Abstract HORTON, AARON M. Novel Reactive Dyes Based on Pyrimidine

Abstract

HORTON, AARON M. Novel Reactive Dyes Based on Pyrimidine and Quinoxaline Systems. (Under the direction of Dr. Harold S. Freeman and Dr. David Hinks).

While reactive dyes have been the subject of much of the dye chemistry literature in the past 50 years, emphasis has moved from the search for new reactive systems and chromagens to novel dyes based on modifications to commercially successful technology. In this regard, researchers at North Carolina State University examined the Teegafix dyes developed using linking groups such as cysteamine to convert commercial dichlorotriazine

(DCT) dyes to bis-DCT and bis-MCT dyes and found that these dyes have higher dye-fiber affinity that the corresponding commercial precursors. This work was subsequently extended to heterobifunctional MCT/VS systems using DCT commercial dyes as the starting point. However, it remained to be determined whether the properties of other reactive systems could be enhanced using the Teegafix dye approach.

With this in mind, the present study pertains to the synthesis and evaluation of novel reactive dyes based on commercial pyrimidine and quinoxaline reactive systems. The synthesis of the target dyes involved a 2-step modification starting with either dichloroquinoxaline (DCQ) or chlorodifluoropyrimidine (DFP) type reactive dyes, using cysteamine to produce intermediate products which were subsequently reacted with chlorotrifluoropyrimidine to produce the target dyes. The target dyes are bis-DFP (yellow and blue) and a heterobifunctional DFP/MFP (red) type dyes. SO3Na SO3Na N S

O NH2 H N SO3Na NH N N S N N O HN NaO3S

O NaOOC HN F H N N N N 2

N NaOOC O Commercial Yellow O COONa N

N N N HN F NH N N F N F Cl SO3Na O Cl Cl N S N Cl NaO S N 3 H HN S N

Two step modification of a commercial yellow dichloroquinoxaline reactive dye.

HO3SOH2CH2CO2S NaO3S N N

N NH2 O HN N F H

N N Cl

NH2 S

NaO3S SO3Na HO3SOH2CH2CO2S NaO3S Commercial Blue N N

N NH2 O HN N S F F H

N N Cl NH2

HN NaO3S SO3Na S

SO3Na SO2CH2CH2OSO3H N N

S N NH O NH2 N H

Cl N N

F NH

NaO3S SO3Na

Cl F

Two step modification of a commercial blue chlorodifluoropyrimidine reactive dye. NaO3S O

NaO3S O F O HN

N H2N N N S O HN

N F N SO3Na H N N

Cl Commercial Red H2N S N SO3Na H

O SO3Na Cl

H N F NH O S

N N N N N

NaO3S N S H

HN N F

N Cl F

Two step modification of a commercial red chlorodifluoropyrimidine reactive dye.

In this study, the affinity of the modified dyes has been assessed using equilibrium exhaustion studies. Studies conducted on both commercial and target dyes at two temperatures and four salt concentrations indicated that the target dyes had greater affinity on cotton than the corresponding commercial dyes. Laboratory scale dyeings were conducted under various conditions, and the results indicated that optimum conditions of target dyes involved padding the fabric and batching under constant rotation at 60°C.

Fastness testing was conducted on fabrics dyed under optimum conditions, where upon results showed that the modification process did not adversely affect the fastness properties.

Novel Reactive Dyes Based on Pyrimidine and Quinoxaline Systems

by Aaron Michael Horton

A thesis submitted to the Graduate Facility of North Carolina State University in partial fulfillment of the requirements for the Degree of Master of Science

Textile Chemistry

Raleigh, North Carolina

2009

APPROVED BY:

______Dr. Harold S. Freeman Dr. David Hinks Chair Advisory Committee Co-Chair Advisory Committee

______Dr. Jeffrey Thompson Dr. Malgorzata Szymczyk Member Advisory Committee Member Advisory Committee

Dedication

I would like to dedicate this work to my wife, Allyson Horton, with her beside me it is possible for me to succeed in everything I attempt. I would also like to dedicate this to my late grandmother, Elvee Wasson Horton, who always believed that I had the potential to achieve any goal I set for myself.

Biography

Aaron Michael Horton was born on May 15, 1984, to Lee and Barbara Horton. He has two older brothers, Tim and Chris. He graduated in 2002 from Wake Forest-Rolesville

High School in Wake Forest, North Carolina. Aaron graduated Cum Laude with a American

Chemical Society certified Bachelor of Science degree in Polymer and Color Chemistry in

2006 from North Carolina State University. He then returned to North Carolina State

University to pursue a Master of Science degree in Textile Chemistry in the fall of 2006. On,

July 26, 2008 he married his high school love, Allyson Horton of Wake Forest, North

Carolina. He currently resides in Raleigh, NC.

iii

Acknowledgments

I would like to thank Dr. Harold S. Freeman for his direction and patience throughout this work. A special thank you to Dr. Malgorzata Szymczyk for her direction and help in dye synthesis. Also thank you to Mr. Jeffery Krauss and Ms. Judy Elson for their knowledge and expertise in laboratory dye procedures. I would also like to thank Dr. Lina Cardenas, Ms.

Rebecca Klossner, and Ms. Reid Clonts for their friendship and support during this work.

I would like to thank my friends and family for the love and support they showed throughout this experience. A special thank you to my parents, Lee and Barb Horton, and my in-laws, Mike and Ginger Greene, for their encouragement and advice. Lastly and most importantly, I would like to thank my wife, Allyson, for pushing me to finish and supporting me throughout this work. Without her this work would not have been possible.

Table of Contents

List of Figures...... x List of Tables ...... xiv 1 Introduction ...... 1 2 Literature Review ...... 2

2.1 Cellulose ...... 2

2.1.1 Cellulose Structure ...... 2

2.1.2 Affinities/Effects of Liquids ...... 5

2.1.2.1 Water ...... 5

2.1.2.2 Organic Liquids ...... 5

2.1.2.3 Aqueous Alkali ...... 6

2.1.3 Degradation of Cellulose ...... 6

2.1.3.1 Acidic Degradation ...... 6

2.1.3.2 Alkaline Degradation ...... 7

2.1.3.3 Oxidative Degradation ...... 7

2.1.3.4 Thermal Degradation ...... 8

2.1.3.5 Enzymatic Degradation ...... 9

2.2 Analytical Methods ...... 9

2.2.1 Chromatography ...... 9

2.2.1.1 Liquid Chromatography ...... 10

2.2.1.2 High Performance Liquid Chromatography ...... 12

2.2.1.3 Thin Layer Chromatography ...... 16

2.2.2 Mass Spectrometry ...... 16

2.2.2.1 Gas-phase Methods ...... 17

2.2.2.2 Desorption Methods ...... 18

2.2.3 Ultraviolet and Visible Spectroscopy ...... 19

2.3 Dyes for Cotton ...... 21

2.3.1 Covalent Bond Formation ...... 21

2.3.2 Reactive Dye Structure ...... 22

2.3.2.1 Chromagen ...... 23

2.3.2.2 Solubilizing Group ...... 25

2.3.2.3 Bridging Groups ...... 26

2.3.2.4 Reactive Group ...... 26

2.3.2.4.1 Nucleophilic Substitution ...... 27

2.3.2.4.1.1 S-Triazine System ...... 28

2.3.2.4.1.2 Pyrimidine System ...... 29

2.3.2.4.1.3 Quinoxaline System ...... 30

2.3.2.4.2 Nucleophilic Addition ...... 31

2.3.2.4.2.1 β-Substituted Ethyl Sulfone/Vinyl Sulfone ...... 31

2.3.2.4.3 Leaving Group ...... 32

2.3.2.4.3.1 Chlorine ...... 32

2.3.2.4.3.2 Fluorine ...... 33

2.3.2.4.3.3 Quaternary Amine ...... 33

2.3.3 Functionality ...... 34

2.3.3.1 Monofunctional ...... 34

2.3.3.2 Homobifunctional ...... 34

2.3.3.3 Heterobifunctional ...... 35

2.3.3.4 Polyfunctional ...... 35

2.3.4 Key Reactions ...... 36

2.3.4.1 Dye-Fiber Bond Formation ...... 36

2.3.4.2 Hydrolysis ...... 36

2.4 Project Proposal ...... 37

3 Experimental ...... 42

3.1 General ...... 42

3.2 Syntheses ...... 43

3.2.1 Dye Intermediates ...... 43

3.2.1.1 Temperature and pH Study ...... 43

3.2.1.1.1 Intermediate 4 ...... 43

3.2.1.1.2 Intermediate 5 ...... 43

3.2.1.1.3 Intermediate 6 ...... 44

3.2.1.2 Cysteamine:Dye Ratio Study ...... 44

3.2.1.2.1 Red Intermediate 10 ...... 44

3.2.1.2.2 Intermediate 5 ...... 45

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3.2.1.2.3 Intermdiate 6 ...... 45

3.2.2 Target Dyes ...... 46

3.2.2.1 Modified Red Dye (11) ...... 46

3.2.2.2 Modified Yellow Dye (8) ...... 46

3.2.2.3 Modified Blue Dye (9) ...... 46

3.3 HPLC Analysis ...... 46

3.4 Mass Spectrometric Analysis ...... 47

3.5 Equilibrium Exhaustion Study ...... 48

3.5.1 Sample Preparation ...... 49

3.5.2 Dyebath Analysis ...... 49

3.6 Laboratory Dyeings ...... 50

3.6.1 Washing Procedure ...... 50

3.6.2 Exhaust Dyeing ...... 51

3.6.2.1 Liquor Ratio 40:1 ...... 51

3.6.2.2 Liquor Ratio 10:1 ...... 52

3.6.2.3 Liquor Ratio 20:1 ...... 52

3.6.3 Pad Batch Dyeing ...... 53

3.6.4 Pad Steam Dyeing ...... 53

3.7 K/S and L*a*b* Analysis ...... 54

3.8 Fastness Testing ...... 54

3.8.1 Colorfastness to Laundering (Accelerated Test) ...... 54

3.8.2 Colorfastness to Crocking ...... 54

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3.9 Calculations ...... 55

3.9.1 Exhaustion of Equilibrium Exhaustion ...... 55

3.9.2 Substantivity Ratio (K’) ...... 55

3.9.3 Standard Affinity (-Δμ) ...... 55

3.9.4 Heat of Dyeing (-ΔH) ...... 56

4 Results and Discussion ...... 57

4.1 Commercial Dyes ...... 57

4.2 Synthesis of Reaction Intermediates ...... 59

4.2.1 Effects of pH and Temperature ...... 59

4.2.2 Effects of Cysteamine:Dye Ratio ...... 70

4.3 Dye Synthesis ...... 78

4.4 Equilibrium Exhaustion ...... 85

4.4.1 Absorption Spectra ...... 85

4.4.2 Exhaustion Values ...... 88

4.4.3 Substantivity Ratio ...... 98

4.4.4 Affinity (-Δμ) ...... 101

4.4.5 Heats of Dyeing, ΔH ...... 108

4.5 Laboratory Dyeings ...... 110

4.5.1 Exhaust Dyeings ...... 111

4.5.2 Pad-Batch Dyeing ...... 111

4.5.3 Pad-Steam Dyeing ...... 112

4.6 L*a*b* and K/S Values ...... 112

4.6.1 Equilibrium Exhaustion ...... 113

4.6.2 Laboratory Dyeings ...... 113

4.7 Fastness Testing ...... 114

4.7.1 Fastness to Laundering (Accelerated) ...... 114

4.7.2 Fastness to Crocking ...... 115

5 Conclusions ...... 116 6 References ...... 117 Appendix ...... 118

List of Figures

Figure 2.1. Cellulose polymeric structure showing AGP unit, cellobiose unit, reducing end group and non-reducing end group...... 3

Figure 2.2. Perhydroxyl ion formation under basic conditions...... 8

Figure 2.3. Electrospray mass spectrometer apparatus [18]...... 19

Figure 2.4. Jablonski diagram showing electron excitation pathways...... 20

Figure 2.5. Structures of pyrimidine, quinoxaline, and pyridine, from left to right...... 22

Figure 2.6. Reactive Red 1 showing dye features of reactive dyes...... 23

Figure 2.7. Chromophoric systems utilized in reactive dyes...... 25

Figure 2.8. Nucleophilic substitution on the triazine system...... 27

Figure 2.9. Fixation and hydrolysis reactions of dichlorotriazine dyes...... 29

Figure 2.10. Reaction of tetrachloropyrimidine resulting in an isomeric mixture...... 30

Figure 2.11. Reaction of chlorocarbonyl to produce dichloroquinoxaline dye...... 31

Figure 2.12. Reversible masking and fixation reactions of sulfatoethylsulfone...... 32

Figure 2.13. Proposed scheme for Reactive Red 123 modification...... 39

Figure 2.14. Proposed scheme for Reactive Yellow 25 modification...... 40

Figure 2.15. Proposed scheme for Reactive Blue 225 modification...... 41

Figure 4.1. HPLC results of Reactive Red 123 (1)...... 57

Figure 4.2. HPLC results of Reactive Yellow 25 (2)...... 58

Figure 4.3. HPLC results of Reactive Blue 225 (3)...... 58

Figure 4.4. Monosubstituted product between Reactive Red 123 and cysteamine...... 59

Figure 4.5. HPLC results from combining Reactive Red 123 and cysteamine at pH 4 and 50°C...... 60

Figure 4.6. HPLC results from combining Reactive Red 123 and cysteamine at pH 5 and 50°C...... 61

Figure 4.7. HPLC results from combining Reactive Red 123 and cysteamine at pH 6 and 50°C...... 61

Figure 4.8. HPLC results from combining Reactive Red 123 and cysteamine at pH 7 and 50°C...... 62

Figure 4.9. Monosubstituted intermedaite of Reactive Yellow 25...... 63

Figure 4.10. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 4 and 50°C...... 63

Figure 4.11. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 5 and 50°C...... 64

Figure 4.12. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 6 and 50°C...... 64

Figure 4.13. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 7 and 50°C...... 65

Figure 4.14. HPLC results from combining Reactive Blue 225 and cysteamine at pH 4 and 50°C...... 66

Figure 4.15. HPLC results from combining Reactive Blue 225 and cysteamine at pH 5 and 50°C...... 66

Figure 4.16. HPLC results from combining Reactive Blue 225 and cysteamine at pH 6 and 50°C...... 67

Figure 4.17. HPLC results from combining Reactive Blue 225 and cysteamine at pH 7 and 50°C...... 67

Figure 4.18. HPLC results from the cysteamine and Reactive Yellow 25 reaction, pH 7, initially at 20°C and then raised to 50°C...... 69

Figure 4.19. HPLC results from the cysteamine and Reactive Blue 225 reaction, pH 7, initially at 20°C and then raised to 50°C...... 69

Figure 4.20. HPLC results from reaction involving a 1:1 cysteamine:dye 1 ratio at pH 5 and 50°C...... 71

Figure 4.21. HPLC results from reaction involving a 2:1 cyteamine:dye 1 ratio at pH 5 and 50°C...... 71

Figure 4.22. HPLC results from reaction involving 1:1 cysteamine:dye 1 ratio at pH 7 and 50°C...... 72

Figure 4.23. HPLC results from reaction involving 2:1 cysteamine:dye 1 ratio at pH 7 and 50°C...... 72

Figure 4.24. HPLC results from reaction involving 1:1 cysteamine:dye 2 ratio at pH 5 and 50°C...... 73

xii

Figure 4.25. HPLC results from reaction involving 2:1 cysteamine:dye 2 ratio at pH 5 and 50°C...... 74

Figure 4.26. HPLC results from reaction involving 1:1 cysteamine:dye 2 ratio at pH 7 and 50°C...... 74

Figure 4.27. HPLC results from reaction involving 2:1 cysteamine:dye 2 ratio at pH 7 and 50°C...... 75

Figure 4.28. HPLC results from reaction involving 1:1 cysteamine:dye 3 ratio at pH 5 and 50°C...... 76

Figure 4.29. HPLC results from reaction involving 2:1 cysteamine:dye 3 ratio at pH 5 and 50°C...... 76

Figure 4.30. HPLC results from reaction involving 1:1 cysteamine:dye 3 ratio at pH 7 and 50°C...... 77

Figure 4.31. HPLC results from reaction involving 2:1 cysteamine:dye 3 ratio at pH 7 and 50°C...... 77

Figure 4.32. HPLC results of optimized Reactive Red 123 percursor (10)...... 78

Figure 4.33. HPLC results of optimized Reactive Yellow 25 precursor (5)...... 79

Figure 4.34. HPLC results of optimized Reactive Blue 225 precursor (6)...... 79

Figure 4.35. Positive ion ESI mass spectra of Red Intermediate 10...... 81

Figure 4.36. Negative ion ESI mass spectra of Red Final Dye 11...... 81

Figure 4.37. Positive ion ESI mass spectra of Yellow Intermediate 5...... 82

Figure 4.38. Negative ion ESI mass spectra of Yellow Final Dye 8...... 82

Figure 4.39. Pyrimidine Modified Red 123 structure...... 83

Figure 4.40 HPLC results from Pyrmidine Modified Reactive Red 123 dye 11...... 83

Figure 4.41 HPLC results from Pyrimidine Modified Reactive Yellow 25 dye 8...... 84

Figure 4.42 HPLC results from Pyrimidine Modified Reactive Blue 225 dye 9...... 84

Figure 4.43. UV/Visible spectrum of Reactive Red 123 (1)...... 86

Figure 4.44. UV/Visible spectrum of Reactive Yellow 25 (2)...... 86

Figure 4.45. UV/Visible spectrum of Reactive Blue 225 (3)...... 87

Figure 4.46. UV/Visible spectrum of Pyrimidine Modified Reactive Red 123 (11)...... 87

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Figure 4.47. UV/Visible spectrum of Pyrimidine Modified Reactive Yellow 25 (8)...... 88

Figure 4.48. Calibration curve for Reactive Red 123 at 504 nm...... 89

Figure 4.49. Calibration curve for Reactive Yellow 25 at 419 nm...... 90

Figure 4.50. Calibration curve for Reactive Blue 225 at 603 nm...... 90

Figure 4.51. Calibration curve for Pyrimidine Modified Red 123 at 505 nm...... 91

Figure 4.52. Calibration curve for Pyrimidine Modified Yellow 25 at 376 nm...... 91

Figure 4.53. Calibration curve for Pyrimidine Modified Blue 225 at 598 nm...... 92

Figure 4.54. Equilibrium exhaustion values for Reactive Red 123 (1) at 0.5-2.0% dyebath concentrations...... 93

Figure 4.55. Equilibrium exhaustion values for Reactive Yellow 25 (2) at 0.5-2.0% dyebath concentrations...... 94

Figure 4.56. Equilibrium exhaustion values for Reactive Blue 225 (3) at 0.5-2.0% dyebath concentrations...... 95

Figure 4.57. Equilibrium exhaustion values for Pyrimidine Modified Red 123 (11) at 0.5-2.0% dyebath concentrations...... 96

Figure 4.58. Equilibrium exhaustion values for Pyrimidine Modified Yellow 25 (8) at 0.5-2.0% dyebath concentrations...... 97

Figure 4.59. Equilibrium exhaustion values for Pyrimidine Modified Blue 225 (9) at 0.5-2.0% dyebath concentrations...... 98

Figure 4.60. Calculated affinities for Reactive Red 123 (1) at 0.5-2.0% owf...... 103

Figure 4.61. Calculated affinities for Reactive Yellow 25 (2) at 0.5-2.0% owf...... 104

Figure 4.62. Calculated affinitiesfor Reactive Blue 225 (3) at 0.5-2.0% owf...... 105

Figure 4.63. Calculated affinities for Pyrimidine Modified Red123 (11) at 0.5-2.0% owf. ... 106

Figure 4.64. Calculated affinities for Pyrimidine Modified Yellow 25 (8) at 0.5-2.0% owf. .. 107

Figure 4.65. Calculated affinities for Pyrimidine Modifed Blue 225 (9) at 0.5-2.0% owf. .... 108

xiv

List of Tables

Table 3.1. Gradient elution component composition for HPLC analysis...... 47

Table 3.2. Aliquot and dilution volumes based on dyebath concentration...... 49

Table 3.3. Washing procedure used in this study...... 50

Table 3.4. Ahiba® Texomat program procedure employed...... 51

Table 3.5. Ahiba Nuance program procedure employed...... 52

Table 4.1. Optimum conditions for synthesizing dye precursors (5, 6, and 10)...... 78

Table 4.2. Absorption maxima dyes prepared in this study...... 85

Table 4.3.Calculated K' values for Reactive Red 123 (1) at 0-70 g/L salt...... 100

Table 4.4. Calculated K' values for Reactive Yellow 25 (2) at 0-70 g/L salt...... 100

Table 4.5. Calculated K' values for Reactive Blue 225 (3) at 0-70 g/L salt...... 100

Table 4.6. Calculated K' values for Pyrimidine Modified Red 123 (11) at 0-70 g/L salt...... 100

Table 4.7. Calculated K' values for Pyrimidine Modified Yellow 25 (8) at 0-70 g/L salt...... 101

Table 4.8. Calculated K' values for Pyrimidine Modified Blue 225 (9) at 0-70 g/L salt...... 101

Table 4.9. Heats of Dyeing, ΔH (kJ/mol), results for Reactive Red 123 (1) at varying salt levels...... 109

Table 4.10. Heats of dyeing, ΔH (kJ/mol), results for Reactive Yellow 25 (2) at varying salt levels...... 109

Table 4.11. Heats of dyeing, ΔH (kJ/mol), results for Reactive Blue 225 (3) at varying salt levels...... 109

Table 4.12. Heats of dyeing, ΔH (kJ/mol), results for Pyrimidine Modified Red 123 (11) at varying salt levels...... 110

Table 4.13. Heats of dyeing, ΔH (kJ/mol), results for Pyrimidine Modified Yellow 25 (8) at varying salt levels...... 110

Table 4.14. Heats of dyeing, ΔH (kJ/mol), results for Pyrimidine Modified Blue 225 (9) at varying salt levels...... 110

1 Introduction

Since the determination that direct dyes could be applied to cotton without the use of a mordanting agent, more classes of synthetic dyes have been developed for use on cotton than for any other fiber type. The driving force behind this effort was the desire for dyed cotton fabric having high resistance to color loss in consumer laundering cycles. As a consequence, vat, sulfur, azoic, and reactive dyes followed the invention of direct dyes.

These dye families were each intended to overcome the propensity for cotton fibers to swell in water and lose color via desorption from the pore structure.

This section provides an overview of the nature of cotton fibers and fiber reactive dyes, the latter being the most widely used colorants for cotton based leisure wear. Also, presented is a summary of widely used analytical methods for characterizing synthetics dyes.

2 Literature Review

2.1 Cellulose

The most abundant naturally occurring polymer found in every land based plant across the globe, is cellulose [1-3]. However, with all available sources of cellulose, very few sources form fibers that the textile industry can utilize. Cotton, jute, flax, linen, and ramie are all used by textile manufacturers with cotton as the dominating fiber source for the apparel industry [2, 3]. The reason for cellulose dominance is attributed to ease of processing and wide abundance of cotton fibers. Structural derivatives of cellulose are created by dissolving the cellulose in particular solvents, sodium hydroxide or ammonia, and then regenerating the cellulose from solution. Cellulose, one of the most simple and unique polysaccharides, is readily described on the single polymeric chain, supramolecular and morphological structural levels [1].

2.1.1 Cellulose Structure

The single polymeric chain is the smallest structural level with which to describe cellulose. Cellulose is a linear syndiotactic homopolymer comprised of D- anhydroglucopyranose (AGP) units [1]. The 1, 4-β-glycosidic linkage of two AGP units gives rise to the dimer, cellobiose. Cellobiose units are also linked by the 1, 4-β-glycosidic bond linkage to form the polymeric structure of cellulose (Figure 2.1). Each AGP unit in a cellulose polymer chain contains two secondary hydroxyl groups and one primary hydroxyl group.

These groups, alcoholic in nature, react in the same manner as simple alcohols would under the same conditions [4]. Each end of the cellulose polymer chain exhibits different behavior due to the nature of glycosidic linkages. The AGP unit that contains the free C-1 hydroxyl

2 group adjacent to the ring oxygen is the reducing end of the polymer chain. The reducing end of the polymer chain exhibits properties of both an alcohol and an aldehyde under the appropriate conditions [2, 3]. The unit containing the free C-4 hydroxyl group does not undergo the same reduction reaction due to the presence of a third secondary hydroxyl group that normally reacts to make the glycosidic linkage.

Cellulose is a naturally occurring polymer in which the degree of polymerization (DP) is determined by the number of AGP units connected to one another to form the polymer chain. Figure 2.1 shows the DP of the polymer chain to be n-units and the bracketed number of units, n-3, allows the bonding structure of a single chain of AGP units to be shown. The DP of natural cellulose is dependent on the source from which is obtained and may be as high as 14,000, but is reduced to 1,000-2,000 during purification treatment involving alkali [2, 3]. Chemically regenerated forms of cellulose have much lower DPs and the differences between the natural and regenerated forms of cellulose are in the supramolecular structure of the polymer.

Cellobiose Unit

OH OH OH 3 OH O OH HO HO O 5 1 O H HO HO O 2 HO O O OH 4 OH OH O OH n-3

Non-reducing end group Anhydroglucose Unit Reducing end group

Figure 2.1. Cellulose polymeric structure showing AGP unit, cellobiose unit, reducing end group and non-reducing end group.

The supramolecular structure of cellulose is the aggregation of polymer chains through hydrogen bonding due to macromolecule conformation and chemical constitution to create ordered structures [1]. Cellulose is a highly crystalline material, but the crystal structure does not mirror that of its monomer units (glucose) which forms discrete crystals

[2, 3]. The order of chain aggregation is not constant over each set of chains resulting in regions of high order (crystalline) and of low order (amorphous). The pattern of aggregation determines the type of cellulose that is formed and is dependent upon the source from which it was obtained, naturally occurring or regenerated from a solution. The two crystal structures important in textile processing are cellulose I and cellulose II coming from native and regenerated sources, respectively [2, 3]. Cellulose I can be further broken down into α and β states. The α state is obtained from bacteria and valonia algae and is metastable. The metastable α-cellulose can be annealed into the thermodynamically more stable β state, which is naturally occurring wood or cotton cellulose [1]. Cellulose II is the creation of regenerated cellulose fibers by precipitating dissolved cellulose from a sodium hydroxide solution into an aqueous medium near room temperature. Large-scale mercerization of cotton fibers is another way to produce cellulose II on the commercial scale [1].

The final way to describe cellulose is through its morphological structure, which is a well organized architecture of fibrils [1]. Microfibrils, the lowest well defined morphological unit, aggregate together to form macrofibrils. Both micro and macrofibrils are involved in the production of cell walls in cellulose fiber formations with differing positions, densities, and textures determined by the source. The cell walls of cotton fibers are layers of cellulose that alternate in their direction of orientation.

2.1.2 Affinities/Effects of Liquids

2.1.2.1 Water

Cellulose has a very hydrophilic character due to the large number of hydroxyl groups in the polymer chain. Cellulose is not soluble in water due to the size of the polymeric chains and their interactions as a result of crystallinity. There is a competition of hydrogen bond formation between polymer chains and water molecules [1]. Hydrogen bonding between water and cellulose occurs more readily in the amorphous regions of cellulose due to the greater mobility of the chains. However, it is also not possible to completely remove water from cellulose because it readily adsorbs water vapor found in the atmosphere that is proportional to the relative humidity and temperature [1-3]. Immersion in water causes a greater retention of water than adsorption through atmospheric humidity.

Cellulose swells as an effect of water molecules on the polymer chains and swelling can be readily reversed by drying the cellulose sample [1].

2.1.2.2 Organic Liquids

Specific literature pertaining to the affinity of organic liquids for cellulose is minimal when compared to studies involving water. The effects of an organic liquid on cellulose are dependent on the liquid involved as well as the structure of the cellulose involved [1]. Liquids capable of forming hydrogen bonds interact to a greater extent than liquids that do not.

Organic liquids, other than aliphatic amines, interact with cellulose to a lesser degree than water [1-3]. Small alcohol molecules capable of hydrogen bonding, methanol and ethanol, swell cellulose to slight degree. Non-polar inclusion compounds of cellulose can be produced by slow sequential replacement swelling liquids, which decrease in polarity, under

5 vacuum [2, 3]. This process creates an inclusion of non-polar liquid inside the cellulose when returned to atmospheric conditions in the absence of more polar liquids.

2.1.2.3 Aqueous Alkali

The submersion of cellulosic materials (e.g. cotton) in solutions of aqueous alkali is a process known as mercerization. Cotton fibers swell depending on the concentration of alkali, temperature and the source of the cellulose [2, 3]. Cotton fibers contain surface convolutions caused by the collapse of the lumen after harvesting. Aqueous alkali swells the cotton by filling the lumen resulting in a more uniform fiber surface. Alkali ions disrupt the hydrogen bonding between polymer chains and allow diffusion of water molecules deep into the structure and creating alkali cellulose [1]. The physical features of mercerized cotton are different from that of natural cotton.

2.1.3 Degradation of Cellulose

A feature of industrial importance is the chemical stability of the cellulosic fibers under a variety of conditions as a product of multiple processing methods. The slightest degradation of cellulose during fiber processing can cause a loss in strength and other properties and make the resulting fiber unsuitable for processing [2, 3]. There are five agents commonly used in textile processing that can cause degradation of cellulose: acid, alkali, oxidation, heat, and enzyme [1-3].

2.1.3.1 Acidic Degradation

The degradation of cellulose by aqueous acid involves the hydrolysis of glycosidic linkages, causing a decrease in the degree of polymerization and fiber strength [2, 3]. Acid hydrolysis follows first order rate laws in which an increase in acid concentration causes an

6 increased rate of cellulosic degradation [1]. Acidic strength also affects the hydrolysis of cellulosic samples [5]. The first areas of degradation of cellulose are the amorphous regions of the polymer because of the accessibility of polar liquids to this region. DP is not an accurate reflection of the extent of hydrolysis due to the plateau effect achieved after all the amorphous regions are hydrolyzed. Hydrolysis can occur in the crystalline regions, but only at chain ends due to the reduced access of the aqueous acid to the glycosidic linkages. A solution of acid in an aprotic solvent increases the rate of hydrolysis. There is water present in cellulose due to adsorption of moisture in the atmosphere. Acid molecules diffuse into cellulose when placed in the aprotic solvent solution creating a concentrated acid solution in direct contact with the polymer chains [2].

2.1.3.2 Alkaline Degradation

The treatment of cellulosic fibers with alkali solution is a textile scouring treatment to remove the hydrophobic materials (fats, oils, and waxes) from the substrate. Cellulose is not readily degraded by alkali. On the contrary, it is stable to aqueous alkali solutions of high concentration below the boil in the absence of oxygen. Temperatures greater than 140°C in the presence of alkali cause a stepwise removal of AGP units from the reducing end of the polymer chain [2]. At temperatures above 150°C a solution of alkali will cause the random cleavage of the glycosidic bonds throughout the polymer chain [3]. However, this must be done at pressures greater than atmospheric and in closed vessels so evaporation due to boiling does not occur.

2.1.3.3 Oxidative Degradation

Cellulose contains four oxygen molecules on each ring (two secondary hydroxyl groups, one primary hydroxyl group, and ring oxygen) and an oxygen in the form of a

7 glycosidic linkage between rings. This abundance of oxygen makes the number of possible oxidation products numerous and there in no single mechanism for the oxidative degradation of cellulose. Two oxidizing agents are utilized in the textile industry to remove natural color bodies from cotton fibers, sodium hypochlorite (NaOCl) and hydrogen peroxide

(H2O2). Hypochlorite bleaching utilizes NaOCl under alkaline conditions to oxidize natural color bodies and remove motes from the substrate and it also causes “yellowing” of the fiber. The use of chlorine as an oxidizing agent produces absorbable organic halogen (AOX) by-products [5-7]. Peroxide bleaching utilizes hydrogen peroxide (H2O2) in alkaline solution to produce perhydroxyl ions (Figure 2.2) as the active bleaching agent. The produced ions then react with impurities. Transition metals, iron (Fe), manganese (Mn), and cobalt (Co) in particular, cause a spontaneous decomposition of the perhydroxyl ion and alkali earth metals, such as magnesium (Mg), are used as stabilizers of peroxide baths [2, 3]. A total oxidation of cellulose to CO2 and H2O is possible by use of K2Cr2O7/H2SO4 at elevated temperatures and is used to do titrimetric determinations [1].

OH OH O HO + H2O HO

Figure 2.2. Perhydroxyl ion formation under basic conditions.

2.1.3.4 Thermal Degradation

Cellulose has moderate thermal stability up to temperatures around 200°C. Above this temperature cellulose starts to decompose, with rapid decomposition occurring between

250 and 350°C [1]. There are two pathways of decomposition of cellulose that are dependent upon temperature. The first is the dehydration of cellulose between 200 and

280°C and the subsequent exothermic reaction creating char and gases. The second is the formation of tar, mainly in the form of laevoglucosan, at temperatures greater than 280°C [2,

3].

2.1.3.5 Enzymatic Degradation

Enzymatic degradation involves the hydrolytic cleavage of the glycosidic bonds present in cellulose molecules. Cellulase, the enzyme responsible for cellulose degradation, is a component mixture of multiple enzymes [5], including cellobiohydralase, endo- glucanase, and exo-glucanase [7, 8]. The enzymatic degradation is dependent on the crystallinity of cellulose because enzyme penetration of crystalline regions is slow. The reaction rate for enzymatic hydrolysis is decreased as the reaction continues due to the lack of accessible sites for reaction [6]. This leads to an incomplete hydrolysis method unless given an exorbitant amount of time.

2.2 Analytical Methods

2.2.1 Chromatography

Chromatography is a widely used method for the separation, identification, and determination of complex mixtures that contain components that are similar in polarity.

There are three general techniques, named after their mobile phase: gas chromatography

(GC), liquid chromatography (LC), and supercritical fluid chromatography (SFC) [9, 15].

Each type of chromatographic separation is based on the extent of interaction of solute molecules between the mobile and stationary phases [10]. GC and LC are chromatographic techniques better suited for dye separations, with LC being the more applicable technique because the sample does not have to be volatilized for separations to occur.

2.2.1.1 Liquid Chromatography

LC is the separation of compounds by the passing of a liquid mobile phase through a stationary phase, that can either be a liquid or solid. The first use of liquid chromatography was in 1906, when plant pigments were separated on calcium carbonate and using alcohol as the eluent [9-11]. The mobile phase in an LC method is always a liquid, but may be comprised of components that vary in polarity to make separation more effective. There are two categories of liquid chromatography, column and planar, that are based on the way the sample is introduced to the stationary phase and carried by the mobile phase [9]. In column chromatography, the stationary phase is placed in a narrow tube and the mobile phase flows through the stationary phase and carries solute molecules as it travels. The mobile phase may travel by capillary action cause by gravity or be forced through the stationary phase by pressure. Planar chromatography brings the mobile phase in contact with the stationary phase, which is supported by a backing, and moves the mobile phase (eluent) through the stationary phase using capillary action. Thin layer chromatography and paper chromatography are examples [9, 11]. Chromatographic separation is further divided by the mechanism of interaction between the solute and the stationary phase as the liquid phase moves, examples of which are partition, adsorption, ion-exchange, molecular exclusion, and affinity chromatography [11].

Partition chromatography, a liquid-liquid chromatography method, involves a bound liquid stationary phase and a liquid mobile phase. In liquid bonded phase columns the liquid inside the column is chemically supported by silica based solids and results in a stable, uniform, porous packed column [9, 11]. This chromatographic method involves dissolution of the sample between mobile and stationary phases causing the separation by varying

10 retention [10]. Partition chromatography can be broken into two types based on the nature of the stationary and mobile phases. Normal-phase partition chromatography uses a polar stationary phase, silica or alumina, through which a non-polar mobile phase is passed. The first eluted component is the least polar one in the mixture. Reversed-phase partition chromatography employs a non-polar stationary phase (C-18 or C-8 bonded silica) and a polar mobile phase (water/polar organic mixtures) [9, 12]. Reverse-phase chromatography accounts for 75% of partition separations conducted today [14].

Adsorption liquid chromatography involves a solid stationary phase and a liquid mobile phase; a liquid-solid chromatography method. The solute present in the mobile phase will adsorb onto the surface of the solid stationary phase and is retained for a period of time before being dislodged by the mobile phase and carried further along the stationary phase, retention. The greater the retention time, the more strongly adsorbed the solute is by the stationary phase [9, 11]. Adsorption chromatography and normal-phase partition chromatography overlap one another because normal-phase partitioning is governed by the adsorption-displacement process of adsorption chromatography [9].

Ion-exchange chromatography involves a stationary phase to which a cationic or anionic species is bonded (ion-exchange resins) and a polar liquid mobile phase to separate solute ions of opposite charge from the stationary phase [9, 11, 14]. The most common ions

- + used for ion-exchange are –SO3 (cationic exchange) and –N(CH3)3 (anionic exchange).

Solutes suitable for this separation method include inorganic ions, water soluble organic acids and bases, ionic chelates, and organometallic compounds [15]. The mobile phase used for separations consists of water and water soluble organic solvents [9]. The

11 separation is effected by the size and effective charge of the molecules present in the solute mixture [14].

Molecular exclusion chromatography is also known as gel filtration, gel permeation

[11], or size exclusion chromatography [9, 14]. This chromatographic method separates solute molecules by size which the largest solute molecules first to elute. The column consists of a stationary phase that is made up of particles that contain pores of a uniform size into which solute and solvent molecules can penetrate [14, 15]. The molecules of larger size than the pore diameter move down the column and are the first to elute with smaller molecules entering the stationary phase and traversing the pore network causing a greater retention time [9, 11-12]. This chromatographic method is different from all others because it does not depend on interactions between solute molecules and the stationary phase [9, 11].

Affinity chromatography is the most selective of the separation methods. It involves the interaction of a certain type of solute molecule with a covalently bound molecule on the stationary phase, producing a ‘lock and key’ model [14]. The mobile phase must be able to solubilize the solute and must also ensure that elution of all molecules, even those targeted for retention, is possible. To ensure elution, changes in pH or ionic strength of the mobile phase are used [9, 11]. This chromatographic method is useful for separations that involve biological species.

2.2.1.2 High Performance Liquid Chromatography

There are four main parts to a high performance liquid chromatography (HPLC) system: the source, sample, column, and detector [14]. HPLC sources use high pressure, achieved by a pump system, to force the mobile phase through a stationary phase. The

12 pressure used is in excess of 6000 psi producing flow rates that vary between 0.1 and 10.0 mL/min [9]. A separation with a constant mobile phase composition throughout the separation process is known as an isocratic elution. One that involves changes in mobile phase composition during the separation process is gradient elution and is achieved by use of a proportioning valve in conjunction with the pump system.

Sampling loops are the most widely used devices for introducing a sample into an

HPLC system without depressurizing the system and causing a dangerous pressure spike.

The size of the sampling loop can vary from 1 to 1000 µL [9, 11]. The loop is part of the injection valve, which when activated, causes the pressurized mobile phase to carry the sample into the system for analysis [11]. Autosamplers, a carousel/tray of sample vials combined with an automated needle, allow for precise and reproducible injection volumes

[14]. The mobile phase containing the solute passes through the column and into a detection device where that the solute is distinguished from the mobile phase.

There are many devices suitable for detection of analytes. The ideal detection device is sensitive to low concentrations of analyte, provides clean, sharp peaks, and is not sensitive to changes in temperature and solvent composition [11]. The latter is mainly of importance if gradient elution methods are employed. Spectrophotometric detectors use light absorption as the criteria of detection, whether it is ultraviolet (UV) or visible (VIS), as most organic compounds absorb energy in one of these two regions. A spectrophotometric system normally contains dual beams that have been split from the same source, a reference beam and a sample beam. In HPLC systems, a single beam system is utilized and equilibrated using the eluent before the sample is injected. The difference in absorption levels when the analyte is present provides a chromatogram [9]. Spectrophotometric

13 detectors can be used with either isocratic or gradient elution methods. Drawbacks of spectrophotometric detectors are that the mobile phase chosen should be as inactive as possible at the desired wavelength of detection [14] and the detector is concentration sensitive device, being based on the Beer-Lambert Law [15]. Refractive index (RI) detectors can detect almost all solutes regardless of flow rate. However, RI detectors are temperature sensitive and have poor detection limits when the analyte concentration is low

[11, 15]. An RI detector cannot be used with gradient elution methods because changes in the mobile phase composition cause the refractive index of the mobile phase to change and may mask the refractive index of the analyte. One of the newest detectors for HPLC systems is the evaporative light scattering (ELS) detector [9]. ELS detectors are useful for detection of analyte that is less volatile than the mobile phase used to elute it [11, 14]. The delivery system for ELS detectors consists of three parts: the nebulizer, drift tube, and light scattering cell [14]. The column effluent is prepared for detection by nebulization, the forcing of the liquid through a small hole by air or nitrogen gas to form uniform droplets. These droplets are then heated in the drift tube, evaporating the mobile phase and leaving analyte molecules to enter the light scattering cell. Upon entering the cell, the analyte molecules scatter a laser light and the intensity of the light is detected by a photodiode detector. ELS is a sensitive detection method and can be used with gradient elutions. The only disadvantage to ELS is that the mobile phase composition is limited to compounds that are readily volatilized and environmentally benign unless collected [9, 11].

Molecules that readily form ions in solution are among the most difficult to separate using HPLC techniques [12]. Ionizable substances present problems with respect to retention, plate efficiency, and peak symmetry [13]. Ion-pair chromatography allows

14 separation of strong acids and bases using a reverse-phase column, a buffering agent, and an organic counter ion [14]. Ion-pairing chromatography is more complicated than regular reverse-phase chromatography because of the associated mechanisms of separation: ion- pair formation and ion-exchange [16]. In the former, the counter ion form an uncharged ion pair with the solute ion and the resulting uncharged species is partitioned with the non-polar stationary phase. Alternately, counter ion is retained in the stationary phase and separation occurs when solute ions interact with the retained counter ions to create a reversible ion-pair complex [9]. In both cases the molecules with the greatest interaction between ion-pairs are the more strongly retained species and last eluted. Gradient elution is only possible with reverse-phase ion pair chromatography because it is difficult to maintain the stability of the stationary phase of a normal-phase column when the gradient changes [13]. Buffer systems are used to ensure the charge stability of the ions being eluted. The choice of buffer used in the system is chosen so the analyte is a charged molecule and the counter ion is of opposite charge [14]. Factors that affect ion pair chromatography are pH, counter ion type, counter ion concentration, electrolyte concentration, organic solvent, and to a smaller extent temperature [16].

Reactive dyes contain sulfonic acids groups which impart solubility to the molecule by creation of an anionic species when in aqueous solution. These negative ions are the reason ion-pair chromatography with a spectrophotometric detector is used when performing HPLC on reactive dyes. The counter ion employed for anionic solute ions is a bulky cationic quaternary ammonium compound; tetra butyl ammonium bromide (TBAB) is an example. The ion pair formed between the dye and the cationic organic compound is then eluted through the column.

2.2.1.3 Thin Layer Chromatography

Planar chromatography is a liquid-solid chromatographic method in which the mobile phase moves through the stationary phase by capillary action or with assistance from gravity or electric potential [9]. Thin layer chromatography (TLC) is normally conducted on silica gel, cellulose, alumina, or polyamide substrates backed with glass, aluminum, or polyester substrates [12, 17]. The polyester or aluminum backed sheets are used because they can be tailored to fit the specific application more easily than glass. A sample to be analyzed is placed 1 cm from the edge of the plate using a capillary tube and the solvent is allowed to evaporate. The samplet spot should have a small diameter and dilute samples are to be spotted multiple times with drying between applications to keep the effective diameter small

[9]. The plate is then placed into a closed vessel containing an eluent that develops the plate. The solute travels up the plate, with each component having the same travel time but different migration distances [17]. The separated components can then be visualized on the plate using ultraviolet light or by staining. 2D-TLC is the development of a plate using two solvent systems. The second solvent system is introduced perpendicular to the development of the first resulting in a greater separation between the components in the mixture [9]. TLC done on reactive dyes mainly involves the unreacted form of the dye because reactive dyes cannot be removed from the substrate without degradation of the dye [12].

2.2.2 Mass Spectrometry

Mass spectrometry (MS) is one of the most sensitive methods of molecular mass analysis based on the production of ions that are separated and analyzed according to their mass-to-charge (m/z) ratio [14, 15]. The charge of the produced species can either be positive or negative and is dependent on the nature of fragmentation. During the early

16 stages of MS development, the analytes needed to be sufficiently volatile to enter the gaseous phase and be introduced to the ionization source. Nowadays there are many different types of ionization that are suitable for analyzing non-volatile and thermally stable compounds. The ionization techniques can be divided into gas-phase and desorption methods.

2.2.2.1 Gas-phase Methods

Electron ionization (EI) is the oldest ionization method used in MS [15]. The sample is volatilized and subjected to bombardment by a 70 eV beam of electrons that cause the loss of electrons from the compound analyzed. EI is a hard ionization technique and the associated energy can cause a high degree of fragmentation which can obscure molecular ion detection [14, 15]. EI is restricted to the analysis of positive ions because negative ions cannot be formed with the loss of an electron [15]. Conventional EI cannot be used for polysulfonated dyes because of excessive fragmentation and inability to volatilize the sample [18].

Chemical ionization (CI) is less energetic than EI, but still causes a high degree of fragmentation of analyte molecules. The active ionization species is a more volatile small molecule, methane, which ionizes and then reacts with the sample molecules to form positively charged molecular ions [14, 15]. Negative ions can also be formed and are dependent on the mechanism by which the chemical reagent-ion source reacts with the analyte molecule.

2.2.2.2 Desorption Methods

Desorption ionization involves surface ionization of solids and liquids to form analyte molecules in the gaseous phase by rapid heating or sputtering by higher energy species

[14-15, 19]. These methods are considered to be“soft” techniques due to low levels of fragmentation of the molecular ion.

Fast atom bombardment (FAB) involves the introduction of the sample into a beam of high energy particles [15]. The analyte is placed into a solvent matrix, such as glycerol, and spread into a thin film on a metal surface [19]. The analyte/matrix is then placed in the beam of high energy particles and molecular desorption occurs. During detection analyte ions and matrix ions travel along the ion beam with matrix ions dominating the lower (higher

MW) end of spectrum [14].

Matrix-assisted laser desorption ionization (MALDI) is similar to FAB, with the ionization source being a laser instead of a beam of high energy particles [14-15, 19].

MALDI involves placing the analyte into a matrix of a benzoic acid derivative and then impacting the analyte/matrix with the photons produced by the laser to desorb the analyte as protonated species from the sample matrix [15]. This method is normally used for large molecules with a molecular mass greater than 10,000 Da [14].

Another widely used desorption technique is electrospray ionization (ESI). This is a field desorption (FD) technique into a bath gas, also known as nebulization [14-15, 19].

There are differing models [14, 19] used to explain how nebulization occurs in ESI, but in general it involves the formation of ionized uniform droplets by running a current through the tip of the nebulization needle to create a charge difference between the needle and the

18 counter electrode (Figure 2.3) [15]. The stream of analyte molecules is dependent on the charge difference. When the difference is too small, the droplets do not move across the gap. The solvent is evaporated in much the same way as in ELS nebulization. One advantage of ESI is its ability to analyze large multivalent molecules [14].

Figure 2.3. Electrospray mass spectrometer apparatus [18].

2.2.3 Ultraviolet and Visible Spectroscopy

Many molecules absorb in the ultraviolet (UV) and/or visible (VIS) regions of the electro-magnetic spectrum. The regions of the spectrum that correlate with UV and VIS radiation are 190-400 nm and 400-800 nm, respectively. Light absorption involving a molecule can be described by the Jablonski diagram (Figure 2.4). When a photon of light is

19 absorbed, electrons move from the ground state (S0) to an excited state of the same spin

(S1). In the excited state, the associated species can do one of several things to lose energy and return to the ground state. For instance, it can release energy in the form of heat by vibrating from one energy level in the excited state to a lower energy level in the same state, a process represented by internal conversion (IC). The excited molecule can also transfer to an energy level of opposite spin (T1), which is known as intersystem crossing (ISC).

Depending on which path the species takes, it can also emit energy in the form of radiation: fluorescence (emission from the excited singlet state to the ground state) or phosphorescence (emission from the triplet state to the ground state). UV/VIS spectroscopy is a base testing method for characterization of dye molecules, but additives like salt or urea may cause shifts in wavelength of maximum absorption of reactive dye solutions [20].

Figure 2.4. Jablonski diagram showing electron excitation pathways.

2.3 Dyes for Cotton

The process essential to any dyeing is the transition of the color from the dyebath to the substrate [25]. There are three ways in which a dye can be retained by a substrate: physical sorption, mechanical retention, and reaction with the fiber. Physical sorption of a dye to a substrate relies on the same intermolecular forces that promoted exhaustion from the dyebath. Dye classes that use physical sorption as a retention mechanism include direct dyes for cellulose. Mechanical retention is the formation of an insoluble pigmentary material out of previously soluble chemicals that diffused into the fiber. Vat, sulfur, and azoic combinations are examples of dye classes that use mechanical retention. The third retention method involves dyes forming a chemical bond with the fiber. Reactive dyes are the only dye class that forms a covalent bond with fibers, whether they are cellulosic or protein. Acid and basic dyes use ionic bond formation as the retention method. A reaction between the dye molecule and the fiber results in a colored derivative of the fiber. The solubility of the dye molecule is decreased exponentially after bond formation while polymer/fiber solubility is not affected.

2.3.1 Covalent Bond Formation

The first covalent bond formed between cellulose and a colorant involved a series of reactions that modified cellulose and ultimately colored the fiber [21]. The process was successful, but the degradation done to the fiber by harsh treatment methods kept the process from being commercially viable. In the years between the work done by Cross and

Bevan and the innovation of the first commercial reactive dyes, only two attempts to create dye-fiber bonds had occurred and led less than attractive results [28, 41]. By the 1950s, reactive dyes were the only dye class that had not been commercialized. Stephen and

Rattee, at ICI, and Hoechst introduced the first reactive dyes for wool in the early 1950s, s- triazine and vinylsulfone based reactive dyes, respectively [22-23, 36]. Rattee and Stephen conducted a series of experiments with dyes and cellulosic fibers under alkaline conditions and found that the addition of salt and mild alkaline pH increased substantivity and reduced hydrolysis for the dyes when applied at 20-40°C.

Reactive dyes were immediately attractive to dyers and chemists because they provided a new retention method and a full color range. The triazine heterocyclic system in the form of di- and monochlorotriazine were the earliest reactive dyes and were capitalized by ICI and Ciba. Other heterocyclic molecules with comparable reactivities including pyrimidine, quinoxaline, and pyridine systems (Figure 2.5) were also investigated by Bayer,

Sandoz, and Geigy [41]. Changes in the labile group attached to the reactive system led to new reactive systems that varied in properties from the initial dyes introduced by ICI.

Presently, the environmental impact of reactive dyes is of high concern because waste water treatment and environmental safety have come to the forefront. Novel dyes created are designed to increase exhaustion and fixation properties to reduce the amount of salt and dye in effluents.

N N N N

N Figure 2.5. Structures of pyrimidine, quinoxaline, and pyridine, from left to right.

2.3.2 Reactive Dye Structure

The molecular structure of a reactive dye cannot be described by a single defining factor, but by the summation of the parts of which it consists. A reactive dye has five major

22 parts: chromagen (C), solibilizing group (S), bridging group (B), reactive group (R), and leaving group (X), as illustrated in Figure 2.6.

Cl B X SO Na 3 N N R N OH HN N Cl N C

NaO3S SO3Na S

Figure 2.6. Reactive Red 1 showing dye features of reactive dyes.

The dyes created by the combination of these features react with cellulosic and protein fibers to produce covalently bound color bodies. Each group contributes to the physical properties of the dye molecule including color, size, substantivity, diffusion, fastness, and solubility [25]. Substantivity is defined as the attraction between a substrate and a dye under specified conditions where the dye is absorbed from a dyebath by the substrate [43]. This term is often used interchangeably with affinity, but should not be. Affinity is a quantitative expression of substantivity defining the difference in chemical potential of the unfixed dye in the fiber and the chemical potential of the dye in dyebath expressed in units of joules per mole.

2.3.2.1 Chromagen

The chromagen is the color producing part of any dye molecule. It is the combination of extended conjugation and one or more chromophores. Color production occurs because

23 photons of visible light excite lone pair or pi electrons from the ground state to the excited state. In the excited state, the electrons lose some energy due to heat and fall to lower excited states. The electron then returns to the ground state from which it was excited by emitting energy in the form of light or by various internal conversion processes. The light emitting process described above is known as fluorescence and occurs when the transition is of the same spin state.

The many types of chromagens in reactive dye design include azo, anthraquinone, phthalocyanine, triphenodioxazine and formazan systems (Figure 2.7). The first three are the main groups used in reactive dye systems with triphenodioxazine and formazan based dyes replacing the tinctorially weaker anthraquinone dyes [24]. Azo reactive dyes range from monoazo to trisazo, with a bathochromic shift accompanying the addition of each azo unit to the chromagen system. Azo reactive dye colors range from red to black, with predominance in the reds, yellows, and oranges for monoazo and blues, browns, and blacks for dis/trisazo. Anthraquinone itself is pale yellow in color, but the addition of electron- donating groups in the 1, 4, 5, or 8 positions leads to bathochromic shifts to the red and blue regions [22]. Copper phthalocyanine is important because it is the only chromagen that gives a turquoise color. Triphenodioxazine and formazan dyes as stated above have started to make a move into the market of reactive dyes by replacing anthraquinone dyes that give similar shades less economically [29, 38]. Bluish violet pigments of high tinctorial strength have been derived from the triphenodioxazine chromagen [22]. The chromagen contributes to the affinity of the dye to fiber because it impacts size and molecular shape as well as possible sites of attraction between the dye and substrate [29].

R R'' NH N

N N

R' O Formazan Anthraquinone

NH N

N N

N HN

Phthalocyanine

R O N N

N R' N O Azo Triphenodioxazine

Figure 2.7. Chromophoric systems utilized in reactive dyes.

2.3.2.2 Solubilizing Group

Reactive dyes are readily water soluble due to the presence of solubilizing groups present on the chromagen [24]. The most notable solubilizing group present in reactive dyes is the sulfonic acid group. Dye molecules lose solubility as the molecular weight is increased and so a greater number of solubilizing groups is required to make the dye soluble. Water solubility increases with the number of sulfonic acid groups on the dye molecule, but as water solubility increases substantivity for the fiber decreases. A balance must be achieved for optimum dyebath exhaustion. Another solubilizing group that imparts water solubility to a reactive dye is sulfonamide (-SO2NH2) group. Solubilizing groups are not generally present on disperse reactive dyes for polyamide fibers [33].

2.3.2.3 Bridging Groups

The bridging group is the group of atoms that connects the reactive group to the chromagen and it must be sufficiently stable under basic and/or acidic conditions [33]. In most cases bridging groups consist of N, O, or S linkages. The strength of the bridge is dependent on the bridge type, the dyeing conditions, and the substituents connected by the bridge. The most typical bridging group for reactive dyes contain N in either the amine or imine structure before reaction. The bridging group effects substantivity based on the composition of the two molecules it is used to bridge, chromagen and reactive group [33,

36]. Bridges containing both amino (-NH2) and mercapto (-SH) groups were investigated by

North Carolina State University [30-32].

2.3.2.4 Reactive Group

The part of the chemical structure that undergoes chemical reaction with a functional group present on the substrate to create a colored derivative is the reactive group. The main characteristic of a reactive group is the presence of electron deficient carbon atoms capable of nucleophilic attack by either substitution or addition. A nucleophile is an atom that has an abundance of electrons, lone pairs, which bond with the electron deficient atom. The two largest problems that face dye chemists when choosing a reactive group are systems that are suitable for efficient reaction with the substrate and also produce high fastness properties [26]. To achieve the latter, the reactive group must be able to align itself with the surface of the substrate to favor reaction. Once the dye-fiber bond is established, the stability of that bond becomes of importance due to subsequent treatment of the colored substrate [28]. In most cases, as reactivity of the group increases the stability of the subsequent bond decreases. The effect of reactive groups on substantivity is dependent on

26 the group. S-triazine and quinoxaline based reactive groups enhance the substantivity of the dye for the fiber, while pyrimidine and vinylsulfone reactive groups do not change substantivity [4].

2.3.2.4.1 Nucleophilic Substitution

Reactive groups that normally undergo nucleophilic substitution are heterocyclic compounds composed of an alternating hetero atom and carbon atom sequence. The alternating heterocycle allows substitution by nucleophilic attack at the carbon atom that has a partial positive charge due to the electronegativity of the heteroatoms, N, O, or S, in the cyclic ring (Figure 2.8). Triazine, the heterocycle in this figure was the first system to be used as a reactive group on a wool substrate. The technology was then extended to cellulose. Many five and six membered rings containing heteroatoms have been examined as possible reactive groups for cellulose and protein substrates with only a few reaching commercial success. Fused ring systems containing heteroatoms were also examined leading to the discovery of the quinoxaline reactive system.

Cl Nuc Cl Nuc

N N + Nuc N N - Cl N N

Chromagen N Cl Chromagen N Cl Chromagen N Cl

Figure 2.8. Nucleophilic substitution on the triazine system.

2.3.2.4.1.1 S-Triazine System

The s-triazine reactive group is a six member cyclic ring containing alternating carbon and nitrogen atoms. The nitrogen heteroatoms pull electron density away from the carbon atom leaving them with a partial positive charge. This makes the carbon atoms more susceptible to attack by a nucleophile. The partial positive charge created on a carbon atom in the s-triazine ring is the greatest of any heterocyclic ring used as a reactive group. The high reactivity of the triazine group arises from the ideal placement of the nitrogen heteroatoms [41].

The reaction of the s-triazine group in the form of cyanuric chloride with a bridging group of chromagen at cold, neutral conditions is the base reaction for the dichlorotriazine reactive dyes. The electronegativity of chlorine polarizes the carbon-chlorine bonds in cyanuric chloride and enhances the positive charge on the ring carbon atoms [34]. The chlorine atoms present on a dichlorotriazine dye are equally reactive to either the substrate or hydrolysis. Figure 2.9 shows the reaction between a dichlorotriazine dye and nucleophile, substrate or desired molecule, at mildly alkaline conditions near room temperature yields a colored substrate (dye-OCell) or the partially hydrolyzed monochlorotriazine dye (dye-OH), respectively. The hydrolyzed monochlorotriazine dyes are much less reactive than their dichloro precursors. Monochlorotriaznyl dyes have also been synthesized for use as reactive systems with reduced reactivity. The reactivity of the monochlorotriazinyl dyes can be enhanced by changing the leaving group present on the carbon atoms of the cyclic ring and substituent molecule that reacted with the dichlorotriazinyl parent.

N N Cl + Cl

OH Dye N Cl N N

Cl Dye N Cl

OCell N N + Cl

Dye N OCell Figure 2.9. Fixation and hydrolysis reactions of dichlorotriazine dyes.

2.3.2.4.1.2 Pyrimidine System

The pyrimidine reactive group is also a six member cyclic ring containing four carbon and two nitrogen atoms that alternate. Any heterocyclic compound containing two nitrogen heteroatoms in the ring are classified as diazines [41]. The electron deficiency of the carbon atoms present on the pyrimidine ring is not a great as on the triazine system and it is not equally distributed. The C-2 carbon, between the nitrogen atoms, is the most electron deficient followed by the C-4 and C-6 positions. The C-5 position has a greater electron density than all other carbons present on the ring due to its placement with respect to the nitrogen atoms of the ring. The first pyrimidine based reactive group was 2, 4, 6- trichloropyrimidine. Reaction with a chromagen containing a bridging group results in a mixture of products. The main product resulting from reaction in either the 4 or 6 position on the ring and the minor product resulting from reaction in the 2 position [41]. The first commercial reactive dyes based on pyrimidinyl chemistry were the 2, 4, 5, 6- tetrachloropyrimidinyl based dyes in the Drimarene and Reactone ranges. Figure 2.10 shows the reaction of tetrachloropyrimidine with a dye chromagen resulting in a mixture of

29 products. Many attempts have been made to alter the reactivity of pyrimidine based reactive groups by changing the labile groups in the 2, 4, and 6 positions and/or the substituent group at the 5 position [27, 36].

Cl Dye Cl Dye

HN Cl HN N Cl N N

Dye NH2 + + N N N Cl Cl Cl

Cl Cl Cl

Figure 2.10. Reaction of tetrachloropyrimidine resulting in an isomeric mixture.

2.3.2.4.1.3 Quinoxaline System

Attempts made to utilize rings that included heteroatoms exhausted five and six membered single ring systems and this led to fused ring systems containing heteroatoms as reactive groups. The most effective fused ring system and the only one to achieve commercial viability was the 2, 3–halogenoquinoxaline system. This system is the benzo derivative of the pyrazine diazine structure [41]. This reactive system is not compatible with normal bridging because once one of the halogens has reacted, the others reactivity is greatly diminished and removes its viability as a reactive group [26]. Synthesis of 6- chlorocarbonyl-2, 3-dichloroquinoxaline allowed for an amide bridging of the reactive group with the chromagen when using nitrogen based bridges because the chlorocarbonyl is more reactive than either halogen on the fused ring system (Figure 2.11) [36]. This allows for reaction with a bridging group as well as reactivity increasing effects on the halogens located in the 2 and 3 positions.

Cl HN Dye

O O

Dye NH2 +

N N N N

Cl Cl Cl Cl

Figure 2.11. Reaction of chlorocarbonyl to produce dichloroquinoxaline dye.

2.3.2.4.2 Nucleophilic Addition

Nucleophilic addition is the reaction of a double bond in a molecule to from two new single bonds and normally consists of two carbon atoms, but can include heteroatoms. The nucleophile attacks the π-bond causing the movement of electrons to the adjacent carbon in the double bond to form a carbanion. Attack by the carbanion on an atom that is electron deficient causes the formation of the second single bond. The only commercially available reactive dyes that undergo nucleophilic addition are the vinylsulfone dyes.

2.3.2.4.2.1 β-Substituted Ethyl Sulfone/Vinyl Sulfone

Substituted ethyl sulfones were first introduced in a dye by Hoechst in the 1950s.

The reactivity of the sulfatoalkyl group was found to be enhanced when hetero atoms were introduced in the β- or γ-positions of the group [26]. The most preferred activating group for vinyl sulfone compounds is the sulfonyl (-SO2-) group [42]. This reactive group (-

SO2CH2CH2-X) can be reacted with many chromagens directly or with bridging groups [27].

The elimination of the leaving group (X) and a hydrogen on the α-carbon under mild alkaline conditions leads to the formation of the π-bond and the vinyl sulfone intermediate of the

31 reactive group (Figure 2.12) [36]. The vinyl sulfone is therefore masked by the leaving group until it is in solution [37]. Upon reaction with the substrate, nucleophile addition across the π- bond occurs and a covalent bond is formed. Generally β-sulfatoethylsulfone reactive groups have a lower substantivity than heterocyclic ring reactive systems [35].

O O O O OH OH OCell S S S S Dye O O Dye Dye OCell O O O

Figure 2.12. Reversible masking and fixation reactions of sulfatoethylsulfone.

2.3.2.4.3 Leaving Group

The leaving group is associated with the reactive group upon reaction of the nucleophile with the electron deficient carbon located on the reactive group. A suitable leaving group is an atom or molecule electronegative in character and relatively stable once in solution [28]. Typical leaving groups for reactive groups that undergo nucleophilic substitution or addition include halogens and molecules that from stable ions in solution, chlorine or fluorine and quaternary ammonium or sulfato respectively. The reactivity of a reactive group can be changed by variation of the electronegativity of the leaving group associated with the system [36].

2.3.2.4.3.1 Chlorine

Chlorine was the first and most widely used labile group when it came to synthesizing a reactive dye. The reason for this was the use of cyanuric chloride, a chlorinated triazine, as the first reactive group added to a direct dye molecule to create a

32 reactive dye. Cyanuric chloride is used mainly to create mono- and dichlorotriazine reactive dyes. Upon reaction with a suitable nucleophile, the chlorine atom is removed by sequential addition and elimination reactions and goes into the reactive dyebath solution as the chloride ion. Other reactive systems originated utilizing chlorine as the labile molecule including tetrachloropyrimidine and 2, 3-dichloroquinoxaline.

2.3.2.4.3.2 Fluorine

Fluorine has also been utilized as a labile group in conjunction with triazine and pyrimidine systems. The introduction of fluorine leads to an increased reactivity when compared to chlorinated reactive groups similar in nature [34, 35]. The increased reactivity allows for lower production process temperatures and milder reaction conditions [36]. The introduction of 4, 6-difluoropyrimidinyl reactive dyes was one of the most recent innovations of reactive dyes [29].

2.3.2.4.3.3 Quaternary Amine

Tertiary amines have also been utilized as leaving groups in reactive dyes. The only requirement for the tertiary amine compound is that the nitrogen atom be sterically accessible [28, 34]. Pyridine and nicotinic acid have both been examined. The tertiary amine is more electronegative than halogens because it ionizes to create a positively charged species which catalyze the fixation reaction [28, 40]. Quaternary ammonium compounds placed in a dyebath in conjunction with a monochlorotriazine based dye increased the rate of fixation [36]. This leaving group is also utilized as a neutral dyeing reactive dye system that only requires increased temperature (100-140°C) for fixation [39].

2.3.3 Functionality

Reactive dyes are colored compounds containing a functional group capable of forming a covalent bond with a substrate [33]. The functionality of a reactive dye corresponds to the number of reactive groups present on the molecule. The reactive groups may be similar or may differ in chemical constitution. Dyes that contain multiple reactive groups similar in nature are classified as homofunctional. Dyes that contain two or more differing reactive groups are considered heterofunctional. The most common functionalities for reactive dyes are mono- and bifunctional with a few instances of dyes with a functionality of three or greater. Advantages of increasing the number of independent reactive groups on a dye molecule are that the dye gives increased fixation and lower amounts present in waste water [27, 34]. Disadvantages include increased washing times of dyed substrates due to higher affinity of the hydrolyzed dye and decreased solubility.

2.3.3.1 Monofunctional

The classification of a dye containing a single reactive group is monofunctional. The chromagen is reacted with only a single reactive group and the dyeing properties of the dye are subject to the conditions favored by the reactive group for reaction with the substrate.

Mono- and dichloro/fluorotriazine, trichloro- and chlorodifluoropyrimidine, quinoxaline and sulfato ethyl sulfone/vinyl sulfone are all examples of monofunctional dyes. The wide variety of dyes containing reactive groups allows for selection of dyes based on reactivity that gives the greatest properties for the process.

2.3.3.2 Homobifunctional

A reactive dye that contains two identical reactive groups is considered to be a homobifunctional dye. Homobifunctional dyes have a greater chance of fixating to the fiber

34 due to the dual independent reactive groups. Hydrolysis of one reactive group would not affect the reactivity of the other group due to their separation causing an increased chance for fixation. The first homobifunctional reactive dye was Reactive Black 5, a bis-β- sulfatoethylsulfone, by Hoechst in 1957 [42]. Work done by a group at North Carolina State

University has involved homobifunctional dyes containing a cysteamine or cysteine bridging group [30]. These dyes were compared to their commercial precursors in a production setting [31].

2.3.3.3 Heterobifunctional

A reactive dye that contains two dissimilar reactive groups is known as a heterobifunctional reactive dye. A dye containing two reactive groups has a greater chance to react, but because of differences in the nature of each reactive group, reaction conditions are different. The advantage of a heterobifunctional dye is the ability to create a two stage application process in which conditions for the first, more reactive, species are met and then increased to the conditions for fixing the second, less reactive species. The second reactive species is subject to a very low degree of hydrolysis at the conditions of the first reactive species, but the first is subject to a high degree of hydrolysis at the conditions of the second species. Sumitomo Chemical was the first to introduce a heterobifunctional dyes to market

[29, 40, 42]. The technology introduced vinyl sulfone and monochlorotriazine reactive groups into the same reactive dyes. Novel bridging groups have also been used to introduce reactive groups to a commercial dye to create a heterobifunctional dye [32].

2.3.3.4 Polyfunctional

Reactive dyes that contain three or four reactive groups are mainly described as polyfunctional whether they be homo or hetero reactive dyes. Only very few dyes with

35 functionalities greater than two have reached marketability and commercialization and most of these are trifunctional [29, 33, 40].

2.3.4 Key Reactions

2.3.4.1 Dye-Fiber Bond Formation

Fixation, dye-fiber reaction, is the desired process, as it forms a covalent bond with the fiber. In the presence of water cellulose and protein fibers adopt either a positive or negative charge dependent on pH and auxiliaries present. The cellulosate anion is formed when cellulosic substrates are placed into alkaline solutions and is nucleophilic in nature.

Nucleophilic attack of the cellulosate ion on a reactive group results in the formation of a covalent bond between the fiber and the dye molecule. Covalent bond formation is also known as fixation of the dye to the fiber.

2.3.4.2 Hydrolysis

While fixation of the reactive dyes to the fiber is the goal of reactive dye application, there is a competing reaction that reduces dyeing efficiency, namely hydrolysis. Usually, hydrolysis occurs when hydroxyl (HO-) ions react with the reactive groups of molecules undergoing nucleophilic substitution or addition reactions. The hydrolysis reaction is slow at near neutral pH, but speeds up as the pH moves away from neutral. The type of reactive group ultimately determines stability of the dyestuff to hydrolysis. Vinyl sulfone dyes undergo a hydrolysis reaction, but it is reversible. The down side to the reversibility of the hydrolysis reaction is that the fixation reaction has the same property. Hydrolysis can occur during storage, while in solution, and during the dyeing process. Countermeasures to hydrolysis

36 during storage include the use of buffer salts and desiccation to control pH and remove excess water.

2.4 Project Proposal

Teegafix® technology, given to North Carolina State University by Procter and

Gamble, pertains to a two-step modification of commercial dichlorotriazine (DCT) dyes to produce homobifunctional dyes with for cellulosic substrates (e.g. cotton). In step 1, the commercial DCT is reacted with either cysteamine or cysteine to produce an intermediate with a new linking group. The resulting intermediate is reacted with either cyanuric chloride or a second DCT molecule to produce bis-DCT or bis-MCT (monochlorotriazine) dyes. A total of four homobireactive dyes produced through these syntheses, a cysteamine linked bis-DCT, a cysteine linked bis-DCT, a cysteamine linked bis-MCT, and a cysteine linked bis-

MCT [30].

A trichromatic set (red, blue, and yellow) of commercial dyes was modified utilizing the Teegafix® technology to produce a series of homobifunctional dyes. The physical properties of the synthesized novel dyes were examined in equilibrium and laboratory settings [30]. Results show that dyes produced by modification with cysteamine linkages had greater affinity for cotton, with no decreases in performance during fastness testing.

Examination of the effect of pH on the distribution of reaction products when the DCT dyes were reacted with cysteamine showed that reaction at the –NH2 end is dominant at pH > 4

[44]. Effect of pH on the substitution pattern of cysteine shows that reaction at the –SH end dominants regardless of pH due to steric effects. Optimization of the synthetic methodology resulted in the examination of the properties of the cysteamine linked bis-DCT Teegafix® dyes in shade matching experiments [31]. The Teegafix® dyes showed a decrease in

37 amount of dye needed to achieve the same shade depths as the commercial dyes.

Expansion of the technology to synthesis of MCT/VS heterobifunctional dyes and evaluation of their properties was also completed [32].

The first part of this study involves the synthesis of bis-chlorodifluoropyrimidine

(CDP) dyes based on commercial red (1) and blue (3) pyrimidine structures and a commercial yellow (2) quinoxaline structure. Figures 2.13-2.15 show the 2-step modification conducted on the commercial dyes to produce an intermediate series (4-6) and a final dye series (7-9). The modification involves the reaction of dyes 1-3 with cysteamine to produce the dye intermediates 4-6 which are subsequently reacted with chlorotrifluoropyrimidine to produce the final dyes 7-9. Following the synthesis of intermediates 4-6 and dyes 7-9, these products and dyes 1-3 will be analyzed using reverse-phase ion pair chromatography and electrospray ionization mass spectrometry.

The second part of this study will involve equilibrium exhaustion studies and laboratory scale dyeings on cotton to assess the physical properties of dyes 1-3 and 7-9.

Equilibrium exhaustion studies at varying temperatures, salt concentrations, and shade depths, will be conducted. Laboratory dyeings will include exhaust and pad methods designed to produce an optimum application method for producing fabric samples dyed using dyes 1-3 and 7-9. Fastness and color assessments will be made.

O SO3Na

NH O F

N N N

NaO3S N F 1 H

pH 4-7 20°C or 50°C O SO3Na NH2 HS

NH2 NH O S

N N N

NH2

NaO3S N S H 4 Cl F pH 7-7.5 20°C N N

F F O SO3Na Cl Cl H N F NH O S

N N N N N

NaO3S N S H

7 HN N F

N Cl

F Figure 2.13. Proposed scheme for Reactive Red 123 modification.

NaO3S NaO3S

HN N N N NH pH 4-7 20°C or 50°C COONa O SH 2 H2N

SO3Na SO3Na

O N N

NH N N Cl Cl N F HN

O NaOOC N N 5

pH 7-7.5 F F 20°C Cl

N NaO3S N NaO3S

S S HN N NH2 N N NH

NH2 COONa O

F Cl

N N N HN

S S 8 F Cl

N NH

N F Figure 2.14. Proposed scheme for Reactive Yellow 25 modification.

HO3SOH2CH2CO2S NaO3S N N

N NH2 O HN N F H

N N Cl

NaO3S SO3Na

pH 4-7 20°C or 50°C SH NH H2N 2 S

HO3SOH2CH2CO2S NaO3S N N

N NH2 O HN N S H

N N Cl NH2

NaO3S SO3Na

F F F

pH 7-7.5 Cl 20°C NH F F S

Cl HO3SOH2CH2CO2S NaO3S N N

N NH2 O HN N S H

N N Cl 9

HN F

NaO3S SO3Na

F Figure 2.15. Proposed scheme for Reactive Blue 225 modification.

3 Experimental

3.1 General

The commercial dyes (Levafix Brill Yellow E3G, Levafix Scarlet E-2GA Gran, and

Levafix Navy Blue EBNA Gran) were obtained from Classic Dyestuffs Inc of High Point, NC.

Cysteamine·HCl, Na2CO3 anhydrous, 1N H2SO4, ammonium phosphate monobasic

(NH4H2PO4), acetonitrile (CH3CN), and tetrabutyl ammonium bromide (TBAB) were obtained from Fisher Scientific. Sodium chloride (salt) was supplied by Morton Salt of

Chicago, IL. Urea ((NH2)2CO) was obtained from Benntag of Durham, NC. Sera Con M-LU

Gran was obtained from Dystar of Charlotte, NC. Superclear® 80 N and ApolloScour SDRS were supplied by Henkel of Ambler, PA and Apollo Chemical of Burlington, NC.

Chlorotrifluoropyrimidine was obtained from SynQuest Laboratories Inc. of Alachua, FL.

Fabric used for equilibrium exhaustion studies was 100% cotton woven crocking squares (0.25±0.01 g), obtained from the American Association of Textile Chemists and

Colorists of Research Triangle Park, NC. Laboratory dyeing studies were conducted using

100% cotton woven (10.00±0.1 g or 5.00±0.1 g rectangular samples) from the undergraduate laboratory in the College of Textiles at North Carolina State University. The fabric had already been desized, scoured, and bleached.

3.2 Syntheses

3.2.1 Dye Intermediates

3.2.1.1 Temperature and pH Study

3.2.1.1.1 Intermediate 4

Commercial dye 1 (2.58 g, 0.004 mol) was dissolved in deionized water (25 mL) at room temperature (20°C). The pH of the dye solution was adjusted to 4-7 using 20% (w/v)

Na2CO3 and 1N H2SO4. The temperature of the dye solution was raised to reaction temperature, 20°C or 50°C. Cysteamine·HCl (0.90 g, 0.008 mol) was dissolved in deionized water (25 mL) and added drop wise to the dye solution while maintaining pH and stirring mechanically. The time of reaction was 24 h. For experiments involving 50°C, the reaction mixture was stirred at 50°C for 3 h and at 20°C for 21 h. The reaction product was precipitated using 10% (w/v) NaCl solution (10-15 mL), collected by gravity filtration, and air dried.

3.2.1.1.2 Intermediate 5

Commercial dye 2 (3.07 g, 0.004 mol) was dissolved in deionized water (25 mL) at

20°C. The pH of the dye solution was adjusted to 4, 5, 6, or 7 using 20% (w/v) Na2CO3 and

1N H2SO4. The temperature of the dye solution was raised to either 20° or 50°C.

Cysteamine·HCl (0.90 g, 0.008 mol) was dissolved in deionized water (25 mL) and added drop wise to the dye solution while maintaining pH and stirring mechanically. The time of reaction was 24 h. For experiments involving 50°C, the reaction mixture was stirred at 50°C for 3 h and at 20°C for 21 h. The reaction product was precipitated using 10% (w/v) NaCl solution (10-15 mL), collected by gravity filtration, and air dried.

3.2.1.1.3 Intermediate 6

Commercial dye 3 (4.10 g, 0.004 mol) was dissolved in deionized water (25 mL) at

20°C. The pH of the dye solution was adjusted to 4, 5, 6, or 7 using 20% (w/v) Na2CO3 and

1N H2SO4. The temperature of the dye solution was raised to either 20° or 50°C.

3.2.1.2 Cysteamine:Dye Ratio Study

3.2.1.2.1 Red Intermediate 10

Commercial dye 1 (2.58 g, 0.004 mol) was dissolved in deionized water (25 mL) at

20°C. Cysteamine·HCl in ratio to dye of 4:1 (1.8 g, 0.016 mol), 2:1 (0.90 g, 0.008 mol), or

1:1 (0.45 g, 0.004 mol) was dissolved in deionized water (25 mL) at 20°C. The pH of the dye solution was adjusted to 5 or 7 using 20% (w/v) Na2CO3 and 1N H2SO4 and the temperature was raised to 20° or 50°C. The cysteamine solution was added drop wise to the dye solution while stirring mechanically. The time of reaction was 24 h. For experiments involving 50°C, the reaction mixture was stirred at 50°C for 3 h and at 20°C for 21 h. The reaction product was precipitated using 10% (w/v) NaCl solution (10-15 mL), collected by gravity filtration, and air dried. The product from pH 7 and 50°C was used to make modified dye 11.

3.2.1.2.2 Intermediate 5

Commercial dye 2 (2.58 g, 0.004 mol) was dissolved in deionized water (25 mL) at

20°C. Cysteamine·HCl in ratio to dye of 4:1 (1.8 g, 0.016 mol), 2:1 (0.90 g, 0.008 mol), or

3.2.1.2.3 Intermediate 6

Commercial dye 3 (2.58 g, 0.004 mol) was dissolved in deionized water (25 mL) at

20°C. Cysteamine·HCl in ratio to dye of 4:1 (1.8 g, 0.016 mol), 2:1 (0.90 g, 0.008 mol), or

3.2.2 Target Dyes

3.2.2.1 Modified Red Dye (11)

Intermediate 10 was dissolved in deionized water (25 mL). Chlorotrifluoropyrimidine

(1.35 g, 0.008 mol) was dissolved in acetone (15mL). The pH of the dye solution was adjusted to 7-7.5 using 20% (w/v) Na2CO3 and 1N H2SO4 at 20°C. The halopyrimindinyl solution was added drop wise while stirring mechanically for 24 h. The reaction product was precipitated using 10% (w/v) NaCl solution, collected by gravity filtration, and air dried.

3.2.2.2 Modified Yellow Dye (8)

Intermediate 5 was dissolved in deionized water (25 mL). Chlorotrifluoropyrimidine

3.2.2.3 Modified Blue Dye (9)

Intermediate 6 was dissolved in deionized water (25 mL). Chlorotrifluoropyrimidine

3.3 HPLC Analysis

The analyte compound (5 mg) was dissolved in deionized water (10 mL). The resulting solution was filtered into an HPLC autosampler vial using a PVDF syringe filter (0.2

µm, 17 mm). The vial was inserted into an Alliance HPLC system, equipped with a Waters

2695 Separation Module and Waters 2996 Photodiode Array Detector run by the Empower

Pro software, in which a 20 µL injection volume was run through an Atlantis® C18 reverse- phase column (inner diameter: 3.9 mm, length: 150 mm, particle size: 3 µm) using a gradient elution (Table 3.1). A two component mobile phase, part A (aqueous) and part B

(organic), was used in the analysis of commercial dyes, synthesized intermediates, and final modified dyes. Component A contained 70% 0.05M NH4H2PO4 (buffer) in 18 MΩ water and

30% of component B. Component B contained 0.025M TBAB (ion pairing agent) in 100% acetonitrile. Each component was filtered through a MAGNA® nylon filter (0.22 µm, 47 mm) before use.

Table 3.1. Gradient elution component composition for HPLC analysis.

Time %A %B 1 min 70 30 5 min 50 50 7 min 70 30

3.4 Mass Spectrometric Analysis

High resolution exact mass measurements of samples submitted to the North

Carolina State University Mass Spectrometry Facility were made using Electrospray

Ionization on an Agilent Technologies 6210 LC-TOF mass spectrophotometer. Samples dissolved in methanol were introduced into the mass spectrometer along with reference ions in a water/methanol mixture (75:25) containing 0.1% NH4OH. The mass spectrometer was operated in positive-ion mode with capillary voltage of 4 kV, nebulizer pressure of 30 psig,

47 and a drying gas flow rate of 13 L/min at 350°C. Negative-ion mode was also used with similar conditions.

3.5 Equilibrium Exhaustion Study

The equilibrium exhaustion experiments were conducted in 50 mL Erlenmeyer flasks equipped with ground glass stoppers and agitated using shaker baths. The exhaustion studies were conducted at either 30° or 60°C in a Boekel Grant ORS200 shaker bath at 100 orbital revolutions per minute. Four 100% cotton crocking squares (~1.0 g) were placed in an Erlenmeyer flask and dyebath was added to achieve a liquor ratio of 40:1. The flasks were then stoppered and placed in the shaker bath for 72 h. To ensure that equilibrium was fully achieved for the near room temperature samples, the baths were raised to 60°C for 2 h and then gradually lowered to 30°C for the remainder of the 72 h period. The samples were then rinsed with cold water for 1 min after being removed from the flasks and placed on paper towels to dry. Color transference between the sample and the paper towel was minimal. The flasks containing the dyebath were sealed and allowed to cool to room temperature for analysis. Aliquots of each dyebath were removed from the flask and labeled for reference.

Dyebath solutions were developed based on a 40:1 liquor ratio. The target dyeings were 0.5, 1.0, and 2.0% owf with 0, 10, 40, or 70 g/L salt. The dyebath preparation started with the addition of salt solution to the Erlenmeyer flask from 140 g/L stock solution to desired salt level. Deionized water was then added to the flask from the calculated volume to bring the bath to 40:1 liquor ratio. Dye was added to the flask from a 4 g/L stock solution in amounts corresponding to the target shade depths based on the weight of the fabric.

3.5.1 Sample Preparation

Dyebath aliquots, volume dependent on dyebath concentration, were taken from each flask, after being cooled to room temperature, by micropipette and placed into polystyrene cuvets. Deionized water was added to the cuvet to bring the total volume to 4 mL.

Table 3.2 shows the aliquot and dilution volumes based on the dyebath concentration for exhaustion study cuvets.

Table 3.2. Aliquot and dilution volumes based on dyebath concentration.

Dyebath Aliquot Dilution Total Volume Concentration Volume (mL) Volume (mL) (mL) 0.50% 2.0 2.0 4.0 1.00% 1.0 3.0 4.0 2.00% 0.5 3.5 4.0

3.5.2 Dyebath Analysis

Wavelength of maximum absorption (λmax), absorbance, and dye concentrations were determined for each dye type and solution using the Cary 3E UV-Visible

Spectrophotometer. Standard calibration curves were generated for each dye using calibration solutions made from 4 g/L stock dye solutions. Six calibration solutions, ranging in concentration from 0.01 g/L to 0.08 g/L, were made in disposable polystyrene cuvets

(Fisher Scientific), 10mm path length, to ensure that the curve followed the Beer-Lambert law of absorbance. Each curve met or exceeded a correlation coefficient (R2) of 0.9990 to ensure the linear regression modeled concentration vs. absorbance effectively.

3.6 Laboratory Dyeings

A series of laboratory dyeing were conducted to determine the most efficient method for applying commercial and modified dyes. All laboratory dyeings were conducted in the pilot plant at North Carolina State University.

3.6.1 Washing Procedure

All dyed fabrics were washed according to the procedure outlined below. The fabric was removed from the dyeing apparatus and rinsed in cold water for 2 min. The rinsed fabric was then transferred to a second cold water bath for a 1 min rinse. Excess water was removed by squeezing. The fabric was then soaped (0.25 g/L ApolloScour SDRS) near the boil (90°C) for 5 min. Excess soap was removed by hot water (90°C) rinse for 5 min.

Centrifugal extraction was employed to remove excess water after rinsing. An infrared screen dryer with a dwell time of 2 min dried the fabric. Table 3.3 outlines this procedure.

Table 3.3. Washing procedure used in this study.

Step Time (min) Description 1 2 Cool water rinse with agitation 2 3 Cool water rinse with agitation 3 0 Remove excess water by blotting 4 5 90°C wash with ApolloScour SRDS 5 5 90°C rinse 6 0 Centrifuge excess water

3.6.2 Exhaust Dyeing

3.6.2.1 Liquor Ratio 40:1

Fabric samples (10 g) of bleached 100% cotton were wet to 100% WPU using deionized water and wound onto Ahiba® Texomat sample holders. Sample dyebaths were prepared based on a 40:1 liquor ratio in cylindrical texomat beakers. The dyeings were 0.5% and 1.0% owf (on weight of fabric) from a 4 g/L stock solution. The salt concentrations for the dyebaths were 0, 10, or 40 g/L from a 25% (w/v) NaCl stock solution. Alkali levels for all samples were 10 g/L from a 20% (w/v) Na2CO3 stock solution. Initially, the dyebath contained deionized water and dye stock to achieve target shade depth. The wound samples were loaded into the machine and the programmed procedure (Table 3.5) run.

Auxiliaries (salt and alkali solutions) were added throughout the dyeing procedure to reach a final liquor ratio of 40:1. Fabric samples were removed from the dyebath and washed.

Aliquots (6 mL) of dyebath were taken for subsequent UV-Vis analysis.

Table 3.4. Ahiba® Texomat program procedure employed.

Step Time (min) Temp (°C) Description 1 0 30 Load samples into machine 2 15 90 Heat bath: Max rate of rise 3 5 90 Hold 90°C for 5 min 4 30-90 30, 60 Cool to dyeing temp: Max rate of cooling 5 10 30, 60 Hold at dyeing temp for 10 min 6 1 30, 60 Add ½ salt solution 7 1 30, 60 Add ½ salt solution 8 15 30, 60 Hold 15 min: Salt exhaustion 9 5 30, 60 Add ¼ alkali 10 5 30, 60 Add ¼ alkali 11 5 30, 60 Add ½ alkali 12 30 30, 60 Hold 30 min: Fixation

3.6.2.2 Liquor Ratio 10:1

Fabric samples (10 g) of bleached 100% cotton were wet to 100% WPU using deionized water, rolled, and placed into Ahiba® Nuance beakers (400 mL capacity) containing dyebath. The initial dyebath consisted of salt solution (0, 10, or 40 g/L) from 25%

(w/v) stock and deionized water to bring the dyebath to a 10:1 ratio. Dye, 0.5% and 1.0%

(owf), was added from 10 g/L stock dye solution. Alkali concentration was 6 g/L Na2CO3 from 20% (w/v) stock solution. The beakers were loaded into the machine which rotated at

35 rpm. Both dye and alkali were added to dyebath via syringe during the dyeing procedure outlined in Table 3.5. Fabrics were removed from the dyeing beakers and washed.

Table 3.5. Ahiba Nuance program procedure employed.

Step Time (min) Temp (°C) Description Salt/Auxiliaries and Fabric 1 0 30 Loaded 2 10 30 Add ½ dye solution 3 10 30 Add ½ dye solution 4 20 30 Add ½ alkali solution 5 15 30 Add ½ alkali solution 6 25 30 Hold 7 0-30 30, 60 Heat to dyeing temp (1°C/min) 8 45 30, 60 Fixation

3.6.2.3 Liquor Ratio 20:1

Fabric samples (5 g) of bleached 100% cotton were wet to 100% WPU using deionized water, rolled, and placed into Ahiba® Nuance beakers (400 mL capacity) containing dyebath. The initial dyebath consisted of salt solution (0, 10, or 40 g/L) from 25%

(w/v) stock and deionized water to bring the dyebath to a 20:1 ratio. Dye, 0.5% and 1.0%

(owf), was added from 10g/L stock dye solution. Alkali concentration was 6 g/L Na2CO3 from 20% (w/v) stock solution. The beakers were loaded into the machine which rotated at

35 rpm. Both dye and alkali were added to the dyebath via syringe during the dyeing procedure. Dyeing procedure follows the same procedure outlined in Table 3.5. Fabrics were removed from the dyeing beakers and washed.

3.6.3 Pad Batch Dyeing

A stock solution of urea (100 g), Na2CO3 (10 g), and Sera Con M-LU Gran (5 g) was prepared in 385 mL of warm deionized water. Superclear® 80N (0.5 g) was added while stirring. Reactive dye (0.075 g or 0.150 g) was dissolved in this solution (15 mL) to achieve

0.5% and 1.0% (owf) dyeings, respectively. The fabric samples (5 g) were wet to 100%

WPU after being placed into resulting dyebath solutions and either rolled onto a glass rod or laid flat into a sealable plastic bag. Samples that were rolled were placed into an oven and batched at 30° or 60°C for 24 h. Flat samples were placed in either an oven or the Ahiba

Nuance® beakers and batched at 30° or 60°C for 24 h. After the batching the samples were washed.

3.6.4 Pad Steam Dyeing

0.5% and 1.0% (owf) dyeings, respectively. Fabric samples (5 g) were wet to 100% WPU after being placed in resulting dyebath and loaded onto the steamer rack. Samples were then steamed at 100°C for 15 min and washed.

3.7 K/S and L*a*b* Analysis

Spectrophotometric readings were taken of samples created in equilibrium exhaustion and laboratory dyeings. Samples were analyzed using the Datacolor

Spectraflash SF600X spectrophotometer and SLI-Form software. L*a*b* and maximum K/S values were determined and recorded for each sample.

3.8 Fastness Testing

Test specimens were taken from laboratory dyeing samples above and made to specified dimensions for the each test.

1. Colorfastness to Laundering (Accelerated) – AATCC Test Method 61-2001

2. Colorfastness to Crocking – AATCC Test Method 8-2001

3.8.1 Colorfastness to Laundering (Accelerated Test)

The colorfastness to laundering of dyed samples was tested according to AATCC

Test Method 61-2001 2A [45]. Fabric samples to be tested were backed with multi-fiber test fabric 10. Specimens were loaded into canisters containing AATCC detergent WOB (0.15% total volume) and steel beads (50 count). The canisters were then loaded into an Atlas

Laundrometer for 45 min at 49°C to simulate 5 commercial launderings. The multi-fiber test fabrics were then evaluated using the AATCC 9-step Chromatic Transference Scale in a light box under D65 illuminate.

3.8.2 Colorfastness to Crocking

The colorfastness to crocking, dry and wet, was tested according to AATCC Test

Method 8-2001 [45]. Specimens were tested using an AATCC Crockmeter. Wet crocking was done after the testing square was wet to the specified level. Testing squares were then

54 evaluated, after drying for wet crocking, using the AATCC 9-step Chromatic Transference

Scale in a light box under D65 illuminate.

3.9 Calculations

3.9.1 Exhaustion of Equilibrium Exhaustion

The exhaustion of each equilibrium exhaustion sample was calculated using the following equation where cs is equal to the concentration of solution before or after exhaustion.

. % = 𝑠𝑠 𝑠𝑠 100 𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑐𝑐.𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝐸𝐸 � 𝑠𝑠 � 𝑥𝑥 𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖

3.9.2 Substantivity Ratio (K’)

Substantivity ratios from equilibrium exhaustion studies were calculated by dividing the concentration of dye in solution (cs) by the concentration of dye in the fiber after exhaustion (cf). The following equation was used to obtain values of K’ for the study.

= 𝑓𝑓 𝑐𝑐 𝐾𝐾′ 𝑠𝑠 𝑐𝑐

3.9.3 Standard Affinity (-Δμ)

The standard affinity of dyes was calculated from K’ for equilibrium exhaustion experiments containing no additional salt using the following equation:

−∆𝜇𝜇 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅′ Where R is the gas constant (8.31433 J mol-1 K-1), T is temperature (K), and K’ is the affinity of the dye for the fiber.

3.9.4 Heat of Dyeing (-ΔH)

The heat of dyeing was calculated for each dye type using the following equation:

= 1 −∆𝐻𝐻 ∆𝑙𝑙𝑙𝑙𝑙𝑙( )′ 𝑅𝑅 ∆ 𝑇𝑇

Where R is the gas constant (8.31433 J mol-1 K-1), T is temperature (K), and K’ is the affinity of the dye for the fiber.

4 Results and Discussion

4.1 Commercial Dyes

Analysis of the starting dyes using reverse-phase (C-18) HPLC afforded the results in Figures 4.1-4.3. The yellow 2 and red 1 dyes are more homogenous than the blue 3 dye, and retention times for dyes 1-3 fell between 3.50 and 5.00 min. The chromatograms for the red and yellow dyes show major peaks at 4.21 min and 3.73 min, respectively. The chromatogram of the blue dye showed two major peaks, 4.43 and 4.80 min, which probably arise from a mixture of vinyl sulfone and sulfatoethyl sulfone forms of the corresponding reactive group. The more polar peaks in the three chromatograms are probably impurities arising from hydrolyzed dye.

Figure 4.1. HPLC results of Reactive Red 123 (1).

Figure 4.2. HPLC results of Reactive Yellow 25 (2).

Figure 4.3. HPLC results of Reactive Blue 225 (3).

4.2 Synthesis of Reaction Intermediates

The target dyes were made by a two step modification of commercial dyes having a dichloroquinoxaline or chlorodifluoropyrimidine reactive system. In step1, the parent dyes (1-

3) were reacted with cysteamine to produce the required intermediates (4-6). Bearing in mind the work of Chen [44], this aspect of the study was carried out at varying pH and temperature levels. In the reaction between Reactive Red 123 and cysteamine, a precipitate formed causing the reaction to stop at the mono-substituted intermediate (10), Figure 4.4.

O SO3Na

NH2 NH O S

N N N

NaO3S N F H

Cl 10 Figure 4.4. Monosubstituted product between Reactive Red 123 and cysteamine.

4.2.1 Effects of pH and Temperature

The reaction of the commercial dyes (1-3) with cysteamine was carried out at pH 4-7 and at 20° and 50°C. Figures 4.5-4.8 show representative results for the product distribution from Reactive Red 123 at 50°C. The chromatograms show a decrease in intensity of the commercial dye peak (retention time = 4.20 min) and an increase in intensity of peaks with shorter retention times, especially the peak at 1.37 min. An increase in pH from acidic to neutral conditions increased the conversion of commercial dye to a less polar intermediate.

Representative results for the product distribution of Reactive Red 123 at 20°C are shown in

59 the appendix (Figures1A-2A). The pH study conducted at 20°C led to similar, less clear results.

Figure 4.5. HPLC results from combining Reactive Red 123 and cysteamine at pH 4 and 50°C.

Figure 4.6. HPLC results from combining Reactive Red 123 and cysteamine at pH 5 and 50°C.

Figure 4.7. HPLC results from combining Reactive Red 123 and cysteamine at pH 6 and 50°C.

Figure 4.8. HPLC results from combining Reactive Red 123 and cysteamine at pH 7 and 50°C.

Representative results for the reaction of Reactive Yellow 25 (2) and cysteamine at pH 4-7 and 50°C are shown in Figures 4.10-4.13. The chromatograms show that Reactive

Yellow 25 readily reacted with cysteamine over the pH range. This is evidenced by the absence of the commercial dye peak at 3.7 min. The yellow dye afforded an increase in peak intensity at shorter retention times as pH of the reaction solution was increased. The major peaks are observed at 1.10, 1.50, and 1.70 min. An increase in pH causes a decrease in the intensity of the 1.70 and 1.50 peaks and an increase in intensity of the 1.10 peak. The

1.50 peak transitioned from increasing in intensity, from pH 5 to 6, to decreasing in intensity, from pH 6 to 7. This is assumed to be an increase from the monosubstituted intermediate

(12), Figure 4.9, to the disubstituted intermediate (5). Results of the 20°C pH study of

Reactive Yellow 25 and cysteamine, Appendix (Figures 7A-8A) were less clear.

NaO3S

N N

O COONa

N H2N HN

NaO3S O

N S

N H

N Cl 12 Figure 4.9. Monosubstituted intermediate of Reactive Yellow 25.

Figure 4.10. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 4 and 50°C.

Figure 4.11. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 5 and 50°C.

Figure 4.12. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 6 and 50°C.

Figure 4.13. HPLC results from combining Reactive Yellow 25 and cysteamine at pH 7 and 50°C.

The chromatograms resulting from the combination of Reactive Blue 225 and cysteamine at 50°C over the pH range are provided in Figures 4.14-4.17. The chromatograms at pH 4 and 5 are less homogeneous than chromatograms at pH 6 and 7.

An increase in pH resulted in a decreased intensity of the commercial dye peak (4.66 min).

The chromatograms displaying results for pH 6 and 7 show increased peak intensity for less retained species. The pH study conducted at 20°C led to similar results. The corresponding chromatograms are provided in the Appendix (Figures 13A-14A).

Figure 4.14. HPLC results from combining Reactive Blue 225 and cysteamine at pH 4 and 50°C.

Figure 4.15. HPLC results from combining Reactive Blue 225 and cysteamine at pH 5 and 50°C.

Figure 4.16. HPLC results from combining Reactive Blue 225 and cysteamine at pH 6 and 50°C.

Figure 4.17. HPLC results from combining Reactive Blue 225 and cysteamine at pH 7 and 50°C.

The observed products from dyes 1-3, peaks with retention times of 1.00-2.00 min, arise from nucleophilic attack of cysteamine at the –NH2 (amino) group or –SH group. Acidic pH levels (<5) cause protonation of the amino group and reactions mainly at the –SH group.

An increase in pH to near neutral conditions increases the concentration of free amino groups and reaction occurs to a greater extent at this site. It has been shown in reactions involving chlorotriazine groups, cysteamine reacts only at the amino group when pH>4 [43].

However, in the present study, nucleophilic substitution at –SH and amino groups produced mixtures. Potential products include those arising from reaction at –SH alone, reaction at –

NH2 alone, and reaction at both groups. Reaction of cysteamine with dye 1-3 led to homogeneity of the intermediates produced at pH 7 and 50°C. Lower pH and reduced temperatures adversely affected the homogeneity of the produced intermediates.

An investigation into the effect of raising the reaction temperature, from an initial level of 20°C to 50°C, was conducted for reactions involving cysteamine and dyes 2 and 3.

The goal was to slow down the reaction and produce a more homogeneous product. Figures

4.18 and 4.19 show the resulting chromatograms from these experiments. The chromatogram from Reactive Yellow 25 (Figure 4.18) shows a more heterogeneous product mixture than either of the constant temperature studies. However, the chromatogram from

Reactive Blue 225 (Figure 4.19) showed an increased homogeneous product mixture with increased peak intensity compared to the constant temperature studies above.

Figure 4.18. HPLC results from the cysteamine and Reactive Yellow 25 reaction, pH 7, initially at 20°C and then raised to 50°C.

Figure 4.19. HPLC results from the cysteamine and Reactive Blue 225 reaction, pH 7, initially at 20°C and then raised to 50°C.

4.2.2 Effects of Cysteamine:Dye Ratio

Cysteamine:dye ratios of 1:1, 2:1, and 4:1 were used at pH 5 and 7 at 20°C and

50°C. This allowed the assessment of the role of cysteamine level on the degree of substitution in the dye precursors (5, 6, and 10). Figures 4.20-4.23 show the chromatograms from reactions involving Reactive Red 123 at 50°, pH 5 and 7, and cysteamine:dye ratios of

1:1 and 2:1. Reaction of dye 1 at pH 5 resulted in commercial dye peaks with greater intensity than the intermediate product peak of interest (1.31 min). An increase in cysteamine concentration increased the intensity 1.31 min peak. An increase of pH resulted in decreased intensity of the commercial dye peak and increased intensity of the dye intermediate peak at both 1:1 and 2:1 ratios. Chromatograms outlining the effect of cysteamine:dye ratio at 20°C are in the Appendix (Figures 3A-6A). The decreased temperature results are similar to the 50°C with reduced homogeneity and unreacted commercial dye. As stated previously, the red intermediates precipitate from solution after reaction. An increase in cysteamine:dye ratio increased the rate of precipitation.

Figure 4.20. HPLC results from reaction involving a 1:1 cysteamine:dye 1 ratio at pH 5 and 50°C.

Figure 4.21. HPLC results from reaction involving a 2:1 cyteamine:dye 1 ratio at pH 5 and 50°C.

Figure 4.22. HPLC results from reaction involving 1:1 cysteamine:dye 1 ratio at pH 7 and 50°C.

Figure 4.23. HPLC results from reaction involving 2:1 cysteamine:dye 1 ratio at pH 7 and 50°C.

Chromatograms outlining the effect of cysteamine:dye ratio on the production of

Reactive Yellow 25 intermediate (5) at pH 5 and 7 at 50°C are shown in Figures 4.24-4.27.

The peaks of interest for the Reactive Yellow 25 intermediate are those at 1.10 and 1.35 min. Based on the difference in the retention times it is clear that the peak at 1.10 min represents a more polar compound than the peak at 1.35 min. These peaks correspond to disubstituted (5) and monosubstituted products, respectively. This occurs because dye modification synthesis replaces a fluoro leaving group with an –NHCH2CH2SH or a –

SHCH2CH2NH2 linking group resulting in a polarity shift. A cysteamine:dye ratio 2:1 shows the greatest intensity for the peak at 1.10 min. The 20°C study of cysteamine:dye ratio shows the peak at 1.35 min to have an increased intensity compared to the peak at 1.10 min. Chromatograms of the results are of the 20°C study are in the Appendix (Figures 9A-

12A).

Figure 4.24. HPLC results from reaction involving 1:1 cysteamine:dye 2 ratio at pH 5 and 50°C.

Figure 4.25. HPLC results from reaction involving 2:1 cysteamine:dye 2 ratio at pH 5 and 50°C.

Figure 4.26. HPLC results from reaction involving 1:1 cysteamine:dye 2 ratio at pH 7 and 50°C.

Figure 4.27. HPLC results from reaction involving 2:1 cysteamine:dye 2 ratio at pH 7 and 50°C.

Representative results from experiments involving the Reactive Blue 225 cysteamine:dye ratio are shown in Figures 4.28-4.31. Acidic reaction conditions at 50°C produced a heterogeneous mixture of products that included a peak for commercial dye 3.

An increase in cysteamine:dye ratio decreased the intensity commercial dye peak, but it was always present at acidic pH. Neutral reaction conditions at 50°C produced a more homogeneous mixture of intermediate products. An increase in cysteamine:dye ratio resulted in a shift of the peak with the greatest intensity from 1.60 min to 1.13 min. The peak at 1.13 is believed to arise from disubstitution, based on the same results from the yellow dye. Results from experiments at 20°C are shown in the Appendix (Figures 15A-18A). The results were similar to those obtained at 50°C.

Figure 4.28. HPLC results from reaction involving 1:1 cysteamine:dye 3 ratio at pH 5 and 50°C.

Figure 4.29. HPLC results from reaction involving 2:1 cysteamine:dye 3 ratio at pH 5 and 50°C.

Figure 4.30. HPLC results from reaction involving 1:1 cysteamine:dye 3 ratio at pH 7 and 50°C.

Figure 4.31. HPLC results from reaction involving 2:1 cysteamine:dye 3 ratio at pH 7 and 50°C.

4.3 Dye Synthesis

In view of the results outlined above, the target dyes (8, 9, and 11) were synthesized using the conditions shown in Table 4.1. This gave precursors (5, 6, and 10) having the chromatograms shown in Figures 4.32-4.34 that were employed in the synthesis of the target dyes. The cysteamine:dye ratio employed was in excess to push the reaction to completion and produce the intermediate with the highest degree of substitution.

Table 4.1. Optimum conditions for synthesizing dye precursors (5, 6, and 10).

Intermediate Dye pH Temperature (°C) Cysteamine:Dye Ratio Reactive Red 123 Precursor (10) 7 50 2 : 1 Reactive Yellow 25 Precursor (5) 7 50 4 : 1 Reactive Blue 225 Precursor (6) 7 50 4 : 1

Figure 4.32. HPLC results of optimized Reactive Red 123 precursor (10).

Figure 4.33. HPLC results of optimized Reactive Yellow 25 precursor (5).

Figure 4.34. HPLC results of optimized Reactive Blue 225 precursor (6).

The intermediates and the final products from the optimized syntheses were analyzed using ESI mass spectrometry (Figures 4.35 -4.38). Figure 4.35 shows the positive

79 ion spectra from the optimized Reactive Red 123 intermediate. The peak with low intensity at 602 m/z corresponds to the molecular ion of Reactive Red 123 (1). The peak with greatest intensity, 659 m/z, comes from reaction of dye 1 with a single cysteamine resulting in structure 10. The substitution of fluorine by cysteamine caused precipitation of the created intermediate and reduced possibility of subsequent reaction with a second cysteamine to produce a disubstituted product (4). The negative ion spectra from the final dye (11) synthesized from intermediate 10 is shown in Figure 4.36. The peak at 805 m/z corresponds to (M+H-2Na)- molecular peak. The molecular weight of dye 11 is 804 g/mol.

Figure 4.35. Positive ion ESI mass spectra of Red Intermediate 10.

Figure 4.36. Negative ion ESI mass spectra of Red Final Dye 11.

Figures 4.37 and 4.38 show the ESI mass spectra for the optimized intermediate yellow dye (5) and final modified dye (8) produced from the optimized intermediate, respectively. The peak at 804 m/z shows the positive ion molecular peak (M+H)+ from intermediate 5 which corresponded to the substitution of the chlorine atoms by cysteamine molecules. The mass spectra for the final product showed a series of peaks at m/z value of

549.5. This corresponds to (M-2Na/2) of the final dye (8).

Figure 4.37. Positive ion ESI mass spectra of Yellow Intermediate 5.

Figure 4.38. Negative ion ESI mass spectra of Yellow Final Dye 8.

The Reactive Red 123 precursor (10) was reacted with 5-chloro-2,4,6- trifluoropyrimidine (CTP) to produce Pyrimidine Modified Red 123 (11), Figure 4.39, containing both 5-chloro-2-fluoropyrimidine (CFP) and 5-chloro-2,4-difluoropyrimidine (CDP) reactive groups rather than the initially targeted dye 7. The Reactive Blue 225 precursor (6) was also reacted with CTP to produce Pyrimidine Modified Blue 225 (9), a bis-CDP/VS trifunctional dye. Reactive Yellow 25 precursor (5) was reacted with CTP to produce

Pyrimidine Modified Yellow 25 (8), a bis-CDP dye. HPLC results for the modified dyes (8, 9, and 11) from the corresponding precursors (5, 6, and 10) are shown in Figures 4.40-4.42.

O SO3Na Cl

H N F NH O S

N N N N N

NaO3S N F H

Cl 11 Figure 4.39. Pyrimidine Modified Red 123 structure.

Figure 4.40 HPLC results from Pyrimidine Modified Reactive Red 123 dye 11.

Figure 4.41 HPLC results from Pyrimidine Modified Reactive Yellow 25 dye 8.

Figure 4.42 HPLC results from Pyrimidine Modified Reactive Blue 225 dye 9.

4.4 Equilibrium Exhaustion

4.4.1 Absorption Spectra

The first major component of comparison for the dyes is the wavelength of maximum absorption (λmax). A scan over the visible region of the electromagnetic spectrum, 360-780 nm, was conducted for both commercial and synthesized dyes. Table 4.2 provides λmax data for each dye. A change in λmax between the commercial and modified dye indicated that the electronic absorption properties of the dye were influenced by the modification process. The blue and red pyrimidine based dyes, 11 and 9, showed slight hypsochromic shifts (≤ 5nm) in

λmax due to the modification from the commercial precursors, 1 and 3. The yellow quinoxaline based dye, 8, was characterized by a pronounced shoulder at 376 nm in addition to the band at 419 nm. Figures 4.43-4.47 show the spectra for commercial and modified dyes.

Table 4.2. Absorption maxima dyes prepared in this study.

Dye λmax (nm) Reactive Red 123 (1) 504 Pyrimidine Modified Red 123 (11) 505 Reactive Yellow 25 (2) 419 Pyrimidine Modified Yellow 25 (8) 376, 419A Reactive Blue 225 (3) 603 Pyrimidine Modified Blue 225 (9) 598 A – pronounced shoulder of commercial dye.

0.3

0.25

0.2

0.15 Absorbance 0.1

0.05

0 360 410 460 510 560 610 660 710 760 Wavelength (nm)

Figure 4.43. UV/Visible spectrum of Reactive Red 123 (1).

0.18

0.16

0.14

0.12

0.1

0.08 Absorbance 0.06

0.04

0.02

0 360 410 460 510 560 610 660 710 760 Wavelength (nm)

Figure 4.44. UV/Visible spectrum of Reactive Yellow 25 (2).

0.3

0.25

0.2

0.15 Absorbance 0.1

0.05

0 360 410 460 510 560 610 660 710 760 Wavelength (nm)

Figure 4.45. UV/Visible spectrum of Reactive Blue 225 (3).

1.8

1.6

1.4

1.2

0.8 Absorbance 0.6

0.4

0.2

0 360 410 460 510 560 610 660 710 760 Wavelength (nm)

Figure 4.46. UV/Visible spectrum of Pyrimidine Modified Reactive Red 123 (11).

0.5 0.45 0.4 0.35 0.3 0.25 0.2 Absorbance 0.15 0.1 0.05 0 360 410 460 510 560 610 660 710 760 Wavelength (nm)

Figure 4.47. UV/Visible spectrum of Pyrimidine Modified Reactive Yellow 25 (8).

4.4.2 Exhaustion Values

Absorption maxima (λmax) were also used to generate calibration curves for each dye type for percent exhaustion determinations. Equilibrium exhaustion studies were conducted on the commercial and modified dyes. The goal was to determine whether the modification process produced an increase in dye affinity and substantivity. The parameters that were varied in these experiments were dyebath concentration, temperature, and salt concentration. Dye concentrations of 0.5%, 1.0% and 2.0% based on the weight of the fabric

(owf) were used. Two temperatures were chosen, 30°C and 60°C, based on the manufacturers recommended temperatures for quinoxaline and pyrimidine based dyes, respectively. To ensure that equilibrium was reached in experiments conducted at 30°C, the temperature was initially set to 60°C and the baths cooled to 30°C after 2 h. Four salt

88 concentrations, 0 g/L, 10 g/L, 40 g/L and 70 g/L, were used to provide low to high levels.

The exhaustion time for all dyeings was 72 h, to simulate exhaustion at infinite time.

Percent exhaustion values were calculated by extrapolation of concentration of a known absorbance using a calibration curve. The calibration was a plot of absorbance versus concentration for a sequential series of dilute solutions of known concentration.

Dyebath concentrations were then determined by measuring the absorbance and extrapolating to the corresponding concentration from the calibration curve. Figures 4.48-

4.53 show the calibration curves for this study. A trend line was added to each graph to emphasize deviations from linearity of the calibration curves.

2.5

1.5

1 Absorbance

0.5

0 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 Concentration (g/L)

Figure 4.48. Calibration curve for Reactive Red 123 at 504 nm.

1.4

1.2

0.8

0.6 Absorbance

0.4

0.2

0 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 Concentration (g/L)

Figure 4.49. Calibration curve for Reactive Yellow 25 at 419 nm.

2.5

1.5

1 Absorbance

0.5

0 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 Concentration (g/L)

Figure 4.50. Calibration curve for Reactive Blue 225 at 603 nm.

2.5

1.5

1 Absorbance

0.5

0 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 Concentration (g/L)

Figure 4.51. Calibration curve for Pyrimidine Modified Red 123 at 505 nm.

0.6

0.5

0.4

0.3 Absorbance 0.2

0.1

0 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 Concentration (g/L)

Figure 4.52. Calibration curve for Pyrimidine Modified Yellow 25 at 376 nm.

2.5

1.5

1 Absorbance

0.5

0 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 Concentration (g/L)

Figure 4.53. Calibration curve for Pyrimidine Modified Blue 225 at 598 nm.

Figures 4.54-4.59 show the data obtained from equilibrium exhaustion studies. In this case, increase in dyebath concentration caused a decrease in exhaustion when salt was used. These results show that increasing salt concentration increased percent exhaustion.

The only exception was a decrease in exhaustion of the modified red dye when salt concentration was increased from 40 g/L to 70 g/L salt (Figure 4.50). At 0 g/L salt, the effect of dyebath concentration on exhaustion varied with each dye. Exhaustion values are reported in the Appendix (Tables 1A-6A).

100.00

90.00

80.00

70.00

60.00 0.5% - 30C

50.00 1.0% - 30C 2.0% - 30C 40.00

% Exhaustion % 0.5% - 60C 30.00 1.0% - 60C

20.00 2.0% - 60C

10.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.54. Equilibrium exhaustion values for Reactive Red 123 (1) at 0.5-2.0% dyebath concentrations.

100.00

90.00

80.00

70.00

60.00 0.5% - 30C

50.00 1.0% - 30C 2.0% - 30C 40.00

% Exhaustion % 0.5% - 60C 30.00 1.0% - 60C

20.00 2.0% - 60C

10.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.55. Equilibrium exhaustion values for Reactive Yellow 25 (2) at 0.5-2.0% dyebath concentrations.

100.00

90.00

80.00

70.00

60.00 0.5% - 30C

50.00 1.0% - 30C 2.0% - 30C 40.00

% Exhaustion % 0.5% - 60C 30.00 1.0% - 60C

20.00 2.0% - 60C

10.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.56. Equilibrium exhaustion values for Reactive Blue 225 (3) at 0.5-2.0% dyebath concentrations.

100.00

90.00

80.00

70.00

60.00 0.5% - 30C

50.00 1.0% - 30C 2.0% - 30C 40.00

% Exhaustion % 0.5% - 60C 30.00 1.0% - 60C

20.00 2.0% - 60C

10.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.57. Equilibrium exhaustion values for Pyrimidine Modified Red 123 (11) at 0.5-2.0% dyebath concentrations.

100.00

90.00

80.00

70.00

60.00 0.5% - 30C

50.00 1.0% - 30C 2.0% - 30C 40.00

% Exhaustion % 0.5% - 60C 30.00 1.0% - 60C

20.00 2.0% - 60C

10.00

0.00 1 2 3 4 Salt Concentration (g/L)

Figure 4.58. Equilibrium exhaustion values for Pyrimidine Modified Yellow 25 (8) at 0.5-2.0% dyebath concentrations.

100.00

90.00

80.00

70.00

60.00 0.5% - 30C

50.00 1.0% - 30C 2.0% - 30C 40.00

% Exhaustion % 0.5% - 60C 30.00 1.0% - 60C

20.00 2.0% - 60C

10.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.59. Equilibrium exhaustion values for Pyrimidine Modified Blue 225 (9) at 0.5-2.0% dyebath concentrations.

4.4.3 Substantivity Ratio

Equilibrium exhaustion results allowed calculation of cs and cf values (Appendix;

Tables 7A-18A). Using these values, the corresponding substantivity ratios (K’) were calculated for each set of experimental conditions. This was essential because it is the attraction of the substrate (cotton) and the dye molecules under a specific set of conditions that influences when dye is transferred from solution to the substrate [43]. Tables 4.3-4.9 show the calculated K’ values under the conditions of the equilibrium exhaustion study. The

98 results for calculated substantivity ratio values correlate with results from equilibrium exhaustion values.

Table 4.3.Calculated K' values for Reactive Red 123 (1) at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 6.25 55.48 195.12 385.77 1.77 38.07 117.42 265.64 1.0 5.79 37.66 132.31 278.64 3.72 28.53 82.73 171.34 2.0 6.80 28.51 89.30 1.77 5.01 21.63 54.99 110.76

Table 4.4. Calculated K' values for Reactive Yellow 25 (2) at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.32 1.95 10.64 13.06 0.31 1.62 9.04 18.37 1.0 0.16 1.89 8.03 12.16 0.16 2.61 11.17 15.56 2.0 0.07 1.19 5.10 0.31 0.16 2.97 6.42 11.89

Table 4.5. Calculated K' values for Reactive Blue 225 (3) at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.53 26.65 76.51 145.26 0.31 23.25 82.85 204.44 1.0 0.13 16.49 43.77 84.22 0.16 15.36 45.71 95.98 2.0 0.67 10.79 25.51 0.31 2.46 10.71 22.52 41.02

Table 4.6. Calculated K' values for Pyrimidine Modified Red 123 (11) at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 7.57 501.47 1303.45 190.01 8.82 202.23 933.89 723.89 1.0 7.86 275.76 207.91 125.05 7.04 184.72 585.56 226.27 2.0 3.90 163.35 124.39 8.82 6.10 114.43 223.76 128.00

100

Table 4.7. Calculated K' values for Pyrimidine Modified Yellow 25 (8) at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 9.32 87.22 482.54 1125.49 9.41 38.32 279.68 558.18 1.0 9.38 47.93 117.13 162.54 8.94 29.71 117.83 173.44 2.0 8.22 29.60 45.90 9.41 7.95 21.84 54.28 68.22

Table 4.8. Calculated K' values for Pyrimidine Modified Blue 225 (9) at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 14.68 170.38 1030.27 2146.76 7.05 102.54 707.54 1624.15 1.0 15.47 114.39 820.51 1704.37 6.97 72.24 562.04 1364.10 2.0 13.57 80.23 655.01 7.05 8.51 47.69 359.44 720.94

4.4.4 Affinity (-Δμ)

Affinity is the difference in chemical potentials of dye in solution and the substrate

(cotton) or tendency of dye to move from solution into the fiber. Negative values for affinity indicate that the dye favors the solvent (dyebath) and positive values indicate a preference for the substrate. The following equation is used to calculate affinity:

= RTlnK

−∆μ ′ Where R is the gas constant (8.3144 J mol-1 K-1), T is temperature in Kelvin (K), and K’ is the substantivity ratio. The logarithmic function creates a node, when -Δμ=0 at K’=1, with

101 negative values of affinity when 01. Figures 4.60-

4.65 show the calculated affinities for dyes used in this study. Results show that the pyrimidine modified dyes exhibited a marked increase in affinity for cotton over all specified experimental condition sets. For instance, Pyrimidine Modified Reactive Blue 225 (9) showed increased affinity when compared to Reactive Blue 225 at all conditions. Salt concentration increased affinity of the dye for the fiber in each case. Salt suppresses the repulsion between dye and fiber and also increases the activity of anionic dyes in solution pushing equilibrium towards dye-fiber interactions [24]. For all dyebaths containing salt, an increase in dye concentration caused a decrease in affinity. Generally, a temperature increase causes an increase of affinity when salt was present [2-3]. This effect is seen when comparing samples dyed at 1.0% or 2.0% (owf). Dyebaths containing 0 g/L salt showed no consistent correlation with dye concentration or temperature. Numerical values for affinity are in the Appendix (Tables 19A-30A). Results from equilibrium exhaustion studies indicated that pyrimidine modified dyes (8, 9, and 11) had greater affinity for cotton than their corresponding commercial dye (1-3).

102

18000.00

16000.00

14000.00

12000.00 0.5% - 303.15K 10000.00 1.0% - 303.15K J/mol) 8000.00 2.0% - 303.15K Δμ ( - 0.5% - 333.15K 6000.00 1.0% - 333.15K 4000.00 2.0% - 333.15K

2000.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.60. Calculated affinities for Reactive Red 123 (1) at 0.5-2.0% owf.

103

10000.00

8000.00

6000.00

4000.00 0.5% - 303.15K 1.0% - 303.15K 2000.00 2.0% - 303.15K J/mol) 0.00

Δμ ( 0.5% - 333.15K - 0 10 40 70 1.0% - 333.15K -2000.00 2.0% - 333.15K -4000.00

-6000.00

-8000.00 Salt Concentration (g/L)

Figure 4.61. Calculated affinities for Reactive Yellow 25 (2) at 0.5-2.0% owf.

104

20000.00

15000.00

10000.00 0.5% - 303.15K 1.0% - 303.15K 2.0% - 303.15K J/mol) 5000.00

Δμ ( 0.5% - 333.15K - 1.0% - 333.15K 0.00 0 10 40 70 2.0% - 333.15K

-5000.00

-10000.00 Salt Concentration (g/L)

Figure 4.62. Calculated affinities for Reactive Blue 225 (3) at 0.5-2.0% owf.

105

20000.00

18000.00

16000.00

14000.00

12000.00 0.5% - 303.15K 1.0% - 303.15K

J/mol) 10000.00 2.0% - 303.15K Δμ ( - 8000.00 0.5% - 333.15K 6000.00 1.0% - 333.15K 4000.00 2.0% - 333.15K

2000.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.63. Calculated affinities for Pyrimidine Modified Red123 (11) at 0.5-2.0% owf.

106

20000.00

18000.00

16000.00

14000.00

12000.00 0.5% - 303.15K 1.0% - 303.15K

J/mol) 10000.00 2.0% - 303.15K Δμ ( - 8000.00 0.5% - 333.15K 6000.00 1.0% - 333.15K 4000.00 2.0% - 333.15K

2000.00

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.64. Calculated affinities for Pyrimidine Modified Yellow 25 (8) at 0.5-2.0% owf.

107

25000.00

20000.00

15000.00 0.5% - 303.15K 1.0% - 303.15K J/mol) 2.0% - 303.15K Δμ ( - 10000.00 0.5% - 333.15K 1.0% - 333.15K 5000.00 2.0% - 333.15K

0.00 0 10 40 70 Salt Concentration (g/L)

Figure 4.65. Calculated affinities for Pyrimidine Modified Blue 225 (9) at 0.5-2.0% owf.

4.4.5 Heats of Dyeing, ΔH

Calculation of heat of dyeing gives a better indication of the role of temperature on equilibrium exhaustion experiments. The heat of dyeing, ΔH (change in enthalpy), is a thermodynamic description of the role of temperature. Exothermic (-ΔH) processes release energy back into the system as the reaction proceeds. Calculation of the heats of dyeing in this study was achieved using the following equation:

= 1 ′ −∆𝐻𝐻 ∆𝑙𝑙𝑙𝑙𝐾𝐾 𝑅𝑅 ∆ � � 𝑇𝑇

108

Where R is the gas constant (8.3144 J mol-1 K-1), T is temperature in Kelvin (K), and K’ is the substantivity ratio. Tables 4.10-4.15 show the results from calculating ΔH using the changes in the substantivity ratio as a function of the change in temperature from 30°C to

60°C. Reactive Red 123 and Pyrimidine Modified Blue 225 (9) show exothermic characteristics, -ΔH values, over all salt and dye concentration combinations. For all other dyes, thermodynamic characteristic of dyeing varied with salt and dye concentrations.

Table 4.9. Heats of Dyeing, ΔH (kJ/mol), results for Reactive Red 123 (1) at varying salt levels.

% Dye 0 g/L 10 g/L 40 g/L 70 g/L 0.5 -35.30 -10.54 -14.22 -10.44 1.0 -12.36 -7.77 -13.14 -13.61 2.0 -8.56 -7.73 -13.57 -12.80

Table 4.10. Heats of dyeing, ΔH (kJ/mol), results for Reactive Yellow 25 (2) at varying salt levels.

% Dye 0 g/L 10 g/L 40 g/L 70 g/L 0.5 -0.15 -5.12 -4.55 9.56 1.0 0.89 8.98 9.23 6.89 2.0 20.65 25.60 6.40 7.13

Table 4.11. Heats of dyeing, ΔH (kJ/mol), results for Reactive Blue 225 (3) at varying salt levels.

% Dye 0 g/L 10 g/L 40 g/L 70 g/L 0.5 -15.30 -3.82 2.23 9.57 1.0 5.84 -1.99 1.21 3.66 2.0 36.54 -0.23 -3.50 0.54

109

Table 4.12. Heats of dyeing, ΔH (kJ/mol), results for Pyrimidine Modified Red 123 (11) at varying salt levels.

% Dye 0 g/L 10 g/L 40 g/L 70 g/L 0.5 4.28 -25.42 -9.33 37.44 1.0 -3.08 -11.22 28.98 16.60 2.0 12.47 -9.96 16.43 17.36

Table 4.13. Heats of dyeing, ΔH (kJ/mol), results for Pyrimidine Modified Yellow 25 (8) at varying salt levels.

% Dye 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.26 -23.02 -15.27 -19.63 1.0 -1.35 -13.39 0.17 1.82 2.0 -0.93 -8.50 4.69 8.91

Table 4.14. Heats of dyeing, ΔH (kJ/mol), results for Pyrimidine Modified Blue 225 (9) at varying salt levels.

% Dye 0 g/L 10 g/L 40 g/L 70 g/L 0.5 -20.55 -14.21 -10.52 -7.81 1.0 -22.30 -12.86 -10.59 -6.23 2.0 -13.08 -14.56 -16.80 -15.86

4.5 Laboratory Dyeings

In this aspect of the project, a series of small-scale dyeings were carried out to identify optimum methods and to compare the dyeing properties of the commercial dyes and their pyrimidine modified forms. Fixation was achieved by the addition of Na2CO3 in all cases. Exhaust dyeings were conducted because of their wide usage in the textile industry.

However, pad dyeings were also evaluated because this method is also used commercially

110 for reactive dye application. For all application methods, excluding pad-steam, the pyrimidine modified dyes (8, 9, and 11) showed better shade depth at higher fixation temperatures (60°C).

4.5.1 Exhaust Dyeings

A series of exhaust dyeings were conducted to mirror the equilibrium exhaustion studies with the added step of fixation. Three salt levels, 0 g/L, 10 g/L, and 40 g/L, and two dye concentrations, 0.5% and 1.0% owf, were used. The initial procedure involved a 40:1

LR. It was labor intensive and the shade depth for modified blue and yellow dyes were very light. Also, the resulting dyeings were unlevel. Changing to 10:1 and 20:1 LRs, as suggested by the dye manufacturers, produced deeper shades and better leveling. Salt concentration increased shade depths, which was consistent with results from equilibrium studies. Fabric samples had to be folded in half to fit into the dyeing beakers, so in some cases the crease was darker than the rest of the sample.

4.5.2 Pad-Batch Dyeing

The padded samples were either rolled or placed flat in sealable plastic bags. Rolled samples were placed in an oven and flat samples were placed in either an oven or a

Nuance® dyeing machine. The rolled samples had good depth of shade at the end of the dyeing process, but they were very unlevel. The samples were not rotated, causing migration to areas where each sample sat on itself in the oven. A set of samples that were placed flat in the plastic bag were placed in an oven as well. This set of samples had good shade depth, but showed poor leveling. The samples had darker stripes (bands) in areas where more direct contact between the bag and fabric occurred. Dye solution had migrated to these areas. The final set of flat samples were sealed in plastic bags and then placed into

111 the beakers of the Nuance® dyeing machine. The beakers were rotated by the machine for

24 h at a constant rate of 35 rpm. This method produced samples that had good shade depth and leveling. The rotation of the machine prevented migration of the dye liquor in these samples.

4.5.3 Pad-Steam Dyeing

In this method, dyebath was padded onto cotton and the fabric was placed in a steamer for 15 min at 100°C. This process caused considerable dye degradation. In the case of the padded and steamed blue fabrics, a change in color to a purple shade was observed. The resultant wash water had significant red character, which accounts for the purple color on the fabric. All samples from the steaming process were duller, but seemed level.

4.6 L*a*b* and K/S Values

The definition of color by use of a model led to the development of the CIE L*a*b* color space. This color space uses D65 illuminant to simulate daylight and a series of transformations to create approximations of what the human eye would perceive. L* denotes the lightness level on a scale of 0 (black) to 100 (white). Values of L*>100 are achieved by use of optical brighteners. The a* and b* values denote red/green and yellow/blue color values, respectively. Negative values indicate green and blue colors and positive values indicate red and yellow colors for a* and b*, respectively. The color can also be defined in terms of the chroma (intensity of the color) and hue angle (color of the substrate working counter-clockwise around the lightness axis, with the positive a* axis the 0°/360° point).

112

K/S is the relationship between a sample’s spectral reflectance (R in %) and its absorption (K) and scattering (S) characteristics. The following equation shows this relationship:

[1 0.01 ]2 = 2[0.01 ] 𝐾𝐾 − 𝑅𝑅 𝑆𝑆 𝑅𝑅 K/S is wavelength dependent and must be calculated over the range of the visible spectrum, usually in 5 or 10 nm increments, to ensure that the maximum K/S can be determined for colored substrate. K/S values correspond linearly to the amount of dye in the fiber.

4.6.1 Equilibrium Exhaustion

The L*a*b* data of the equilibrium exhaustion correlated with the exhaustion data collected by assigning colorimetric values to the fabric samples and are shown in the appendix (Tables 31A-36A). All of the fabrics obtained from the modified dyes showed lower

L* values when compared to the fabrics dyed with commercial dyes. K/S values recorded in the region 400 nm to 750 nm correlated with the UV/Vis spectra with the maximum K/S values being one of the two 10 nm increments on either side of λmax. The max K/S values for the Pyrimidine Modified Yellow 25 dye fabric samples were lower than expected because their λmax fell outside the K/S range used in this study. K/S values increase as the dye concentration increases. Graphical representations of K/S for the equilibrium exhaustion are in the Appendix (Figures 19A-36A).

4.6.2 Laboratory Dyeings

L*a*b* data of the laboratory dyeings shows that the L* values for modified dye fabrics were higher than values for the corresponding commercial dye based fabrics at

113 similar conditions. This is opposite of what was found in the equilibrium exhaustion study.

K/S maximum was used to compare the depth of shade for fabric samples dyed in the laboratory procedures. In this study, K/Smax corresponded to the largest value of K/S over the scanned range. The padding processes imparted deeper shades than exhaust dyeings and pad-batch using the Nuance® dyeing machine gave highest K/Smax values for the modified dye containing fabrics. The exhaust dyeing (LR 10:1) along with the padding procedures provided similar shade depths for the commercial dyes. Table 44A (Appendix) shows L*, a*, b*, and K/Smax values of commercial and modified samples dyed in the laboratory dyeings.

4.7 Fastness Testing

The fabric samples tested were the following:

1. Exhaust dyeing (10:1 LR) samples 19-36 and 55-72 (Appendix; Tables 37A-38A)

2. Exhaust dyeing (20:1 LR) samples 19-36 and 55-72 (Appendix; Tables 39A-40A)

3. Pad-Batch rolled samples 7-12 and 19-24 (Appendix; Table 41A)

4. Pad-Batch flat samples 7-12 and 19-24 (Appendix; Table 42A)

5. Pad-Batch Nuance samples 7-12 and 19-24 (Appendix; Table 43A)

Samples from the 40:1 LR exhaust laboratory dyeing were excluded due to the poor K/S values of the pyrimidine modified dyes.

4.7.1 Fastness to Laundering (Accelerated)

All fibers in the multifiber fabric except for cotton experienced no staining, leading to a rating of 5 for all samples. The cotton section of the multi-fiber fabric had a rating of 3.0-

5.0. Both the yellow commercial dye and the pyrimidine modified yellow dye (8) gave

114 excellent fastness (ratings = 5.0) to laundering. Regarding the commercial red dye (1) and the pyrimidine modified red dye (11), the commercial dye gave ratings that were 0.5-1.0 units higher than the modified red. The commercial and modified blue dyes gave comparable ratings, which were 4.0-5.0.

4.7.2 Fastness to Crocking

Tables in the appendix outline ratings assigned to the fabrics employed following crock fastness testing, dry and wet. Assessment ratings of 3.0-5.0 were obtained. It was evident that modification of each dye did not adversely affect the fastness to crocking. It was also evident that depth of shade reduced fastness to crocking. This is due to an increased amount of unfixed dye.

115

5 Conclusions

Commercial chlorodifluoropyrimidine and dichloroquinoxaline dyes can be modified by a two-step process involving a reaction with cysteamine followed by reaction with chlorotrifluoropyrimidine. It has been found that HPLC analysis is a good tool for identifying optimized reaction conditions for converting the commercial dyes to reactive dyes having a cysteamine linking group. In the case of chlorodifluoropyrimidine and dichloroquinoxaline commercial dyes, optimized conditions for preparing cysteamine linked reactive dyes involves pH 7 and 50°C in the presence of excess cysteamine. ESI Mass Spectrometry was an effective tool for characterizing dye intermediates and final dye structures.

In equilibrium exhaustion studies, the modified dyes exhibited higher affinity on cotton than their commercial prototypes. Temperature had little effect on the affinity of either the target or commercial dyes. However, salt concentration increased the affinity of modified and commercial dyes.

Regarding dye application, pad-steam application causes significant dye degradation and is to be avoided. Exhaust dyeing of the target dyes showed an increased exhaustion over the commercial dyes, but poor shade depth. Conditions giving the best shade depths from the modified dyes involve padding the fabric with dye and rotating the sample while batching at 60°C. Application method has little impact on shade depth of the commercial dyes, while elevated application temperatures increase shade depth of the modified dyes.

Crockfastness and washfastness properties were not adversely affected by the modification process or application method.

116

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11. Harris, D.C. Quantitative Chemical Analysis, 6th ed.; W. H. Freeman: New York, 2003.

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15. Neissen, W. M. A. Liquid Chromatography-Mass Spectrometry, 2nd ed.; Marcel Dekker: New York, 1999.

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17. Fried. B; Sherma, J. Thin-Layer Chromatography, 4th ed.; Marcel Dekker: New York, 1999.

18. Holcapek M.; Jandera, P.; Prikryl, J. Analysis of Sulphonated Dyes and Intermediates by Electrospray Mass Spectrometry. Dyes Pigm. 1999, 43, 127-137.

19. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong. S. F.; Whitehouse C. M. Electrospray Ionization – Principles and Practice. Mass Spectrom. Rev. 1990, 9 (1), 37-70.

20. Hamlin, J. D.; Phillips, D. A. S.; Whiting, A. UV/Visible Spectroscopic Studies of the Effect of Common Salt and Urea upon Reactive Dye Solutions. Dyes Pigm. 1999, 41 (1-2), 137-142.

21. Cross, C. F.; Bevan, J. Researches on Cellulose 1895-1900, 2nd ed.; Longmans, Green: London, 1907.

22. Colorants and Auxiliaries: Volume 1 – Colorants, 2nd ed.; Shore, J., Ed.; Society of Dyers and Colourists: West Yorkshire, 2002.

23. Aspland, J. R. Chapter 5: Reactive Dyes and Their Application. Text. Chem. Color. 1992, 24 (5), 31-36.

24. The Chemistry and Application of Dyes; Waring, D. R.; Hallas, G., Eds.; Plenum Press: New York, 1990.

25. Aspland, J. R. Textile Dyeing and Coloration. American Association of Textile Chemists and Colorists: Research Triangle Park, 1997.

26. Rosenthal, P. The Chemistry and Application of Reactive Dyes – A Literature Review, Sept 1971-July 1975. Rev. Prog. Color. 1976, 7, 23-31.

27. Rattee, I. D. Reactive Dyes in the Coloration of Cellulosic Materials. J. Soc. Dyers Color. 1969, 85 (1), 23-31.

28. Taylor, J. A. Recent Developments in Reactive Dyes. Rev. Prog. Color. 2000, 30 (1), 93-108.

29. Berger, R. R. Fiber Reactive Dyes with Improved Affinity and Fixation Efficiency. M. S. Thesis, North Carolina State University, Raleigh, NC, 2005.

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30. Farrell, M. J. Color Matching and Utilization of Teegafix High Efficiency Fiber Reactive Dyes in a Production Setting. M. S. Thesis, North Carolina State University, Raleigh, NC, 2007.

31. Zhao, M. Synthesis and Application of Novel Heterobifunctional Reactive Dyes. M. S. Thesis, North Carolina State University, Raleigh, NC, 2006.

32. Zollinger, H. Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments, 3rd ed.; Wiley-VCH: Germany, 2003.

33. Stead, C. V. Halogenated Heterocycles in Reactive Dyes. Dyes Pigm. 1982, 3, 161- 171.

34. Stead, C.V. Developments in Azo Colorants. Rev. Prog. Color. 1967, 1 (1), 23-30.

35. Rattee, I. D. Reactive Dyes for Cellulose. Rev. Prog. Color. 1984, 14 (1), 50-57.

36. Aspland, J. R. Chapter5/Part2: Practical Application of Reactive Dyes. Tex. Chem. Color. 1992, 24 (6), 35-40.

37. Freeman, H.S.; Sokolowska, J. Developments in Dyestuff Chemistry. Rev. Prog. Color. 1999, 29 (1), 8-22.

38. Lewis, D. M.; Broadbent, P. J.; Vo, L. T. T. Covalent Fixation of Reactive Dyes on Cotton under Neutral Conditions. AATCC Review 2008, 8 (1), 35-41.

39. Renfrew, A. H. M.; Taylor, J. A. Cellulose Reactive Dyes: Recent Developments and Trends. Rev. Prog. Color. 1990, 20 (1), 1-9.

40. Beech, W. F. Fibre-Reactive Dyes; Logos Press Limited: London, 1970.

41. Renfrew, A. H. M. Reactive Dyes for Textile Fiber: The chemistry of activated π- bonds as reactive groups and miscellaneous topics; Society of Dyers and Colourists: West Yorkshire, 1999.

42. Society of Dyers and Colourists. Colour Terms and Definitions. J. Soc. Dyers Colour. 1973, 89, 411-422.

43. Chen, K. Analysis of Reactive Dyes Mixtures: Characterization of Products from bis- chlorotriazines Dye Synthesis. Ph. D. Thesis, North Carolina State University, Raleigh, 2006.

44. AATCC Technical Manual. American Association of Textile Chemists and Colorists, 2003.

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Appendix

120

Figure 1A. HPLC results from combining Reactive Red 123 and cysteamine at pH 5 and 20°C.

Figure 2A. HPLC results from combining Reactive Red 123 and cysteamine at pH 7 and 20°C.

121

Figure 3A. HPLC results from reaction involving a 1:1 cysteamine:dye 1 ratio at pH 5 and 20°C.

Figure 4A. HPLC results from reaction involving a 2:1 cysteamine:dye 1 ratio at pH 5 and 20°C.

122

Figure 5A. HPLC results from reaction involving a 1:1 cysteamine: dye 1 ratio at pH 7 and 20°C.

Figure 6A. HPLC results from reaction involving a 2:1 cysteamine:dye 1 ratio at pH 7 and 20°C.

123

Figure 7A. HPLC results from combining Reactive Yellow 25 and cysteamine at pH5 and 20°C.

Figure 8A. HPLC results from combining Reactive Yellow 25 and cysteamine at pH7 and 20°C.

124

Figure 9A. HPLC results from reaction involving a 1:1 cysteamine:dye 2 ratio at pH 5 and 20°C.

Figure 10A. HPLC results from reaction involving a 2:1 cysteamine:dye 2 ratio at pH 5 and 20°C.

125

Figure 11A. HPLC results from reaction involving a 1:1 cysteamine:dye 2 ratio at pH 7 and 20°C.

Figure 12A. HPLC results from reaction involving a 2:1 cysteamine:dye 2 ratio at pH 7 and 20°C.

126

Figure 13A. HPLC results from combining Reactive Blue 225 and cysteamine at pH 5 and 20°C.

Figure 14A. HPLC results from combining Reactive Blue 225 and cysteamine at pH 7 and 20°C.

127

Figure 15A. HPLC results from reaction involving a 1:1 cysteamine:dye 3 ratio at pH 5 and 20°C.

Figure 16A. HPLC results from reaction involving a 2:1 cysteamine:dye 3 ratio at pH 5 and 20°C.

128

Figure 17A. HPLC results from reaction involving a 1:1 cysteamine:dye 3 ratio at pH 7 and 20°C.

Figure 18A. HPLC results from reaction involving a 2:1 cysteamine:dye 3 ratio at pH 7 and 20°C.

129

Table 1A. Equilibrium exhaustion values for Reactive Red 123 at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.50% 13.89 58.88 83.47 90.86 4.42 49.82 75.38 87.39 1.00% 13.17 49.23 77.18 87.62 8.72 42.40 68.37 80.88 2.00% 15.17 42.86 70.05 82.19 11.66 36.19 59.18 74.58

Table 2A. Equilibrium exhaustion values for Reactive Yellow 25 at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.50% 0.80 4.74 21.39 25.17 0.80 4.00 18.96 32.24 1.00% 0.40 4.61 16.94 23.68 0.40 6.06 21.73 27.94 2.00% 0.20 3.06 11.86 19.60 0.42 7.22 13.87 23.02

Table 3A. Equilibrium exhaustion values for Reactive Blue 225 at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.50% 1.36 40.94 66.64 78.94 0.80 38.00 68.66 84.30 1.00% 0.34 29.68 52.56 68.35 0.40 27.30 52.74 70.26 2.00% 1.73 22.26 40.48 51.79 6.11 22.14 37.70 52.43

Table 4A. Equilibrium exhaustion values for Pyrimidine Modified Red 123 at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.50% 16.51 92.98 97.20 83.30 18.62 84.11 96.06 94.98 1.00% 17.12 87.71 84.34 76.61 15.95 83.17 93.97 85.74 2.00% 9.26 81.01 76.43 63.95 14.03 75.28 85.65 77.25

130

Table 5A. Equilibrium exhaustion values for Pyrimidine Modified Yellow 25 at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.50% 19.41 68.75 92.46 96.62 19.54 49.95 87.95 93.58 1.00% 19.31 55.09 75.01 80.50 18.98 43.92 75.65 82.00 2.00% 17.54 43.63 54.72 56.77 17.26 36.59 59.14 64.62

Table 6A. Equilibrium exhaustion values for Pyrimidine Modified Blue 225 at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.50% 27.84 81.82 96.43 98.26 15.38 72.29 94.78 97.65 1.00% 29.02 75.04 95.60 97.82 15.14 64.94 93.52 97.22 2.00% 26.43 68.16 94.59 97.18 17.87 54.99 90.29 94.91

Table 7A. Calculated cs values (g/L) - concentration of Reactive Red 123 in solution at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.108 0.051 0.021 0.011 0.119 0.063 0.031 0.016 1.0 0.217 0.127 0.057 0.031 0.228 0.144 0.079 0.048 2.0 0.424 0.286 0.150 0.089 0.442 0.319 0.204 0.127

Table 8A. Calculated cf values (g/kg) – concentration of Reactive Red 123 in fiber at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.673 2.852 4.031 4.406 0.212 2.388 3.614 4.187 1.0 1.257 4.779 7.547 8.627 0.850 4.108 6.542 8.190 2.0 2.885 8.145 13.374 15.582 2.213 6.900 11.222 14.080

131

Table 9A. Calculated csvalues (g/L) - concentration of Reactive Yellow 25 in solution at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.124 0.119 0.098 0.094 0.124 0.120 0.101 0.085 1.0 0.249 0.238 0.208 0.191 0.249 0.235 0.196 0.180 2.0 0.499 0.485 0.441 0.402 0.498 0.464 0.431 0.385

Table 10A. Calculated cf values (g/kg) – concentration of Reactive Yellow 25 in fiber at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.039 0.232 1.045 1.221 0.039 0.194 0.916 1.556 1.0 0.039 0.452 1.668 2.321 0.040 0.613 2.186 2.803 2.0 0.037 0.576 2.249 3.706 0.077 1.377 2.763 4.578

Table 11A. Calculated csvalues (g/L) - concentration of Reactive Blue 225 in solution at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.123 0.074 0.042 0.026 0.124 0.078 0.039 0.020 1.0 0.249 0.176 0.119 0.079 0.249 0.182 0.118 0.074 2.0 0.491 0.389 0.298 0.241 0.469 0.389 0.312 0.238

Table 12A. Calculated cf values (g/kg) – concentration of Reactive Blue 225 in fiber at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.065 1.967 3.190 3.823 0.038 1.802 3.246 4.011 1.0 0.033 2.900 5.191 6.664 0.041 2.792 5.401 7.137 2.0 0.328 4.196 7.592 9.698 1.156 4.168 7.014 9.755

132

Table 13A. Calculated csvalues (g/L) - concentration of Pyrimidine Modified Red 123 in solution at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.104 0.009 0.004 0.021 0.102 0.020 0.005 0.006 1.0 0.207 0.031 0.039 0.058 0.210 0.042 0.015 0.036 2.0 0.454 0.095 0.118 0.180 0.430 0.124 0.072 0.114

Table 14A. Calculated cf values (g/kg) – concentration of Pyrimidine Modified Red 123 in fiber at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.790 4.403 4.562 3.967 0.897 4.016 4.595 4.546 1.0 1.628 8.471 8.142 7.313 1.479 7.773 8.830 8.064 2.0 1.771 15.511 14.658 12.407 2.621 14.144 16.057 14.561

Table 15A. Calculated csvalues (g/L) - concentration of Pyrimidine Modified Yellow 25 in solution at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.101 0.039 0.009 0.004 0.101 0.063 0.015 0.008 1.0 0.202 0.112 0.062 0.049 0.203 0.140 0.061 0.045 2.0 0.412 0.282 0.226 0.216 0.414 0.317 0.204 0.177

Table 16A. Calculated cf values (g/kg) – concentration of Pyrimidine Modified Yellow 25 in fiber at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.939 3.407 4.546 4.750 0.947 2.397 4.212 4.477 1.0 1.893 5.382 7.319 7.926 1.811 4.165 7.174 7.805 2.0 3.390 8.342 10.391 10.725 3.291 6.925 11.090 12.067

133

Table 17A. Calculated csvalues (g/L) - concentration of Pyrimidine Modified Blue 225 in solution at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 0.090 0.023 0.004 0.002 0.106 0.035 0.007 0.003 1.0 0.177 0.062 0.011 0.005 0.212 0.088 0.016 0.007 2.0 0.368 0.159 0.027 0.014 0.411 0.225 0.049 0.025

Table 18A. Calculated cf values (g/kg) – concentration of Pyrimidine Modified Blue 225 in fiber at 0-70 g/L salt.

30°C 60°C % Dye 0 g/L 10 g/L 40 g/L 70 g/L 0 g/L 10 g/L 40 g/L 70 g/L 0.5 1.324 3.871 4.595 4.680 0.745 3.552 4.613 4.775 1.0 2.745 7.138 9.026 9.272 1.480 6.331 9.105 9.494 2.0 4.992 12.773 17.711 17.888 3.493 10.732 17.454 18.341

Table 19A. Numerical affinity values for Reactive Red 123 at 303.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 4620.02 10122.33 13292.26 15010.27 1.0 4426.60 9145.73 12313.10 14190.27 2.0 4832.47 8444.44 11322.14 13017.89

Table 20A. Numerical affinity values for Reactive Red 123 at 333.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 1583.93 10081.08 13200.94 15462.23 1.0 3641.18 9281.83 12230.84 14247.57 2.0 4463.39 8514.84 11099.61 13039.16

134

Table 21A. Numerical affinity values for Reactive Yellow 25 at 303.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 -2899.29 1677.61 5959.65 6475.85 1.0 -4657.80 1609.29 5251.11 6297.17 2.0 -6557.58 436.46 4108.37 5598.94

Table 22A. Numerical affinity values for Reactive Yellow 25 at 333.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 -3201.21 1337.15 6099.38 8062.46 1.0 -5030.91 2657.15 6684.35 7602.21 2.0 -5162.64 3012.60 5148.52 6858.39

Table 23A. Numerical affinity values for Reactive Blue 225 at 303.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 -1603.93 8274.38 10932.45 12548.43 1.0 -5098.88 7065.06 9524.74 11174.57 2.0 -1018.10 5996.45 8164.33 9312.44

Table 24A. Numerical affinity values for Reactive Blue 225 at 333.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 -3276.29 8715.51 12234.92 14736.90 1.0 -5025.71 7567.38 10587.39 12642.50 2.0 2497.15 6567.49 8626.34 10287.53

135

Table 25A. Numerical affinity values for Pyrimidine Modified Red 123 at 303.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 5100.46 15671.37 18079.04 13225.30 1.0 5195.22 14164.05 13452.24 12170.85 2.0 3433.10 12844.21 12157.49 10666.05

Table 26A. Numerical affinity values for Pyrimidine Modified Red 123 at 333.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 6028.91 14706.79 18944.63 18239.07 1.0 5404.62 14455.84 17651.63 15017.86 2.0 5007.37 13129.44 14987.02 13439.84

Table 27A. Numerical affinity values for Pyrimidine Modified Yellow 25 at 303.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 5627.40 11262.62 15574.40 17709.03 1.0 5643.47 9753.71 12005.99 12831.79 2.0 5310.22 8538.91 9644.54 9840.77

Table 28A. Numerical affinity values for Pyrimidine Modified Yellow 25 at 333.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 6210.33 10099.30 15604.90 17519.00 1.0 6067.94 9394.23 13210.61 14281.34 2.0 5744.05 8542.29 11063.55 11696.70

136

Table 29A. Numerical affinity values for Pyrimidine Modified Blue 225 at 303.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 6771.99 12950.50 17486.22 19336.64 1.0 6903.78 11946.20 16912.43 18754.99 2.0 6573.32 11052.29 16344.62 18014.37

Table 30A. Numerical affinity values for Pyrimidine Modified Blue 225 at 333.15K.

Salt Concentration (g/L) % Dyeing 0 10 40 70 0.5 5408.01 12825.44 18175.78 20477.46 1.0 5379.92 11855.46 17538.11 19994.13 2.0 5929.53 10705.08 16299.87 18227.77

137

Table 31A. L*a*b* data for Reactive Red 123 equilibrium exhaustion.

Name1 L* a* b* Red123_0.5_0_30 81.91 24.56 4.22 Red123_0.5_10_30 65.46 47.30 14.20 Red123_0.5_40_30 62.69 49.31 15.18 Red123_0.5_70_30 62.23 49.34 14.78 Red123_1.0_0_30 79.08 28.98 5.60 Red123_1.0_10_30 62.93 48.24 14.81 Red123_1.0_40_30 57.52 53.68 18.08 Red123_1.0_70_30 56.07 54.90 18.61 Red123_2.0_0_30 75.83 33.30 6.89 Red123_2.0_10_30 58.15 54.04 18.63 Red123_2.0_40_30 51.66 58.51 23.69 Red123_2.0_70_30 50.28 59.24 24.86 Red123_0.5_0_60 82.75 23.53 4.77 Red123_0.5_10_60 65.46 47.54 16.79 Red123_0.5_40_60 62.01 50.40 18.03 Red123_0.5_70_60 60.07 52.27 18.57 Red123_1.0_0_60 80.12 27.54 5.49 Red123_1.0_10_60 62.07 51.47 18.80 Red123_1.0_40_60 57.17 55.62 21.75 Red123_1.0_70_60 55.05 56.90 22.40 Red123_2.0_0_60 77.01 31.59 6.80 Red123_2.0_10_60 59.59 52.98 19.64 Red123_2.0_40_60 52.75 58.09 24.53 Red123_2.0_70_60 51.47 57.68 24.22

1Note for sample name: Dye_dye conc._salt conc._temp.

138

Table 32A. L*a*b* data for Reactive Yellow 25 equilibrium exhaustion.

Name1 L* a* b* Yell25_0.5_0_30 95.40 -0.74 4.23 Yell25_0.5_10_30 94.12 -4.62 21.86 Yell25_0.5_40_30 93.44 -5.97 31.71 Yell25_0.5_70_30 92.99 -6.38 36.54 Yell25_1.0_0_30 95.11 -1.41 7.19 Yell25_1.0_10_30 93.38 -4.89 27.26 Yell25_1.0_40_30 92.68 -5.50 36.38 Yell25_1.0_70_30 91.78 -5.58 38.13 Yell25_2.0_0_30 94.98 -1.74 8.89 Yell25_2.0_10_30 93.10 -5.37 31.72 Yell25_2.0_40_30 92.01 -5.75 43.40 Yell25_2.0_70_30 91.33 -6.06 47.71 Yell25_0.5_0_60 95.23 -1.11 5.26 Yell25_0.5_10_60 93.73 -5.23 25.61 Yell25_0.5_40_60 92.73 -6.12 38.66 Yell25_0.5_70_60 92.15 -5.99 43.78 Yell25_1.0_0_60 95.29 -1.77 7.82 Yell25_1.0_10_60 93.32 -6.09 34.45 Yell25_1.0_40_60 92.00 -6.00 48.30 Yell25_1.0_70_60 91.44 -5.38 51.67 Yell25_2.0_0_60 95.07 -1.97 9.22 Yell25_2.0_10_60 92.99 -5.78 35.05 Yell25_2.0_40_60 91.59 -5.59 49.25 Yell25_2.0_70_60 90.64 -4.93 58.15

1Note for sample name: Dye_dye conc._salt conc._temp.

139

Table 33A. L*a*b* data for Reactive Blue 225 equilibrium exhaustion.

Name1 L* a* b* Blue225_0.5_0_30 84.65 -5.46 -6.78 Blue225_0.5_10_30 56.47 -8.89 -18.17 Blue225_0.5_40_30 50.68 -8.84 -19.19 Blue225_0.5_70_30 48.29 -8.71 -19.44 Blue225_1.0_0_30 80.64 -6.54 -8.86 Blue225_1.0_10_30 54.01 -8.70 -17.81 Blue225_1.0_40_30 48.30 -8.36 -18.37 Blue225_1.0_70_30 45.28 -8.25 -18.76 Blue225_2.0_0_30 75.20 -7.47 -11.57 Blue225_2.0_10_30 49.22 -8.95 -19.42 Blue225_2.0_40_30 41.30 -8.02 -20.10 Blue225_2.0_70_30 38.16 -7.51 -20.05 Blue225_0.5_0_60 84.01 -5.49 -6.67 Blue225_0.5_10_60 58.11 -8.40 -16.76 Blue225_0.5_40_60 50.17 -8.51 -18.38 Blue225_0.5_70_60 46.79 -8.58 -18.94 Blue225_1.0_0_60 79.87 -6.61 -8.80 Blue225_1.0_10_60 54.19 -8.94 -17.92 Blue225_1.0_40_60 45.08 -8.41 -19.37 Blue225_1.0_70_60 40.33 -7.99 -19.91 Blue225_2.0_0_60 75.37 -7.46 -10.64 Blue225_2.0_10_60 51.65 -8.99 -17.96 Blue225_2.0_40_60 42.16 -8.05 -19.48 Blue225_2.0_70_60 37.19 -7.24 -19.40

1Note for sample name: Dye_dye conc._salt conc._temp.

140

Table 34A. L*a*b* data for Pyrimidine Modified Red 123 equilibrium exhaustion.

Name1 L* a* b* MRed123_0.5_0_30 72.78 37.23 12.18 MRed123_0.5_10_30 57.39 52.91 22.33 MRed123_0.5_40_30 57.56 54.54 24.04 MRed123_0.5_70_30 60.91 52.21 21.64 MRed123_1.0_0_30 68.68 41.65 14.21 MRed123_1.0_10_30 51.2 57.14 27.79 MRed123_1.0_40_30 52.72 57.03 27.54 MRed123_1.0_70_30 57.38 54.91 24.25 MRed123_2.0_0_30 64.92 45.5 16.26 MRed123_2.0_10_30 46.76 57.75 30.61 MRed123_2.0_40_30 48.83 57.91 30.49 MRed123_2.0_70_30 52.41 58.23 29.52 MRed123_0.5_0_60 71.76 38.3 12.89 MRed123_0.5_10_60 58.86 52.34 21.87 MRed123_0.5_40_60 56.56 55.02 24.63 MRed123_0.5_70_60 56.64 55.75 25.34 MRed123_1.0_0_60 67.56 42.83 15.19 MRed123_1.0_10_60 52.61 57.02 27.69 MRed123_1.0_40_60 51.73 57.52 28.32 MRed123_1.0_70_60 52.46 58.22 29.01 MRed123_2.0_0_60 62.17 47.78 18.01 MRed123_2.0_10_60 47.77 57.23 30.66 MRed123_2.0_40_60 47.5 58.42 31.15 MRed123_2.0_70_60 49.45 59 31.26

1Note for sample name: Dye_dye conc._salt conc._temp.

141

Table 35A. L*a*b* data for Pyrimidine Modified Yellow 25 equilibrium exhaustion.

Name1 L* a* b* MYell25_0.5_0_30 94.66 -3.31 13.61 MYell25_0.5_10_30 93.31 -6.2 33.42 MYell25_0.5_40_30 92.97 -6.43 36.9 MYell25_0.5_70_30 93.26 -6.31 33.63 MYell25_1.0_0_30 94.35 -4.55 19.86 MYell25_1.0_10_30 92.68 -6.53 40.74 MYell25_1.0_40_30 92.25 -6.65 44.83 MYell25_1.0_70_30 92.57 -6.36 41.49 MYell25_2.0_0_30 93.72 -5.08 24.11 MYell25_2.0_10_30 92.26 -6.2 44.14 MYell25_2.0_40_30 91.88 -6.64 49.73 MYell25_2.0_70_30 92.18 -6.33 44.41 MYell25_0.5_0_60 94.24 -2.71 11.14 MYell25_0.5_10_60 93.45 -5.95 29.51 MYell25_0.5_40_60 92.56 -6.57 39.2 MYell25_0.5_70_60 92.55 -6.56 39.83 MYell25_1.0_0_60 94.58 -3.35 14.21 MYell25_1.0_10_60 92.84 -6.3 36.79 MYell25_1.0_40_60 91.94 -6.07 45.84 MYell25_1.0_70_60 91.88 -6.46 48.1 MYell25_2.0_0_60 94.06 -4.41 20.28 MYell25_2.0_10_60 92.06 -5.92 42 MYell25_2.0_40_60 91.45 -5.77 49.54 MYell25_2.0_70_60 91.43 -6.24 52.91

1Note for sample name: Dye_dye conc._salt conc._temp.

142

Table 36A. L*a*b* data for Pyrimidine Modified Blue 225 equilibrium exhaustion.

Name1 L* a* b* MBlue225_0.5_0_30 66.41 -7.33 -12.55 MBlue225_0.5_10_30 47.8 -8.11 -15.95 MBlue225_0.5_40_30 48.81 -7.77 -16.64 MBlue225_0.5_70_30 52.31 -7.66 -16.97 MBlue225_1.0_0_30 59.01 -8.04 -14.53 MBlue225_1.0_10_30 40.15 -7.85 -16.79 MBlue225_1.0_40_30 38.23 -6.91 -16.8 MBlue225_1.0_70_30 40.61 -7.28 -17.73 MBlue225_2.0_0_30 50.54 -8.57 -16.38 MBlue225_2.0_10_30 35.07 -6.85 -16.53 MBlue225_2.0_40_30 35.24 -6.44 -16.78 MBlue225_2.0_70_30 35.63 -5.94 -16.49 MBlue225_0.5_0_60 69.31 -6.91 -11.6 MBlue225_0.5_10_60 47.84 -8.34 -15.98 MBlue225_0.5_40_60 40.21 -7.45 -16.36 MBlue225_0.5_70_60 48.23 -7.83 -17.17 MBlue225_1.0_0_60 60.88 -7.51 -13.63 MBlue225_1.0_10_60 40.5 -7.77 -16.61 MBlue225_1.0_40_60 36.07 -6.67 -16.54 MBlue225_1.0_70_60 40.85 -7.32 -17.63 MBlue225_2.0_0_60 52.19 -8.13 -15.4 MBlue225_2.0_10_60 34.61 -6.89 -16.29 MBlue225_2.0_40_60 31.56 -5.61 -15.85 MBlue225_2.0_70_60 32.44 -5.82 -16.2

1Note for sample name: Dye_dye conc._salt conc._temp.

143

4.5

3.5

3 Red123_0.5_0_30 Red123_0.5_10_30 2.5 Red123_0.5_40_30 K/S 2 Red123_0.5_70_30 Red123_0.5_0_60 1.5 Red123_0.5_10_60 1 Red123_0.5_40_60

0.5 Red123_0.5_70_60

0 400 500 600 700 Wavelength (nm)

Figure 19A. K/S graph for Reactive Red 123 at 0.5% owf and varying salt and temperature levels.

144

5 Red123_1.0_0_30 Red123_1.0_10_30 4 Red123_1.0_40_30 K/S 3 Red123_1.0_70_30 Red123_1.0_0_60 2 Red123_1.0_10_60 Red123_1.0_40_60 1 Red123_1.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 20A. K/S graph for Reactive Red 123 at 1.0% owf and varying salt and temperature levels.

145

8 Red123_2.0_0_30 Red123_2.0_10_30 Red123_2.0_40_30 6 K/S Red123_2.0_70_30 Red123_2.0_0_60 4 Red123_2.0_10_60 Red123_2.0_40_60 2 Red123_2.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 21A. K/S graph for Reactive Red 123 at 2.0% owf and varying salt and temperature levels.

146

0.9

0.8

0.7

0.6 Yell25_0.5_0_30 Yell25_0.5_10_30 0.5 Yell25_0.5_40_30 K/S 0.4 Yell25_0.5_70_30 Yell25_0.5_0_60 0.3 Yell25_0.5_10_60 0.2 Yell25_0.5_40_60

0.1 Yell25_0.5_70_60

0 400 500 600 700 Wavelength (nm)

Figure 22A. K/S graph for Reactive Yellow 25 at 0.5% owf and varying salt and temperature levels.

147

1.4

1.2

1 Yell25_1.0_0_30 Yell25_1.0_10_30 0.8 Yell25_1.0_40_30 K/S 0.6 Yell25_1.0_70_30 Yell25_1.0_0_60 0.4 Yell25_1.0_10_60 Yell25_1.0_40_60 0.2 Yell25_1.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 23A. K/S graph for Reactive Yellow 25 at 1.0% owf and varying salt and temperature levels.

148

1.8

1.6

1.4 Yell25_2.0_0_30 1.2 Yell25_2.0_10_30 Yell25_2.0_40_30 1 K/S Yell25_2.0_70_30 0.8 Yell25_2.0_0_60 0.6 Yell25_2.0_10_60 0.4 Yell25_2.0_40_60

0.2 Yell25_2.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 24A. K/S graph for Reactive Yellow 25 at 2.0% owf and varying salt and temperature levels.

149

4.5

3.5 Blue225_0.5_0_30 3 Blue225_0.5_10_30 Blue225_0.5_40_30 2.5 K/S Blue225_0.5_70_30 2 Blue225_0.5_0_60 1.5 Blue225_0.5_10_60 1 Blue225_0.5_40_60

0.5 Blue225_0.5_70_60

0 400 500 600 700 Wavelength (nm)

Figure 25A. K/S graph for Reactive Blue 225 at 0.5% owf and varying salt and temperature levels.

150

6 Blue225_1.0_0_30 5 Blue225_1.0_10_30 Blue225_1.0_40_30 4 K/S Blue225_1.0_70_30 3 Blue225_1.0_0_60 Blue225_1.0_10_60 2 Blue225_1.0_40_60 1 Blue225_1.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 26A. K/S graph for Reactive Blue 225 at 1.0% owf and varying salt and temperature levels.

151

7 Blue225_2.0_0_30 6 Blue225_2.0_10_30 Blue225_2.0_40_30 5 K/S Blue225_2.0_70_30 4 Blue225_2.0_0_60 3 Blue225_2.0_10_60 2 Blue225_2.0_40_60

1 Blue225_2.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 27A. K/S graph for Reactive Blue 225 at 2.0% owf and varying salt and temperature levels.

152

5 MRed123_0.5_0_30 MRed123_0.5_10_30 4 MRed123_0.5_40_30 K/S 3 MRed123_0.5_70_30 MRed123_0.5_0_60 2 MRed123_0.5_10_60 MRed123_0.5_40_60 1 MRed123_0.5_70_60

0 400 500 600 700 Wavelength (nm)

Figure 28A. K/S graph for Pyrimidine Modified Red 123 at 0.5% owf and varying salt and temperature levels.

153

7 MRed123_1.0_0_30 6 MRed123_1.0_10_30 MRed123_1.0_40_30 5 K/S MRed123_1.0_70_30 4 MRed123_1.0_0_60 3 MRed123_1.0_10_60 2 MRed123_1.0_40_60

1 MRed123_1.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 29A. K/S graph for Pyrimidine Modified Red 123 at 1.0% owf and varying salt and temperature levels.

154

10 MRed123_2.0_0_30 MRed123_2.0_10_30 8 MRed123_2.0_40_30 K/S 6 MRed123_2.0_70_30 MRed123_2.0_0_60 4 MRed123_2.0_10_60 MRed123_2.0_40_60 2 MRed123_2.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 30A. K/S graph for Pyrimidine Modified Red 123 at 2.0% owf and varying salt and temperature levels.

155

0.8

0.7

0.6 MYell25_0.5_0_30 0.5 MYell25_0.5_10_30 MYell25_0.5_40_30 0.4 K/S MYell25_0.5_70_30 0.3 MYell25_0.5_0_60 MYell25_0.5_10_60 0.2 MYell25_0.5_40_60 0.1 MYell25_0.5_70_60

0 400 500 600 700 Wavelength (nm)

Figure 31A. K/S graph for Pyrimidine Modified Yellow 25 at 0.5% owf and varying salt and temperature levels.

156

1.2

0.8 MYell25_1.0_0_30 MYell25_1.0_10_30 MYell25_1.0_40_30 0.6 K/S MYell25_1.0_70_30 MYell25_1.0_0_60 0.4 MYell25_1.0_10_60 MYell25_1.0_40_60 0.2 MYell25_1.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 32A. K/S graph for Pyrimidine Modified Yellow 25 at 1.0% owf and varying salt and temperature levels.

157

1.6

1.4

1.2 MYell25_2.0_0_30 1 MYell25_2.0_10_30 MYell25_2.0_40_30 0.8 K/S MYell25_2.0_70_30 0.6 MYell25_2.0_0_60 MYell25_2.0_10_60 0.4 MYell25_2.0_40_60 0.2 MYell25_2.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 33A. K/S graph for Pyrimidine Modified Yellow 25 at 2.0% owf and varying salt and temperature levels.

158

5 MBlue225_0.5_0_30 MBlue225_0.5_10_30 4 MBlue225_0.5_40_30 K/S 3 MBlue225_0.5_70_30 MBlue225_0.5_0_60 2 MBlue225_0.5_10_60 MBlue225_0.5_40_60 1 MBlue225_0.5_70_60

0 400 500 600 700 Wavelength (nm)

Figure 34A. K/S graph for Pyrimidine Modified Blue 225 at 0.5% owf and varying salt and temperature levels.

159

6 MBlue225_1.0_0_30 MBlue225_1.0_10_30 5 MBlue225_1.0_40_30 K/S 4 MBlue225_1.0_70_30 MBlue225_1.0_0_60 3 MBlue225_1.0_10_60 2 MBlue225_1.0_40_60

1 MBlue225_1.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 35A. K/S graph for Pyrimidine Modified Blue 225 at 1.0% owf and varying salt and temperature levels.

160

8 MBlue225_2.0_0_30 MBlue225_2.0_10_30 MBlue225_2.0_40_30 6 K/S MBlue225_2.0_70_30 MBlue225_2.0_0_60 4 MBlue225_2.0_10_60 MBlue225_2.0_40_60 2 MBlue225_2.0_70_60

0 400 500 600 700 Wavelength (nm)

Figure 36A. K/S graph for Pyrimidine Modified Blue 225 at 2.0% owf and varying salt and temperature levels.

161

Table 37A. Fastness values from exhaust dyeing samples at LR 10:1 and 60°C.

Crocking Wash Sample Dye % Dyeing Salt (g/L) Dry Wet acetate cotton nylon poly. acrylic wool LR 10 - 19 Red 0.5 0 5 4 5 4.5 5 5 5 5 LR 10 - 20 Red 0.5 10 4.5 4 5 4.5 5 5 5 5 LR 10 - 21 Red 0.5 40 4 4 5 4.5 5 5 5 5 LR 10 - 22 Yellow 0.5 0 5 5 5 5 5 5 5 5 LR 10 - 23 Yellow 0.5 10 5 5 5 5 5 5 5 5 LR 10 - 24 Yellow 0.5 40 5 5 5 5 5 5 5 5 LR 10 - 25 Blue 0.5 0 4.5 4 5 5 5 5 5 5 LR 10 - 26 Blue 0.5 10 4.5 4.5 5 4.5 5 5 5 5 LR 10 - 27 Blue 0.5 40 5 4.5 5 4.5 5 5 5 5 LR 10 - 28 Red 1.0 0 5 4 5 4.5 5 5 5 5 LR 10 - 29 Red 1.0 10 4 4 5 4.5 5 5 5 5 LR 10 - 30 Red 1.0 40 5 4 5 4.5 5 5 5 5 LR 10 - 31 Yellow 1.0 0 5 5 5 5 5 5 5 5 LR 10 - 32 Yellow 1.0 10 5 5 5 5 5 5 5 5 LR 10 - 33 Yellow 1.0 40 5 4.5 5 5 5 5 5 5 LR 10 - 34 Blue 1.0 0 4 4 5 5 5 5 5 5 LR 10 - 35 Blue 1.0 10 4 4 5 4.5 5 5 5 5 LR 10 - 36 Blue 1.0 40 4.5 4 5 4.5 5 5 5 5

162

Table 38A. Fastness values from exhaust dyeing samples at LR 10:1 and 60°C.

Crocking Wash Sample Dye % Dyeing Salt (g/L) Dry Wet acetate cotton nylon poly. acrylic wool LR 10 - 55 M. Red 0.5 0 4.5 4 5 4 5 5 5 5 LR 10 - 56 M. Red 0.5 10 4 4 5 4.5 5 5 5 5 LR 10 - 57 M. Red 0.5 40 3.5 3.5 5 4 5 5 5 5 LR 10 - 58 M. Yellow 0.5 0 5 5 5 5 5 5 5 5 LR 10 - 59 M. Yellow 0.5 10 5 5 5 5 5 5 5 5 LR 10 - 60 M. Yellow 0.5 40 5 5 5 5 5 5 5 5 LR 10 - 61 M. Blue 0.5 0 4.5 4 5 4.5 5 5 5 5 LR 10 - 62 M. Blue 0.5 10 5 4 5 4.5 5 5 5 5 LR 10 - 63 M. Blue 0.5 40 5 3.5 5 5 5 5 5 5 LR 10 - 64 M. Red 1.0 0 4.5 4 5 4.5 5 5 5 5 LR 10 - 65 M. Red 1.0 10 4.5 3.5 5 4 5 5 5 5 LR 10 - 66 M. Red 1.0 40 3.5 3.5 5 4 5 5 5 5 LR 10 - 67 M. Yellow 1.0 0 5 5 5 5 5 5 5 5 LR 10 - 68 M. Yellow 1.0 10 5 5 5 5 5 5 5 5 LR 10 - 69 M. Yellow 1.0 40 5 5 5 5 5 5 5 5 LR 10 - 70 M. Blue 1.0 0 5 4 5 4.5 5 5 5 5 LR 10 - 71 M. Blue 1.0 10 5 3.5 5 4.5 5 5 5 5 LR 10 - 72 M. Blue 1.0 40 4.5 3 5 4 5 5 5 5

163

Table 39A. Fastness values from exhaust dyeing samples at LR 20:1 and 60°C.

Crocking Wash Sample Dye % Dyeing Salt (g/L) Dry Wet acetate cotton nylon poly. acrylic wool LR 20 - 19 Red 0.5 0 5 4.5 5 4.5 5 5 5 5 LR 20 - 20 Red 0.5 10 5 4 5 4.5 5 5 5 5 LR 20 - 21 Red 0.5 40 4.5 4 5 5 5 5 5 5 LR 20 - 22 Yellow 0.5 0 5 5 5 5 5 5 5 5 LR 20 - 23 Yellow 0.5 10 5 5 5 5 5 5 5 5 LR 20 - 24 Yellow 0.5 40 5 5 5 5 5 5 5 5 LR 20 - 25 Blue 0.5 0 5 4.5 5 5 5 5 5 5 LR 20 - 26 Blue 0.5 10 5 4 5 5 5 5 5 5 LR 20 - 27 Blue 0.5 40 5 4 5 4.5 5 5 5 5 LR 20 - 28 Red 1.0 0 5 4 5 4.5 5 5 5 5 LR 20 - 29 Red 1.0 10 5 3.5 5 4.5 5 5 5 5 LR 20 - 30 Red 1.0 40 5 3.5 5 4.5 5 5 5 5 LR 20 - 31 Yellow 1.0 0 5 5 5 5 5 5 5 5 LR 20 - 32 Yellow 1.0 10 5 4.5 5 5 5 5 5 5 LR 20 - 33 Yellow 1.0 40 5 4.5 5 5 5 5 5 5 LR 20 - 34 Blue 1.0 0 4.5 4 5 4.5 5 5 5 5 LR 20 - 35 Blue 1.0 10 4.5 4 5 4.5 5 5 5 5 LR 20 - 36 Blue 1.0 40 5 3.5 5 4 5 5 5 5

164

Table 40A. Fastness values from exhaust dyeing samples at LR 20:1 and 60°C.

Crocking Wash Sample Dye % Dyeing Salt (g/L) Dry Wet acetate cotton nylon poly. acrylic wool LR 20 - 55 M. Red 0.5 0 4.5 4.5 5 4.5 5 5 5 5 LR 20 - 56 M. Red 0.5 10 5 4 5 4 5 5 5 5 LR 20 - 57 M. Red 0.5 40 4 4 5 4 5 5 5 5 LR 20 - 58 M. Yellow 0.5 0 5 5 5 5 5 5 5 5 LR 20 - 59 M. Yellow 0.5 10 5 5 5 5 5 5 5 5 LR 20 - 60 M. Yellow 0.5 40 5 4.5 5 5 5 5 5 5 LR 20 - 61 M. Blue 0.5 0 5 4.5 5 5 5 5 5 5 LR 20 - 62 M. Blue 0.5 10 5 4 5 4.5 5 5 5 5 LR 20 - 63 M. Blue 0.5 40 4.5 3.5 5 4.5 5 5 5 5 LR 20 - 64 M. Red 1.0 0 5 4.5 5 4 5 5 5 5 LR 20 - 65 M. Red 1.0 10 5 4 5 4 5 5 5 5 LR 20 - 66 M. Red 1.0 40 4.5 3.5 5 4 5 5 5 5 LR 20 - 67 M. Yellow 1.0 0 5 4.5 5 5 5 5 5 5 LR 20 - 68 M. Yellow 1.0 10 5 4.5 5 5 5 5 5 5 LR 20 - 69 M. Yellow 1.0 40 5 4 5 5 5 5 5 5 LR 20 - 70 M. Blue 1.0 0 4.5 4 5 4.5 5 5 5 5 LR 20 - 71 M. Blue 1.0 10 4.5 3.5 5 4.5 5 5 5 5 LR 20 - 72 M. Blue 1.0 40 4.5 3 5 4 5 5 5 5

165

Table 41A. Fastness values from pad-batch samples at 60°C, rolled samples.

Crocking Wash Sample Dye % Dyeing Dry Wet acetate cotton nylon poly. acrylic wool PBR - 7 Red 0.5 5 4.5 5 4.5 5 5 5 5 PBR - 8 Red 1.0 5 4 5 4 5 5 5 4.5 PBR - 9 Yellow 0.5 5 5 5 5 5 5 5 5 PBR - 10 Yellow 1.0 5 4.5 5 5 5 5 5 5 PBR - 11 Blue 0.5 4.5 4.5 5 5 5 5 5 5 PBR - 12 Blue 1.0 4.5 4 5 4.5 5 5 5 4.5 PBR - 19 M. Red 0.5 4.5 4 5 3.5 5 5 5 4.5 PBR - 20 M. Red 1.0 5 3.5 5 3 5 5 5 4.5 PBR - 21 M. Yellow 0.5 5 4.5 5 5 5 5 5 5 PBR - 22 M. Yellow 1.0 5 4.5 5 5 5 5 5 5 PBR - 23 M. Blue 0.5 4.5 4 5 4.5 5 5 5 5 PBR - 24 M. Blue 1.0 4.5 3.5 5 4.5 5 5 5 5

166

Table 42A. Fastness values from pad-batch samples at 60°C, flat samples.

Crocking Wash Sample Dye % Dyeing Dry Wet acetate cotton nylon poly. acrylic wool PBF - 7 Red 0.5 4.5 4.5 5 4.5 5 5 5 5 PBF - 8 Red 1.0 5 4 5 4.5 5 5 5 5 PBF - 9 Yellow 0.5 5 5 5 5 5 5 5 5 PBF - 10 Yellow 1.0 5 4.5 5 5 5 5 5 5 PBF - 11 Blue 0.5 5 4.5 5 5 5 5 5 5 PBF - 12 Blue 1.0 5 4 5 4.5 5 5 5 5 PBF - 19 M. Red 0.5 5 4 5 4 5 5 5 5 PBF - 20 M. Red 1.0 5 3.5 5 3.5 5 5 5 5 PBF - 21 M. Yellow 0.5 5 4.5 5 5 5 5 5 5 PBF - 22 M. Yellow 1.0 5 4.5 5 5 5 5 5 5 PBF - 23 M. Blue 0.5 5 4 5 4.5 5 5 5 5 PBF - 24 M. Blue 1.0 4.5 3.5 5 4 5 5 5 5

167

Table 43A. Fastness values from pad-batch samples at 60°C, Nuance® samples.

Crocking Wash Sample Dye % Dyeing Dry Wet acetate cotton nylon poly. acrylic wool PBN - 7 Red 0.5 5 4.5 5 4.5 5 5 5 5 PBN - 8 Red 1.0 5 4 5 4.5 5 5 5 5 PBN - 9 Yellow 0.5 5 5 5 5 5 5 5 5 PBN - 10 Yellow 1.0 5 4.5 5 5 5 5 5 5 PBN - 11 Blue 0.5 5 4.5 5 4.5 5 5 5 5 PBN - 12 Blue 1.0 5 4 5 4.5 5 5 5 5 PBN - 19 M. Red 0.5 5 4 5 4 5 5 5 5 PBN - 20 M. Red 1.0 4.5 3.5 5 3.5 5 5 5 5 PBN - 21 M. Yellow 0.5 5 4.5 5 5 5 5 5 5 PBN - 22 M. Yellow 1.0 5 4.5 5 5 5 5 5 5 PBN - 23 M. Blue 0.5 5 4 5 4.5 5 5 5 5 PBN - 24 M. Blue 1.0 4.5 3.5 5 4 5 5 5 5

168

Table 44A. Laboratory dyed samples and corresponding spectrophotometric data.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L* = 67.42 L* = 72.69 LR – 40:1 a* = 44.88 a* = 39.14 0.5% owf b* = 18.41 b* = 13.84 0 g/L NaCl K/S = 2.15 K/S = 1.17 Exhaust 40 - 1 30°C Exhaust 40 - 37 Exhaust Dyeing L*= 65.11 L*= 70.17 LR – 40:1 a*= 48.01 a*= 42.11 0.5% owf b*= 20.66 b*= 15.33 10 g/L NaCl K/S= 2.78 K/S= 1.51 Exhaust 40 - 2 30°C Exhaust 40 - 38 Exhaust Dyeing L*= 63.08 L*= 72.27 LR – 40:1 a*= 50.69 a*= 39.22 0.5% owf b*= 22.84 b*= 13.63 40 g/L NaCl K/S= 3.56 K/S= 1.2 Exhaust 40 - 3 30°C Exhaust 40 - 39 Exhaust Dyeing L*= 93.09 L*= 94.14 LR – 40:1 a*= -5.12 a*= -3.51 0.5% owf b*= 23.05 b*= 14.02 0 g/L NaCl K/S= 0.25 K/S= 0.12 Exhaust 40 - 4 30°C Exhaust 40 - 40 Exhaust Dyeing L*= 92.88 L*= 93.94 LR – 40:1 a*= -5.94 a*= -4.54 0.5% owf b*= 29.97 b*= 19.20 10 g/L NaCl K/S= 0.39 K/S= 0.19 Exhaust 40 - 5 30°C Exhaust 40 - 41 Exhaust Dyeing L*= 92.33 L*= 93.67 LR – 40:1 a*= -6.58 a*= -5.20 0.5% owf b*= 37.93 b*= 22.99 40 g/L NaCl K/S= 0.63 K/S= 0.26 Exhaust 40 - 6 30°C Exhaust 40 - 42 Exhaust Dyeing L*= 56.39 L*= 69.89 LR – 40:1 a*= -9.14 a*= -6.60 0.5% owf b*= -18.51 b*= -12.86 0 g/L NaCl K/S= 2.35 K/S= 0.73 Exhaust 40 - 7 30°C Exhaust 40 - 43

Exhaust Dyeing L*= 52.10 L*= 66.15 LR – 40:1 a*= -9.32 a*= -6.93 0.5% owf b*= -19.47 b*= -13.95 10 g/L NaCl K/S= 3.25 K/S= 0.99 Exhaust 40 - 8 30°C Exhaust 40 - 44

169

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 46.92 L*= 65.73 LR – 40:1 a*= -9.23 a*= -6.78 0.5% owf b*= -20.45 b*= -14.09 0 g/L NaCl K/S= 4.75 K/S= 1.02 Exhaust 40 - 9 30°C Exhaust 40 - 45 Exhaust Dyeing L*= 62.62 L*= 69.45 LR – 40:1 a*= 50.32 a*= 43.21 1.0% owf b*= 22.60 b*= 16.04 0 g/L NaCl K/S= 3.57 K/S= 1.63 Exhaust 40 - 10 30°C Exhaust 40 - 46 Exhaust Dyeing L*= 59.71 L*= 67.11 LR – 40:1 a*= 53.28 a*= 46.19 1.0% owf b*= 25.36 b*= 17.96 10 g/L NaCl K/S= 4.90 K/S= 2.10 Exhaust 40 - 11 30°C Exhaust 40 - 47 Exhaust Dyeing L*= 57.29 L*= 70.02 LR – 40:1 a*= 55.72 a*= 42.52 1.0% owf b*= 28.26 b*= 15.47 40 g/L NaCl K/S= 6.57 K/S= 1.56 Exhaust 40 - 12 30°C Exhaust 40 - 48 Exhaust Dyeing L*= 92.86 L*= 93.83 LR – 40:1 a*= -5.95 a*= -4.55 1.0% owf b*= 30.87 b*= 19.37 0 g/L NaCl K/S= 0.42 K/S= 0.20 Exhaust 40 - 13 30°C Exhaust 40 - 49 Exhaust Dyeing L*= 92.27 L*= 93.42 LR – 40:1 a*= -6.41 a*= -5.41 1.0% owf b*= 38.72 b*= 25.31 10 g/L NaCl K/S= 0.66 K/S= 0.31 Exhaust 40 - 14 30°C Exhaust 40 - 50 Exhaust Dyeing L*= 91.51 L*= 93.08 LR – 40:1 a*= -6.33 a*= -5.86 1.0% owf b*= 46.46 b*= 25.31 40 g/L NaCl K/S= 1.02 K/S= 0.40 Exhaust 40 - 15 30°C Exhaust 40 - 51

Exhaust Dyeing L*= 48.58 L*= 63.34 LR – 40:1 a*= -9.26 a*= -7.16 1.0% owf b*= -20.04 b*= -14.71 0 g/L NaCl K/S= 4.19 K/S= 1.24 Exhaust 40 - 16 30°C Exhaust 40 - 52

170

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 44.31 L*= 59.51 LR – 40:1 a*= -9.02 a*= -7.33 1.0% owf b*= -20.59 b*= -15.57 10 g/L NaCl K/S= 5.71 K/S= 1.64 Exhaust 40 - 17 30°C Exhaust 40 - 53 Exhaust Dyeing L*= 40.12 L*= 57.58 LR – 40:1 a*= -8.73 a*= -7.31 1.0% owf b*= -20.85 b*= -16.13 40 g/L NaCl K/S= 7.77 K/S= 1.85 Exhaust 40 - 18 30°C Exhaust 40 - 54 Exhaust Dyeing L*= 75.28 L*= 68.72 LR – 40:1 a*= 33.77 a*= 43.07 0.5% owf b*= 12.40 b*= 16.53 0 g/L NaCl K/S= 0.88 K/S= 1.74 Exhaust 40 - 19 60°C Exhaust 40 - 55 Exhaust Dyeing L*= 69.66 L*= 64.77 LR – 40:1 a*= 41.87 a*= 47.44 0.5% owf b*= 17.19 b*= 19.25 10 g/L NaCl K/S= 1.68 K/S= 2.60 Exhaust 40 - 20 60°C Exhaust 40 - 56 Exhaust Dyeing L*= 66.24 L*= 63.37 LR – 40:1 a*= 46.61 a*= 48.95 0.5% owf b*= 20.33 b*= 20.23 40 g/L NaCl K/S= 2.49 K/S= 3.04 Exhaust 40 - 21 60°C Exhaust 40 - 57 Exhaust Dyeing L*= 94.22 L*= 94.18 LR – 40:1 a*= -2.32 a*= -2.85 0.5% owf b*= 9.35 b*= 11.92 0 g/L NaCl K/S= 0.07 K/S= 0.10 Exhaust 40 - 22 60°C Exhaust 40 - 58 Exhaust Dyeing L*= 93.73 L*= 93.71 LR – 40:1 a*= -4.33 a*= -4.71 0.5% owf b*= 18.83 b*= 20.52 10 g/L NaCl K/S= 0.18 K/S= 0.22 Exhaust 40 - 23 60°C Exhaust 40 - 59

Exhaust Dyeing L*= 92.84 L*= 93.02 LR – 40:1 a*= -5.70 a*= -5.73 0.5% owf b*= 28.44 b*= 29.82 40 g/L NaCl K/S= 0.37 K/S= 0.42 Exhaust 40 - 24 60°C Exhaust 40 - 60

171

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 61.33 L*= 68.62 LR – 40:1 a*= -8.69 a*= -6.78 0.5% owf b*= -16.69 b*= -12.65 0 g/L NaCl K/S= 1.60 K/S= 0.81 Exhaust 40 - 25 60°C Exhaust 40 - 61 Exhaust Dyeing L*= 54.24 L*= 63.51 LR – 40:1 a*= -9.11 a*= -7.12 0.5% owf b*= -18.58 b*= -13.82 10 g/L NaCl K/S= 2.72 K/S= 1.20 Exhaust 40 - 26 60°C Exhaust 40 - 62 Exhaust Dyeing L*= 48.67 L*= 59.62 LR – 40:1 a*= -9.20 a*= -7.49 0.5% owf b*= -19.83 b*= -14.90 40 g/L NaCl K/S= 4.13 K/S= 1.61 Exhaust 40 - 27 60°C Exhaust 40 - 63 Exhaust Dyeing L*= 70.44 L*= 64.92 LR – 40:1 a*= 39.80 a*= 47.34 1.0% owf b*= 15.39 b*= 19.28 0 g/L NaCl K/S= 1.49 K/S= 2.57 Exhaust 40 - 28 60°C Exhaust 40 - 64 Exhaust Dyeing L*= 64.36 L*= 59.86 LR – 40:1 a*= 48.05 a*= 52.18 1.0% owf b*= 21.66 b*= 22.97 10 g/L NaCl K/S= 2.96 K/S= 4.24 Exhaust 40 - 29 60°C Exhaust 40 - 65 Exhaust Dyeing L*= 60.35 L*= 58.80 LR – 40:1 a*= 52.34 a*= 53.29 1.0% owf b*= 25.44 b*= 24.15 40 g/L NaCl K/S= 4.66 K/S= 4.84 Exhaust 40 - 30 60°C Exhaust 40 - 66 Exhaust Dyeing L*= 93.92 L*= 93.79 LR – 40:1 a*= -3.30 a*= -3.81 1.0% owf b*= 13.83 b*= 16.53 0 g/L NaCl K/S= 0.11 K/S= 0.16 Exhaust 40 - 31 60°C Exhaust 40 - 67

Exhaust Dyeing L*= 92.97 L*= 93.05 LR – 40:1 a*= -5.44 a*= -5.17 1.0% owf b*= 25.33 b*= 26.45 10 g/L NaCl K/S= 0.30 K/S= 0.34 Exhaust 40 - 32 60°C Exhaust 40 - 68

172

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 91.98 L*= 92.13 LR – 40:1 a*= -6.33 a*= -5.86 1.0% owf b*= 37.65 b*= 36.58 40 g/L NaCl K/S= 0.65 K/S= 0.64 Exhaust 40 - 33 60°C Exhaust 40 - 69 Exhaust Dyeing L*= 54.41 L*= 61.89 LR – 40:1 a*= -9.15 a*= -7.50 1.0% owf b*= -18.42 b*= -14.53 0 g/L NaCl K/S= 2.69 K/S= 1.38 Exhaust 40 - 34 30°C Exhaust 40 - 70 Exhaust Dyeing L*= 47.30 L*= 56.08 LR – 40:1 a*= -9.14 a*= -7.83 1.0% owf b*= -19.82 b*= -15.68 10 g/L NaCl K/S= 4.54 K/S= 2.11 Exhaust 40 - 35 60°C Exhaust 40 - 71 Exhaust Dyeing L*= 41.71 L*= 50.88 LR – 40:1 a*= -8.77 a*= -7.87 1.0% owf b*= -20.61 b*= -16.08 40 g/L NaCl K/S= 6.84 K/S= 3.00 Exhaust 40 - 36 60°C Exhaust 40 - 72 Exhaust Dyeing L*= 63.16 L*= 69.72 LR – 20:1 a*= 50.48 a*= 43.04 0.5% owf b*= 22.99 b*= 16.19 0 g/L NaCl K/S= 3.50 K/S= 1.62 Exhaust 20 - 1 30°C Exhaust 20 - 37 Exhaust Dyeing L*= 60.60 L*= 70.30 LR – 20:1 a*= 53.63 a*= 41.84 0.5% owf b*= 25.90 b*= 15.32 10 g/L NaCl K/S= 4.76 K/S= 1.50 Exhaust 20 - 2 30°C Exhaust 20 - 38 Exhaust Dyeing L*= 59.71 L*= 72.53 LR – 20:1 a*= 54.26 a*= 39.34 0.5% owf b*= 26.48 b*= 13.67 40 g/L NaCl K/S= 5.18 K/S= 1.21 Exhaust 20 - 3 30°C Exhaust 20 - 39

Exhaust Dyeing L*= 93.83 L*= 94.15 LR – 20:1 a*= -5.53 a*= -4.97 0.5% owf b*= 26.48 b*= 23.07 0 g/L NaCl K/S= 0.30 K/S= 0.26 Exhaust 20 - 4 30°C Exhaust 20 - 40

173

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 92.92 L*= 93.48 LR – 20:1 a*= -6.65 a*= -5.94 0.5% owf b*= 39.71 b*= 31.39 10 g/L NaCl K/S= 0.67 K/S= 0.45 Exhaust 20 - 5 30°C Exhaust 20 - 41 Exhaust Dyeing L*= 91.25 L*= 93.41 LR – 20:1 a*= -5.06 a*= -6.35 0.5% owf b*= 49.72 b*= 33.17 40 g/L NaCl K/S= 1.21 K/S= 0.50 Exhaust 20 - 6 30°C Exhaust 20 - 42 Exhaust Dyeing L*= 52.63 L*= 60.93 LR – 20:1 a*= -9.38 a*= -6.57 0.5% owf b*= -18.83 b*= -14.90 0 g/L NaCl K/S= 3.10 K/S= 1.42 Exhaust 20 - 7 0°C Exhaust 20 – 43 Exhaust Dyeing L*= 46.65 L*= 53.13 LR – 20:1 a*= -9.37 a*= -7.05 0.5% owf b*= -20.10 b*= -16.59 10 g/L NaCl K/S= 4.85 K/S= 2.52 Exhaust 20 - 8 30°C Exhaust 20 – 44 Exhaust Dyeing L*= 45.06 L*= 53.99 LR – 20:1 a*= -9.09 a*= -6.40 0.5% owf b*= -20.09 b*= -16.61 40 g/L NaCl K/S= 5.37 K/S= 2.32 Exhaust 20 - 9 30°C Exhaust 20 - 45 Exhaust Dyeing L*= 58.75 L*= 67.35 LR – 20:1 a*= 54.75 a*= 46.11 1.0% owf b*= 27.02 b*= 18.06 0 g/L NaCl K/S= 5.61 K/S= 2.09 Exhaust 20 - 10 30°C Exhaust 20 - 46 Exhaust Dyeing L*= 55.58 L*= 68.21 LR – 20:1 a*= 57.49 a*= 44.60 1.0% owf b*= 30.60 b*= 17.04 10 g/L NaCl K/S= 8.17 K/S= 1.88 Exhaust 20 - 11 30°C Exhaust 20 - 47

Exhaust Dyeing L*= 54.22 L*= 71.65 LR – 20:1 a*= 58.14 a*= 40.57 1.0% owf b*= 31.56 b*= 14.69 40 g/L NaCl K/S= 9.23 K/S= 1.34 Exhaust 20 - 12 30°C Exhaust 20 - 48

174

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 93.09 L*= 93.82 LR – 20:1 a*= -6.44 a*= -5.82 1.0% owf b*= 37.08 b*= 27.93 0 g/L NaCl K/S= 0.57 K/S= 0.37 Exhaust 20 - 13 30°C Exhaust 20 - 49 Exhaust Dyeing L*= 91.95 L*= 92.94 LR – 20:1 a*= -6.55 a*= -6.02 1.0% owf b*= 50.92 b*= 36.83 10 g/L NaCl K/S= 1.23 K/S= 0.63 Exhaust 20 - 14 30°C Exhaust 20 - 50 Exhaust Dyeing L*= 90.73 L*= 93.20 LR – 20:1 a*= -5.51 a*= -6.36 1.0% owf b*= 63.54 b*= 35.27 40 g/L NaCl K/S= 2.34 K/S= 0.56 Exhaust 20 - 15 30°C Exhaust 20 - 51 Exhaust Dyeing L*= 45.46 L*= 56.38 LR – 20:1 a*= -9.37 a*= -6.63 1.0% owf b*= -20.18 b*= .1603 0 g/L NaCl K/S= 5.31 K/S= 1.97 Exhaust 20 - 16 30°C Exhaust 20 - 52 Exhaust Dyeing L*= 39.84 L*= 48.58 LR – 20:1 a*= -8.72 a*= -7.05 1.0% owf b*= -20.73 b*= -17.58 10 g/L NaCl K/S= 7.96 K/S= 3.49 Exhaust 20 - 17 30°C Exhaust 20 - 53 Exhaust Dyeing L*= 36.80 L*= 47.54 LR – 20:1 a*= -8.06 a*= -6.48 1.0% owf b*= -20.52 b*= -17.93 40 g/L NaCl K/S= 9.73 K/S= 3.69 Exhaust 20 - 18 30°C Exhaust 20 - 54 Exhaust Dyeing L*= 63.17 L*= 65.24 LR – 20:1 a*= 50.13 a*= 46.59 0.5% owf b*= 23.56 b*= 18.77 0 g/L NaCl K/S= 3.50 K/S= 2.45 Exhaust 20 - 19 60°C Exhaust 20 - 55

Exhaust Dyeing L*= 60.57 L*= 62.72 LR – 20:1 a*= 53.18 a*= 48.14 0.5% owf b*= 26.38 b*= 19.80 10 g/L NaCl K/S= 4.76 K/S= 3.06 Exhaust 20 - 20 60°C Exhaust 20 - 56

175

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 59.87 L*= 62.10 LR – 20:1 a*= 53.63 a*= 49.97 0.5% owf b*= 26.81 b*= 21.30 40 g/L NaCl K/S= 5.12 K/S= 3.69 Exhaust 20 - 21 60°C Exhaust 20 - 57 Exhaust Dyeing L*= 93.49 L*= 93.48 LR – 20:1 a*= -5.57 a*= -5.61 0.5% owf b*= 27.28 b*= 26.18 0 g/L NaCl K/S= 0.32 K/S= 0.34 Exhaust 20 - 22 60°C Exhaust 20 - 58 Exhaust Dyeing L*= 92.74 L*= 92.76 LR – 20:1 a*= -6.68 a*= -6.26 0.5% owf b*= 39.67 b*= 36.93 10 g/L NaCl K/S= 0.68 K/S= 0.64 Exhaust 20 - 23 60°C Exhaust 20 - 59 Exhaust Dyeing L*= 91.73 L*= 91.33 LR – 20:1 a*= -6.65 a*= -6.62 0.5% owf b*= 50.92 b*= 46.29 40 g/L NaCl K/S= 1.25 K/S= 1.10 Exhaust 20 - 24 60°C Exhaust 20 - 60 Exhaust Dyeing L*= 52.33 L*= 59.62 LR – 20:1 a*= -9.17 a*= -7.22 0.5% owf b*= -18.83 b*= -15.22 0 g/L NaCl K/S= 3.14 K/S= 1.61 Exhaust 20 - 25 60°C Exhaust 20 - 61 Exhaust Dyeing L*= 46.21 L*= 54.66 LR – 20:1 a*= -9.09 a*= -7.23 0.5% owf b*= -19.97 b*= -15.58 10 g/L NaCl K/S= 4.92 K/S= 2.25 Exhaust 20 - 26 60°C Exhaust 20 – 62 Exhaust Dyeing L*= 44.51 L*= 53.07 LR – 20:1 a*= -8.83 a*= -6.95 0.5% owf b*= -20.19 b*= -15.82 40 g/L NaCl K/S= 5.53 K/S= 2.48 Exhaust 20 - 27 60°C Exhaust 20 - 63

Exhaust Dyeing L*= 58.32 L*= 61.16 LR – 0:1 a*= 54.78 a*= 50.89 1.0% owf b*= 28.32 b*= 21.98 0 g/L NaCl K/S= 6.03 K/S= 3.47 Exhaust 20 - 28 60°C Exhaust 20 - 64

176

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 55.40 L*= 58.54 LR – 20:1 a*= 57.01 a*= 52.63 1.0% owf b*= 31.32 b*= 23.63 10 g/L NaCl K/S= 8.36 K/S= 4.74 Exhaust 20 - 29 60°C Exhaust 20 - 65 Exhaust Dyeing L*= 54.25 L*= 58.51 LR – 20:1 a*= 57.30 a*= 53.49 1.0% owf b*= 31.78 b*= 24.52 40 g/L NaCl K/S= 9.13 K/S= 5.00 Exhaust 20 - 30 60°C Exhaust 20 - 66 Exhaust Dyeing L*= 92.86 L*= 92.80 LR – 20:1 a*= -6.22 a*= -5.67 1.0% owf b*= 36.21 b*= 33.95 0 g/L NaCl K/S= 0.56 K/S= 0.55 Exhaust 20 - 31 60°C Exhaust 20 - 67 Exhaust Dyeing L*= 91.73 L*= 91.97 LR – 20:1 a*= -6.43 a*= -6.24 1.0% owf b*= 50.05 b*= 45.00 10 g/L NaCl K/S= 1.20 K/S= 1.01 Exhaust 20 - 32 60°C Exhaust 20 - 68 Exhaust Dyeing L*= 90.53 L*= 90.84 LR – 20:1 a*= -5.53 a*= -5.33 1.0% owf b*= 61.37 b*= 54.29 40 g/L NaCl K/S= 2.18 K/S= 1.64 Exhaust 20 - 33 60°C Exhaust 20 - 69 Exhaust Dyeing L*= 44.54 L*= 55.24 LR – 20:1 a*= -9.13 a*= -7.23 1.0% owf b*= -20.31 b*= -15.97 0 g/L NaCl K/S= 5.63 K/S= 2.18 Exhaust 20 - 34 60°C Exhaust 20 - 70 Exhaust Dyeing L*= 38.86 L*= 48.68 LR – 20:1 a*= -8.38 a*= -7.27 1.0% owf b*= -20.70 b*= -16.72 10 g/L NaCl K/S= 8.43 K/S= 3.44 60°C Exhaust 20 - 35 Exhaust 20 - 71

Exhaust Dyeing L*= 36.39 L*= 45.29 LR – 0:1 a*= -7.59 a*= -6.67 1.0% owf b*= -20.40 b*= -16.55 40 g/L NaCl K/S= 9.78 K/S= 4.21 Exhaust 20 - 36 60°C Exhaust 20 - 72

177

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L* = 63.13 L* = 70.67 LR – 10:1 a* = 49.94 a* = 41.08 0.5% owf b* = 22.41 b* = 14.78 0 g/L NaCl K/S = 3.39 K/S = 1.41 Exhaust 10 - 1 30°C Exhaust 10 - 37 Exhaust Dyeing L*= 62.09 L*= 71.94 LR – 10:1 a*= 51.32 a*= 39.26 0.5% owf b*= 23.64 b*= 13.69 10 g/L NaCl K/S= 3.83 K/S= 1.22 Exhaust 10 - 2 30°C Exhaust 10 - 38 Exhaust Dyeing L*= 61.76 L*= 74.21 LR – 10:1 a*= 52.16 a*= 36.45 0.5% owf b*= 24.26 b*= 12.17 40 g/L NaCl K/S= 4.08 K/S= 0.97 Exhaust 10 - 3 30°C Exhaust 10 - 39 Exhaust Dyeing L*= 92.50 L*= 93.48 LR – 10:1 a*= -5.08 a*= -5.88 0.5% owf b*= 38.89 b*= 32.56 0 g/L NaCl K/S= 0.66 K/S= 0.48 Exhaust 10 - 4 30°C Exhaust 10 - 40 Exhaust Dyeing L*= 92.52 L*= 93.26 LR – 10:1 a*= -5.79 a*= -5.94 0.5% owf b*= 43.73 b*= 35.59 10 g/L NaCl K/S= 0.83 K/S= 0.57 Exhaust 10 - 5 30°C Exhaust 10 - 41 Exhaust Dyeing L*= 91.69 L*= 93.41 LR – 10:1 a*= -5.64 a*= -5.85 0.5% owf b*= 53.35 b*= 33.57 40 g/L NaCl K/S= 1.38 K/S= 0.50 Exhaust 10 - 6 30°C Exhaust 10 - 42 Exhaust Dyeing L*= 50.62 L*= 56.64 LR – 10:1 a*= -9.07 a*= -7.05 0.5% owf b*= -19.32 b*= -16.03 0 g/L NaCl K/S= 3.55 K/S= 1.98 Exhaust 10 - 7 30°C Exhaust 10 - 43

Exhaust Dyeing L*= 48.97 L*= 53.61 LR – 10:1 a*= -9.01 a*= -7.09 0.5% owf b*= -19.49 b*= -16.58 10 g/L NaCl K/S= 3.99 K/S= 2.45 Exhaust 10 - 8 30°C Exhaust 10 - 44

178

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 45.92 L*= 53.66 LR – 10:1 a*= -8.83 a*= -7.06 0.5% owf b*= -19.97 b*= -17.62 0 g/L NaCl K/S= 4.96 K/S= 2.49 Exhaust 10 - 9 30°C Exhaust 10 - 45 Exhaust Dyeing L*= 58.67 L*= 68.02 LR – 10:1 a*= 54.24 a*= 44.55 1.0% owf b*= 26.66 b*= 16.79 0 g/L NaCl K/S= 5.49 K/S= 1.86 Exhaust 10 - 10 30°C Exhaust 10 - 46 Exhaust Dyeing L*= 56.59 L*= 69.52 LR – 10:1 a*= 56.04 a*= 41.99 1.0% owf b*= 28.85 b*= 15.11 10 g/L NaCl K/S= 6.93 K/S= 1.56 Exhaust 10 - 11 30°C Exhaust 10 - 47 Exhaust Dyeing L*= 55.68 L*= 72.24 LR – 10:1 a*= 56.90 a*= 38.94 1.0% owf b*= 29.94 b*= 13.46 40 g/L NaCl K/S= 7.72 K/S= 1.20 Exhaust 10 - 12 30°C Exhaust 10 - 48 Exhaust Dyeing L*= 92.08 L*= 93.01 LR – 10:1 a*= -5.38 a*= -6.04 1.0% owf b*= 44.26 b*= 37.74 0 g/L NaCl K/S= 0.88 K/S= 0.65 Exhaust 10 - 13 30°C Exhaust 10 - 49 Exhaust Dyeing L*= 91.31 L*= 92.89 LR – 10:1 a*= -5.41 a*= -6.03 1.0% owf b*= 56.47 b*= 39.69 10 g/L NaCl K/S= 1.64 K/S= 0.72 Exhaust 10 - 14 30°C Exhaust 10 - 50 Exhaust Dyeing L*= 90.48 L*= 93.07 LR – 10:1 a*= -4.53 a*= -5.87 1.0% owf b*= 64.86 b*= 36.41 40 g/L NaCl K/S= 2.50 K/S= 0.60 Exhaust 10 - 15 30°C Exhaust 10 - 51

Exhaust Dyeing L*= 42.80 L*= 50.02 LR – 10:1 a*= -8.83 a*= -7.35 1.0% owf b*= -20.52 b*= -17.59 0 g/L NaCl K/S= 6.33 K/S= 3.21 Exhaust 10 - 16 30°C Exhaust 10 - 52

179

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 40.27 L*= 46.95 LR – 10:1 a*= -8.40 a*= -7.16 1.0% owf b*= -20.45 b*= -17.90 10 g/L NaCl K/S= 7.50 K/S= 3.96 Exhaust 10 - 17 30°C Exhaust 10 - 53 Exhaust Dyeing L*= 38.35 L*= 48.47 LR – 10:1 a*= -8.07 a*= -6.81 1.0% owf b*= -20.34 b*= -18.35 40 g/L NaCl K/S= 8.53 K/S= 3.55 Exhaust 10 - 18 30°C Exhaust 10 - 54 Exhaust Dyeing L*= 62.21 L*= 64.06 LR – 10:1 a*= 51.45 a*= 48.57 0.5% owf b*= 24.60 b*= 19.92 0 g/L NaCl K/S= 3.92 K/S= 2.79 Exhaust 10 - 19 60°C Exhaust 10 - 55 Exhaust Dyeing L*= 62.20 L*= 62.27 LR – 10:1 a*= 51.02 a*= 49.94 0.5% owf b*= 24.15 b*= 20.93 10 g/L NaCl K/S= 3.82 K/S= 3.30 Exhaust 10 - 20 60°C Exhaust 10 - 56 Exhaust Dyeing L*= 61.54 L*= 62.46 LR – 10:1 a*= 51.99 a*= 50.42 0.5% owf b*= 2505 b*= 21.36 40 g/L NaCl K/S= 4.21 K/S= 3.41 Exhaust 10 - 21 60°C Exhaust 10 - 57 Exhaust Dyeing L*= 93.16 L*= 92.79 LR – 10:1 a*= -6.11 a*= -5.36 0.5% owf b*= 36.93 b*= 34.17 0 g/L NaCl K/S= 0.57 K/S= 0.56 Exhaust 10 - 22 60°C Exhaust 10 - 58 Exhaust Dyeing L*= 92.35 L*= 92.21 LR – 10:1 a*= -6.20 a*= -5.68 0.5% owf b*= 45.60 b*= 42.13 10 g/L NaCl K/S= 0.93 K/S= 0.87 Exhaust 10 - 23 60°C Exhaust 10 - 59

Exhaust Dyeing L*= 91.66 L*= 91.26 LR – 10:1 a*= -5.89 a*= -5.54 0.5% owf b*= 52.22 b*= 47.51 40 g/L NaCl K/S= 1.32 K/S= 1.20 Exhaust 10 - 24 60°C Exhaust 10 - 60

180

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 51.52 L*= 54.82 LR – 10:1 a*= -8.75 a*= -7.09 0.5% owf b*= -18.95 b*= -15.83 0 g/L NaCl K/S= 3.26 K/S= 2.23 Exhaust 10 - 25 60°C Exhaust 10 - 61 Exhaust Dyeing L*= 48.71 L*= 50.57 LR – 10:1 a*= -8.58 a*= -7.11 0.5% owf b*= -19.40 b*= -16.27 10 g/L NaCl K/S= 3.97 K/S= 3.00 Exhaust 10 - 26 60°C Exhaust 10 - 62 Exhaust Dyeing L*= 46.18 L*= 493.96 LR – 10:1 a*= -8.49 a*= -7.10 0.5% owf b*= -19.68 b*= -16.97 40 g/L NaCl K/S= 4.76 K/S= 3.16 Exhaust 10 - 27 60°C Exhaust 10 - 63 Exhaust Dyeing L*= 57.57 L*= 60.18 LR – 10:1 a*= 55.13 a*= 52.75 1.0% owf b*= 28.72 b*= 23.51 0 g/L NaCl K/S= 6.34 K/S= 4.20 Exhaust 10 - 28 60°C Exhaust 10 - 64 Exhaust Dyeing L*= 56.17 L*= 58.00 LR – 10:1 a*= 56.03 a*= 54.22 1.0% owf b*= 29.93 b*= 24.92 10 g/L NaCl K/S= 7.34 K/S= 5.17 Exhaust 10 - 29 60°C Exhaust 10 - 65 Exhaust Dyeing L*= 55.62 L*= 58.64 LR – 10:1 a*= 56.61 a*= 54.04 1.0% owf b*= 30.71 b*= 24.72 40 g/L NaCl K/S= 7.88 K/S= 4.98 Exhaust 10 - 30 60°C Exhaust 10 - 66 Exhaust Dyeing L*= 92.29 L*= 91.66 LR – 10:1 a*= -5.88 a*= -5.73 1.0% owf b*= 44.62 b*= 42.81 0 g/L NaCl K/S= 0.89 K/S= 0.94 Exhaust 10 - 31 60°C Exhaust 10 - 67

Exhaust Dyeing L*= 91.29 L*= 90.71 LR – 10:1 a*= -5.49 a*= -5.21 1.0% owf b*= 55.17 b*= 50.53 10 g/L NaCl K/S= 1.55 K/S= 1.43 Exhaust 10 - 32 60°C Exhaust 10 - 68

181

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b* Exhaust Dyeing L*= 90.47 L*= 89.81 LR – 10:1 a*= -4.69 a*= -4.64 1.0% owf b*= 63.35 b*= 57.86 40 g/L NaCl K/S= 2.35 K/S= 2.06 Exhaust 10 - 33 60°C Exhaust 10 - 69 Exhaust Dyeing L*= 42.96 L*= 46.52 LR – 10:1 a*= -8.40 a*= -7.39 1.0% owf b*= -20.34 b*= -17.66 0 g/L NaCl K/S= 6.11 K/S= 4.11 Exhaust 10 - 34 30°C Exhaust 10 - 70 Exhaust Dyeing L*= 39.80 L*= 43.71 LR – 10:1 a*= -7.89 a*= -6.98 1.0% owf b*= -20.43 b*= -17.35 10 g/L NaCl K/S= 7.59 K/S= 4.88 Exhaust 10 - 35 60°C Exhaust 10 - 71 Exhaust Dyeing L*= 37.79 L*= 41.45 LR – 10:1 a*= -7.52 a*= -6.59 1.0% owf b*= -20.37 b*= -17.64 40 g/L NaCl K/S= 8.70 K/S= 5.69 Exhaust 10 - 36 60°C Exhaust 10 - 72

L*= 60.88 Pad Batch L*= 62.00 a*= 52.21 0.5% owf a*= 48.84 b*= 25.39 30°C b*= 19.72 K/S= 4.45 Rolled K/S= 3.19 PB Rolled - 1 PB Rolled - 13

L*= 53.38 Pad Batch L*= 57.78 a*= 57.48 1.0% owf a*= 52.84 b*= 32.60 30°C b*= 23.31 K/S= 10.04 Rolled K/S= 4.9 PB Rolled - 2 PB Rolled - 14

L*= 91.08 Pad Batch L*= 90.54 a*= -6.36 0.5% owf a*= -7.04 b*= 56.71 30°C b*= 52.47 K/S= 1.69 Rolled K/S= 1.56 PB Rolled - 3 PB Rolled - 15

L*= 88.82 Pad Batch L*= 89.81 a*= -3.25 1.0% owf a*= -6.21 b*= 72.11 30°C b*= 61.09

K/S= 3.95 PB Rolled - 4 Rolled PB Rolled - 16 K/S= 2.40

182

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b*

L*= 44.36 Pad Batch L*= 46.47 a*= -8.53 0.5% owf a*= -7.21 b*= -20.17 30°C b*= -16.89 K/S= 5.52 Rolled K/S= 4.00 PB Rolled - 5 PB Rolled - 17

L*= 36.30 Pad Batch L*= 39.48 a*= -7.35 1.0% owf a*= -6.54 b*= -20.47 30°C b*= -17.58 K/S= 9.80 Rolled K/S= 6.51 PB Rolled - 6 PB Rolled - 18

L*= 59.82 Pad Batch L*= 57.11 a*= 53.61 0.5% owf a*= 53.33 b*= 2701 60°C b*= 24.40 K/S= 5.13 Rolled K/S= 5.37 PB Rolled - 7 PB Rolled - 19

L*= 54.31 Pad Batch L*= 52.68 a*= 57.36 1.0% owf a*= 56.09 b*= 32.51 60°C b*= 28.04 K/S= 9.40 Rolled K/S= 8.34 PB Rolled - 8 PB Rolled - 20

L*= 91.60 Pad Batch L*= 90.63 a*= -6.29 0.5% owf a*= -6.02 b*= 51.99 60°C b*= 48.80 K/S= 1.36 Rolled K/S= 1.38 PB Rolled - 9 PB Rolled- 21

L*= 89.78 Pad Batch L*= 89.05 a*= -4.40 1.0% owf a*= -5.92 b*= 65.25 60°C b*= 56.40 K/S= 2.78 Rolled K/S= 2.14 PB Rolled - 10 PB Rolled - 22

L*= 46.11 Pad Batch L*= 44.61 a*= -8.88 0.5% owf a*= -7.05 b*= -19.77 60°C b*= -17.06 K/S= 4.98 Rolled K/S= 4.59 PB Rolled - 11 PB Rolled - 23

L*= 36.92 Pad Batch L*= 37.97 a*= -7.78 1.0% owf a*= -6.18 b*= -20.48 60°C b*= -17.42

K/S= 9.53 PB Rolled - 12 Rolled PB Rolled - 24 K/S= 7.21

183

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b*

L*= 58.25 Pad Batch L*= 62.00 a*= 52.79 0.5% owf a*= 48.37 b*= 26.48 30°C b*= 19.43 K/S= 5.62 Flat K/S= 3.16 PB Flat - 1 PB Flat - 13

L*= 53.54 Pad Batch L*= 58.42 a*= 57.32 1.0% owf a*= 51.83 b*= 32.18 30°C b*= 22.29 K/S= 9.80 Flat K/S= 4.51 PB Flat - 2 PB Flat - 14

L*= 90.30 Pad Batch L*= 91.37 a*= -5.37 0.5% owf a*= -6.40 b*= 61.03 30°C b*= 52.30 K/S= 2.19 Flat K/S= 1.47 PB Flat - 3 PB Flat - 15

L*= 89.46 Pad Batch L*= 90.62 a*= -4.26 1.0% owf a*= -5.34 b*= 71.94 30°C b*= 60.31 K/S= 3.76 Flat K/S= 2.22 PB Flat - 4 PB Flat - 16

L*= 44.39 Pad Batch L*= - - a*= -8.60 0.5% owf a*= -

b*= -20.08 30°C b*= - PB Flat- 17 K/S= 5.31 Flat K/S= - PB Flat - 5

L*= 36.31 Pad Batch L*= - - a*= -7.36 1.0% owf a*= -

b*= -20.56 30°C b*= - PB Flat - 18 K/S= 9.85 Flat K/S= - PB Flat - 6

L*= 59.56 Pad Batch L*= 57.77 a*= 53.58 0.5% owf a*= 53.36 b*= 27.30 60°C b*= 25.07 K/S= 5.28 Flat K/S= 5.27 PB Flat - 7 PB Flat - 19

L*= 54.83 Pad Batch L*= 52.53 a*= 57.83 1.0% owf a*= 56.94 b*= 33.02 60°C b*= 29.68

K/S= 9.25 PB Flat - 8 Flat PB Flat - 20 K/S= 9.01

184

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b*

L*= 90.15 Pad Batch L*= 91.09 a*= -3.94 0.5% owf a*= -5.32 b*= 54.75 60°C b*= 53.14 K/S= 1.70 Flat K/S= 1.58 PB Flat - 9 PB Flat - 21

L*= 88.47 Pad Batch L*= 89.61 a*= -2.35 1.0% owf a*= -3.99 b*= 65.20 60°C b*= 62.56 K/S= 3.04 Flat K/S= 2.64 PB Flat - 10 PB Flat - 22

L*= 44.91 Pad Batch L*= 44.74 a*= -8.68 0.5% owf a*= -7.05 b*= -19.78 60°C b*= -16.41 K/S= 5.29 Flat K/S= 4.48 PB Flat - 11 PB Flat - 23

L*= 36.70 Pad Batch L*= 36.91 a*= -7.77 1.0% owf a*= -6.09 b*= -20.29 60°C b*= -16.69 K/S= 9.62 Flat K/S= 7.65 PB Flat - 12 PB Flat - 24

L*= 60.42 Pad Batch L*= 57.23 a*= 54.02 0.5% owf a*= 54.38 b*= 27.58 60°C b*= 25.79 K/S= 5.13 Nuance K/S= 5.69 PB Nuance - 7 PB Nuance - 19

L*= 54.42 Pad Batch L*= 51.58 a*= 57.74 1.0% owf a*= 56.57 b*= 33.11 60°C b*= 28.85 K/S= 9.71 Nuance K/S= 9.38 PB Nuance - 8 PB Nuance - 20

L*= 91.37 Pad Batch L*= 91.18 a*= -5.77 0.5% owf a*= -6.44 b*= 51.71 60°C b*= 49.04 K/S= 1.39 Nuance K/S= 1.36 PB Nuance - 9 PB Nuance - 21

L*= 89.43 Pad Batch L*= 89.73 a*= -3.50 1.0% owf a*= -3.85 b*= 60.59 60°C b*= 56.60

K/S= 2.45 PB Nuance - 10 Nuance PB Nuance - 22 K/S= 2.22

185

Table 44A. Continued.

L*a*b* Commercial Parameters Modified L*a*b*

L*= 46.99 Pad Batch L*= 45.27 a*= -9.22 0.5% owf a*= -7.68 b*= -19.79 60°C b*= -16.98 K/S= 4.68 Nuance K/S= 4.49 PB Nuance -11 PB Nuance - 23

L*= 37.27 Pad Batch L*= 38.30 a*= -7.91 1.0% owf a*= -6.41 b*= -20.61 60°C b*= -17.00 K/S= 9.40 Nuance K/S= 7.04 PB Nuance - 12 PB Nuance - 24

L*= 59.59 L*= 56.80 Pad Steam a*= 49.99 a*= 49.36 0.5% owf b*= 24.10 b*= 22.50 100°C K/S= 4.59 K/S= 5.02 PS - 1 PS - 7

L*= 54.89 L*= 51.11 Pad Steam a*= 54.13 a*= 52.90 1.0% owf b*= 29.10 b*= 26.99 100°C K/S= 7.91 K/S= 8.89 PS - 2 PS - 8

L*= 87.29 L*= 85.14 Pad Steam a*= -4.28 a*= -2.20 0.5% owf b*= 38.65 b*= 46.10 100°C K/S= 0.98 K/S= 1.67 PS - 3 PS- 9

L*= 86.78 L*= 83.06 Pad Steam a*= -4.39 a*= -0.12 1.0% owf b*= 53.08 b*= 58.27 100°C K/S= 1.98 K/S= 3.21 PS - 4 PS - 10

L*= 58.80 L*= 50.96 Pad Steam a*= 5.67 a*= 7.23 0.5% owf b*= -10.31 b*= -9.47 100°C K/S= 1.19 K/S= 2.06 PS - 5 PS - 11

L*= 51.61 L*= 41.85 Pad Steam a*= 4.26 a*= 5.76 1.0% owf b*= -12.18 b*= -11.55 100°C K/S= 1.98 PS - 6 PS - 12 K/S= 3.77

186