool/acrylic blend with acid and reactive dyes

Pretreated wool/acrylic fibre was obtained by a facile amidoximation process. Fibre characterisation (nitrogen content, tensile strength, shrinkage, infrared spectra and X‐ray diffraction) proved the success of the pretreatment. Union dyeing of wool/acrylic fabrics with acid and reactive dyes, namely CI Acid Red 40, CI Acid Blue 25, CI Reactive Red 194 and CI Reactive Blue 25, was obtained using a one‐bath dyeing process. Different factors that may affect the dyeability of the blend fibre, such as dyebath pH, liquor ratio, temperature, time and dye concentration, were evaluated with respect to the dye exhaustion, fixation, colour strength, levelling and fastness properties. Excellent to good fastness was obtained for all samples, irrespective of the dye used. The result of the investigation offers a new viable method for union dyeing of wool/acrylic fibres in a one‐dyebath process.     

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     

Decolorisation of reactive dye wastewater and the effect of surfactants using laccase

Laccase (benzenediol, oxidoreducase; Enzyme Commission Number) is a multi‐copper oxidase from biomass. Laccase enzyme recycling on molecular oxygen as an electron acceptor can be applied for the decolorisation of synthetic dyes. The decolorisation of 49 commercial reactive dyes using laccase was investigated. The effects of diverse structure surfactants on decolorisation are discussed. The absorption spectra of reactive dyes after a laccase biodegradable reaction were analysed. Reactive dyes based on anthraquinone and azo structures could be decolorised using the enzyme and their chemical structures broken. Reactive dyes based on an anthraquinone structure were easier to decolorise than those based on an azo structure. Surfactants could affect the decolorisation of dyes with an enzyme. The effect of nonionic surfactant on the decolorisation of anthraquinone dyes was the reverse. The cationic surfactant could improve the decolorisation rate of diazo dye. The effect of the anionic surfactant on dye decolorisation was small. Most commercial reactive dyes could be decolorised and biodegraded using a laccase enzyme under mild conditions. Laccase enzyme biotechnology has potential applications in the decolorisation of reactive dye wastewater.