A. Factors Affecting Wrinkling 1. Fiber Factors 99 2. Yarn Factors 99 3. Fabric Factors II. THEORY OF CREASE RECOVERY 100 A. Crosslinking Cellulose 100 B. History of Crease Recovery C. Definitions ..101 III. CELLULOSE CROSSLINKERS 102 A. Reactions of Formaldehyde 102 1. Formation of Hydroxymethyl Derivatives 102 a. With Alcohols b. With amides c. Activated C-H 103 2. Reactions of Hydroxymethyl 103 a. With alcohols 103 b. With N-Methyl B. Resin Formers (Aminoplasts) 1. Urea/Formaldehyde (U/F) 104 a. Synthesis of Dimethylol Urea 104 b. Important Features 104 2. Melamine/ Formaldehyde 104 a. Synthesis of Trimethylol Melamine 105 b. Synthesis of Trimethoxy Melamine 105 c. Synthesis of Hexamethoxymethyl Melamine .105 C. Reactants 105 1. Dimethylolethylene Urea (DMEU 106 a. Synthesis of Monomer 106 b. Methylolation Reaction 106 c. Important Features 2. Dimethylol-4, 5-Dihydroxyethylene Urea DMDHEU). 106 a. Synthesis of 4, 5. Dihydroxyethylene Urea 107 b. Methylolation 107 c. Important Features 107 3. Carbamates a. Synthesis 108 b. Important Features 108 IV CONTROLLING FORMALDEHYDE EXPOSURE 108 A. Atmospheric Formaldehyde B. Formaldehyde in Fabrics 109 1. Free Formaldehyd ...109 2. Formaldehyde Release 109 Linkages Responsible for HCHO Release 110
a. Cellulose hemiacetal ..110 b. Pendent_ N-Methylols 110 c. Cellulose Crosslinks 110 4. Fabric pH and Formaldehyde release 110 V METHODS OF REDUCING FORMALDEHYDE RELEASE 111 A. Scavengers 111 B. Modified DMDhEU 112 1. Methylated DMDHEU 112 2. Diethyleneglycolated DMDHEU (ULF) 112 C. Important Features of Alkylated DMDHEU 113 VI. NON-FORMALDEHYDE DP FINISHES 114 A. Dimethyl-4, 5, Dihydroxyethylene UREa DMeDHEu) 114 1. Synthes 114 2. Important Features 114 B. Butanetetracarboxylic Acid ( BTCA) 114 1. Catalyst 115 a. Sodium Hypophosphite 115 b. Sodium Phosphate 115 C. Reactive Silicones 116 D. Liquid Amm 116 VII. DURABLE PRESS CATALYST 116 A. Bronsted Acids 117 a. Ionization Constant 117 b. Hydrogen Ion Concentration 117 1. Latent Acid 118 a. Dissociation of Amine Hydrochlorides 118 b. Dissociation of Ammonium Chloride 118 c. Reaction of Ammonia with Formaldehyde 118 B. Lewis acids True Lewis Acids 119 2. Metal Hydrates 119 3. Important Considerations 119 C. Specific Catalyst and their Use 119 1. Free acids 119 2. Latent acids 120 3. Metal salt 120 4. Hot Catalyst D. Buffers and Alkalinity 120 1. Buffe 2. Alkalinity 120 VIII CHEMICAL MECHANISMS 121 A. Methylolation 1. Base Catalyzed Methylolation 2. Acid Catalyzed Methylolation
B. Alkylation of N-Methylol Compound 1. Proton Activated Alkylation 2. Cellulose Crosslinking with Lewis Acids C. Reaction of Alkoxylated Products 124 1. Crosslinking with Alkoxykated N-Methylol 125 D. Stability of Crosslink to Laundering 125 1. Hydrolysis of Cellulose Crosslinks 125 IX. FABRIC PROPERTIES A. Durable Press Performance versus Add-on 126 1. Important points 126 B. Effectiveness of Different Crosslinkers 127 C. Tensile, Tear and Abrasion Resistance 128 1. Points to Consider 130 D. Crease Recovery versus Curing Temperature 130 1. Points to Consider e. Other Fabric Properties 132 1. Shrinkage 2. Yellowing 132 3. Chlorine resistance a. Mechanism of Chlorine Damage 4. Fabric odor CHAPTER 8 HAND MODIFICATION 134 I. HANDBUILDERS 134 A. Non-durable 1. Starch 2. Polyvinyl Alcohol B. Durable 135 1. Thermosetting Polymers 135 a. Melamine/Formaldehyde 135 b. Urea/Formaldehyde 135 2. Thermoplastic Polymers II. FABRIC SOFTENERS 136 A. Coefficient of friction B. Viscosity C. Other Points of Concern 137 D. Softener Selection Summary 138 E. Raw materials 139 1. Raw Material Sources 139 a. Fat Derived Raw Materials b. Petrochemical Derived Raw Materials
III. SOFTENER CLASSIFICATIONS A. Anionic Softeners 1. Sulfates 140 a. Fatty Alcohol Sulfates 140 b. Sulfated Fatty Acid Esters 141 2. Sulfonated Fatty Amides and Esters 142 a. Sulfoethyl Fatty Esters_ (IGEPON_A) 142 b. Sulfoethyl Fatty Amides_(GEPON T 142 3. Properties of Anionic Softeners 142 a. Advantages 142 b. Disadvantages 143 B. Cationic Soft eners 1. Amine Functional Cationic Softeners a. Primary Fatty Amines 144 b. Difatty Amines 144 c. Fatty Diamines 144 d. Cationic Amine salts .144 2. Fatty Aminoesters 144 a. Synthesis 145 3. Fatty Amidoamides 145 a. Synthesis of Amidoamides 145 b. Synthesis of Amidoamide Salt 145 4. Imidazolines 145 a. Synthes 146 5. Quaternary Ammonium Salts 146 a. Synthesis of Monofatty Quats 146 b. Synthesis of Difatty Quat 146 c. Synthesis of Imidazoline Quats 147 6. Properties of Cationic Softeners 14 a. Advantages 147 b. Disadvantages 147 C. Nonionic Softeners 147 1. Polyethylene Emulsions 148 a. Composition of Polyethylene Emulsions 148 2. Ethoxylated Nonionic Softeners 148 a. Ethoxylation with Ethylene Oxide 148 b. Esterification with Polyglycol 149 c. Typical Ethoxylates 149 3. Silicone Chemistry 149 Formation of Organofunctional Reactive 149 b. Reaction of Monochlorosilanes with Water 150 c. Reaction of Dichlorosilanes with Water 150 d. Reactions of Trichlorosilanes with Water 150
e. Reaction of Hydrogen Silanes with Water 4. Silicone Softeners ...,.,.151 a. Dimethyl fluids 151 b. Methylhydrogen Fluids c. Amino Functional Silicones d. Epoxy Functional Silicones 152 5. Properties 153 a. Advantages 153 153 CHAPTER 9 REPELLENT FINISHES . PHYSICAL CHEMISTRY OF WETTING 155 A. Work of adhesion 155 B. Critical Surface Tension 156 C. Contact Angles in Real Systems 158 D. Repellent Finishes 158 II. HYDROCARBON HYDROPHOBES A. Paraffin Waxes 158 B. Fiber Reactive Hydrocarbon Hydrophobes 159 1. N-Methylol Stearamide 159 a. Synthesis and Reactions 159 2. Pyridinium Compounds 160 a. Synthesis and reactions 160 3. Resin Formers 160 a. Synthesis of Melamine Wax Type Water Repellents .161 4. Metal Complexes 161 a. Synthesis and reactions 162 III. SILICONE WATER REPELLENTS A. Synthesis of Methyl Hydrogen Fluids 163 B. Crosslinking Reactions 163 1. Hydrolysis of Si-H 163 2. Condensation of silanols C. Application to Fabrics 163 D. Advantages and disadvantages 163 IV. FLUOROCHEMICAL REPELLENTS 164 A. Commercial Products 165 1. Synthesis and Reactions 165 a. Monomer Synthesis 165 b. Emulsion Polymer Synthesis 3. Applied to Fib 166 B. Effect of Perfluoro Side- Chair 166 C. Effect of Polymer Backbone 167