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/ 2
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. 3
Understanding Leads to Progress
„ Serendipitous discovery of other dyes
„ Kekulé 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/ 4
Outline
„ Dye Background
‰ Terminology
‰ Classification
‰ Classes
„ Reactive Dyes
„ Reactive Pretreatments
„ Unanticipated Benefits
„ Conclusion

5
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

6
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

7
Textile Fibers
Sources

Animal Plant Synthetic

Proteins Carbohydrates Polymers

Wool Cotton Nylon

8
Acidic and Basic Dyes
„ Ionic interactions
„ Fastness issues

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

9
Mordant Dye
„ Metal complex
„ Improved fastness
„ Environmental concerns

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

10
Vat Dyes
„ Entrapment
„ Good fastness
„ Complex dyeing process

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

11
Direct Dyes
„ Intermolecular forces
„ Moderate to poor wash fastness
„ Inexpensive

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

12
Outline
„ Dye Background
„ Reactive Dyes
‰ Nucleophilic Aromatic Substitution
‰ Michael Addition
„ Reactive Pre-treatments
„ Unanticipated Benefits
„ Conclusion

13
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.
14
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.

15
Research and Patents
„ Patents for textile dyes for 1998

Dye Class Eastern Western Total

Countries Countries

Acid 4 0 4
Direct 0 5 5
Reactive 10 12 22

Vat 1 0 1

„ Dominant dye form over the past 50 years

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

16
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.

17
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.

18
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.

19
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.

20
Leaving Groups
„ Variation of substituents = variations in fixation
‰ “Cold” dyes = fixation temperature of 30-40°C
‰ “Warm” dyes = fixation temperature of 50-80°C
‰ “Hot” dyes = fixation temperature of >80°C

Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107.

Stead, C. V. Dyes and Pigments, 1982, 3, 161-171. 21
Vinylsulfone Dyes
„ Introduced by Höchst (Dystar) in 1958

Renfrew, A. H. Reactive Dyes for Textile Fabrics Society of Dyers and Colorists: West Yorkshire, 1999.
22
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

23
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. 24
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.
25
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. 26
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. 27
Other Vinylsulfone Strategies
„ Höchst (Dystar)
„ Two opportunities for fixation

Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107.

Höchst, EP 513 657 1992. 28
Disulfide Strategy

Lewis, D. M., Renfrew, A. H., Siddique, A. A. Dyes and Pigments, 2000, 47, 151-167.
29
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.
30
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 1960’s

Lewis, D. M. J.S.D.C, 1993, 109, 357-364.

Taylor, J. A. Rev. Prog. Coloration, 2000, 30, 93-107. 31
Heterobifunctional Reactive Dyes
„ Introduced in the early 1980’s
‰ 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. 32
Preferred Bonding Sites
„ Is one reactive group responsible for the majority of
fixation?
„ Is cross-linking possible?
‰ To what degree?

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

33
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.; Müller, S.; Rys. P. Textilveredlung 1991, 26, 80-86.

34
Direct Evidence of Covalent Bond
„ 13C NMR analysis of colored mixture
‰ Comparison of shifts to model compounds

35
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.; Müller, S.; Rys. P. Textilveredlung 1991, 26, 80-86.

36
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. 37
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

38
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

39
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.
40
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. 41
Polymeric Agents
„ Hercosett 125

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

42
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.

43
Ring Dyeing and Leveling

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

44
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.

45
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.

46
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. 47
Kim, T.-K.; Son. Y. –A. Dyes and Pigments 2005, 65, 261-266.
Outline
„ Dye Background
„ Reactive Dyes
„ Reactive Pretreatments
„ Unanticipated Benefits
‰ Fastness Issues
‰ Protection of Fibers
„ Conclusion

48
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 49
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. 50
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.
51
Dye Fiber Interaction
„ Other interactions may provide this benefit as well

Rastogi, D.; Sen, K.; Gulrajani, M. Color. Technol. 2001, 117, 193-198.
52
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.

53
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.

54
Analysis of Dyeing Solution
„ HPLC
‰ A) Standard
‰ B) Stripped solution from wool
‰ C) Dye bath after dyeing A

Time
Lewis, D. M.; Smith, S. M. J.S.D.C. 1991, 107, 357-362.
55
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

56
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

57
Supplemental

58
Acid Cleavage of MCT group
„ Proposed mechanism for acidic hydrolysis

59