Reactive Dyes

Kris Kolonko Reich group November 3, 2005

Colorants
Used extensively in food, clothing, paints, plastics, etc.
Increase the appeal of material Color affects our mood

Start of chemical industry

Many chemical companies began as primarily dye producers

Christie, R.M. Colour Chemistry Royal Society of Chemistry: Cambridge, 2001. http://www.ibiblio.org/wm/paint/auth/marc/

Synthetic Dyes and Chemical Industry

Synthetic dye mauveine
William Henry Perkin in 1856
First production of chemicals on a large scale Actual composition unknown until 1994

Perkin, W. H. J. Chem. Soc. 1896, 69, 596. Meth-Cohn, O.; Smith, M. J. Chem. Soc. Perkin Trans. 1994, 1, 5.

Understanding Leads to Progress

Serendipitous discovery of other dyes Kekul proposes cyclic structure of benzene 1865 Structural determination of natural dyes
Done through lengthy degradation studies Synthesis and modification

By the dawn of the 20th century synthetic dyes accounted for 90% of the market Wide variety of dyes are available today
Colour Index International lists 27,000 products

Christie, R.M. Colour Chemistry Royal Society of Chemistry: Cambridge, 2001. http://www.colour-index.org/

Outline
Dye Background
Terminology Classification Classes

Reactive Dyes Reactive Pretreatments Unanticipated Benefits Conclusion

Dye Terminology
Exhaustion
Proportion of dye taken up by the fiber at any stage of the process relative to the amount originally available

Fixation
Proportion of dye remaining on the fiber at the end of the process relative to the amount originally available

Fastness
Resistance to fading due to washing, light, etc.

Shamey, R.; Hussein, T. Textile Progress 2005, 37, 1-84

Dye Classification
Dyes vs. Pigments
Solubility

Classified by functional group

Azo, Carbonyl, etc.

Classified by their use in the dyeing process

Relates to the dye-substrate interaction to obtain adhesion

Textile Fibers
Sources Animal Proteins Wool Plant Carbohydrates Cotton Synthetic Polymers Nylon

Acidic and Basic Dyes

Ionic interactions Fastness issues

Christie, R.M. Colour Chemistry Royal Society of Chemistry: Cambridge, 2001.

Mordant Dye
Metal complex Improved fastness Environmental concerns

Christie, R.M. Colour Chemistry Royal Society of Chemistry: Cambridge, 2001.

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Vat Dyes
Entrapment Good fastness Complex dyeing process

McGovern, P. E.; Michel, R. H. Acc. Chem. Res. 1990, 23, 152-158.

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Direct Dyes
Intermolecular forces Moderate to poor wash fastness Inexpensive

Christie, R.M. Colour Chemistry Royal Society of Chemistry: Cambridge, 2001.

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Outline
Dye Background Reactive Dyes
Nucleophilic Aromatic Substitution Michael Addition

Reactive Pre-treatments Unanticipated Benefits Conclusion

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Reactive Dyes
Form a covalent bond between the dye and fiber Introduced to the market by ICI in 1956
Inspired by esterification of cellulose in 1895 with benzoyl chloride

Show improved fastness properties

Great improvement for cellulosic fibers

Simplify dyeing procedure

No oxidation/reduction

Venkataraman, K. The Chemistry of Synthetic Dyes, Vol. 7. Academic Press: New York, 1972.

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Mechanism of Reactive Dye Fixation

Utilizes dichlorotriazine as reactive linker Nucleophilic aromatic substitution Allows for a wide variety of chromophores to be used
Requires a nucleophilic group on the chromophore

Stead, C. V. Dyes and Pigments, 1982, 3, 161-171.

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Research and Patents

Patents for textile dyes for 1998
Dye Class Eastern Countries Acid Direct Reactive Vat 4 0 10 1 Western Countries 0 5 12 0 Total

4 5 22 1

Dominant dye form over the past 50 years

Freeman, H. S.; Sokolowska, J. Rev. Prog. Coloration, 1999, 29, 8-22.

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Indirect Evidence of Covalent Bond

Direct evidence?
Chemical degradation of fiber
Degradation of dye or degradation of linkage

Reactive dyes can not be removed by extraction Solubility changes of the fiber Further chemical derivatization of linkage

Vickerstaff, T. J.S.D.C. 1957, 73, 237-246.

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Side Reaction
Hydrolysis of dichlorotriazine
Results in wasted dye Economic and environmental concern

Typically fixation of around 60% is obtained

Stead, C. V. Dyes and Pigments, 1982, 3, 161-171.

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Dyeing Conditions
Time allowed for diffusion of dye into substrate
Concentration of dye in fiber is up to 500 times greater than in solution

Acidity difference creates ~25-fold excess cellulose anions

Stead, C. V. Dyes and Pigments, 1982, 3, 161-171.

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Other Heterocycles
Many other companies followed ICI using other halogenated heterocyclic linkers Triazine ring is the most electrophilic
Charge density calculations

Stead, C. V. Dyes and Pigments, 1982, 3, 161-171.

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Leaving Groups
Variation of substituents = variations in fixation
Cold dyes = fixation temperature of 30-40C Warm dyes = fixation temperature of 50-80C Hot dyes = fixation temperature of >80C

Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107. Stead, C. V. Dyes and Pigments, 1982, 3, 161-171.

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Vinylsulfone Dyes
Introduced by Hchst (Dystar) in 1958

Renfrew, A. H. Reactive Dyes for Textile Fabrics Society of Dyers and Colorists: West Yorkshire, 1999.

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Synthesis of Vinylsulfone Dyes

Maximize number of usable chromophores Aromatic ring used as a bridge between reactive group and dye Sulphato group is easy to introduce

Kim, Y. Z.; Kim, J. P. Synth. Comm. 2002, 32, 1601-1605

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Other Michael Acceptors

Bromo acrylamides
Used primarily for wool Comparable reactivity to vinylsulfone dyes
Dye-fiber bond marginally sensitive to pH

Cross-linking?

Phillips, D. A.; Taylor, J. A.; Kao, Y. C.; Ansari, I. Dyes and Pigments 1999, 43, 153-160. Renfrew, A. H. Reactive Dyes for Textile Fabrics Society of Dyers and Colorists: West Yorkshire, 1999.

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Masking Groups
Aliphatic amines can be eliminated under acid conditions
Requires higher temperatures

Renfrew, A. H. Reactive Dyes for Textile Fabrics Society of Dyers and Colorists: West Yorkshire, 1999.

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Cationic Vinylsulfone Dyes

Increased electrostatic absorption into the fiber
Lower salt usage Aimed at current modified Nylon produced by DuPont
Colorsafe system (DuPont and Dystar)

Lewis, D. M.; Sun, L. J. Color. Technol., 2003, 119, 286-291. Lewis, D. M.; Sun, L. J. Color. Technol., 2003, 119, 327-330.

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Fiber Dye Interaction

Requires higher pH and temperature Better exhaustion and fixation (97.5% and 95% respectively)

Lewis, D. M.; Sun, L. J. Color. Technol., 2003, 119, 286-291. Lewis, D. M.; Sun, L. J. Color. Technol., 2003, 119, 327-330.

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Other Vinylsulfone Strategies

Hchst (Dystar) Two opportunities for fixation

Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107. Hchst, EP 513 657 1992.

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Disulfide Strategy

Lewis, D. M., Renfrew, A. H., Siddique, A. A. Dyes and Pigments, 2000, 47, 151-167.

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Side Reactions
Requires high pH for optimal fixation
Reduces by product formation

Requires large amount of salt for good exhaustion

Lewis, D. M., Renfrew, A. H., Siddique, A. A. Dyes and Pigments, 2000, 47, 151-167.

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Homobifunctional Reactive Dyes

Two reactive groups = 20% increase in fixation Easy modification of current monofunctional dyes
Gained market a significant market share in the late 1960s

Lewis, D. M. J.S.D.C, 1993, 109, 357-364. Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107.

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Heterobifunctional Reactive Dyes

Introduced in the early 1980s
Typically combine triazine and vinylsulfone Differing reactivities tolerate variations in the dyeing process

Phillips, D. A.; Taylor, J. A.; Kao, Y. C.; Ansari, I. Dyes and Pigments 1999, 43, 153-160. Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107.

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Preferred Bonding Sites

Is one reactive group responsible for the majority of fixation? Is cross-linking possible?
To what degree?

Meyer, U.; Mller, S.; Rys. P. Textilveredlung 1991, 26, 80-86.

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Direct Evidence of Covalent Bond

Enzymatic degradation of dyed cotton
Selective cleavage of sugar linkages

Isolation of colored compounds

Comparison of the two different covalent linkages

Meyer, U.; Mller, S.; Rys. P. Textilveredlung 1991, 26, 80-86.

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Direct Evidence of Covalent Bond

13C

NMR analysis of colored mixture

Comparison of shifts to model compounds

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Connectivity
Triazine reaction
25% unreacted 25% hydrolyzed 50% bonded to glucose through the triazine group

Vinylsulfone reaction
25% hydrolyzed 75% bonded to glucose through the vinyl sulfone group

Estimation of up to 25% cross-linkage

Meyer, U.; Mller, S.; Rys. P. Textilveredlung 1991, 26, 80-86.

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Tri and Polyfunctional Dyes

Limited increase in fixation with trifunctional dyes
Some commercial success

Polyfunctional dyes
Include 4 or more reactive groups
More costly

Suffer from slow diffusion rates

Often leads to non-uniform dyeing (leveling problems)

Phillips, D. A.; Taylor, J. A.; Kao, Y. C.; Ansari, I. Dyes and Pigments 1999, 43, 153-160. Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107.

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Summary of Reactive Dyes

Advantages
Simplifies dyeing process Improve fastness

Disadvantages
Hydrolysis accompanies fixation
Waste of dye Extra wash step
Colored effluent discharge processing

Large amount of electrolytes used

Basic conditions create anionic repulsion of dye and fiber

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Outline
Dye Background Reactive Dyes Reactive Pretreatments
Increase the nucleophilicity of cellulose Change the charge of the cellulose Polarity reversal of fabric and dye

Unanticipated Benefits Conclusion

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Increasing Nucleophilicity
Carbon disulfide
Benefits
Allows for dyeing of cotton at neutral pH

Downsides
Toxicity Stability of the linkage to hydrolysis

Amine pretreatments have also show to increase fixation as well

Renfrew, A. H. Reactive Dyes for Textile Fabrics Society of Dyers and Colorists: West Yorkshire, 1999.

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Changing the Charge

Allows for easy dyeing at neutral pH without the use of a salt during exhaustion phase
Nearly quantitative fixation observed Short wash off times

Lewis, D. M.; Lei, X. P. J.S.D.C. 1991, 107, 102-109. Lewis, D. M.; J.S.D.C. 1993, 109, 357-364.

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Polymeric Agents
Hercosett 125

Burkinshaw, S. M.; Lei, X. P.; Lewis, D. M. J.S.D.C. 1989, 105, 319-325.

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Polymeric Agents - Hercosett 125

Good fixation of reactive dichlorotriazine dyes Unsatisfactory light fastness Examination of fiber
Center of fiber colorless Hercosett resin located on surface of the fiber
Slow diffusion of the dye results in ring dyeing

Burkinshaw, S. M.; Lei, X. P.; Lewis, D. M. J.S.D.C. 1989, 105, 319-325.

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Ring Dyeing and Leveling

Evans, G. E.; Shore, J.; Stead, C. V. J.S.D.C. 1984, 100, 304-315.

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Polarity Reversal - N-methylol-acrylamide

Previously used for producing a durable-press cotton Pendant alkene for further derivatization

Lewis, D. M.; Lei, X. P. J.S.D.C. 1991, 107, 102-109.

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Following the Reaction with FTIR

Transmittance, %

Transmittance, %

Wavenumber,cm-1

Wavenumber,cm-1

Lewis, D. M.; Lei, X. P. J.S.D.C. 1991, 107, 102-109.

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Polarity Reversal
Number of linkage strategies Costly implementation
Additional steps Production of new nucleophilic dyes

Lei, X. P.; Lewis, D. M. Dyes and Pigments 1991, 16, 273-289. Lewis, D. M.; Ho, Y. C. Dyes and Pigments 1995, 28, 171-192. Kim, T.-K.; Son. Y. A. Dyes and Pigments 2005, 65, 261-266.

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Outline
Dye Background Reactive Dyes Reactive Pretreatments Unanticipated Benefits
Fastness Issues Protection of Fibers

Conclusion

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Anticipated Benefits
Improved wet fastness
Covalent bonding interaction

Some linkages still prone to hydrolysis

Acidic dichlorotriazines Basic vinyl sulfones

Improvements in detergents
Perborates radical cleavage of pyrimidinyl group

Rattee, I. D.; Rocha Gomes, J. I. N. J.S.D.C. 1985, 101, 319-325. http://www.sportoculars.com

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Unanticipated Benefits
Improved light fastness of reactive dyes

Covalent bond facilitates energy transfer?

Rastogi, D.; Sen, K.; Gulrajani, M. Color. Technol. 2001, 117, 193-198. Allen, N. S.; Fatinikun, K. O.; Davies, A. K.; Parsons, B. J.; Phillips, G. O. Poly. Photochem. 1981, 1, 275-283.

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Added Light Stability of Reactive Dyes

Based on a comparison of the color fading of a reactive dye to its hydrolyzed form on the same fabric

Rastogi, D.; Sen, K.; Gulrajani, M. Color. Technol. 2001, 117, 193-198.

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Dye Fiber Interaction

Other interactions may provide this benefit as well

Rastogi, D.; Sen, K.; Gulrajani, M. Color. Technol. 2001, 117, 193-198.

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Wool Degradation
Protein structure of wool sensitive to steam or basic conditions
Cystine group plays significant role Generation of hydrogen sulfide

Lewis, D. M.; Smith, S. M. J.S.D.C. 1991, 107, 357-362.

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Prevention of Wool Damage

Empirically demonstrated that degree of wool fiber damage is lessened by increasing reactive dye concentration Could vinyl sulfone be reacting with the generated hydrogen sulfide?

Lewis, D. M.; Smith, S. M. J.S.D.C. 1991, 107, 357-362.

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Analysis of Dyeing Solution

HPLC
A) Standard B) Stripped solution from wool C) Dye bath after dyeing

Time
Lewis, D. M.; Smith, S. M. J.S.D.C. 1991, 107, 357-362.

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Conclusions
Dyeing of fabrics involves a number of strategies for adhesion Reactive dyes provide substantial benefits over other dyes As the prevalence of synthetic fibers grow, new reactive groups or approaches may have to be developed to improve the economy and fastness of colorants

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Acknowledgements
Prof. Hans Reich
Prof. Ieva Reich

Practice talk attendees

Matt Bowman Whitney Erwin Luke Lavis Chris Paradise Brian Smith Laura Wysocki

Reich Group
Amanda Jones Kristin Plessel

Erin McElroy

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Supplemental

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Acid Cleavage of MCT group

Proposed mechanism for acidic hydrolysis

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