TECHNOLOGY OF SYNTHETIC RESINS AND EMULSION POLYMERS

TECHNOLOGY OF SYNTHETIC RESINS AND EMULSION POLYMERS

Written By :

Dr. Himadri Panda, Ph.D.,F.I.C.,F.I.C.S.

Industrial Consultant Fellow of the Essential Association of India, Fellow of the Indian Pulp & Paper Technical Association of India, Fellow of the Indian National Science Congress, Fellow of the Oil & Colour Chemist's Association, U.K. Member of Chinese Academy of Forests, Former Chemist, I.T.R. Co. Ltd. Bareilly, (U.P.), Former Cheif Chemist (Q.C. & R & D) Tarpina Pvt. Ltd., Ramnagar, Uttranchal

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Preface
Paint and colour are as old as man himself. Over 35 000 years ago, in seeking refuge from the weather and marauding beasts, man lived in caves. With the aid of naturally occurring materials, such as clays and chalks, and using animal fats as binders, he decorated his cave walls with drawings of animals and his fellow man. The Egyptians in about 2500 BC were still using the same pigments except that a clear blue had been added to relieve the earth colours. This blue is thought to have been derived by finely powdering azurite, a semiprecious stone, while the animal fat medium had given way to gums, wax, size, and perhaps albumen. Painters still recorded in tombs and temples, the happenings of the day, the battles, the pharaohs eye, the priestly rites. In the first millennium BC the Greeks come into sharp focus as they pursue the art of painting, not only in their own country, but abroad in Rome. The Greeks developed a new technique, that of mixing colours not with water but with hot wax. This made a thicker, creamier type of paint which allowed the artist to model his forms by blending light and dark shades of colour. By now considerable advances had been made with various new pigments and nearly every colour was obtainable - green chalk came from Smyrna , orpiment and red lead from Pontus , whilst vermilion was obtainable from the Ephesians. A purple pigment was made by heating yellow earth to redness and then plunging it into vinegar. Another purple was also produced from the murex, a species of sea mussel, and for tint changing, madder root was used. After the Roman world had been over run by the Barbarians in the fifth century AD, many art techniques were lost. But with the slow revival of commerce, properity and the peaceful arts in the twelfth and thirteenth centuries came a growing interest in colourful decoration. The Church was the hub, which accounts for the magnificent religious paintings made over this period. The Renaissance swept Europe like a fire. Men came out of their fortified towns and interchange of thought and culture was eagerly sought. Journeyman artist painters traveled Europe with their own secret paint recipes. By the eighteenth century paint factories were operating in Europe and later in America. By the early nineteenth century, artisan painters were

working extensively, as people fully realized the big part that architectural paint plays in decorating and protecting property. Paint crept into common and daily use throughout most of the Western world. House painting, hitherto a luxury longer recognized as a mark of social distinction. Paint, once a costly product of hand labour by master craftsmen who prepared and mixed their own raw materials from secret formulae handed down from generation to generation, was now reachin the mass proction stage. The twentieth century witnessed the birth of the paint industry as a specialized branch of the chemical industry and saw the transformation of paintmaking from an art to a science. The availability of raw materials increased from a few - such as linseed oil, turpentine, white lead, mineral earth and inorganic colours - to a vast range of complex organic chemicals, the use of which required technical specialists. The first production of paint in India is claimed to date from about the 1910s but it was the First World War, through its inevitable shortages and restrictions on imports, which really prompted the establishment of local manufacturing. Today the Indian paint industry comprises some 200 plants, the majority of which are located in Mumbai, Delhi and Kolkata, adjacent to the main centres of population and industry. The industry has an annual turnover of bout Rs 500 crore and employs approximately 10,000 people, of which about 20 per cent have some form of technical qualification. The industry plays an important role in the Indian economy, for every industry uses paints and coatings in one form or another. About half the industrys production takes the form of the more familiar architectural and decorative paints used to protect and beautify our homes, offices, industrial buildings and the like. In the architectural and decorative paint market over the past few years, whilst the production of solvent thinned paints has decreased, there has been a marked increase in the production of water based and latex paints. The other half of the industrys output is supplied as industrial coatings, which are formulated to meet special conditions encountered in numerous industrial and special end-uses. These include the protection and finishing of motor vehicles of all types, agricultural equipment , ships and aircraft, a wide variety of manufactured consumer durable products (including refrigerators, washing machines, furniture), technical equipment, toys and containers of numerous types. Specialized coatings provide specifically designed properties for electrical installations, lining of food and beverage

containers, fire retardency, chemical resistance and a multitude of other properties. The development of the surface coating industry, particularly over the last thirty or so years, has been no less rapid than that in engineering, science and electronics which have been more obvious and spectacular. The technological advances have been such that paint manufacturing, which was regarded as an arts and crafts industry has now virtually becomes a technical branch of the chemical industry. Whilst paint manufacturers still rely on many natural sources of raw materials, there has been a continuing shift in the direction of purely synthetic materials, which offer important benefits including consistency in quality and supply. During recent years we have experienced a steady increase in the range of new and improved raw materials. These newer products have enabled paint manufacturers to improve the performance properties of their paints and coatings and so satisfy the more stringent requirements of our modern industrial society. Furthermore,it is clear that more extensive demands will be made for improved working conditions, to provide safe and healthy environments within factory locations. In improving occupational health and safety standards, in the long run, emphasis is likely to be placed on the reduction of hazards by requiring changes in workplace design and practice, rather than by the use of personal protection equipment such as maks or respirators. Mandatory product safety management programs will require manufacturers to provide employees and customers with comprehensive information to enable them to handle products in a safe manner, take appropriate precautions, and be aware of actions to be followed in the event of a spillage, accident or unanticipated incident involving a given product. In order to deal with and overcome the various complex, technical problems which will be encountered, the industrys scientific and technological innovative skills will be continually challenged. In responding to these challenges the industry will be involved in inventing, improving and refining products and processes at a rate faster than ever before. However, we can be confident that to satisfy the emerging demands of society, our industry will respond in a positive manner and we will see the development of energy efficient products that are environmentally acceptable and safe. This book, is intended for students in paint courses, technologists, scientists and research scholars associated with surface coating industries and for new employees in the oil, resin, pigment and paint industries.

A work of this kind is made possible only reviewing and compiling the brilliant ideas and ingenious experimental techniques which have been published in scientific literature. However, despite the best of human efforts there will be inevitable errors of omission and commission. It is my earnest desire that these be brought to our attention so that future revisions may be more satisfactory. The random thoughts in this book are intended for those who do not live by bread alone. Life becomes barren when the pursuit of material things is its sole object. To live successfully it is necessary to maintain equilibrium among materials, mental and spiritual activities. Also, there is the need to give and to receive the stimulus of noble thoughts expressed by illustrious predecessors or by those with whom we associate. This is a good opportunity to thank the various industrialists for supplying technical datas and the publisher for his broadness of vision. Dr. Himadri Panda Ph.D.,F.I.C.,F.I.C.S.
Industrial Consultant Fellow of the Essential Association of India, Fellow of the Indian Pulp & Paper Technical Association of India Fellow of the Indian National Science Congress, Fellow of the Oil & Colour Chemist's Association, U.K. Member of Chinese Academy of Forests, Former Chemist, I.T.R. Co. Ltd. Bareilly, (U.P.) Former Cheif Chemist (Q.C. & R & D) Tarpina Pvt. Ltd., Ramnagar, Uttranchal

CONTENTS AND SUBJECT INDEX

Chapter 1 Page No. Chapter
-

Page No.
26 32 33 35 35 36 37 37 38 39 40 40 44 44 44 45 45 47 47 51 52 52 53 53 53 53 54 55 56 56 58 58 59 61 61 61 63 64 65 66 68

The Chemistry of Resin Formation and Resin Properties

- Introduction - Fundamentals of Polymer formation - Functions of Reactive Groups - Cross-linked Polymers - Formation of Polymers - Polycondensation - Interfacial Polycondensation - Sequence of Reaction - Copolymer Formation - Rate of Polymerization - Addition Polymerization in Practice - Chain Transfer Reactions - Stereopsecific Polymerization - Polyaddition Reactions - Types of Polymers - Polyesters - Formation of Alkyds - Saturated and Unsaturated Polyesters - Polyamides - Phenolic Resins - Amino Resins - Epoxide Resins - Vinyl Polymers - Polyvinyl Alcohol - Silicones - Practical Applications

1-24

1 1 2 4 5 5 6 6 8 8 9 9 10 11 12 12 12 13 13 14 17 19 20 21 22 24

The Chemical Engineering of Oil and Resin Processing

- General Requirements for for Processing Equipments

25-70

25

Materials of Construction Branches and Connections Stirring Equipment Types of Agitators Sealing Drive Units Fume Disposal and Scrubbing Desing Consideration Sludge Handling Equipment Condensing and Refluxing Design and Layout of Tubes Water Receiver Ancillary Equipment Agitators Heating Reflux Condenser Thermometer Steam Arrangements Vacuum Pumps Pressure and Flow Indication Fume Extraction Lagging Miscellaneous Heating and Cooling Criteria for Selection of Heating and Cooling system Calculation of Film Coefficients Heat Transfer Coefficient Steam Heating Pressurised Hot Water Heating at Higher Temperature Direct Firing Immersion Tubes Kestner Coil Typical Arrangement Cooling The advantages of this type of heating system are : Heating by Electricity Immersion Heating Heating through The Vessel Wall Induction Heating 'Isoductive' Heating System

Chapter
- Heating of Pipework and Ancillaries

Page No. Chapter

68

Page No.
109 110

Alkyd Resins
-

71-101

The nature of Alkyd Resin 71 Raw Materials 72 Dibasic Acids 72 Polyhydric Alcohols 73 Modifier for Alkyd Resins 74 Formulation of Alkyd Resins 75 Formula Development 78 Calculation of Alkyd Formulations 78 Typical Formulations 82 Manufacture of Alkyd Resin 85 Alcoholysis 85 Catalysts 87 Control of Alcoholysis 87 Acidolysis 88 Fatty Acid Process 88 Esterification 89 Alkyd Manufacturing Plant 90 Applications of Alkyd Resins 96 Oil Free Alkyds 101

Properties of Cured Products - Commonly used polyols and their advantages are : - The effect of unsaturated monomers on properties of cured products - Polyester coating composition - Radiation Cure - Methods of Application

111 113 114

Amino Resins
-

116-129
117 117 118 118 118 119 120 120 121 122 123 123 123 124 124 125 126 126 126 127 129 129

Polyesters

102-115

- Saturated Polyesters 102 - Condensation and Addition 102 Polymerization - Main Components of 103 Unsaturated Polyesters - Brief History of Surface Coatings103 - Characteristics of Unsaturated 104 Polyesters - Two points should be noted here 105 - Functions of initiators, 106 Accelerators, Inhibitors - Effect of structure of 107 Polyester Backbone on Properties of Cured products - Effect of Chemical Structure 108 on Melting points of Linear Polyesters - Effect of Structure on 108

Formation of Amino Resins Methylol formation Alkylation Urea Formaldehyde Resins Methylol Formation Etherification reaction Melamine Formaldehyde Resin Melamine Methyl Formation Alkylation of Melamine Methylols Other Amino Resins Glycoluril Production Amino Resins Properties of Amino Resins Uses of Amino Resins Self- Polymerization Co-reaction with alkyd and polyester resins Co-reaction with Acrylic Resins Epoxy resins Acid Catalysed Lacquers Water Based Coatings Appendix 1 Solvent Tolerance Appendix 2 Non-Volatile Content

Polyurethane Resins
-

130-151
131 133 133 134 135 136

Chemistry Raw Materials Isocyanates Tolylene Diisocyanate (TDI) 4,4' Diphenylmethane Diisocyanate (MDI) - Hydroxyl Component

Chapter

Page No. Chapter

137 138 139 140 145 145 146 Resin Coatings for Electrodeposition - Epoxy Aqueous Powder Suspension (APS)

Page No.

- Hazards of Isocyanates - Classification of Polyurethanes - Urethane Oils and Urethane Alkyds - Moisture-cured urethanes - Blocked Isocynatee Systems - Two-component catalystCured Polyurethanes - Two-Component Polyol Type Polyurethanes

171

Silicone Resins
-

173-188
174 175 175 175 176 176 176 177 177 177 178 178 179 180

Epoxy Resins

152-166
154 156 158 160 161 161 162 162 163 163 163 164 164 164 165

- Epoxy Resins Manufacture and Characterization - Curing Agents for Epoxy Resins - Principles in Formulating with Epoxy Resins - Solventless and High Solids Coatings - Tar Epoxy Coatings - Flooring Compounds - Fibreglass Laminates - Solvent Based Paint - High Solids Coatings - Solventless Tar Epoxy Coatings - Solventless Coating for Airless Spray Equipment - Single-Pack Epoxy Maintenance Paints - Epoxy Esters - Single Pack Thermoplastic Epoxy Systems - Epoxy Industrial Baking Finishes

Water Dispersible Epoxy Resins

167-172
167 168 170

- Epoxy/Polyamide Emulsions - Epoxy Baking Enamels - Water Dispersible Epoxy

Direct Process Grignard Process Preparation of Silanols Polymerization Silicone resins Pure Silicone Resins R : Si Ratio Methyl-and phenyl-content Viscosity Properties of pure Silicone Surface Coating Resins Resistance to Weathering : Blending Resins Silicone Intermediates : Silicone Organic Copolymers Preparation and Formulation of Silicone Resin Based Coatings Cure Catalyst Driers Pigments and Dyes Thinners Application Guides Surface Preparation Priming Applying the Coatings Curing Uses Toxicity Other Silicone Resin Application Electrical Varishes Release Resins Masonry Water Repellants Other Silicones for Surface Coatings

181 181 182 183 184 184 184 185 185 186 186 186 186 186 186

Chapter 10

Page No. Chapter

-

Page No.
233 233 234 235 237 238

Acrylic Solution Resins

-

189-206
190 190 191 193 195 197 198 199 199 200 200 201 202 203 204 205

Backbone Monomers Synthesis Addition Polymerization Copolymerization Thermoplastic Acrylics Solution Polymerization Properties and End Uses Thermosetting Acrylics Selection of Monomer Classification and properties Acrylamide Copolymers Acid Copolymers Hydroxy Copolymers Curing Reactions Aqueous Solution Acrylics Non-Aqueous Dispersions (NAD)

11

Rubber Resins
-

207-231
207 208 210 211 212 212 215 216 219 220 221 223 226

Introduction Natural Rubber Synthetic Rubbers Procedure Rubber Resins and Latexes Chlorinated Rubber Resins Lifting Parlon Cyclized Rubber Resins High Styrene-Butadiene Rubber Resins - Chrlorinated Biphenyls - Chlorinated Paraffins - Synthetic Rubber Resins Latexes

Surfactants Initiators Water Polymerization in Emulsion Systems Based on Styrene Influence of Monomer Composition on properties and performance Hardening Monomers Vinyl Acetate Styrene Methyl Methacrylate Flexibilizing Monomers Esters of Acrylic Acids Esters of Maleic or Fumaric Acids Vinyl Esters Olefins-Butadiene Olefins- Ethylene Specific Monomers Effect of Monomer Composition on Film Properties Effect of Water Phase and Particle Size Particle Size Manufacture and Testing Process Variables Emulsion Testing Application of Emulsion Polymers Adhesive Industry The Printing Ink Industry The Textile Industry The Leather Industry The Floor Polish Industry The Paper Industry The Agriculture Industry

238 238 238 239 239 239 240 240 240 241 241 242 245 249 251 254 259 264 280 281 282 282 283 283 284

13

12

Emulsion Polymers
- Key- Components in Emulsion Polymerization

232-284
232

Water Reducible Resins

Water Soluble Polymers Maleinized drying oils Alkyd Reins Acrylic-modified water-

285-329
285 286 287 290

Chapter

Page No. Chapter

290 291 291 291 292 293 293 300 300 302 302 302 303 303 304 304 306 306 306 308 309 310 310 310 310 311 Stability Gloss Cosolvents Coupling Efficiency Viscosity Variation of Cosolvent water ratio Stability Drying properties Foam Control Drier for air dry and Force dry systems Cross Linking of Water Soluble coatings Additives for Coatings Pigments Formulation of WaterSoluble Coatings Trouble Shooting with Water- Soluble Polymers

Page No.
312 312 313 315 316 316 316 316 317 317 319 321 322 322 326

Soluble Alkyds - Disadvantages are - Polyesters - Silicone-modified Alkyds and Polyesters - Epoxy Resins - Anhydrides - Defunctioalizing the Epoxide Ring - Cationic Polymers - Thermoplastic Polymers - Thermosetting Polymers - Amino Resins - Urea Formaldehyde - Melamine Formaldehydes - Substituted Guanamine Formaldehyde - Self-cross-linking - Other Water soluble Polymers - Viscosity Characteristics - Amines - Viscosity - Drying - Stability - Foam Control - Colour Retention - Toxicity - Variation of Amine Levels - Viscosity - Drying Properties

14

Water Soluble Polymers

-

330-345
330 335 337 341

Classification Properties of Cellulose Ethers Application Uses