Index

acid dyes see also dye solubility values; reactive dyes on cotton 67 lyotropic liquid crystals; Bragg angle 188 photodegradation of dyes C.l. acid orange 7 89 chromotropic acid 264 c.l. acid red 1 83 cotton c.l. acid red 151 95 pore size and distribution C. 1. acid red 266 99 methods for characterization 72-73 deuterium spectra 102 critical micelle concentration 84 optical micrograph 100 crystal form and habit x-ray diffraction patterns 103 control of C.l. food yellow 3 during pigment synthesis 137 deuterium spectra 101 following pigment synthesis 137-141 effect of urea on aggregation 104 definition 107 optical micrograph 100 crystal formation order parameters 102 growth 138 phase diagram 101 single crystals x-ray diffraction patterns 102 quinacridones 114 edicol sunset yellow 68, 69 crystal habit general description 83 agglomerates 126 orange 2 (C.l. acid orange 10) 68, 69 crystal shape 132-136 acidities effect on rheological properties 134 low acidity crystal size and state of defined 8 aggregation 126-131 moderate acidity effect on color strength 126 definition 11 light scattering theory 127 high acidity flocculates 126 definition 13 morphology 125-126 Ames test 255 packing 129 anionic azo dyes primary particles 126 aggregates 88-89 crystal lattice properties C.l. acid orange 7 crystallinity 125 interplanar separation 88 techniques for assessment 125 important classes 83-84 dpp pigment molecules 119 azo coupling isomorphism 123-125 highly acidic aromatic diazo C.I. pigment blue 15 124 components 5 C.I. pigment yellow 3 analogs 124 limitation involving 2-amino-4- diarylides 124 chloro-5-formylthiazole 31 molecule versus crystal 112-121 polymorphism 121-123 benzidines c.l. pigment red 3 123 dyes derived from C.L pigment yellow 17 123 mechanistic studies 265, 273 copper phthalocyanine 123 mutagenicity testing 258 quinacridone 123 genotoxicity solid solutions 124-125 N -acetylated derivatives 273, 275 x-ray diffraction analysis 122 3,3' -dichlorobenzidine 275 3,3' -dihydroxybenzidine 260 4,4' -diaminoazobenzene 262 removal of 260-262 4,4' -diaminobenzanilide 262 ortho-tolidine 260 diazotization 1 Bessel functions 2-amino-4-chloro-5-formylthiazole disperse dyes on polyester 46 in highly acid media 31 294 INDEX diazotization contd 5-phenyl-l,3 ,4-thiadiazole-2- one-stage process 40-41 diazonium ion 19 protonation steps 35 under industrial reaction 2-amino-4-chloro-5-forrnyl-3-thiophene• conditions 23-41 carbonitrile influence of reactor 40 competitive reactions 34, 36 methods for optimizing maximum yield 37 procedures 34-41 2-aminothiazole weakly basic aromatic amines 4 byproducts of 34 decomposition of diazotized characterization of diazonium ion 29 form 6-7 nmr data 33 diazotization rates protonation 29 carbocyclic aromatic amines 8-17 rate and selectivity 29-30 high acidities 13-17 analytical methods for low acidities 8-11 monitoring 24-25 moderate acidities 11-13 and azo coupling dependence on acidity 7-23 one-stage process 40-41 heterocyclic aromatic amines 17 - 20 two-stage process 35-40 4-aminopyridine 17-19 contact zone 41 5-amino-3-R-l ,2,4-thiadiazole 19 2-bromo-6-cyano-4-nitroaniline difference from carbocyclic aromatic competitive acid-catalyzed amines 19 hydrolysis 27-29 4-nitroaniline and derivatives 17 maximum yield of diazonium ion 31 rate-acidity profile 16 2-bromo-4,6-dinitroaniline acidity constants 16 half-life time 27 diffusion coefficient 47, 49 kinetics 26-29 for c.l. disperse violet 1 46-47 nmr data 28-29 for reactive dyes on cotton 69 uv-visible data 28 diffusion layer theory 5 48 2-cyano-4-nitroaniline diffusional boundary layer 47, 54 kinetics 35-40 diffusion through 53 maximum yield 39 direct dyes cyano-substitued aromatic C.l. direct brown 202 96 amines 21-23, 35 C.l. direct red 2 90 competitive acid-catalyzed C.l. Direct Red 28 (congo red) 82 hydrolysis 21-23,35-40 general description 83 kinetics 21-22 non-genotoxic, for ink-jet printing 262 rate constants 22 disperse dye particle size reactions in highly acid media 22-23 influence on thermodynamic 2,6-dichloro-4-nitroaniline solubility 47 kinetics 25-27 rate of dissolution 47-49 nmr data 25, 27 factors affecting 49-50 uv-visible data 26 saturation solubility 47 heteroarmatic amines disperse dyes see also dye solubility 4-aminopyridine 17 -19 values; dyeing with; photodegradation of 5-amino-3- R-l ,2,4-thiadiazole 19 dyes 2-aminothiazole 20 blue monoazo in highly acidic media 13, 22 examples 3 kinetics and mechanisms 1 synthetic route 2 dimensionless quantities 38-39 C.I. disperse blue 56 48 mechanistic pathways 12, 19 C.l. disperse orange 3 multistage 8 diffusion coefficient 57 rate constants 7,21-22,36-38 C.l. disperse red 15 rate curves 26-29 activation energy for diffusion 56-57 rate equations 9-13, 15-16, 18 C.l. disperse red 60 48 limiting step 10 diffusion coefficients proton transfer 15 effects of free volume 58 reversibility relationship to molecular volume 58 4-chloro-3-cyano-5-formyl-2-thio• typical values 56-57 phenediazonium ion 19 factors affecting dissolution 49-50 INDEX 295

crystal polymorphism 49 flow cell used 66 thermodynamic parameters 50 leveling dyeing cellulose with fiber reactive dyes description of process 59 activation energy driving force 59 for fiber diffusion 76 relation to partition coefficient 61 for fixation 76 schematic representation 60 adaptation of Fick's second law 63 transport to fiber surface 52-56 associated boundary rate equation 52 conditions 63-64 equilibrium partition coefficient 53 competitive hydrolysis reaction dye solubility associated rate equations 64 computational methods 184-185 schematic representation 62 activity coefficients of mixtures 184 fiber diffusion utility and limitations 185 activation energy 76 empirical/estimation key factors 70-73 experimental methods 192-193 utility of available models 73 influence of particle size and form 148 water swollen pore 71 measured solubilities 150-184 with simultaneous chemical in organic solvents 180-184 reaction 73-79 in water 151, 179-180 mechanism influence of non-surface-active adsorption immobilization 78 solutes 179 cellophane as a model 74-75 miscellaneous contributmg ionization of cellulose 61 factors 180 nucleophilic substitution 76 measurement methods 149-150 transitional kinetics choice of filter materials 149 dependence of half-time of C.L disperse blue 79 150 dyeing 55 c.1. disperse red 121 149 uptake of dye from bulk solution Reactive Bright Red 6S 150 acid dyes as models 68 Reactive Violet 4K 150 microscopic diffusional boundary regression analysis 190-192 layer 65 solubility parameters 187 -189 interfacial flux 68 applications 189-190 internal fiber interface 65 cohesive energy 187 into surface pore structure 67 free energy of mixing 188 rate equation 69 heat of mixing 187 representative reactive dyes 67 solubility values 152-163 surface induced association 70 acid dyes 182, 183 dyeing processes basic dyes 154, 155, 161 mathematical treatments disperse dyes 152-153. 156 associated equations 46 miscellaneous for a finite dyebath 46 anthraquinones 152-153 for an infinite dyebath 46 miscellaneous azo dyes 156-160 origin 46 reactive dyes 182 dyeing with disperse dyes solvent dyes 156. 160 batchwise dyeing of polyester 48 vat dyes 162 carriers dyestuff aggregation mode of action 58 acid dyes see also acid dyes. C.I. food diffusion within the fibre 56-59 yellow 3 Arrhenius equation 56 low molecular weight dyes 88 descriptive models 58 sulfonic acid groups 88 Fick's first law 56 aggregate stacks volume fraction 57 intermolecular spacing 85 finite vs infinite kinetics 50-52 direct dyes determining factors 51 aggregation numbers 90 general description 51 governing factors 84-86 transitional kinetic regime 52 electrostatic repulsive forces 86 heterogeneous kinetics hydrogen bonding 85 dissolution process 47 pi-pi interactions 8<; dyeing polyester 44-61 Van der Waals forces 85-86 296 INDEX

dyestuff aggregation contd c.l. direct black 38 273, 276 hydrophobic effects c.l. direct blue 15 273, 276 alkyl chains in anionic dyes 89 C.l. direct blue 218 276 micelle formation 84 C.l. direct orange 6 265 reactive dyes C.l. direct red 2 273 effect on properties 90 c.l. disperse yellow 3 282 x-ray analysis 90 c.l. pigment yellow 12 273, 279 role in textile dyeing 103-104 c.l. solvent yellow 2 267,273,278 techniques for measuring C.l. solvent yellow 3 269 associated difficulties 86-88 C.l. solvent yellow 14 282 diffusion methods 86-87 congo red 273,282 nmr 87 defined 254 small angle x-ray scattering (saxs) 87 gurr chrysoidine y 281 visible spectrophotometry 87 in vitro 255 wide angle x-ray scattering in vivo 255 (waxs) 88 mechanisms and metabolism DNA interactions 270-272 enthalpy changes 85 disazo dyes 273-275 environmental issues endoplasmic reticulum (ER) 270 fate of azo disperse dyes disaggregation C.l. disperse blue 79 284 flavin-induced activation 269 metallized dyes 284-288 N -hydroxylation 267-270 free vs bound metal 286-287 metabolic activation 265,268,271 natural dyes 286 monoazo dyes 267-273 removal of dyes from wastewater nitroxide radical formation 268 physical methods 284 reductive-cleavage 269,272, removal of free metals from 273-274 wastewater 288 t-RNA interactions 272-273 sediments methyl orange 264 reducing property 284 mutagenicity singlet oxygen sensitization 285 pathways leading to 256 toxicity of metal ions 284-286 schematic diagram of the assay 256 phenylenediamines Fick's second law of diffusion 46, 63 removal of 265 flavin mononucleotide (FMN) 257, 258 structure-activity-relationships functional dyes computer-assisted 280-283 photolytic behavior 237-239,242 empirical 275-280 properties and uses 137-138 test methods for assessing structures 240-241 Fusobacterium sp. 2 258-259 hamster liver hepatocytes 259 genotoxicity see also benzidines intestinal anaerobes 258-259 aromatic amines Prival modification 257-258 anilines and related amines 264 rat cecal flora 258 benzidines and related diamines 260 Salmonella mutagenicity 4,4' -diaminoazobenzene 262 assay 255-257 4,4' -diaminobenzanilide 262 glucopyranose structure 62 N,N -dimethyl-1,4- glucose 6-phosphate dehydrogenase dimethylaminobenzene 264 (NADH) 257 assessment by instrumental methods electron microscopy 270 h-acid 264 esr 267 Hammett acidity function 8 biophores heterogeneous dyeing process defined 282 schematic representation 45 C.l. acid black 52 264 hydrogen bonding C.l. acid yellow 151 276 organic pigments 114, 121 C.l. d&c red 9 282 C.l. d&c yellow 6 282 c.l. direct black 17 275 interplanar spacing C.l. direct black 19 276 dpp molecules 116 INDEX 297

Jablonski diagram 198 diazotized amines 13 Fermi-contact shift 15 lightfastness fundamental principles physical factors influencing 202-203 dipole-dipole interactions 92 lyotropic liquid crystal formation order parameter 93 definition 91 quadrapole interactions 93 measurement techniques Zeeman interaction 92 nmr spectroscopy 92-93 23Na spectra optical microscopy 91-92,100 C.1. food yellow 3 102 x-ray diffraction 93-94 nitrogen e5N) spectra principal categories 91 nitrosyl sulphuric acid 13-14 stable mesophases nitrous acid-nitrosonium ion 15 description 91-92 proton eH) spectra techniques for 91 diazotized amines 13. 25. 27 lyotropic liquid crystals Nusselt number 49 chromonic 94 C.l. acid red 266 98 organic pigments c.l. food yellow 3 98 aggregates 112 nematic and middle mesophases anthraquinoid C.I. food yellow 3 99 C.1. pigment blue 60 110 herringbone array 96, 97 C.I. pigment red 177 110 p-type systems azo C.l. acid red 266 99-100 c.1. pigment orange 36 110 C.l. food yellow 3 100 c.1. pigment red 144 110 C. 1. reactive red 3: 1 98 c.1. pigment yellow 183 110 orthorhombic symmetry 98 azomethine quasi-crystalline form 97 C.1. pigment yellow 110 110 semetic-like mesophases c.1. pigment yellow 139 110 acid dyes 95 characteristics 108 direct dyes 95-96 c.I. pigment blue 15 123-124 c.I. pigment blue 15:3 132 metabolic activation 255,265.268,272 TEM 133 micelle formation c.I. pigment blue 60 110 disperse dye solubility 48-49 C. 1. pigment orange 36 110 impact of disperse dye uptake 50 TEM 133 mutagenic activity c.l. pigment orange 43 134 quantitative measure 255 C. I. pigment orange 65 mutagens TEM 142 direct acting 256 C. I. pigment red 1 132 promutagens 255,271 c.I. pigment red 3 123. 132 mutations C. 1. pigment red 31 125 reverse 255 c.1. pigment red 57: I 132 types 255 TEM 133 c.l. pigment red 112 132 nitrosating electrophiles c.1. pigment red 144 110. 124 diazo anhydrides 4, 6 TEM 133 dinitrogen trioxide C.I. pigment red 177 110 mechanism 9 C. I. pigment red 179 110 kexp-expressions 10-11 C. I. pigment red 214 lIO nitrosonium ion 1 c.r. pigment red 224 lIO mechanism 10 C. I. pigment red 254 llO 15N nmr signal 14 TEM 133 nitrosyl sulphuric acid C. I. pigment violet 19 110 decomposition of 5 c.1. pigment violet 23 110 15N nmr signal 14-15 c.1. pigment yellow 1 132 reactions of ami des in 23 c.1. pigment yellow 12 124 nuclear magnetic resonance (nmr) C.I. pigment yellow 13 127. 132 analysis of liquid crystals 93,101-102 C. I. pigment yellow 14 124 carbon (13C) spectra C. 1. pigment yellow 17 123 298 INDEX organic pigments contd fluorescence and phosphorescence 199 c.r. pigment yellow 24 130-131 photo-redox reactions 200 C.r. pigment yellow 63 124 photosensitization 199-200 c.r. pigment yellow 74 132 singlet oxygen involvement 201-202, C.r. pigment yellow 110 110 205-208,210,215-218,220-224, C.r. pigment yellow 139 110 229-230,236,239 C.l. pigment yellow 183 110 photodegradation of dyes classical arylazonaphthols 207-208 definition and examples 109-111 arlyazopyrazolones 208-209 utility 110 c.r. acid blue 40 233 copper phthalocyanine c.r. acid blue 277 214 beta-modification 114 C.r. acid green 25 215,226,234 crystal mixtures 130 C.l. acid orange 60 205, 234 pleochroic behavior 120 C.l. acid orange 156 234 scanning electron micrographs 113, C.r. acid red 143 226 115 C.I. acid red 361 234 crystal formation C.l. acid violet 47 226 driving forces 114 C.l. acid yellow 29 226 crystal shape 132-136 C.r. acid yellow 127 226 diketopyrrolopyrrole C.I. basic violet 3 (crystal c.l. pigment red 254 111 violet) 217-218,220,239 polarized reflection spectra 121 C.l. disperse blue 14 227 visible absorption spectra 120 c.r. disperse blue 56 226 SEM photographs 117 C. r. disperse red 15 227 TEM photographs 139 C.l. disperse yellow 50 226 TGA measurements 122 c.r. vat green 1 19 x-ray crystal structure 118, 119 c.r. vat orange 9 216, 230 x-ray diffraction diagrams 116 C.l. vat yellow 2 230 dioxazine c.l. vat yellow 26 230 C.r. pigment violet 23 110 catalytic fading dispersibility 129 acid dyes 226 high performance disperse dyes 226-228 definition and examples 110, 111 quinophthalone 226 utility 110 malachite green 218 molecular structure mechanisms influence on crystal anthraquinone dyes 212-217 properties 110-111 azo dyes 204-212 naphthol 119 azomethine dyes 225 performance and selection fluorescent brightening criteria 106-107 agents 223-224 perylene indigoid dyes 220-221 c.r. pigment red 179 110 quinophthalone dyes 221-222 C.l. pigment red 224 110 rhodamine dyes 224 quinacridone triphenylmethane dyes 217-220 c.l. pigment violet 19 110 mono-substituted azobenzenes structural features 108 cis-trans isomerization 211-212 utility 107,141-142 ortho-nitrosubstituted azo dyes 209, Ostwald ripening 211 copper phthalocyanine pigment 130 photodegradation of dyed polymers dpp pigment 138 natural fibers Ostwald's law 114 phototendering of cotton 228-232 oxygen molecule yellowing of wool 229 electronic states 202 polyamide fibers 232-234 polyester fibers 235 photochemistry polypropylene fibers 235-236 basic principles 197-202 titanium oxide-sensitized 236 electron transitions 197 -198 photostabilization of dye potential energy diagram 199 polymers 232-233,236-237 INDEX 299 pi-pI mteractions 108, 114, 118 solvent mapping 140-141 prototropic equilibrium 20 solubility parameters for commmon solvents 141 reactive dyes spontaneous revertants 256 C.l. reactive blue 4 67, 79 specific free energy 49 C.l. reactive blue 19 Stokes-Einstein equation 87 x-ray scattering data 90 c.l. reactive orange 4 67,79 TEM (transmission electron micrograph) fixation pictures interfacial kinetics 79 organic pigments 133, 135, 139, 142 fixation to cellulose 84 tortuosity 58 general description 84 hydrolysis 104 uv /visible spectroscopy reductive-cleavage charge-transfer bands 13 chemically-induced 258 diazotized amines 26 regular solution theory nitrosyl sulfuric acid solution 13 basic premise 187 revertant colonies 255 x-ray diffraction see also acid dyes, c.l. acid red 266 and C. 1. food yellow 3 Salmonella typhimurium diffraction patterns bacterial strains 255 for lyomesophase structures 93-94 saturation solubility 48 of a middle phase 94 Scherrer-Bragg approximation 88 utility 129