Dyestuff Chemistry
Reactive Dyes
Introduction to Reactive Dyes
Although fiber-reactive dyes have been a goal for quite some time, the breakthrough came fairly late, in 1954. Prior to then, attempts to react the dye and fibers involved harsh conditions that often resulted in degradation of the textile.
The best dyes, by far, to use for cotton and other cellulose fibers are the fiber reactive dyes. They are much brighter longer-lasting, and easier-to-use
Fiber reactive dye is the most permanent of all dye types. Unlike other dyes, it actually forms a covalent bond with the cellulose or protein molecule.
Once the bond is formed, what you have is one molecule, as the dye molecule has become an actual part of the cellulose fiber molecule
The first fiber-reactive dyes were designed for cellulose fibers, and they are still used mostly in this way. There are also commercially available fiberreactive dyes for protein and polyamide fibers.
In theory, fiber-reactive dyes have been developed for other fibers, but these are not yet practical commercially.
The first fiber-reactive dyes contained the 1,3-5-triazinyl group, and were shown by Rattee and Stephen to react with cellulose in mild alkali solution. No significant fiber degradation occurred. ICI launched a range of dyes based on this chemistry, called the Procion dyes.
This new range was superior in every way to vat and direct dyes, having excellent wash fastness and a wide range of brilliant colors. Procion dyes could also be applied in batches, or continuously.
Chemistry of Reactive dyes
Chromogen
Bridging group
Fiber Reactive group
water solubilizing group
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Reaction with Dye
This reaction takes place in presence of a base
Dye-Cl + H-O-cellulose base Dye-OH +salt The bond formed is covalent which provides excellent wash fastness and is stronger then the hydrogen bonds of a direct dye on cellulose.
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Reaction with water
In reaction with water the reactive group is hydrolyzed and the dye looses its ability to react with hydroxyl group of cotton or amino groups of poly amide Dye-Cl +H-OH base dye-OH + salt
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The chromogen is as mentioned before (Azo, carbonyl or phthalocyanine class). The water solubilizing group (ionic groups, often sulphonate salts), which has the expected effect of improving the solubility, since reactive dyes must be in solution for application to fibers.
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The bridging group links the chromogen and the fiber-reactive group. Frequently the bridging group is an amino, NH-, group. This is usually for convenience rather than for any specific purpose.
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The fiber-reactive group is the only part of the molecule able to react with the fiber.
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A cellulose polymer has hydroxyl functional groups, and it is these that the reactive dyes utilize as nucleophiles. Under alkali conditions, the cellulose-OH groups are encouraged to deprotonate to give cellulose-O- groups.
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These can then attack electron-poor regions of the fiber-reactive group, and perform either aromatic nucleophilic substitution to aromatics or nucleophilic addition to alkenes
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Reactive dyes can react both with water and fiber but the main reaction is with fiber for 2 reasons Rate of chemical reaction with cellulose is much faster than the reaction with water
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the probability of a diffused dye molecule reacting with an OH group on cellulose is much larger than the cellulose group of water In dyeing of cellulose with reactive most of the dye reacts with fiber but some dye do react with water.
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Unfixed dye composes of hydrolyzed dye and unreacted dye The amount of unfixed dye can be 20-30% of the total amount of dye used
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Properties of reactive dyes
Advantages Available in a complete range of colors Very good wash fastness Good to very good light fastness High flexibility in the choice of method of application
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Easy to obtain level dyeing Readily soluble in water
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Disadvantages Cost of using reactive dyes is high Loss of substantial dye during application Excessive time required for the dyeing process Sensitive to oxidation
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Auxiliaries used in dyeing with reactive
In the dyeing of cellulose with reactive dyes, alkali is necessary it acts as a catalyst in the reaction between the dyestuff and the fiber.
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The important point is not the type or amount of alkali but rather the pH of the dye bath, which must be closely supervised. Adding base increases the exhaustion of the dye on the fiber
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It increases the rate of chemical reaction and faster the rate of reaction, the faster the rate of exhaustion Ionic nature of base further enhances the exhaustion
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The most suitable pH for dyeing varies with the temperature being approx. 11.5 for common warm dyeing (dyeing at approx. 60 degrees ) 10-11 for hot dyeing (80 ) 12.5 for cold dyeing (40 degrees)
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Auxiliaries used in Reactive Dyeing contd
Inorganic salts have two main functions in exhaustion dyeing with reactive dyestuffs: Improving the affinity of the dyestuff Acceleration of the dyestuff's association and lowering of its solubility.
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Improving the affinity and thus the exhaustion of dyestuff during primary exhaustion serves to raise the exhaustion rate of reactive dyestuffs. Because reactive dyestuffs have a lower affinity than direct dyestuffs, more inorganic salt is required when using reactive dyestuffs in order to accelerate absorption
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The following graph displays the amount of Glauber's salt used, the exhaustion rate and the fixing rate for a conventional dye and a high-fixation dye (Sumifix Supra E-XF).
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Because inorganic salts accelerate the association of water-soluble dyestuffs and lower the solubility of dyestuffs, an excess of inorganic salt may in fact impede the absorption of some dyestuffs, and so care is necessary when one is used.
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The effectiveness of the inorganic salt is not decided by the ratio of its quantity to the quantity of fabric (o.w.f.) but rather by its concentration in the dye bath (g/l) so it is by lowering its concentration that the effect of an inorganic salt can be reduced.
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Suitable fiber substrate
Cellulosic fibers Protein fibers Polyamide fibers
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Methods of application
Exhaustion method It consists of three stages Exhaust Dyeing Fixation After scouring
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Cold Pad-batch method Semi- continuous method Fabric is padded with a solution of dyes and the base and then wound onto a roller. which are covered in plastic sheets Left for 2hours to overnight depending on the rate of fixation
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Continuous dyeing with reactive dyes There are 2 methods currently in use by industry Two-Bath Method the dyes and base are applied separately
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One-bath method In this the dyes and the base are applied together onto the fabric from the same padding bath
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Chemical striping of reactive dyes
Once reactive dyes have been applied and the unfixed, hydrolyzed dye has been removed. there is no longer a possibility of leveling or stripping by simple physical means.
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If a reactive dyeing is unsatisfactory, economics will probably dictate what steps must be taken to deal with the problem.
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For heavy shades, a reduction of about 20-40% in depth of shade can sometimes be achieved by hydrolysis of the dye-fiber bond with alkali in the presence of salt at 95C (200F)
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Depending on the individual dyes, complete chemical stripping (color destruction) may be carried out in one of the following four ways
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reduction only; Reduction followed by oxidation; Oxidation only oxidation followed by reduction.
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all traces of chemicals should be removed prior to any re-dyeing attempts on a sample of the stripped goods.
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General fastness properties
light fastness- good to very good on most fibers Washing- good, sensitive to chlorine bleach Dry cleaning- good Perspiration- good Crocking- good
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