TECHNOLOGY OFSYNTHETIC RESINS
AND EMULSIONPOLYMERS
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 & PaperTechnical 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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4/54, Roop Nagar, Delhi-110007
TECHNOLOGY OFSYNTHETIC RESINS
AND EMULSIONPOLYMERS
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Preface
Paint and colour are as old as man himself. Over 35 000 years ago, inseeking refuge from the weather and marauding beasts, man lived in caves.With the aid of naturally occurring materials, such as clays and chalks, andusing animal fats as binders, he decorated his cave walls with drawings ofanimals and his fellow man.
The Egyptians in about 2500 BC were still using the same pigmentsexcept that a clear blue had been added to relieve the earth colours. Thisblue is thought to have been derived by finely powdering azurite, a semi-precious 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 pharaoh’s eye, the priestly rites.
In the first millennium BC the Greeks come into sharp focus as theypursue 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 withwater but with hot wax. This made a thicker, creamier type of paint whichallowed the artist to model his forms by blending light and dark shades ofcolour. By now considerable advances had been made with various newpigments and nearly every colour was obtainable - green chalk came fromSmyrna , orpiment and red lead from Pontus , whilst vermilion was obtainablefrom the Ephesians. A purple pigment was made by heating yellow earth toredness and then plunging it into vinegar. Another purple was also producedfrom the murex, a species of sea mussel, and for tint changing, madder rootwas used.
After the Roman world had been over –run by the Barbarians in the fifthcentury AD, many art techniques were lost. But with the slow revival ofcommerce, properity and the peaceful arts in the twelfth and thirteenthcenturies came a growing interest in colourful decoration. The Church wasthe hub, which accounts for the magnificent religious paintings made overthis period. The Renaissance swept Europe like a fire. Men came out of theirfortified towns and interchange of thought and culture was eagerly sought.Journeyman artist – painters traveled Europe with their own secret paintrecipes.
By the eighteenth century paint factories were operating in Europe andlater in America. By the early nineteenth century, artisan painters were
working extensively, as people fully realized the big part that architecturalpaint plays in decorating and protecting property. Paint crept into commonand daily use throughout most of the Western world. House painting, hithertoa luxury longer recognized as a mark of social distinction. Paint, once acostly product of hand labour by master craftsmen who prepared and mixedtheir own raw materials from secret formulae handed down from generationto generation, was now reachin the mass proction stage.
The twentieth century witnessed the birth of the paint industry as aspecialized branch of the chemical industry and saw the transformation ofpaintmaking from an art to a science. The availability of raw materialsincreased from a few - such as linseed oil, turpentine, white lead, mineralearth 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 the1910s but it was the First World War, through its inevitable shortages andrestrictions on imports, which really prompted the establishment of localmanufacturing. Today the Indian paint industry comprises some 200 plants,the majority of which are located in Mumbai, Delhi and Kolkata, adjacent tothe main centres of population and industry. The industry has an annualturnover 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 everyindustry uses paints and coatings in one form or another. About half theindustry’s production takes the form of the more familiar architectural anddecorative paints used to protect and beautify our homes, offices, industrialbuildings and the like. In the architectural and decorative paint market overthe past few years, whilst the production of solvent thinned paints hasdecreased, there has been a marked increase in the production of waterbased and latex paints.
The other half of the industry’s output is supplied as industrial coatings,which are formulated to meet special conditions encountered in numerousindustrial and special end-uses. These include the protection and finishingof motor vehicles of all types, agricultural equipment , ships and aircraft, awide variety of manufactured consumer durable products (includingrefrigerators, washing machines, furniture), technical equipment, toys andcontainers of numerous types. Specialized coatings provide specificallydesigned properties for electrical installations, lining of food and beverage
containers, fire retardency, chemical resistance and a multitude of otherproperties.
The development of the surface coating industry, particularly over thelast 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, whichwas regarded as an arts and crafts industry has now virtually becomes atechnical branch of the chemical industry. Whilst paint manufacturers stillrely on many natural sources of raw materials, there has been a continuingshift in the direction of purely synthetic materials, which offer importantbenefits including consistency in quality and supply. During recent years wehave experienced a steady increase in the range of new and improved rawmaterials. These newer products have enabled paint manufacturers toimprove the performance properties of their paints and coatings and sosatisfy the more stringent requirements of our modern industrial society.
Furthermore,it is clear that more extensive demands will be made forimproved working conditions, to provide safe and healthy environments withinfactory locations. In improving occupational health and safety standards, inthe long run, emphasis is likely to be placed on the reduction of hazards byrequiring changes in workplace design and practice, rather than by the useof personal protection equipment such as maks or respirators. Mandatoryproduct safety management programs will require manufacturers to provideemployees and customers with comprehensive information to enable themto handle products in a safe manner, take appropriate precautions, and beaware of actions to be followed in the event of a spillage, accident orunanticipated incident involving a given product.
In order to deal with and overcome the various complex, technicalproblems which will be encountered, the industry’s scientific and technologicalinnovative skills will be continually challenged. In responding to thesechallenges the industry will be involved in inventing, improving and refiningproducts and processes at a rate faster than ever before. However, we canbe confident that to satisfy the emerging demands of society, our industrywill 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 industriesand for new employees in the oil, resin, pigment and paint industries.
A work of this kind is made possible only reviewing and compiling thebrilliant ideas and ingenious experimental techniques which have beenpublished in scientific literature. However, despite the best of human effortsthere will be inevitable errors of omission and commission. It is my earnestdesire that these be brought to our attention so that future revisions may bemore satisfactory.
The random thoughts in this book are intended for those who do not liveby bread alone. Life becomes barren when the pursuit of material things isits sole object. To live successfully it is necessary to maintain equilibriumamong materials, mental and spiritual activities. Also, there is the need togive and to receive the stimulus of noble thoughts expressed by illustriouspredecessors or by those with whom we associate. This is a good opportunityto thank the various industrialists for supplying technical datas and thepublisher for his broadness of vision.
Dr. Himadri PandaPh.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 INDEXChapter Page No. Chapter Page No.
1
The Chemistry of Resin 1-24Formation and ResinProperties- Introduction 1- Fundamentals of Polymer 1
formation- Functions of Reactive Groups 2- Cross-linked Polymers 4- Formation of Polymers 5- Polycondensation 5- Interfacial Polycondensation 6- Sequence of Reaction 6- Copolymer Formation 8- Rate of Polymerization 8- Addition Polymerization 9
in Practice- Chain Transfer Reactions 9- Stereopsecific Polymerization 10- Polyaddition Reactions 11- Types of Polymers 12- Polyesters 12- Formation of Alkyds 12- Saturated and 13
Unsaturated Polyesters- Polyamides 13- Phenolic Resins 14- Amino Resins 17- Epoxide Resins 19- Vinyl Polymers 20- Polyvinyl Alcohol 21- Silicones 22- Practical Applications 24
2
The Chemical 25-70Engineering of Oil andResin Processing- General Requirements for 25
for Processing Equipments
- Materials of Construction 26- Branches and Connections 32- Stirring Equipment 33- Types of Agitators 35- Sealing 35- Drive Units 36- Fume Disposal and Scrubbing 37- Desing Consideration 37- Sludge Handling Equipment 38- Condensing and Refluxing 39- Design and Layout of Tubes 40- Water Receiver 40- Ancillary Equipment 44- Agitators 44- Heating 44- Reflux Condenser 45- Thermometer 45- Steam Arrangements 47- Vacuum Pumps 47- Pressure and Flow Indication 51- Fume Extraction 52- Lagging 52- Miscellaneous 53- Heating and Cooling 53- Criteria for Selection of 53
Heating and Cooling system- Calculation of Film Coefficients 53- Heat Transfer Coefficient 54- Steam Heating 55- Pressurised Hot Water 56- Heating at Higher Temperature 56- Direct Firing 58- Immersion Tubes 58- Kestner Coil 59- Typical Arrangement 61- Cooling 61- The advantages of this type 61
of heating system are :- Heating by Electricity 63- Immersion Heating 64- Heating through The Vessel Wall 65- Induction Heating 66- 'Isoductive' Heating System 68
Chapter Page No. Chapter Page No.
- Heating of Pipework and 68Ancillaries
3
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
4
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 onProperties of Cured products
- Effect of Chemical Structure 108on Melting points of LinearPolyesters
- Effect of Structure on 108
Properties of Cured Products- Commonly used polyols and 109
their advantages are :- The effect of unsaturated 110
monomers on propertiesof cured products
- Polyester coating composition 111- Radiation Cure 113- Methods of Application 114
5
Amino Resins 116-129- Formation of Amino Resins 117- Methylol formation 117- Alkylation 118- Urea Formaldehyde Resins 118- Methylol Formation 118- Etherification reaction 119- Melamine Formaldehyde Resin 120- Melamine Methyl Formation 120- Alkylation of Melamine Methylols 121- Other Amino Resins 122- Glycoluril 123- Production Amino Resins 123- Properties of Amino Resins 123- Uses of Amino Resins 124- Self- Polymerization 124- Co-reaction with alkyd 125
and polyester resins- Co-reaction with Acrylic Resins 126- Epoxy resins 126- Acid Catalysed Lacquers 126- Water Based Coatings 127- Appendix 1 Solvent Tolerance 129- Appendix 2 Non-Volatile Content 129
6
Polyurethane Resins 130-151- Chemistry 131- Raw Materials 133- Isocyanates 133- Tolylene Diisocyanate (TDI) 134- 4,4' Diphenylmethane 135
Diisocyanate (MDI)- Hydroxyl Component 136
Chapter Page No. Chapter Page No.
- Hazards of Isocyanates 137- Classification of Polyurethanes 138- Urethane Oils and 139
Urethane Alkyds- Moisture-cured urethanes 140- Blocked Isocynatee Systems 145- Two-component catalyst- 145
Cured Polyurethanes- Two-Component Polyol Type 146
Polyurethanes
7
Epoxy Resins 152-166- Epoxy Resins Manufacture 154
and Characterization- Curing Agents for Epoxy Resins 156- Principles in Formulating 158
with Epoxy Resins- Solventless and High Solids 160
Coatings- Tar Epoxy Coatings 161- Flooring Compounds 161- Fibreglass Laminates 162- Solvent Based Paint 162- High Solids Coatings 163- Solventless Tar Epoxy Coatings 163- Solventless Coating for 163
Airless Spray Equipment- Single-Pack Epoxy 164
Maintenance Paints- Epoxy Esters 164- Single Pack Thermoplastic 164
Epoxy Systems- Epoxy Industrial Baking 165
Finishes
8
Water Dispersible 167-172Epoxy Resins- Epoxy/Polyamide Emulsions 167- Epoxy Baking Enamels 168- Water Dispersible Epoxy 170
Resin Coatings forElectrodeposition
- Epoxy Aqueous Powder 171Suspension (APS)
9
Silicone Resins 173-188- Direct Process 174- Grignard Process 175- Preparation of Silanols 175- Polymerization 175- Silicone resins 176- Pure Silicone Resins 176- R : Si Ratio 176- Methyl-and phenyl-content 177- Viscosity 177- Properties of pure Silicone 177
Surface Coating Resins- Resistance to Weathering : 178- Blending Resins 178- Silicone Intermediates : 179
Silicone— Organic Copolymers- Preparation and Formulation 180
of Silicone Resin BasedCoatings
- Cure Catalyst Driers 181- Pigments and Dyes 181- Thinners 182- Application Guides 183- Surface Preparation 184- Priming 184- Applying the Coatings 184- Curing 185- Uses 185- Toxicity 186- Other Silicone Resin 186
Application- Electrical Varishes 186- Release Resins 186- Masonry Water Repellants 186- Other Silicones for 186
Surface Coatings
Chapter Page No. Chapter Page No.
10
Acrylic Solution 189-206Resins- Backbone Monomers 190- Synthesis 190- Addition Polymerization 191- Copolymerization 193- Thermoplastic Acrylics 195- Solution Polymerization 197- Properties and End Uses 198- Thermosetting Acrylics 199- Selection of Monomer 199- Classification and properties 200- Acrylamide Copolymers 200- Acid Copolymers 201- Hydroxy Copolymers 202- Curing Reactions 203- Aqueous Solution Acrylics 204- Non-Aqueous 205
Dispersions (NAD)
11
Rubber Resins 207-231- Introduction 207- Natural Rubber 208- Synthetic Rubbers 210- Procedure 211- Rubber Resins and Latexes 212- Chlorinated Rubber Resins 212- Lifting 215- Parlon 216- Cyclized Rubber Resins 219- High Styrene-Butadiene 220
Rubber Resins- Chrlorinated Biphenyls 221- Chlorinated Paraffins 223- Synthetic Rubber Resins 226
Latexes
12
Emulsion Polymers 232-284- Key- Components in 232
Emulsion Polymerization
- Surfactants 233- Initiators 233- Water 234- Polymerization in 235
Emulsion Systems- Based on Styrene 237- Influence of Monomer 238
Composition on propertiesand performance
- Hardening Monomers 238- Vinyl Acetate 238- Styrene 238- Methyl Methacrylate 239- Flexibilizing Monomers 239- Esters of Acrylic Acids 239- Esters of Maleic or 240
Fumaric Acids- Vinyl Esters 240- Olefins-Butadiene 240- Olefins- Ethylene 241- Specific Monomers 241- Effect of Monomer Composition 242
on Film Properties- Effect of Water Phase 245
and Particle Size- Particle Size 249- Manufacture and Testing 251- Process Variables 254- Emulsion Testing 259- Application of Emulsion 264
Polymers- Adhesive Industry 280- The Printing Ink Industry 281- The Textile Industry 282- The Leather Industry 282- The Floor Polish Industry 283- The Paper Industry 283- The Agriculture Industry 284
13
Water Reducible 285-329Resins- Water Soluble Polymers 285- Maleinized drying oils 286- Alkyd Reins 287- Acrylic-modified water- 290
Chapter Page No. Chapter Page No.
Soluble Alkyds- Disadvantages are 290- Polyesters 291- Silicone-modified Alkyds 291
and Polyesters- Epoxy Resins 291- Anhydrides 292- Defunctioalizing the 293
Epoxide Ring- Cationic Polymers 293- Thermoplastic Polymers 300- Thermosetting Polymers 300- Amino Resins 302- Urea Formaldehyde 302- Melamine Formaldehydes 302- Substituted Guanamine 303
Formaldehyde- Self-cross-linking 303- Other Water soluble Polymers 304- Viscosity Characteristics 304- Amines 306- Viscosity 306- Drying 306- Stability 308- Foam Control 309- Colour Retention 310- Toxicity 310- Variation of Amine Levels 310- Viscosity 310- Drying Properties 311
- Stability 312- Gloss 312- Cosolvents 313- Coupling Efficiency 315- Viscosity 316- Variation of Cosolvent 316
water ratio- Stability 316- Drying properties 316- Foam Control 317- Drier for air dry and 317
Force dry systems- Cross Linking of Water 319
Soluble coatings- Additives for Coatings 321- Pigments 322- Formulation of Water- 322
Soluble Coatings- Trouble Shooting with 326
Water- Soluble Polymers
14
Water Soluble 330-345Polymers- Classification 330- Properties of Cellulose Ethers 335- Application 337- Uses 341
