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Department of Chemical & Petrochemical Technology, National Research and Development Institute for Chemistry and Petrochemistry (ICECHIM), Bucharest, Romania
Received: June 02, 2011 / Accepted: October 14, 2011 / Published: February 25, 2012.
Abstract: The main aim of the paper was to obtain new reactive dyes with a minimum impact on the environment and on the human health. The synthesized reactive dyes are based on s-triazine reactive system, and they’re dyeing cotton in red, violet, and blue shades. The new dyes were analyzed by specific physico-chemical methods (e.g., thin layer chromatography, absorption spectroscopy in UV-VIS range, photocolorimetry) and then were applied on cotton. The coloristical performances of the studied dyes were analyzed by the well known standardized tests (dyeing intensity, light fastness, water fastness, acid perspiration fastness, wet and drying rubbing fastness). The results allow us to appreciate that the new dyes have physico-chemical and coloristical performances at the level of the actual marks marketed in the world.
Key words: Reactive dye, absorption spectroscopy, cotton dyeing, coloristical fastness.
1. Introduction??
Today the textile products market (fabrics, stockinet, ready-made clothes) has an unprecedented dynamic. Because of the increasing in standard of living the people around the world has the tendency to take up the“throw-away” fashion, wear once and change it. The fashion has become a gross business. From season to season the changes are very fast, being imposed by the changes in the unitary and mixture fashion hues and by the environmental legislation. In these conditions dyes manufacturers are required to adjust their range of products, in a fast and flexible way, to the consumers requirements regarding the color positions, the hues and models of the textile and ready-made clothes. The restrictions included in the environmental legislation have orientated the textile dyes market toward reactive dye class with lower ecological impact comparatively to direct, vat, acid or metal-complex dyes.
The reactive dyes class is special and unique due to its capacity to form covalent bonds with the cellulose and protein support. The result of the dyeing process is a colored macromolecule having high stability at wet treatments and good light fastness. A reactive dye corresponds to the general Eq. (1):
umido-heat fastness).
For analysis the dyes were purified in abs.ethanol. The purity of the studied dyes was checked by thin layer chromatography on silica gel, ascending techniques, in different eluents, such as: n-Buthyl-acetate: Py:water = 1:2:1 (vol/vol); Py: NH3 17%: n-AmOH = 1:1:1 (vol/vol).
The best separations of the position isomers having similar shades, were obtained using the second eluent. Performed chromatogram in the second eluent revealed that the synthesis products show a high degree of purity, the main spot is accompanied by spots of isomers products.
Dye concentration was determined by spectrophotometry analysis in the VIS range, a method of equalizing the intensity of coloration, considering purified dyes as standards. In this way, were actually determined the relative concentrations; relative concentration of the synthesized dyes, compared with the corresponding purified dyes are presented in Table 1.
The studied dyes are very soluble in water. Determination of the maximum absorption wavelength in UV-Vis range highlights the bathochrome effect, by changing the structure of diazotizing compound in reactive mono-azo dyes and in reactive disazo dyes. Table 1 presents the physico-chemical and coloristical
characteristics of the studied reactive dyes.
The coloristical performances of the studied dyes are excellent.
3.1 Structurally
A series of azoic reactive dyes, resulting from the same reactive specific coupling compound, and containing a monochlortriazine reactive system, was prepared. The structural modification of the diazotizing compound results in modification of the physico-chemical properties (solubility, absorption maximum wavelength values, chromatographical characteristics) and coloristical performances (dyeing intensity, light fastness, water fastness, acid perspiration fastness, wet and dry rubbing fastness). Therefore, by minor structural modifications in the diazotizing compound, are obtained significant chromatographical and spectral effects and coloristical effects on cotton from red to blue shades, as well.
3.2 Technologically
It has been found that at the coupling step is important to use a reactive specific coupling compound, containing a heterocyclic-aromatic reactive system. The preparation of this reactive coupling compound is indicated to take place by H acid acylation with a cyanuryl chloride previous monoacylated with an aromatic or heterocyclic amine. In these conditions takes place preferential the coupling reaction with a specific diazotizing compound, resulting a higher purity of the monochlortriazine reactive dyes, emphasized by chromatographical and spectral analysis.
4. Conclusions
There were synthesized, analyzed, and tested 6 new reactive dyes structures, having monochlortrizine as reactive system, based on four monofunctional reactive azo dyes, one monofunctional reactive disazo dye and one bifunctional reactive disazo dye, in red, violet and blue shades.
There were drown up ecological synthesis and dyeing technologies for the new reactive dyes; raw materials, intermediates and final products have reduced eco-toxicological risks.
The physico-chemical and coloristical performances of the resulted dyes are, on our knowledge, at the level of the actual marks marketed in the world.
[1] K. Othmer, Reactive Dyes, Encyclopedia of Chemical Technology, 4th ed., vol.8, 1993, pp. 380-390.
[2] I. Alexandrescu, R. Bidalah, M. Cernat, M. Dobrovat, A. Grigoriu, Theoretical and Practical Guidelines for Textiles Dyeing, CERTEX, Bucharest, 1994, pp. 113-120.
[3] J.A. Taylor, Recent developments in reactive dyes, Review of Progress in Coloration and Related Topics 30(1) (2000) 93-108.
[4] H. Tappe, W. Helmling, P. Mischke, K. Rebsamen, W. Russ, L. Schl?ffer, et al., Reactive Dyes, Ullmann’s Encyclopedia of Industrial Chemistry, 6th Edition, Wiley-VCH, 2002, www.wiley.com/WILEYCDA/ wileyTitle/productCD-3527303855.html.
[5] J. Danheim, Water-soluble red fiber-reactive dyes, processes for their preparation and their use, Ger Offen DE 19,611,636 (Cl. CO9B 62/085), Oct.2, (1997) 11.
[6] H. Loeffler, M. Patsch, Reactive disazo dyes, processes for their preparation and their use, Eur. Pat. Appl. EP 795,586 (Cl. C09B 67/22), Sept.17 (1997) 15.
[7] W. Byczynska, I. Gayewski, Manufacture of bireactive monoazo dyes containing s-triazine and vinylsulfone groups, Pol. PL 173,542 (Cl. C09B 29/24), Mar.31 (1998) 6.
[8] J. Danheim, K. Rebsamen, W.H. Russ, Water-soluble vinylsulfone fiber-ractive dyes, their preparation and their use, Eup. Pat. Appl. EP 905,200 (Cl. C09B 62/51), Mar..31, (1999) 15.
[9] P. Schebli, P. Aeschlimann, Dyeing and printing reactive dyes”, Eur. Pat. Appl. EP 922,735 (Cl. C09B 67/22), Jun.16 (1999) 41.
[10] R.P. Pedemeonte, W.H. Russ, J. Steckelberg, C. Schumacher, Dye mixtures comprising water-soluble fiber-reactive azo dyes, preparation thereof and use thereof, US Patent 6, 136, 045 (Cl. C09B 67/24), Oct.24, (2000) 9.
[11] W.H. Russ, B. Gr?bel, C. Schumacher, Dye mixtures
Aug.7, (2003) 17.
[13] R. Wald, M. Gisler, Fiber-reactive mono-azo-dyes, US Patent 2004/0127693 (Cl. C09B 62/347), Jul.1, (2004) 14.
[14] A. Tzikas, B. Müller, G. Roentgen, Fiber-reactive azo dyes, their preparation and their use, US Patent 7,087,730 B2 (Cl. C09B 62/507), Aug. 8, (2006) 24.
Received: June 02, 2011 / Accepted: October 14, 2011 / Published: February 25, 2012.
Abstract: The main aim of the paper was to obtain new reactive dyes with a minimum impact on the environment and on the human health. The synthesized reactive dyes are based on s-triazine reactive system, and they’re dyeing cotton in red, violet, and blue shades. The new dyes were analyzed by specific physico-chemical methods (e.g., thin layer chromatography, absorption spectroscopy in UV-VIS range, photocolorimetry) and then were applied on cotton. The coloristical performances of the studied dyes were analyzed by the well known standardized tests (dyeing intensity, light fastness, water fastness, acid perspiration fastness, wet and drying rubbing fastness). The results allow us to appreciate that the new dyes have physico-chemical and coloristical performances at the level of the actual marks marketed in the world.
Key words: Reactive dye, absorption spectroscopy, cotton dyeing, coloristical fastness.
1. Introduction??
Today the textile products market (fabrics, stockinet, ready-made clothes) has an unprecedented dynamic. Because of the increasing in standard of living the people around the world has the tendency to take up the“throw-away” fashion, wear once and change it. The fashion has become a gross business. From season to season the changes are very fast, being imposed by the changes in the unitary and mixture fashion hues and by the environmental legislation. In these conditions dyes manufacturers are required to adjust their range of products, in a fast and flexible way, to the consumers requirements regarding the color positions, the hues and models of the textile and ready-made clothes. The restrictions included in the environmental legislation have orientated the textile dyes market toward reactive dye class with lower ecological impact comparatively to direct, vat, acid or metal-complex dyes.
The reactive dyes class is special and unique due to its capacity to form covalent bonds with the cellulose and protein support. The result of the dyeing process is a colored macromolecule having high stability at wet treatments and good light fastness. A reactive dye corresponds to the general Eq. (1):
umido-heat fastness).
For analysis the dyes were purified in abs.ethanol. The purity of the studied dyes was checked by thin layer chromatography on silica gel, ascending techniques, in different eluents, such as: n-Buthyl-acetate: Py:water = 1:2:1 (vol/vol); Py: NH3 17%: n-AmOH = 1:1:1 (vol/vol).
The best separations of the position isomers having similar shades, were obtained using the second eluent. Performed chromatogram in the second eluent revealed that the synthesis products show a high degree of purity, the main spot is accompanied by spots of isomers products.
Dye concentration was determined by spectrophotometry analysis in the VIS range, a method of equalizing the intensity of coloration, considering purified dyes as standards. In this way, were actually determined the relative concentrations; relative concentration of the synthesized dyes, compared with the corresponding purified dyes are presented in Table 1.
The studied dyes are very soluble in water. Determination of the maximum absorption wavelength in UV-Vis range highlights the bathochrome effect, by changing the structure of diazotizing compound in reactive mono-azo dyes and in reactive disazo dyes. Table 1 presents the physico-chemical and coloristical
characteristics of the studied reactive dyes.
The coloristical performances of the studied dyes are excellent.
3.1 Structurally
A series of azoic reactive dyes, resulting from the same reactive specific coupling compound, and containing a monochlortriazine reactive system, was prepared. The structural modification of the diazotizing compound results in modification of the physico-chemical properties (solubility, absorption maximum wavelength values, chromatographical characteristics) and coloristical performances (dyeing intensity, light fastness, water fastness, acid perspiration fastness, wet and dry rubbing fastness). Therefore, by minor structural modifications in the diazotizing compound, are obtained significant chromatographical and spectral effects and coloristical effects on cotton from red to blue shades, as well.
3.2 Technologically
It has been found that at the coupling step is important to use a reactive specific coupling compound, containing a heterocyclic-aromatic reactive system. The preparation of this reactive coupling compound is indicated to take place by H acid acylation with a cyanuryl chloride previous monoacylated with an aromatic or heterocyclic amine. In these conditions takes place preferential the coupling reaction with a specific diazotizing compound, resulting a higher purity of the monochlortriazine reactive dyes, emphasized by chromatographical and spectral analysis.
4. Conclusions
There were synthesized, analyzed, and tested 6 new reactive dyes structures, having monochlortrizine as reactive system, based on four monofunctional reactive azo dyes, one monofunctional reactive disazo dye and one bifunctional reactive disazo dye, in red, violet and blue shades.
There were drown up ecological synthesis and dyeing technologies for the new reactive dyes; raw materials, intermediates and final products have reduced eco-toxicological risks.
The physico-chemical and coloristical performances of the resulted dyes are, on our knowledge, at the level of the actual marks marketed in the world.
[1] K. Othmer, Reactive Dyes, Encyclopedia of Chemical Technology, 4th ed., vol.8, 1993, pp. 380-390.
[2] I. Alexandrescu, R. Bidalah, M. Cernat, M. Dobrovat, A. Grigoriu, Theoretical and Practical Guidelines for Textiles Dyeing, CERTEX, Bucharest, 1994, pp. 113-120.
[3] J.A. Taylor, Recent developments in reactive dyes, Review of Progress in Coloration and Related Topics 30(1) (2000) 93-108.
[4] H. Tappe, W. Helmling, P. Mischke, K. Rebsamen, W. Russ, L. Schl?ffer, et al., Reactive Dyes, Ullmann’s Encyclopedia of Industrial Chemistry, 6th Edition, Wiley-VCH, 2002, www.wiley.com/WILEYCDA/ wileyTitle/productCD-3527303855.html.
[5] J. Danheim, Water-soluble red fiber-reactive dyes, processes for their preparation and their use, Ger Offen DE 19,611,636 (Cl. CO9B 62/085), Oct.2, (1997) 11.
[6] H. Loeffler, M. Patsch, Reactive disazo dyes, processes for their preparation and their use, Eur. Pat. Appl. EP 795,586 (Cl. C09B 67/22), Sept.17 (1997) 15.
[7] W. Byczynska, I. Gayewski, Manufacture of bireactive monoazo dyes containing s-triazine and vinylsulfone groups, Pol. PL 173,542 (Cl. C09B 29/24), Mar.31 (1998) 6.
[8] J. Danheim, K. Rebsamen, W.H. Russ, Water-soluble vinylsulfone fiber-ractive dyes, their preparation and their use, Eup. Pat. Appl. EP 905,200 (Cl. C09B 62/51), Mar..31, (1999) 15.
[9] P. Schebli, P. Aeschlimann, Dyeing and printing reactive dyes”, Eur. Pat. Appl. EP 922,735 (Cl. C09B 67/22), Jun.16 (1999) 41.
[10] R.P. Pedemeonte, W.H. Russ, J. Steckelberg, C. Schumacher, Dye mixtures comprising water-soluble fiber-reactive azo dyes, preparation thereof and use thereof, US Patent 6, 136, 045 (Cl. C09B 67/24), Oct.24, (2000) 9.
[11] W.H. Russ, B. Gr?bel, C. Schumacher, Dye mixtures
Aug.7, (2003) 17.
[13] R. Wald, M. Gisler, Fiber-reactive mono-azo-dyes, US Patent 2004/0127693 (Cl. C09B 62/347), Jul.1, (2004) 14.
[14] A. Tzikas, B. Müller, G. Roentgen, Fiber-reactive azo dyes, their preparation and their use, US Patent 7,087,730 B2 (Cl. C09B 62/507), Aug. 8, (2006) 24.