Investigation of alkaline hydrolysis of phthalimide‐based azo dye and its application to after‐treatment optimisation for high‐fastness dyeing of polyesters

4‐Amino‐N‐methylphthalimide was prepared from phthalimide for use as a diazo component and was coupled with N,N‐Diethylaniline to produce a phthalimide‐derived monoazo disperse dye. The pseudo first‐order kinetics were confirmed by analyzing the dye hydrolysis under alkaline conditions using high performance liquid chromatography, and the optimal dyeing pH and alkali‐clearing conditions were proposed. The synthesised phthalimidyl disperse dyes exhibited excellent colour fastness with a mild alkaline after‐treatment instead of reduction clearing which results in a high biological oxygen demand and pH in conventional disperse dyeing wastewater.     

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.     

Novel hydrolysable azo disperse dyes based on N‐ester‐1,8‐naphthalimide: dyeing of polyester–cotton blends

The dyeing of polyester–cotton blends with new alkali‐hydrolysable azo disperse dyes based on N‐ester‐1,8‐naphthalimide was investigated. Polyester–cotton blend fabrics were dyed using both one‐ and two‐bath methods. Dyes 3 and 4 offered lower colour yield on polyester using the one‐bath method. For the rest of the dyes, employing either the one‐ or two‐bath method resulted in a similar colour yield on polyester fabric. The results for fastness properties and colour yield of the dyeings showed that the dyes were suitable for dyeing polyester–cotton blends using the one‐bath method. The kinetic study of hydrolysis of the dyes in alkali media obeyed the pseudo first‐order reaction rate.     

One‐step dyeing of polyethylene terephthalate fabric,combining pretreatment and dyeing using alkali‐stable disperse dyes

In the conventional dyeing process, polyester and its blended fabrics are usually dyed in a weak acidic medium. In order to reduce cost and improve production efficiency, a new dyeing method – one‐step dyeing of polyethylene terephthalate fabrics, combining pretreatment and dyeing in alkali conditions – was investigated. The alkali‐stable disperse dyes Red 900, Red 902, Yellow BROB and Blue 825 were used to dye polyethylene terephthalate fabrics. The dyeing properties of polyethylene terephthalate fabrics in the case of one‐step dyeing at various pH values or sodium hydroxide concentrations were discussed in terms of colour yield, colour parameters and fastness. The performance of one‐step dyeing using alkali‐stable disperse dyes was excellent. The dyed fabric had good fastness. Wet processing could be combined and shortened. One‐step dyeing of polyethylene terephthalate fabrics could reduce the consumption of water and energy and improve production efficiency. One‐step dyeing of polyethylene terephthalate has potential application in cleaner textile production.     

Physico–chemical and Dyeing Properties of Disperse Dyes containing Phthalimide Residues

The relationship between the constitution and the physico–chemical and dyeing properties of disperse dyes containing phthalimide residues has been studied. The influence of the –NH or –NCH₃ group in the phthalimide residues on the thermal and spectral properties of dyes has been investigated. Their influence on the dyeing process and on the colour and fastness properties of dyed polyester have also been studied.     

Properties of Monoazo Disperse Dyes,Derivatives of 3– and 4–Aminophthalimide

The synthesis of several disperse dyes, from 3–amino–12–phthalimide and its N–methyl derivative as diazo component and N, N–dialky lanilines as coupling component is described. The dyeing behaviour and some physical properties of these dyes are investigated and compared with those of isomeric dyes containing azo groups in the 4–position, previously studied [5]. These properties were found to be considerably affected by the presence of an alkyl sub–stituent on the nitrogen atom of imide group. Further, dyes containing unsubstituted –NH groups showed somewhat better thermal properties (higher melting points and dyeings of better fastness to sublimation), but at the same time their dyeability was worse for all the known processes of dyeing polyester fibres. Based on the i. r. and visible spectra of the dyes under investigation, it was concluded that the dyes containing unsubstituted –NH groups are highly associated; dyes containing azo groups in the 4–position associate to give one product, whereas association of the dyes with azo groups in the 3–position leads to two different products.     

A facile synthesis and tautomeric structure of novel 4‐arylhydrazono‐3‐(2‐hydroxyphenyl)‐2‐pyrazolin‐5‐ones and their application as disperse dyes

The main target of this paper was the synthesis of novel azo disperse dyes with better dyeing properties, together with a systematic investigation to determine their dominant tautomer(s) from 12 possible tautomeric structures. In this regard, novel azopyrazolin‐5‐one dyes were synthesised via the reaction of hydrazine hydrate with 2,3,4‐chromantrione‐3‐arylhydrazones. The acid dissociation constants both in the ground and in the excited state for the series prepared were determined and correlated by the Hammett equation. The results of this correlation, together with spectral data, indicated that the compounds under scrutiny exist predominantly in the keto‐hydrazo structure as a Z‐configuration, both in the ground and in the excited state. Finally, the synthesised dyes were applied as disperse dyes for dyeing polyester fabrics, and their fastness properties were evaluated. Also, the position of colour in CIELAB coordinates was estimated and discussed.     

Synthesis,spectral and dyeing properties of phenylazopyrazolone‐containing acylamide disperse dyes designed for poly(lactic acid)

A series of phenylazopyrazolone disperse dyes containing an acylamide moiety were synthesised from carboxyl‐containing acid dyes via chlorination and amidation with different sorts of amines. The structures of these new dyes were confirmed by Fourier Transform–infrared, proton nuclear magnetic resonance, mass spectroscopy and elemental analysis. Their solvatochromic properties in different solvents were also investigated and the absorbance spectra of the acylamide dyes in solution exhibited a red shift when dissolved in dimethylformamide, compared with acetone. Their dyeing behaviour, including dye sorption, colour build‐up and colour fastness properties on poly(lactic acid) fibres, was also determined, whereupon it was found that the tertiary acylamide dyes simultaneously exhibited high dye sorption and satisfactory colour build‐up and fastness properties on the poly(lactic acid) fabric.     

Organoclays assisted vat and disperse dyeing of poly(ethylene terephthalate) nanocomposite fabrics via melt spinning

Polyethylene terephthalate nanocomposites containing six modified montmorillonite nanoclays were prepared by a melt compounding technique. The effect of intercalated compounds of montmorillonite on textile mechanical properties of resultant polyethylene terephthalate nanocomposite fabrics was investigated. Winding was not possible, when the polymers were first compounded with the desired amount of montmorillonite and then spun, as filament breakage occurred. Spinable polymer were only obtained by mixing polyethylene terephthalate master batches with 4 wt% montmorillonite, which contained tallow intercalating compound with pure untreated polyethylene terephthalate to a montmorillonite content of 0.5 wt%, thus decreasing the concentration of thermally degraded polymer chains. After spinning the fibres were drawn and knitted into fabric samples for further testing. The prepared polyethylene terephthalate nanocomposite fabrics using montmorillonite exhibited higher colour strength using vat and disperse dyes compared with those of the reference fabrics made from fibres spun without montmorillonite clay content and regular fabrics. The carbocyclic‐based vat dyes have higher colour strength values on polyethylene terephthalate nanocomposite fabrics if compared with heterocyclic‐based vat dyes. The colour fastness ratings for both vat and disperse dyeings secured very good to excellent washing and perspiration fastness on polyethylene terephthalate nanocomposite fabrics. All dyed fabrics showed excellent light fastness using vat and disperse dyes. The preparation of polyethylene terephthalate nanocomposite fabrics with improved textile mechanical and vat dyeing properties needs further investigations.     

Dispersant‐free dyeing of poly(lactic acid) fabric with temporarily solubilised disperse dyes from azopyridone derivatives

Poly(lactic acid) fibre is derived from annually renewable crops and known to be 100% compostable. In order to extend its environmental friendliness into the dyeing process, dispersant‐free dyeing of poly(lactic acid) fabric with three temporarily solubilised azo disperse dyes based on hydroxypyridone moiety containing a β‐sulphatoethylsulphonyl group was investigated. The dyes were successfully applied to poly(lactic acid) fabric without the use of dispersants. The colour yields of the dyes on poly(lactic acid) fabric were observed to be dependent on dyebath pH and dyeing temperature. The optimum results were obtained at pH 4–5 and 110 °C. One of the dyes showed a colour yield as good as that of a commercial disperse dye and good build‐up on poly(lactic acid) fabric. All of the dyes could be alkali cleared owing to ionisation of the dye under mild alkaline conditions. Wash fastness was good to very good, and light fastness was good. The chemical oxygen demand levels of the poly(lactic acid) dyeing effluent from the dyes were considerably lower than those from a commercial disperse dye.     

Coloration properties and clearability of phthalimide‐derived monoazo disperse dyes containing ester groups

The coloration properties and clearability of disperse dyes prepared from phthalimide‐derived diazo components and a coupling component containing two carboxylic acid ester groups have been investigated. Members of the series featured C₂–C₄ alkyl substituents on their phthalimidyl nitrogen atom. The nature of the N‐alkyl group made no consistent difference to dye uptake on polyester. No correlation was found between percentage exhaustion and calculated solubility parameters. Wash fastness was extremely good. Comparison with analogues indicated that the diester motif was of significant extra benefit to wash fastness for phthalimide‐derived dyes, but did not increase photostability above the lower range of commercial acceptability. Clearability was compared with that of dyes lacking one or both hydrolysable structural features, as well as with that of some industrial dyes. The novel dyes exhibited a greater tendency to be solubilised, consistent with hydrolysis of their ester and/or phthalimide functionalities.     

Neutral dyeing of wool and wool/polyester blend fabrics using sulphatoethylsulphone reactive‐disperse dyes

Two models of temporarily anionic sulphatoethylsulphone reactive disperse dyes were applied to wool, polyester and wool/polyester blend fabrics at different dyeing pH. Maximum exhaustion values and colour yield were observed at pH 7. The results showed that reactive disperse dyes containing bis‐sulphatoethylsulphone reactive groups were more convenient for neutral dyeing of wool and wool/polyester blend fabrics if compared with a dye containing a mono‐sulphatoethylsulphone group. Excellent to very good wet fastness properties on all dyed fabrics were achieved.     

Dyestuffs for synthetic polymer fibres: 4-N-morpholinoazobenzenes

A series of monoazo disperse dyes derived from the coupling to N-phenylmorpholine of diazotised anilines and aminothiazole derivatives is described. The colour, dyeing and fastness properties of the dyes is compared to those of the analogous dyes based on N-ethyl-N-β-hydroxy-ethylaniline. Dyes from the ring closed heterocyclic coupling components dye synthetic-polymer fibres in deep colours of good fastness properties and show significant hypsochromic colour shifts compared to the uncyclised derivatives.     

One‐bath union dyeing of wool/polytrimethylene terephthalate blends†

The one‐bath dyeing of blends of polytrimethylene terephthalate (PTT) staple and wool has been investigated. The exhaustion of selected Terasil disperse dyes on PTT fibre and Lanasol reactive dyes on wool was measured as a function of temperature, together with the cross‐staining of the Terasil dyes on the wool component and the Lanasol dyes on PTT component. Most Terasil disperse dyes achieved satisfactory dye uptake on PTT at 110 °C, whereas on conventional polyester (polyethylene terephthalate) temperatures of up to 130 °C are required. An optimised union‐dyeing technique for wool/PTT blends was developed which minimised the staining of Terasil disperse dyes on wool and produced dyed goods with high levels of wet colour fastness. Carriers were not required to enhance the dyeability of PTT at low temperatures. The wool component appeared to be protected against damage at 110 °C by the reactive dyes. The results indicate the potential for blending PTT fibre and wool to produce fabrics that are easier to dye at lower temperatures than conventional wool/polyester blends.     

Reactive dyeing of silk using commercial acid dyes based on a three‐component Mannich‐type reaction

Acid dyes are employed for commercially dyeing silk, which results in ionic bonds between the silk fibroin and the dye. This generally leads to low wet fastness properties for dyed silk fabrics. In this work, three commercial acid dyes with aromatic primary amine structures were selected to dye silk using a Mannich‐type reaction, resulting in improved wet fastness of dyed silk by forming covalent bonds between silk fibroin and dye. The Mannich‐type reactive dyeing was applied to silk fabrics at both 30 and 90°C in trials. Dyeing at 90°C can shorten the dyeing time compared with dyeing at 30°C, even although dye exhaustion and relative fixation at 90°C were a little lower. The dyeing process was optimised when the dyeing temperature was 90°C, dyebath pH 4, dye‐to‐formaldehyde ratio 1:30 and holding dyeing time 60 minutes. The results showed that the dye exhaustion on silk fabrics for the three aromatic primary amine‐containing acid dyes exceeded 94% and their relative fixation was over 80%. Their washing and rubbing fastness reached grade 4 or higher. Hence, the colour fastness properties of dyed silk fabrics using the Mannich‐type reactive dyeing method is superior to the conventional acid dyeing method using the same aromatic primary amine‐containing acid dyes. The Mannich‐type reactive dyeing for silk fabrics at 90°C can be developed into a novel and rapid reactive dyeing method, promising an effective dyeing process with excellent colour fastness.     

Deep‐coloured polyester/cotton blends with low concentrations of polymethylol dyes by a one‐pass continuous dyeing process

An obvious limitation of the one‐pass continuous dyeing process for polyester/cotton blends is its inability to achieve deep colour depth, which is caused by the low dye fixation yields of commercial reactive dyes. In this study, the performances of polyester/cotton blends dyed with high‐fixation polymethylol dyes and disperse dyes were compared with those of polyester/cotton blends dyed with a mixture of reactive dyes and disperse dyes. Polymethylol dyes were observed to be suitable for dyeing polyester/cotton blends when used in low concentrations; the required concentrations of polymethylol dyes were only 23–58% of the concentrations of commercial reactive dyes required to reach a given colour level on polyester/cotton blends. The wash and crocking fastness of polyester/cotton blends dyed with polymethylol dyes were similar to those of polyester/cotton blends dyed with reactive dyes.     

Synthesis and application of yellow azo‐anthraquinone disperse dyes for polylactide fibres

1‐Phenyl‐3‐methyl‐5‐pyrazolonyl azo‐anthraquinone dyes having high light fastness on polylactide fibres were synthesised from 1‐aminoanthraquinone via a diazotisation‐coupling reaction with 1‐phenyl‐3‐methyl‐5‐pyrazolones. The structures of these new dyes were confirmed using mass spectrometry, infrared and proton nuclear magnetic resonance spectroscopy and combustion analyses. Their dyeing behaviour on polylactide fibres was also determined, whereupon it was found that the title dyes could be applied at a relatively low dyeing temperature and that the corresponding dyed fabrics had good fastness properties.     

Dyeing of poly(lactic acid) fibres with synthesised novel heterocyclic disazo disperse dyes

Poly(lactic acid) (PLA) is the first melt‐processable, renewable, sustainable and biodegradable natural‐based synthetic fibre. It has a broad range of uses and combines ecological advantages with outstanding performance in textiles. PLA fibre, as an aliphatic polyester, can be dyed with disperse dyes. Apart from the limited number of commercial disperse dyes, disperse dye exhaustion on PLA is generally lower than that on  poly(ethylene terephthalate) (PET). In this study, new heterocyclic disazo disperse dyes, substituted with methyl, nitro and chloro groups at their ortho‐, meta‐ and para‐ positions, synthesised in our previous study, were applied to PLA and PET fibres to examine their dyeing performance, and colour fastness and dye exhaustion properties. Different shades of yellow, orange, reddish brown and brown were obtained. Most of the synthesised novel heterocyclic disazo disperse dyes exhibited good build‐up properties with high K/S levels on both fibres. Para‐ bonding substituent provided higher K/S values than meta‐ and ortho‐ positions for –NO₂ and –Cl substituents for both fibres. Overall, the most synthesised novel heterocyclic disazo disperse dyes in this study exhibited good build‐up properties with high K/S, exhaustion and wet fastness levels on both PLA and PET fibres.      

Synthesis,spectral properties and dyeing on polyester of monoazo dyes from indol‐2‐one derivatives

Three series of phenylazo disperse dyes were prepared by coupling diazotised 4‐aniline dyes with 5‐indol‐2‐one dyes. The structures of these dyes were determined by proton nuclear magnetic resonance, Fourier Transform–infrared and elemental analysis. The effects of solvent on the ultraviolet–visible absorption spectra of these dyes were studied. The dyes displayed a λ_max shift of between 399 and 438 nm. The dyes were finally applied in the dyeing of polyester fibres in order to investigate their colour range and dyeing properties. Most of the dyes displayed high rubbing fastness and good washing and sublimation fastnesses on polyester fibres.     

One‐bath dyeing of polyester/cotton blends with disperse and bis‐3‐carboxypyridinium‐s‐triazine reactive dyes. Part 2: Application of substantive reactive dyes to cotton at 130 °C and neutral pH†

An earlier paper reported that the reactive dyes (not the disperse dyes) were responsible for the inability to achieve heavy depths of shade, when dyeing polyester/cotton blends by a one‐bath process at 130 °C and neutral pH using reactive dyes containing a 3‐carboxypyridinium‐s‐triazinyl group. It was shown that the poor colour yield of the bis‐3‐carboxypyridinium‐s‐triazine reactive dyes was because of their low exhaustion level at 130 °C and pH of 7.0–7.5. We now report the synthesis and evaluation of some bis‐3‐carboxypyridinium‐s‐triazine reactive dye structures, possessing highly substantive chromophores, as a means of obtaining high colour yield, on 100% unmercerised cotton, under the specified dyeing conditions. The technical performance of these dyes under such conditions was compared with that of selected Novacron (Cibacron) LS and Procion H‐E dyes, applied under their recommended (atmospheric) dyeing conditions.