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TECHNOLOGY OF SYNTHETIC RESINS AND EMULSION POLYMERS

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

& R & D) Tarpina Pvt. Ltd., Ramnagar, Uttranchal 4449, Nai Sarak, Main Road, Delhi-110 006

4449, Nai Sarak, Main Road, Delhi-110 006 (India)

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Printed and Published by : 4449, Nai Sarak, Main Road, Delhi-110 006 (India) Ph. : 91-11-23918117,

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ISBN : 978-81-89765-96-5

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regarding this book are Subject to Delhi Jurisdiction only Printed and Published by Sudhir Gupta for
regarding this book are Subject to Delhi Jurisdiction only Printed and Published by Sudhir Gupta for

Printed and Published by Sudhir Gupta for "Engineers India Research Institute", 4449, Nai Sarak, Main Road, New Delhi-110 006 and Printed at Swastik Offset, Delhi

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 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 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 industry’s 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 industry’s 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 industry’s 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 Page No. Chapter Page No.
Chapter
Page No.
Chapter
Page No.

1

The Chemistry of Resin Formation and Resin Properties

1-24

- Introduction

1

- Fundamentals of Polymer formation

1

- 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 in Practice

9

- Chain Transfer Reactions

9

- Stereopsecific Polymerization

10

- Polyaddition Reactions

11

- Types of Polymers

12

- Polyesters

12

- Formation of Alkyds

12

- Saturated and Unsaturated Polyesters

13

- 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 Engineering of Oil and Resin Processing

25-70

- General Requirements for for Processing Equipments

25

- 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 Heating and Cooling system

53

- 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 of heating system are :

61

- 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 Ancillaries 68 Properties of
Chapter
Page No.
Chapter
Page No.
- Heating of Pipework and
Ancillaries
68
Properties of Cured Products
- Commonly used polyols and 109
their advantages are :
3
- The effect of unsaturated 110
monomers on properties
Alkyd Resins
71-101
of cured products
- The nature of Alkyd Resin
71
- Polyester coating composition 111
- Raw Materials
72
- Radiation Cure
113
- Dibasic Acids
72
- Methods of Application 114
- Polyhydric Alcohols
73
- Modifier for Alkyd Resins
74
5
- Formulation of Alkyd Resins
75
Amino Resins
116-129
- Formula Development
78
- Calculation of Alkyd Formulations 78
- Formation of Amino Resins
117
- Typical Formulations
82
- Methylol formation 117
- Manufacture of Alkyd Resin
85
- Alkylation
118
- Alcoholysis
85
- Urea Formaldehyde Resins
118
- Catalysts
87
- Methylol Formation 118
- Control of Alcoholysis
87
- Etherification reaction
119
- Acidolysis
88
- Melamine Formaldehyde Resin
120
- Fatty Acid Process
88
- Melamine Methyl Formation
120
- Esterification
89
- Alkylation of Melamine Methylols 121
- Alkyd Manufacturing Plant
90
- Other Amino Resins 122
- Applications of Alkyd Resins
96
- Glycoluril
123
- Oil Free Alkyds
101
- Production Amino Resins 123
- Properties of Amino Resins
123
4
- Uses of Amino Resins 124
- Self- Polymerization 124
Polyesters
102-115
- Co-reaction with alkyd 125
- Saturated Polyesters
102
and polyester resins
- Condensation and Addition 102
Polymerization
- Co-reaction with Acrylic Resins
126
- Epoxy resins
126
- Main Components of 103
Unsaturated Polyesters
- Acid Catalysed Lacquers
126
- Water Based Coatings 127
- Brief History of Surface Coatings103
- Appendix 1 Solvent Tolerance
129
- Characteristics of Unsaturated 104
Polyesters
- Appendix 2 Non-Volatile Content 129
- Two points should be noted here105
6
- Functions of initiators, 106
Polyurethane Resins
130-151
Accelerators, Inhibitors
- Effect of structure of 107
Polyester Backbone on
Properties of Cured products
- Chemistry
131
- Raw Materials
133
- Isocyanates
133
- Effect of Chemical Structure 108
on Melting points of Linear
Polyesters
- Tolylene Diisocyanate (TDI)
134
- 4,4' Diphenylmethane
Diisocyanate (MDI)
135
- Effect of Structure on 108
- Hydroxyl Component
136
Chapter Page No. Chapter Page No. - Hazards of Isocyanates 137 - Classification of Polyurethanes
Chapter
Page No.
Chapter
Page No.
- Hazards of Isocyanates
137
- Classification of Polyurethanes
138
Resin Coatings for
Electrodeposition
- Urethane Oils and
Urethane Alkyds
139
- Epoxy Aqueous Powder
Suspension (APS)
171
- Moisture-cured urethanes
140
9
- Blocked Isocynatee Systems
145
- Two-component catalyst-
Cured Polyurethanes
145
Silicone Resins
173-188
- Direct Process
174
- Two-Component Polyol Type
Polyurethanes
146
- Grignard Process 175
- Preparation of Silanols
175
7
- Polymerization
175
- Silicone resins
176
Epoxy Resins
152-166
- Pure Silicone Resins
176
- Epoxy Resins Manufacture
and Characterization
154
- R : Si Ratio
176
- Methyl-and phenyl-content
177
- Curing Agents for Epoxy Resins 156
- Viscosity
177
- Principles in Formulating
with Epoxy Resins
158
- Properties of pure Silicone
Surface Coating Resins
177
- Solventless and High Solids
Coatings
160
- Resistance to Weathering :
178
- Blending Resins
178
- Tar Epoxy Coatings 161
- Silicone Intermediates :
179
- Flooring Compounds 161
Silicone— Organic Copolymers
- Fibreglass Laminates 162
- Preparation and Formulation
of Silicone Resin Based
Coatings
180
- Solvent Based Paint 162
- High Solids Coatings 163
- Solventless Tar Epoxy Coatings 163
- Cure Catalyst Driers
181
- Solventless Coating for
163
- Pigments and Dyes 181
Airless Spray Equipment
- Thinners
182
- Single-Pack Epoxy 164
- Application Guides
183
Maintenance Paints
- Surface Preparation
184
- Epoxy Esters
164
- Priming
184
- Single Pack Thermoplastic
Epoxy Systems
164
- Applying the Coatings
184
- Curing
185
- Epoxy Industrial Baking
Finishes
165
- Uses
185
- Toxicity
186
- Other Silicone Resin
186
8
Application
- Electrical Varishes
186
Water Dispersible
Epoxy Resins
167-172
- Release Resins
186
- Masonry Water Repellants
186
- Other Silicones for
Surface Coatings
186
- Epoxy/Polyamide Emulsions
167
- Epoxy Baking Enamels
168
- Water Dispersible Epoxy
170
Chapter Page No. Chapter Page No. 10 - Surfactants 233 - Initiators 233 Acrylic Solution
Chapter
Page No.
Chapter
Page No.
10
- Surfactants
233
- Initiators
233
Acrylic Solution
189-206
- Water
234
Resins
- Polymerization in
235
Emulsion Systems
- Backbone Monomers
190
- Based on Styrene 237
- Synthesis
190
- Influence of Monomer
Composition on properties
238
- Addition Polymerization
191
- Copolymerization
193
and performance
- Thermoplastic Acrylics
195
- Hardening Monomers
238
- Solution Polymerization
197
- Vinyl Acetate
238
- Properties and End Uses
198
- Styrene
238
- Thermosetting Acrylics
199
- Methyl Methacrylate
239
- Selection of Monomer
199
- Flexibilizing Monomers
239
- Classification and properties
200
- Esters of Acrylic Acids
239
- Acrylamide Copolymers
200
- Esters of Maleic or
Fumaric Acids
240
- Acid Copolymers
201
- Hydroxy Copolymers
202
- Vinyl Esters
240
- Curing Reactions
203
- Olefins-Butadiene
240
- Aqueous Solution Acrylics
204
- Olefins- Ethylene
241
- Non-Aqueous
Dispersions (NAD)
205
- Specific Monomers 241
- Effect of Monomer Composition
242
11
on Film Properties
245
Rubber Resins
207-231
- Effect of Water Phase
and Particle Size
- Particle Size
249
- Introduction
207
- Manufacture and Testing
251
- Natural Rubber
208
- Process Variables 254
- Synthetic Rubbers
210
- Emulsion Testing 259
- Procedure
211
- Application of Emulsion
Polymers
264
- Rubber Resins and Latexes
212
- Chlorinated Rubber Resins
212
- Adhesive Industry 280
- Lifting
215
- The Printing Ink Industry
281
- Parlon
216
- The Textile Industry
282
- Cyclized Rubber Resins
219
- The Leather Industry
282
- High Styrene-Butadiene
Rubber Resins
220
- The Floor Polish Industry
283
- The Paper Industry
283
- Chrlorinated Biphenyls
221
- The Agriculture Industry
284
- Chlorinated Paraffins
223
- Synthetic Rubber Resins
Latexes
226
13
Water Reducible
285-329
12
Resins
Emulsion Polymers
232-284
- Water Soluble Polymers
285
- Key- Components in
Emulsion Polymerization
232
- Maleinized drying oils
286
- Alkyd Reins
287
- Acrylic-modified water-
290
Chapter Page No. Chapter Page No. Soluble Alkyds - Stability 312 - Disadvantages are 290
Chapter
Page No.
Chapter
Page No.
Soluble Alkyds
- Stability
312
- Disadvantages are
290
- Gloss
312
- Polyesters
291
- Cosolvents
313
- Silicone-modified Alkyds
and Polyesters
291
- Coupling Efficiency 315
- Viscosity
316
- Epoxy Resins
291
- Anhydrides
292
- Variation of Cosolvent
water ratio
316
- Defunctioalizing the
Epoxide Ring
293
- Stability
316
- Drying properties 316
- Cationic Polymers
293
- Foam Control
317
- Thermoplastic Polymers
300
- Thermosetting Polymers
300
- Drier for air dry and 317
Force dry systems
- Amino Resins
302
- Cross Linking of Water
Soluble coatings
319
- Urea Formaldehyde
302
- Melamine Formaldehydes
302
- Additives for Coatings
321
- Substituted Guanamine
Formaldehyde
303
- Pigments
322
- Formulation of Water-
Soluble Coatings
322
- Self-cross-linking
303
- Other Water soluble Polymers
304
326
- Viscosity Characteristics
304
- Trouble Shooting with
Water- Soluble Polymers
- Amines
306
14
- Viscosity
306
- Drying
306
Water Soluble
330-345
- Stability
308
Polymers
- Foam Control
309
- Colour Retention
310
- Classification
330
- Toxicity
310
- Properties of Cellulose Ethers
335
- Variation of Amine Levels
310
- Application
337
- Viscosity
310
- Uses
341
- Drying Properties
311