6/29/2013

Dyes: Chemistry and Applications Classification of Dyes The dye manufacturers and dye chemists prefer classifying dyes according to the chemical type. The dye users prefer classification according to the application method. The classification of dyes according to their usage is arranged according to the color index CI. It shows the principal substrates, the methods of application, and the representative chemical types for each application class. The classification of dyes according to their usage is summarized in Table 8.1, which is arranged according to the CI application classification.
1

6/29/2013

Acid dyes Acid dyes are water-soluble anionic dyes, containing one or more sulfonic acid substituent or other acidic groups. The polar acidic groups interact with the basic groups of the fabric. The ionic bonding between the dye and the fiber is the result of the reaction of the amino groups on the fiber with acid groups on the dye . The dyeing process is reversible and may be described as follows: Dye- + H+ + Fiber Dye-H+ - Fiber

6/29/2013

Acid dyes (cont:) Acid dyes are applied from acidic dye baths to nylon, silk, wool, and modified acrylics. They are also for paper, leather, ink-jet printing, food, and cosmetics. The fastness of this dye depends on the rate with which the dye can diffuse through the fiber under the conditions of washing. Metal complex (cobalt or chromium) acid dyes are used mainly on wool for improved fastness. Azoic dyes Azo dyes contain at least one azo group (N=N) attached to one or often two aromatic rings. They are produced in textile fibers (usually cotton, rayon, and polyester), by diazotization of a primary aromatic amine followed by coupling of the resulting diazonium salt with an electron-rich nucleophile (azo coupling) 5

Azoic dyes (cont:) The treatment of aniline with nitrous acid, produces a diazonium salt, in a reaction called diazotization. Diazonium salts are important synthetic intermediates that can undergo coupling reactions to form azo dyes and substitution reaction to effect the functional group present on aromatic rings. A variety of shade can be obtained by proper choice of diazo and coupling components.

6/29/2013

Basic (cationic) dyes Basic dye is a stain that is cationic (+ ve charged) and so will react with material that is (-ve) negatively charged. They are mostly amino and substituted amino compounds soluble in acid and made insoluble by the solution being made basic. They become attached to the fibers by formation of salt linkages (ionic bonds) with anionic groups in the fiber. They are used to dye paper, polyacrylonitrile, modified nylons, and modified polyesters.

6/29/2013

Basic (cationic) dyes (cont:) The principal chemical classes are triaryl methane or xanthenes. Basic brown 1 is an example of a cationic dye that is readily protonated under the pH 2 to 5 conditions of dyeing Basic dyes possess cationic functional groups such as -NR3+ or =NR2+. The name 'basic dye' refers to when these dyes were still used to dye wool in an alkaline bath. Protein in basic conditions develops a negative charge as the -COOH groups are deprotonated to give -COO-.

Basic (cationic) dyes (cont:) Generally forms salts with negatively charged (acidic) substances in tissue (chromatin, ergastoplasm, cartilage matrix, some granules). Affinity for such dyes, is called basophilia. Basic dyes perform poorly on natural fibres, but work very well on acrylics. It is this anionic property which makes acrylics suitable for dyeing with cationic dyes, since there will be a strong ionic interaction between dye and polymer (in effect, the opposite of the acid dye-protein fiber interaction).

10

6/29/2013

Study Guide Q1. Q2. Q3. Q4. Q5. Q6. Q7. Q8. How to classify the dyes? State the classes of dyes. Write the difference between acidic and basic dyes. What is an advantage for applying metal in acidic dye? State the type of interaction between acidic dye and fiber. Define an Azo dye. How does azo dye produce in the textile fiber? Basic (cationic) dye contains azo group, however, it is not azo dye. Explain. 11

Direct dyes Direct dyes are water-soluble anionic dyes, but are not classified as acid dyes because the acid groups are not the means of attachment to the fiber. The "direct dye" classification in the Color Index system refers to various planar, highly conjugated molecular structures that also contain one or more anionic sulfonate group. It is because of these sulfonate groups that the molecules are soluble in water. They are used for the direct dyeing of cotton and regenerated cellulose, paper, and leather. They are also used to dye union goods (mixed cotton, and wool or silk) and to a lesser extent nylon fiber.

12

6/29/2013

Direct dyes (cont:) The solubility of the dye in the dye bath is often reduced by adding common salt or Glauber's salt (sodium sulfate decahydrate, Na2SO410H2O ) The presence of excess sodium ions favors establishment of equilibrium with a minimum of dye remaining in the dye bath. Dyes designed for cellulosic polymers are direct, azoic, vat, sulfur, and reactive dyes. Direct dyes are so named because they were the first colourants that had affinity for cotton in the absence of a binding agent known as a mordant.

13

Direct dyes (cont:) Benzidine-based direct dyes they tend to be linear molecules they are able to gain close proximity to the cellulose chain, to maximize the effects of intermolecular interactions such as Hbonding.

14

6/29/2013

Fiber-reactive dyes These dyes react with the cellulosic fiber to form a covalent bond. This produces dyed fiber with extremely high wash fastness properties. Cotton, rayon, and some nylons are dyed by this relatively simple dye. The principal chemical classes of reactive dyes are azo, triphendioxazine, phthalocyanine, formazan, and anthraquinone.

15

Sulfur dyes Sulfur dyes are applied to cotton from an alkaline reducing bath with sodium sulfide as the reducing agent. They are soluble in their reduced form and exhibit affinity for cellulose and are subsequently converted back to their water-insoluble form, giving good permanence under wet conditions. They dye by adsorption; but on exposure to air, they are oxidized to reform the original insoluble dye inside the fiber. The cost is low and they have good fastness to light, washings, and acids. The actual structures of sulfur dyes are unknown. They possess sulfurcontaining heterocyclic rings.

16

6/29/2013

Vat dyes The vat dyes are insoluble complex polycyclic molecules based on the quinone structure (keto-forms). They are reduced with sodium hydrosulfite in a strongly alkaline medium to give soluble leuco forms that have a great affinity for cellulose. After the reduced dye has been absorbed on the fiber, the leuco forms are reoxidized to the insoluble keto forms. The dyeings produced in this way have high wash and light-fastness.

Leuco forms :The 'colorless' form of a dye created as a result of its insoluble form 17 interacting with an alkaline liquor. Color returns to the dye upon oxidation.

Vat dyes (Cont:) Included in the family of vat dyes is the well known natural dye indigo. Its a-typically small size causes this vat dye to be very susceptible to removal in a laundering process, giving jeans a faded appearance even after one wash.

Mordant dyes Some dyes combine with metal salts (mordanting) to form insoluble colored complexes (lakes). These materials are usually used for the dyeing of cotton, wool, or other protein fiber. The fiber is first treated with an aluminum, chromium, and iron salt and then contacted with a lake-forming dye (azo and anthraquinone derivatives). 18

6/29/2013

Mordant dyes (cont:) The metallic precipitate is formed in the fiber producing very fast colors highly resistant to both light and washing. Example: Alizarin is the best-known anthraquinone derivative. The hydroxyl groups attached to anthraquinone nuclei are capable of reaction with metals in the mordant material (aluminum hydroxide) to form mordant dyes (aluminum lake). Mordant dyes have declined in importance because easier methods using developing dyes and vat dyes have replaced this process.

19

Food, drug, and cosmetic dyes The most frequently used synthetic dyes for food, drugs, and cosmetics belong to azo, anthraquinone, carotenoid, and triarylmethane chemical types. The following two azo series food dyes are good examples

20

10

6/29/2013

Study Guide Q9. Q10. What is the main functional group in the Basic dye? Which synthetic polymer is suitable for dyeing with basic (cationic) dye? Explain why basic cationic dyes need to use alkaline bath to dye the wool. Why fiber-reactive dyes are high water fastness? Sulfur dye and vat dye require reducing agents. Explain. Explain why natural vat dye Indigo used in jeans faded easily after one wash. How to apply mordant dye?
21

Q11.

Q12. Q13. Q14.

Q15. Q16.

Give examples for food and drug dyes.

Textile Fibers The world textile industry is one of the largest consumers of dyestuffs. An understanding of the chemistry of textile fibers is necessary to select an appropriate dye The natural fibers: - Plant sources (such as cotton and flax), - Animal sources (such as wool and silk), or - Chemically modified natural materials (such as rayon and acetate fibers). The synthetic fibers include - nylon, - polyester, - acrylics, - polyolefins, and - spindex.
22

11

6/29/2013

Cotton The cotton fiber is essentially cellulosic in nature and may be chemically described as poly (1,4-B-D-anhyrdoglucopyranose), with the repeat unit (about 3000 units):

The structure has primary and secondary alcohol groups uniformly interspersed. These hydroxyl units impart high water absorption characteristics to the fiber and can act as reactive sites. The cotton fibers are hydrophilic and swell in water. It is hydrolyzed by hot acid and swollen by concentrated alkali. The cotton is treated with caustic soda solution (12 to 25 percent) under tension to develop a silk-luster and stop longitudinal shrinkage. This process and is called mercerization. Mercerized cotton exhibits increased moisture 23 dye absorption.

The dyeing of cotton fiber is accomplished by three principal processes. (1) Cotton may be chemically reacted with fiber-reactive dyes in solution. The dyeing takes place by reaction with hydroxyl groups in cotton. A second method is the use of substantive dyes that diffuse directly into fiber from a dye solution. The dyeing rate is increased by the addition of electrolytes. The third method is referred to as mordant dyeing in which the dye in solution reacts with metals previously applied to the fiber to form insoluble colored compounds on the cotton. Vat dyes are another important class of dyes for cotton. These are applied in a soluble reduced form and after application they are oxidized, forming an insoluble molecule
24

(2)

(3)

12

6/29/2013

Rayon Rayon, the first commercial manmade fiber, is composed of cellulose in a quite pure form. (semi-synthetic fibers) It is produced by the treatment of wood pulp with alkali and carbon disulfide to form a viscous solution of cellulose xanthate. This viscous solution, called viscose, is extruded through spinnerets into an aqueous acid bath that coagulates the cellulose xanthate, decomposes it, and regenerates the cellulose. Rayon fibers are easily wetted by water and provide easy access to dye molecules. Dyeing may take place by absorption or by reaction with the hydroxyl groups. Rayon fibers may also be dyed with mordant and vat dyes.

25

Wool and silk Wool is animal hair from the body of sheep. Silk is a lustrous, tough elastic fiber produced by silkworms. Both wool and silk fibers are protein substances with both acidic and basic properties. The building blocks for these fibers are amino acids are arranged in a polypeptide chain. Owing to the presence of many amine, carboxylic acid, amide, and other polar groups, wool and silk are hydrophilic in nature, wetted by water, and are dyed with either acid or basic dyes through the formation of ionic bonds (salt linkages). They may also be dyed with reactive dyes that form covalent bonds with available amino groups.

26

13

6/29/2013

Polyamides Nylon 6,6 and Nylon 6 was the first synthetic polyamide as a fiber. In both nylon polymers one chain end consists of an amino group, which can be presented in the free state or in the acetylated form.

Amino groups are of special importance for dyeing because they form ammonium groups in an acidic dye bath by addition of a proton. The lower dye uptake in comparison to wool is caused by the comparatively low number of amino groups. The depth of color achieved in nylon 6 is less than that in nylon 6,6. During dyeing a pH below 2.4 should be avoided, because fiber damage occurs at low pH. Reactive dyes that bond to available amino groups may also be used.
27

Acrylics Acrylics are produced by the polymerization of acrylonitrile. They have the repeating unit, [ CH2CH(CN)]n, with up to 15 percent of the polymer comprising one or two other monomeric units (vinyl acetate and an acrylate or methacrylate ester) is used to improve fiber properties. Acrylic fibers are hydrophobic with excellent chemical stability. Anionic property which makes acrylics suitable for dyeing with cationic dyes (basic dyes).

28

14

6/29/2013

The Application of Dyes The basic operations of dyeing (1) Preparation of the fiber (2) Preparation of the dye bath (3) Application of the dye (4) Finishing Pretreatment before dyeing Fiber preparation ordinarily involves scouring to remove foreign material and ensure even access to dye liquor from the dye bath. Wool must be washed to remove wax and dirt and sometimes bleached. Cotton must be boiled and bleached to remove pectins and cotton seeds and is mercerized. Sizes and spinning oils must be eliminated

29

Preparation of the dye bath The dyeing of fiber from an aqueous dye bath depends on the dye-fiber interaction. Depending on the nature of dye and the nature of fiber, the dye is fixed onto the fiber chemically or physically. Additives such as wetting agents, salts, carriers, retarders, and others may be added to the dye bath along with the dye if required to facilitate the dyeing process.

30

15

6/29/2013

Application of the dye Dyes are applied to textile fibers by batch as well as continuous methods. Batch dyeing Hand operation by the simple process of moving the fibrous material in an open bath containing the dye liquor. In machine dyeing (e.g., the Lancashire jigger machine) , the yarn or cloth is moved in the dye bath, which is kept stationary except for the agitation of the liquor because of the movement of the yarn or cloth. Machine dyeing depend on the physical structure of fibers, employs a different type of machine. They include jig dyeing, beck dyeing, jet dyeing, package dyeing, skein dyeing, pad-batch, beam dyeing, and others.
31

32

16

6/29/2013

Continuous dyeing

It is designed for long runs using a padding machine. The machine consists of : (1) a dye beck of relatively small volume provided with guide rollers together with two or more squeezing rollers for removal of excess liquor. (2) more than one padding machine in series may be used.

33

Finishing (1) Followed by various rinsing, soaping, and other after treatments (finishing steps) that may be necessary. (2) The drying equipment normally works with infrared heat or with a hot air stream or a combination of both.

34

17

6/29/2013

Environmental and Health Aspects Dermatologists have reported cases of skin reactions suspected to be caused by textile dyes. The positive link between benzidine derivatives and 2-naphthylamine with bladder cancer is also well documented. (Carcinogens) Exposure of workers to dye dust and the discharge of chemicals, colors, and other effluents must be controlled. Wastewaters from both dye manufacturing plants and dye houses are treated before leaving the plant. Various treatment methods such as neutralization of acidic and alkaline effluents, removal of heavy metals, aerobic and anaerobic biological treatments, and chemical oxidation are used . Color is removed by adsorption on activated carbon, or by chemical treatment of the effluent with a flocculating agent such as ferric (Fe3+) 35 or aluminum (Al3+) ions.

Study Guide Q17. Q18. Q19. Q20. Q21. Q22. Classify the textile fibers. State the reactive sites of cotton. What is mercerized cotton? What is rayon? What is the structural building block of wool and silk? What types of dye are appropriate to dye the following textile fibers? (i) rayon (ii) wool and silk (iii) poly amide State the basic operation of dyeing. What are steps in finishing after application of dye on textile? How to treat the waste water from dye manufacturing plants?
36

Q23. Q24. Q25.

18