Triazinylamino-alkylphosphonate reactive dyes for cellulosic fibres

A bifunctional reactive bis-phosphonoalkylaminotriazine dye was synthesised by condensing 2 mol of aminoethylphosphonic acid with the commercially available bis-monochloro- s -triazinyl dye, CI Reactive Red 120. A similar but much lower molecular weight dye was prepared by condensing the commercially available dichloro- s -triazine dye, Procion Red MX 8B, with aminomethylphosphonate. A model aryl-phosphonate dye was also prepared by diazotising m -aminobenzene-phosphonic acid and coupling the diazonium salt to R-salt. These dyes were isolated as their free acids and then converted to their ammonium salts. Pad liquors containing dye, cyanamide and ammonium dihydrogen phosphate were applied to cotton fabric. In the case of the bis-phosphonoethylamino- s -triazine dye, very high dye–fibre fixation values (>90%) were achieved using a pad–batch–bake procedure; for the Procion T model dye, the comparative maximum fixation was only modest. In the absence of cyanamide, no fixation could be obtained for the arylphosphonate dye but both bis-phosphonoalkylaminotriazine dyes gave significant fixation.     

Use of a novel water-soluble arylating agent to dye wool and wool blends with disperse dyes

A series of water-soluble fibre-reactive arylating agents were synthesised and evaluated from the stand-point of improving fibre coloration with disperse dyes. In particular, the compound, sodio-2,4-dianilino-6-[4'- β -sulphatoethylsulphonylanilino]- s -triazine (FAA 200) was found to be promising; this compound could be applied in the same bath as a disperse dye at pH 5–6. Under the latter conditions this compound showed high substantivity to wool and at the boil readily underwent β -elimination of the sulphate ester residue to give the vinyl sulphone reactive group which adds on to nucleophilic sites in the fibre to form a covalent bond. Coapplication with commercially available disperse dyes gave bright, level dyeings that exhibited promising wet fastness. FAA 200 was used as an auxiliary to dye disperse dyes on both fibre components of a wool–polyester blend fabric; it was found that addition of hydrogen peroxide or sodium thiocyanate was necessary to obviate reduction of certain disperse dyes when dyeing at 120 °C.     

One-bath dyeing of polyester/cotton with disperse and bis-3-carboxypyridinium-s-triazine reactive dyes. Part 1: Factors limiting production of heavy shades

Over the last 20 years, selected disperse dyes and bis-3-carboxypyridinium- s -triazine reactive dyes have been widely promoted for the exhaust dyeing of polyester/cotton blends in a one-bath-one-stage ('all-in') process under neutral conditions. However, despite the time and energy savings afforded by this elegant dyeing process, there is a belief in the dyeing industry that economical production is limited to pale and medium depths of shade. In this paper, the two dye classes (disperse dyes on polyester and bis-3-carboxypyridinium- s -triazine reactive dyes on cotton) have been investigated to understand why heavy depths of shade cannot readily be obtained economically using this process.     

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.     

Influence of dichloro-s-triazinyl reactive dyes on the fibrillation propensity of lyocell fibres

Four dichloro- s -triazinyl dyes and 2,4-dichloro-6- p -sulphoanilino-1,3,5-triazine have been applied by exhaustion methods to dried lyocell fibres. The method of application, of both dyes and agent, influenced the cross-linking performance and, in turn, the wet abrasion resistance of the treated fibre. However, dyeing alone, with any of the MX dyes used in this study, was insufficient to protect the fibre from wet abrasion problems during laundering. A comparison between one of the MX dyes, Chloranyl Orange MX-2R, and 2,4-dichloro-6- p -sulphoanilino-1,3,5-triazine on a mol-for-mol fixed basis, showed 2,4-dichloro-6- p -sulphoanilino-1,3,5-triazine to be greatly superior at protecting lyocell against wet abrasion.     

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.     

Functionalisation of lyocell. Part 1: Amination of lyocell with m-phenylenediaminesulphonic acid derivatives

A series of four colourless, water-soluble agents, based on m -phenylenediaminesulphonic acid, and designed to aminate lyocell, have been synthesised. Each agent carried one or two aromatic amino groups ortho to a water solubilising sulphonic acid group, together with one or two electrophilic groups. The electrophilic groups studied were dichlorotriazinyl, monochlorotriazinyl, vinylsulphonyl and triazinyl betaine. The agents were applied to lyocell by padding techniques, and neutral-exhaustion dyeing of the aminated fibres, with low, medium and high reactivity reactive dyes, in the presence of salt, were performed. Only the high reactivity dichlorotriazinyl dye gave encouraging results. The aminated fabrics, containing aromatic amino groups with an o -sulphonic acid, were insufficiently nucleophilic to allow significant covalent bonding with the low/medium reactivity dyes at both 60 and 80 °C.     

Synthesis of heteromultifunctional dye-resist agents containing chloro-s-triazine and α-bromoacrylamide and their dye-resist properties in wool fabrics

Five heteromultifunctional dye-resist agents containing chloro- s -triazine and α -bromoacrylamide were synthesised and their resist effectiveness on wool were compared. The dye-resist agent with the dichlorotriazinyl group showed better resist effectiveness than the dye-resist agent with the monochlorotriazinyl group. Also, their resist effectiveness was improved by increasing the number of sulphonate groups in the dye-resist agents and the reactive groups in the reactive dyes applied over them.     

Crosslinking a hydroxyethylsulphonyl dye on cotton to achieve covalent fixation in a long-liquor process

A heterobifunctional [dichlorotriazine and vinylsulphone (DCT-VS)] reactive crosslinker, 2,4-dichloro-6-{ρ-[(2'-sulphatoethyl)sulphonyl]phenylamino}-1,3,5-triazine (DC-SES) was synthesised and coapplied with nicotinic acid to covalently fix hydrolysed Cl Reactive Black 5 (HBB) (hydroxyethylsulphonyl dye) to cotton in a long-liquor process. It is suggested that a very active quaternised nicotinic acid ammonium salt of DC-SES was generated in situ , which reacts readily with HBB and cellulose leading to dye fixation. Further dye fixation can be obtained by the addition of alkali at 60 °C; the final fixation value from this system is very good. Application of this system as an aftertreatment in the conventional Cl Reactive Black 5 dyeing bath, results in 10–15% higher exhaustion and fixation values compared to the usual dyeing procedure.     

Crosslinking nucleophilic dyes on wool

Nucleophilic amino-alkyl dyes have been synthesised by the simple expedient of reacting existing reactive dyes with ethylene diamine. These dyes when applied to wool behave as acid dyes, although there is a small amount of covalent bonding to the fibre, presumably through Michael addition at dehydroalanine residues formed from cystine degradation.

If substantive crosslinking agents could be applied then it might be expected that excellent dye-fibre covalent bonding could be achieved to produce dyeings with very high wet fastness properties. The crosslinking agent might be added either before, during or after the amino-alkyl dye application; the latter procedure should, in principle, give the most level dyeings. Crosslinking agents evaluated include hexamine, triacroylamino-hexahydro-s-triazine, methylene-bisacrylamide and 2-chloro-4.6-di(aminobenzene-4′-sul-phatoethylsulphone)-s-triazine. Hexamine and methylene-bisacrylamide are available commercially but the other agents were synthesised. Results obtained are very promising and offer potential wool dyeing methods which have better levelness than existing reactive dye systems.     

Haloacetyl reactive dyes-synthesis and application to silk

A series of haloacetyl reactive dyes have been synthesised. The reactivity of haloacetyl groups and the dyeing properties of the dyes on silk fabric were studied. The results show that the bromoacetyl group is more reactive than the chloroacetyl group and molecules containing a bromoacetyl group would dye silk under relatively mild dyeing conditions. Both the exhaustion and fixation on silk fabric are increased if a second reactive group is present in the molecule     

A study of novel bisazo reactive red dyes with good wet fastness

Three series of bisazo reactive red dyes were synthesised using 6‐amino‐1‐naphthol‐3‐sulphonic acid and its derivatives as the coupling components. The dyeing parameters and wash fastness of these dyes on knitted cotton were evaluated and the relationships between the structure and dyeing properties were investigated. It was found that the hydrophilic groups introduced into the dye molecules decrease the substantivity and fixation of the dyes, but increase the build‐up and migration properties. The defined wash‐off factor can directly reflect the wash fastness of the dyes and the build‐up property can be improved by commercialisation using certain auxiliaries. The results indicate that there is the possibility of synthesising a red reactive dye with a satisfying balance between high fixation and good wash fastness and several such dyes have been developed.     

多活性基活性染料及其拼混应用

活性染料已成为最重要的染料类别，多活性基染料是染料的发展方向。本文叙述了常见几类活性基团的特性以及活性基团间桥接基对染料性能的影响。两类多活性基染料已具有商业价值：根据染料的相客性、染色条件以及染料的结构特性来选择拼混染料。不同类染料可以进行拼混。两种相同活性基团的多活性基染料的拼混可以得到很好的拼混染料，国外已经提出并发表了多种类型的拼混情况。拼混应用已成为活性染料重点研究的方向之一。     

蓝色活性染料的合成及拼混增效

本文设计合成了22只含复合双活性基的蓝色活性染料。测定了活性染料的四个特征参数S、E、R和F值,考察了染料结构与直接性的关系。测定了染料的提升力,根据染料的相容性和染料的结构特征选择拼混染料;不同类活性染料的拼混和同类活性染料的拼混都得到染深性很好的混合染料。测定了活性染料的耐碱性,耐碱性好的染料与耐碱性差的染料通过适当比例混合后,混合染料具有优异的耐碱性。     

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.     

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.     

A Study of the Reactions of Reactive Dyes with Wool under Industrial Dyeing Conditions

The extent of reaction with wool of five representative reactive dyes (having different reactive groups) has been determined at two depths of dyeing (0.5% and 3%) under conditions of dyeing recommended by the manufacturers. The covalent bonding of the dye to the reactive groups of the fibre was determined by analytical techniques based on the use of fdnb (1-fluoro-2,4-dinitrobenzene). It has been shown that these and other similar techniques may introduce fundamental errors in the estimation of basic groups covalently bound. The results indicate that, under the acidic conditions recommended, the role of the basic group in keratin is less significant than previously reported. By application of correction factors, a stoichiometric relation has been obtained between the amount of dye molecules bound and the number of reactive groups in the fibre which are blocked.     

Modification of cellulose with N-(2-chloroethyl)diethylamine hydrochloride: mechanism of improved dyeability with 5-chloro-2,4-difluoropyrimidinyl dyes

Monofluorotriazinyl and 5-chloro-2,4-difluoropyrimidinyl dyes were each reacted, in turn, with trimethyl- and triethyl-amine in aqueous solution. Trimethylamine was quaternised by both the fluoroheterocyclic reactive dyes. In the case of the chlorodifluoropyrimidinyl dye, NMR spectroscopy showed that displacement of the C-2 fluorine atom had occurred. Triethylamine, on the other hand, failed to react with either fluoroheterocycle, strongly suggesting that the covalent bond formation reaction of DEAE-cotton, with a 5-chloro-2,4-difluoropyrimidinyl dye under neutral conditions, does not involve initial quaternisation. A mechanism involving the deprotonation of the cellulose hydroxy groups, catalysed by the basic groups in DEAE-cotton, is proposed.     

Synthesis and dyeing performance of a novel yellow crosslinking polymeric dye

A polymeric dye was synthesised via the reaction of 2,4-dinitrochlorobenzene and polyallylamine prepared from the homopolymerisation of monoallylammonium chloride. The polymeric dye was fixed to cotton and silk via a crosslinking agent [2-chloro-4,6-di(aminobenzene-4'-β-sulphatoethylsulphone)-1,3,5- s -triazine]. The fixation of this polymeric dye reached 99% and the dyeing was fast to dimethylformamide at the boil, indicating that the dye fixation was through covalent bonding with the crosslinking agent, which acted as a bridge between the fibre polymer and the dye molecule. The dyed samples showed excellent fastness to washing and rubbing.     

Improvement of the dyeing and fastness properties of a naphthalimide fluorescent dye using poly(amidoamine) dendrimer

In this study, 4‐amino‐9‐methoxypropylnaphthalimide fluorescent dye (dye 1 ) was reacted with poly(amidoamine) dendrimer G = ?0.5 to prepare a naphthalimide–dendrimer hybrid dye (dye 2 ). The chemical structures of the synthesised dyes were confirmed by elemental analysis, Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, and ultraviolet‐visible spectroscopy. The solvatochromism of the dyes was evaluated in various solvents with respect to visible absorption properties, and positive solvatochromism was observed by solvent polarity change from chloroform to ethanol. The dyeing ability of the synthesised dyes was investigated by their application onto nylon fabric, and nylon substrates dyed with dye 2 exhibited marked enhancement both in terms of colour strength and general fastness properties. The results of this study clearly demonstrated the high potential and performance of dye 2 as a novel promising fluorescent dye as compared with dye 1 . Overall, it was inferred that the modification of the naphthalimide fluorescent dye with poly(amidoamine) denderimer could markedly improve the dyeing and fastness properties of the naphthalimide fluorescent dye on nylon fabrics.