Dyes
Dileep Grad student (dil2dilu@yahoo.com)
Basic concepts of of Bandscolor of red, orange, yellow, blue, indigo, green and violet.
Visible region 400-700nm
ACHROMATIC colors white (complete reflection of light) Black (Complete absorption) Grey (absorption of a fairly constant fraction throughout the 400-700nm range) CHROMATIC colors show ABSORPTION BANDS in the visible region
naphthale ne
Anthracene
Tetracene
Increased conjugation brings the HOMO and LUMO orbitals closer together.
colorless
colored
Early dyes
The preparation and application of dyestuffs is one of the oldest forms of human activities. It was in 2600 BC when earliest written records of the use of dyestuffs were found in China. Natural Dyes: Ex: Indigo - extracted from a plant called woad Tyrian Purple - extracted from sea molluscs Problems associated: - variable supply and quality - inconsistent dyeing - fast fading property
William Henry Perkin chanced upon first synthetic dye stuff 'Aniline Mauve' (Mauveine)
(C
10H13N) +
O2H
20H24N2O2
The Luck Hid in the Impurities Perkin inferred the presence of toluidine in mauve from its elemental analysis. The aniline sample that he was using was not pure; it contained toluidines in considerable quantities. - aniline reacted withtoluidineimpurities
Aniline
Toulidines:
- 2 molecules ofaniline, one ofp-toluidineand one ofo-toluidine aniline, p-toluidine and o-toluidine (one molecule each)
Chromophores and Auxochromes Chromophore is a group of atoms which control the colour of the dye
Auxochrome was a salt-forming group, which helped to improve the colour of the dye (auxochromes are normally electron-donating) -OH, -OR, -NH2, -NHR, -NR2, -X How a dye molecule's hue be altered: A bathochromic shift may be caused by increasing the electronwithdrawing power of the chromophore (X or Y), increasing the electron-donating power of the auxochrome (Y or X) and by increasing the length of the conjugated system connecting the two
Strength Themolar extinction co-efficientindicates the strength of a dye at low concentrations. It can be calculated using the Beer-Lambert Law A =bc where A is the absorbance of the dye at a particular wavelength,is the molar extinction co-efficient, c is the concentration of the dye and l is the path-length through the cell2. Brightness The brightness is best described by the shape of the absorbance band; if the band is narrow and sharp, then the dye is bright, if broad, then the dye is dull. This is due to other wavelengths absorbed by the dye, other than the one which causes the hue. The superposition of these determines how broad an absorption band is
Fastness
It is the property of a pigment or dye, or the leather, cloth, paper, ink, etc., containing the coloring matter, to retain its original hue, especially without fading, running, or changing. Running Running occurs principally during washing and exposure to detergents and solvents. Due to weak affinity for the material it is attached to OR much stronger affinity for a non-aqueous solvent. Fading Fading is caused by the chemical alteration of unstable dye molecules to a less strongly coloured or colourless form. Caused by the action of sunlight, or by the oxidising action of the atmosphere10. The UV radiation - cause unstable bonds to break or reform. Oxygen and atmospheric water will react with unstable bonds to alter the structure and affect its colour.
chemical structure azo dyes (-N=N- group) anthraquinones (-C=O) Nitro dyes(-NO2) how it is applied to materials. Acid Basic Direct Disperse Reactive Solvent Vat Mordant
AZO DYES
Azo compound class accounts for 60-70% of all dyes. All contain an azo group, -N=N-, which links two sp2hybridised carbon atoms. Usually the basic structure Ar-N=N-Ar. Supply more yellows, oranges and reds Azo dyes give bright, high intensity colours fair to good fastnessproperties Cost-effective Synthesis
Acid dyes
Water-soluble anionic dyes Contain one or more sulfonic acid substituents (present as sodium sulphonate salts) or other acidic groups Applied from acidic dye baths to nylon, silk, wool, and modified acrylics. Ionic bonding between acid groups on the dye with the amino groups on the fiber. Ex: Acid Yellow 36
Basic dyes
Water-soluble and produce colored cations in solution. (-NR3+or =NR2+) Mostly amino and substituted amino compounds soluble in acid Attached to the fibers by formation of salt linkages (ionic bonds) with anionic groups in the fiber. Used to dye paper, polyacrylonitrile, modified nylons, and modified polyesters Ex: Basic brown 1 Triaryl methane or xanthenes.
Direct dyes
Used for the direct dyeing of cotton and regenerated cellulose, paper and leather. Ex: mostly polyazo compounds Their flat shape and their length enable them to lie along-side fibres and maximise the Van-der-Waals, dipole and hydrogen bonds. Lack of fastness during washing They are cheap - popular for items which are less likely to require fastness during washing (for example paper)
Disperse dyes
Water-insoluble nonionic dyes Used for application onto synthetic hydrophobic fibers from aqueous dispersions. Adsorbed onto the fibers
Ex:
General structure of a polyester Fairly hydrophobic The polymer chains in a sample of polyester are highly crystalline (for a polymer) and quite tightly packed together.
Fiber-reactive dyes
Form a covalent bond with the appropriate textile functionality Extremely high wash fastness properties. Cotton, rayon, and some nylons are dyed by this relatively simple dye. Ex:
Cellulose polymer has hydroxy functional groups, - reactive dyes utilize as nucleophiles Under alkali conditions - cellulose-O-groups attack electron-poor regions of the dye; Perform either nucleophilic substitution to aromatics nucleophilic addition to alkenes
To encourage nucloephilic substitution, groups can be added to the aromatic ring which will decrease the electron density at a position and facilitate attack
Nucleophilic substitution is facilitated by the electron withdrawing properties of the aromatic nitrogens, and the chlorine, and the anionic intermediate is resonance stabilised as well. This resonance means that the negative charge is delocalised onto the electronegative nitrogens
Nucleophilic addition to alkenes Nucleophilic additions occur if there are sufficient electron withdrawing groups are attached to the alkene Ex: Remazol reactive dye (reacts in the presence of a base such as HO-)
Vat dyes
Insoluble complex polycyclic molecules based on the quinone structure (ketoforms). 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 (by hydrogen peroxide, sometimes atmospheric oxygen) to the insoluble keto forms. High wash and light fastness.
Mordant dyes
Mordants are usually metal salts; used to improve the colour fastness of dyes Some dyes combine with metal salts (mordanting) to form insoluble colored complexes (lakes). The fiber is first treated with an aluminum, chromium and iron salt and then contacted with a lake forming dye (azo and anthraquinone derivatives). Ex: Alizarin
That property of a pigment or dye, or the leather, cloth, paper, ink, etc., containing the coloring matter, to retain its original hue, especially without fading, running, or changing when wetted, washed, cleaned; or stored under normal conditions when exposed to light, heat, or other influences. Essentially, this means that different dyes will have different fastnesses on different materials. Running Running occurs principally during washing and exposure to detergents and solvents- everyone knows what happens if a red sock or blue pants are accidentally put in a white wash.A dye will run if it has a weak affinity for the material it is attached to, or a much stronger affinity for a non-aqueous solvent. Detergents may cause running because they help to stabilise the hydrophobic regions of dye molecules due to their ability to form micelles. Fading Fading is caused by the chemical alteration of unstable dye molecules to a less strongly coloured or colourless form. This is often caused by the action of sunlight, or by the oxidising action of the atmosphere10. The UV radiation in sunlight has enough energy to cause unstable bonds to break or reform. Oxygen and atmospheric water will react with unstable bonds to alter the structure and affect its colour. There is no way to stop an unstable dye from fading.
http://www.dyespigments.com/what-is-dye.html http://www.morechemistry.com/publ/colours_dyes/slide044.html
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/UVVis/spectrum.htm
A History of Dyes.http://www.straw.com/sigdyehist.html
Dileep