Synthesis,stability and printing properties of a novel 2‐sulphophenoxy‐4‐chloro‐s‐triazine reactive dye for ink‐jet printing of wool

We report here the synthesis and characterisation of a new medium‐reactivity reactive dye containing 2‐sulphophenoxy‐4‐chloro‐s‐triazine, having enhanced the activity of the chlorine atom for further substitution by the functional groups carried by wool fibre. In addition, a dichloro‐s‐triazine dye was also synthesised for the purpose of comparison. The progress of synthesis reactions and purity of the dyes were determined using capillary electrophoresis and thin layer chromatography. The molecular structure and the chemical compositions of the synthesised dyes were confirmed using Fourier Transform–infrared spectral data and elemental analyses. The inks containing the synthesised dyes were formulated and ink‐jet‐printed onto wool fabrics and then the printed fabrics were steamed at 102°C. Compared with the dichloro‐s‐triazine dye, superior performance in terms of ink stability, K/S and dye fixation was observed for the new 2‐sulphophenoxy‐4‐chloro‐s‐triazine dye. In addition, the light fastness of the fabric printed with the inks containing the new dye was 0.5‐grade greater than that of the fabric printed with the inks containing the dichloro‐s‐triazine dye, and no changes in shade and staining were observed following wash fastness tests of the fabrics printed with the inks containing the new dye.     

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.     

Synthesis of a di‐(p‐sulphophenoxy)‐s‐triazine reactive dye and its application in wool fabric ink‐jet printing

Reactive dyes based on p‐sulphophenoxy‐s‐triazines were synthesised, characterised and applied to wool fabric by ink‐jet printing. The extent of dye‐fibre covalent bonding (% fixation) was measured on prints produced using different development methods. The most promising method to obtain high dye‐fibre fixation values was to interleave the printed wool with a pre‐wetted cotton fabric and store for 3 h. Steam fixation was also investigated but gave lower fixation values. The degree of dye hydrolysis vs time in the ink formulation was evaluated because ink stability is critical in commercial operation; a reformulated ink based on a phosphate buffer was found to improve ink stability.     

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.     

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.     

Modified 2,4‐difluoro‐5‐chloro‐pyrimidine dyes and their application in ink‐jet printing on wool fabrics

This paper describes the modification of three commercially available 2,4‐difluoro‐5‐chloropyrimidine dyes (Drimarene Brilliant Red K‐4BL, Drimarene Brilliant Blue K‐BL and Drimarene Golden Yellow K‐2R) by the reaction of the parent dye with 4‐hydroxybenzensulphonic acid sodium salt. Capillary electrophoresis was used to monitor both the course of the above reaction and to ascertain the dye stability of the dyes in an ink formulation. Inks prepared from the modified dyes showed much higher storage stability compared with the parent dye‐containing inks; this was confirmed by capillary electrophoresis analysis. Inks containing the modified dyes were printed on wool fabrics and diffusion/fixation achieved by ‘batching’ the prints at 25 °C; high fixation values were obtained for all three modified dyes. These prints exhibited excellent colour fastness to washing, rubbing and light, the former test confirming a high degree of dye–fibre covalent bonding.     

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.     

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 and properties of poly(styrene-co-maleic acid) macromolecular reactive dyes

To obtain a new type of macromolecular reactive dye with high fixation and good light fastness, poly(styrene-co-maleic acid) was synthesised by co-polymerisation of styrene and maleic anhydride, then, through nitration, reduction, diazotisation and coupling reaction, novel macromolecular reactive dyes were prepared with a solubility greater than 60 g/L. The dyes were used to dye cotton fabrics; the results showed their fixation was more than 92%, and both the rub and wash fastness of the dyes were good. The light fastness of the red and blue dyes with the ethoxy group on melamine was grade 4, and for the yellow dye reached grade 5. The poly(styrene-co-maleic acid) macromolecular reactive dyes exhibit very good application prospects in practice.     

Dyeing of nylon 6 fabric with a new bifunctional vinyl sulphone reactive disperse dye

A new bifunctional reactive disperse dye containing a temporarily anionic sulphatoethylsulphone and a nonionic disulphide bis(ethylsulphone) groups was synthesised and applied to nylon 6 fabric by the exhaust dyeing at a variety of pH and temperature conditions. A monofunctional reactive disperse dye containing only nonionic disulphide bis(ethylsulphone) group was also synthesised and its dyeing behaviour was compared with the bifunctional dye. The bifunctional reactive disperse dye exhibited high exhaustion and fixation values at pH 6 and 120 °C. The results also indicate that the combination of temporarily anionic and nonionic reactive groups of the bifunctional dye provided great enhancement in dyeing performance compared to that of the monofunctional dye. The dyes also showed very good levelling and fastness properties on nylon 6 fabric.     

Synthesis and characterization of poly(arylene ether s‐triazine)s containing alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties in the main chain

Soluble and heat‐resistant polymers have great potential for use as processable, high‐temperature polymeric materials. In this study, four types of new poly(arylene ether s‐triazine)s containing alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties in the main chain were prepared through direct solution polycondensation of 2,4‐bis(4‐fluorophenyl)‐6‐phenyl‐s‐triazine with each of methyl‐, phenyl‐ and chloro‐substituted phthalazinones. A key feature of these polymers is the incorporation of phthalazinone and side groups into the poly(arylene ether s‐triazine) backbone to endow them with good solubility while maintaining other attractive properties. The polymers were obtained in high yields, and had inherent viscosities ranging from 0.38 to 0.55 dL g^?1. Their structure was characterized using Fourier transform infrared and NMR spectra and elemental analysis. The polymers were almost amorphous, and soluble in N‐methyl‐2‐pyrrolidone, pyridine, N,N‐dimethylacetamide, hot N,N‐dimethylformamide and sulfolane. Tough and nearly transparent films obtained by direct solution casting exhibited good mechanical properties. The resulting polymers displayed glass transition temperatures ranging from 255 to 265 °C and thermal decomposition temperatures for 10% mass loss ranging from 476 to 599 °C, according to differential scanning calorimetry and thermogravimetric analysis, respectively. The reactivity of substituted phthalazinones in nucleophilic displacement reactions and the effect of the side groups on the physical properties of the polymers were also investigated. The results obtained revealed that such s‐triazine‐containing polymers possessed good solubility while maintaining acceptable thermal stability and high mechanical strength with the incorporation of alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties into their backbones, which makes them an attractive series of high‐performance structural materials. Copyright © 2010 Society of Chemical Industry     

Synthesis of an amino coumarin‐based fluorescent reactive dye and its application to wool fibres

The objective of the current study was to introduce the coumarin structure into a conventional reactive dye system. A fluorescent reactive dye was synthesised based upon 7‐amino‐4‐methylcoumarin. The dye was obtained by a multi‐step sequence initiated by displacement of a chlorine group from 2,4,6‐trichloro‐1,3,5‐triazine using H‐acid. Diazo coupling of 3‐aminobenzenesulphato‐ethylsulphone to this adduct, followed by a second chlorine displacement using aminomethylcoumarin completed the sequence. The fluorescent dye and the non‐fluorescent precursor were characterised by mass spectrometry, infrared spectroscopy and capillary electrophoresis. The newly synthesised dye was applied to wool fibres using an exhaust dyeing method. The exhaustion, fixation and total efficiency values were calculated by ultraviolet–visible spectrophotometric analysis of the dyebath. The synthesised red dye presented high values for exhaustion, fixation and total efficiency on the wool fibres. The novel dye, after its application to the wool fibres, exhibited fluorescence under an ultraviolet light. This feature confirmed that the novel dye retained the inherent characteristic feature of fluorescence on the wool fibres. The dyed wool fibres exhibited level 4–5 of light fastness when compared with international wool light fastness standards.     

Green synthesis of reactive dye for ink‐jet printing

Chloropyrimidine‐based reactive dyes are reported as well suited to textile printing; however, nucleophilic aromatic substitution of chloropyrimidines with amino‐containing chromophores is slow and often suffers from poor yields. In this study, a novel and simple method was developed for the synthesis of chloropyrimidine‐based reactive dye under microwave irradiation. In addition, the dye was also synthesised by conventional heating for comparison, which took both the reaction time and yield into account. The progress of the synthesis reactions concerned were monitored using capillary electrophoresis and the purity of the dye obtained was assessed by thin‐layer chromatography. The structure of the synthesised trichloropyrimidine dye was confirmed by Fourier Transform–infrared spectroscopy and elemental analysis. It was found that the reaction rate of the nucleophilic aromatic substitution carried out under microwave irradiation was 4‐fold faster than that carried out under conventional heating, although the enhancement in product yield was modest. These results suggest that microwave irradiation is an effective technique for the synthesis of chloropyrimidine‐based reactive dyes. The synthesised chloropyrimidine dye was formulated into an ink and applied onto a wool fabric by ink‐jet printing. The printed fabrics were steamed at 102°C for 5‐25 minutes at 5‐minute intervals. Good K/S and rate of dye fixation were obtained, both of which improved with increasing steaming time. The prints obtained exhibited reasonably good light and wash fastness properties.     

Dyes derived from 3‐formyl‐2(1H)‐quinolone – synthesis,spectroscopic characterisation,and their behaviour in the presence of sulfhydryl and non‐sulfhydryl amino acids

Novel dyes based on a 3‐formyl‐2(1H)‐quinolone skeleton were synthesised and characterised using ¹H nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic properties of these dyes, such as their absorption spectra, emission spectra, and quantum fluorescence yields, were also examined. The behaviour of the obtained compounds at a pH of 7.4 in the absence and in the presence of thiol amino acids, such as l ‐cysteine, l ‐glutathione, and N‐acetyl‐l ‐cysteine, were studied. The spectroscopic responses of the tested dyes towards other amino acids were also investigated. A reference compound was synthesised to understand the reaction mechanism between the thiols and the obtained dyes. The experimental results show that the synthesised dyes have the potential to act as sensors for thiols.     

Synthesis and characterisation of microencapsulated 7‐alkyloxy‐4‐trifluoromethylcoumarin dyes

Five new 7‐alkyloxy‐4‐trifluoromethylcoumarin fluorescent dyes were synthesised using the Pechmann and Williamson etherification reactions. The structures of these coumarin dyes were characterised by Fourier Transform–infrared, proton and carbon nuclear magnetic resonance and mass spectra. One of the new coumarin compounds, 7‐isopropyloxy‐4‐trifluoromethylcoumarin, was microencapsulated with melamine–formaldehyde as the shell material by in situ polymerisation. The microcapsules were characterised in terms of Fourier Transform–infrared spectrum, particle size distribution and scanning electron microscopy morphology. The cotton fabric finished with the microencapsulated coumarin dye showed strong fluorescence under ultraviolet light.     

Application of heterobifunctional reactive dyes on silk

The behaviour of heterobifunctional reactive dyes, containing a monochlorotriazine and a vinyl sulphone group, on silk has been investigated. Maximum exhaustion and fixation were obtained in a neutral medium at 90d? C. The addition of sodium sulphate was found to promote the exhaustion of reactive dyes at _pH values above the isoelectric point of silk. A reduction in the solubility of dyed silk indicated that crosslinks were formed with bifunctional reactive dyes.     

Synthesis and characterisation of benzothiazole‐based solid‐state fluorescent azo dyes

Novel solid‐state fluorescent azo dyes containing a 2‐[4‐(dimethylamino)phenyl]benzo[d]thiazol‐6‐amine as the electron donor group were synthesised. These dyes showed a molar extinction coefficient in the range of 20 000–30 000 l/mol/cm. These compounds were characterised by strong solid‐state fluorescence under long ultraviolet light (365 nm). Absorption and fluorescence spectra revealed that electron coupling originating from broad π‐electron delocalisation and the keto–enol form is responsible for the large Stokes shift. These dyes were readily soluble in common solvents such as dichloromethane, chloroform, dimethyl formamide , tetrahydrofuran and dimethyl sulphoxide and were characterised by means of elemental analysis, proton nuclear magnetic resonance and mass spectrometry. Thermogravimetric analysis of solid‐state fluorescent dyes show thermal stability up to 270 °C and can therefore be used for polymer application. The coloristic properties of these dyes were evaluated on polyester by the disperse dyeing method.     

Triazine‐containing benzoxazine and its high‐performance polymer

A new synthetic route was designed to significantly increase the content of triazine structure in benzoxazine resin. 2,4,6‐Tri(4‐hydroxylphenyl)‐13,5‐s‐triazine (TP) was synthesized by cyclotrimerization of 4‐cyanolphenol and then benzoxazine monomer‐containing triazine [2,4,6‐tri(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazin‐6‐yl)‐1,3,5‐s‐triazine (BZ‐ta)] was synthesized via Mannich reaction from TP. Finally, the cross‐linked polymer P(BZ‐ta) was produced by thermal polymerization of BZ‐ta. BZ‐ta was characterized by nuclear magnetic resonance spectroscopy (NMR), fourier transform infrared spectroscopy (FTIR), mass spectrum, elemental analysis, and viscosity measurement. Curing behavior of BZ‐ta was studied by differential scanning calorimetry, FTIR, and gel permeation chromatography. The structure and properties of P(BZ‐ta) were investigated by powder X‐ray diffraction, dynamic mechanical analysis, and thermogravimetric analysis. The results showed that the P(BZ‐ta) had high glass temperature (T_g = 322°C), excellent thermal oxidation stability (5 and 10% weight loss temperatures in air up to 403 and 453°C, respectively), high char yield (64%, 800°C in nitrogen), and high flame‐retardance (limiting oxygen index, 39.7). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dyeing of nylon 6 fabric with a bifunctional sulphatoethylsulphone reactive disperse dye

A bifunctional reactive disperse dye containing two temporarily anionic sulphatoethylsulphone groups was synthesised and applied to nylon 6 fabric by exhaust dyeing at a variety of pH levels and temperatures. A monofunctional reactive disperse dye containing one temporarily anionic sulphatoethylsulphone group was also synthesised, and its dyeing behaviour was compared with the bifunctional dye. The bifunctional reactive disperse dye exhibited high exhaustion and total fixation yield under alkaline conditions. The results also indicate that the introduction of two temporarily anionic sulphatoethylsulphone groups of the bifunctional dye gave an enhancement in dyeing performance compared with that of the monofunctional dye. The dyes also showed very good levelling and fastness properties on nylon 6 fabric.     

Cyanuric Acid/Epichlorohydrin Energetic Prepolymers

In this work new energetic prepolymers are synthesised and characterised. The structure of the prepolymers exhibits the 1,3,5‐s‐triazine ring with lateral chains derived from the epichlorohydrin ring opening. The chlorine atoms in these precursors are here substituted by azido groups. The presence of these groups was confirmed by FTIR and ¹H NMR spectroscopy and elemental and thermal analysis. OH group content in the energetic prepolymers was found slightly lower than expected having in view the used inert precursors, while molar mass values were similar. Whereas the precursors show an endothermic thermal decomposition, the synthesised prepolymers show a clear exothermic thermal decomposition in DSC analyses. Due to the presence of the 1,3,5‐s‐triazine ring, the exothermic peaks were observed in a wide range of temperatures. The measured glass transition temperatures vary from −15.5 °C to −43.3 °C. High densities and a wide range of viscosities were found.