Table Of ContentA. Knop, L.A. Pilato
Phenolic Resins
Chemistry,
Applications and Performance
Future Directions
With 109 Figures and 114 Tables
Springer-Verlag
Berlin Heidelberg GmbH
Dr. Andre Knop
Rütgerswerke AG, Frankfurt, FRG
Dr. Louis A. Pilato
Temecon Group International Inc., Bound Brook, NJ, USA
With participation of Volker Böhmer (Chapter 4)
This volume continues the monograph "Chemistry and Application
of Phenolic Resins" by A. Knop and W. Scheib
ISBN 978-3-662-02431-7 ISBN 978-3-662-02429-4 (eBook)
DOI 10.1007/978-3-662-02429-4
Library of Congress Cataloging in Publication Data.
Knop, A. (Andre), 1941-Phenolic resins. Includes bibliographies. I. Phenolic resins. I. Pilato, L. (Louis), 1934-.
II. Title. TP1180.P39K562 1985 668.4'222 85-14708
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© by Springer-Verlag Berlin Heidelberg 1985
Originally published by Springer-Verlag Berlin Heidelberg New York Tokyo in 1985
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Preface
In 1983/84 American Chemical Society, N.Y., Kammer der Technik, Berlin/GDR,
and chemical companies closely associated with phenolic resins underscored the
embryonie efforts ofLeo H. Baekeland and celebrated the 75th anniversary ofthe frrst
wholly synthetic plastic material during symposia held in Washington, D.C., August
1983, and Berlin, September 1984, respectively.
Since their introduction in 1910, the highly versatile family of phenolic resins has
demonstrated an important role in the continuing development ofthe electrical, auto
motive, construction and appliance industries. In the 80's the wave ofhigh technology
has fostered their active participation in "high tech" areas ranging from electronics,
computers, communication, outer spacejaerospace, biomaterials, biotechnology and
advanced composites. Many phenolic resin systems are actively involved in the
"leading edge" of these innovative technologies. Thus, they demonstrate an uncanny
versatility to be adaptable to prevailing times as today's society is transforming from
an industrial to an informationjcommunication society.
The excellent participation at the recent scientific symposia and the acceptance of
the early edition "Chemistry and Application of Phenolic Resins" by A. Knop and
W. Scheib-including the Japanese and Russian translation- by the industrial and
chemical community demonstrated a high Ievel of interest in the broad subject of
phenolic resins and has provided the stimuli of this present publication.
This volume covers fundamentals, the chemical and technological progress, and
new applications including the Iiterature generally up to July 1984. Special emphasis
was assigned to advanced instrumental and analytical techniques and environmental
aspects.
We would like to express our gratitude to all colleagues engaged in the phenolic
discipline, in particular to those who have assisted us with advice and suggestions.
Frankfurt and Bound Brook, July 1985 A.Knop
L. Pilato
Table of Contents
Abbreviations . XIII
Units .XV
1 Introduction .
1.1 Origin ...
1.2 Commercial Development of Phenolic Resins 3
1.3 References . . 4
2 Raw Materials . . . . . . 5
2.1 Phenols . . . . . . . . . 5
2.1.1 Physical Properties of Phenol 5
2.1.2 Supply and U se of Phenol . 6
2.1.3 Phenol Production Processes 7
2.1.4 Cresols and Xylenols - Synthesis Methods 9
2.1.5 Alkylphenols . . . . . . . . . 10
2.1.6 Phenols from Coal and Petroleum 11
2.1.7 Other Phenolic Compounds . . . 13
2.2 Aldehydes ......... . 14
2.2.1 Formaldehyde, Properties, and Processing. 14
2.2.2 Paraformaldehyde . . . . . . . 18
2.2.3 Trioxane and Cyclic Formals . . 19
2.2.4 Hexamethylenetetramine, HMTA 20
2.2.5 Furfural .... 20
2.2.6 Other Aldehydes 21
2.3 References . . . 22
3 Reaction Mechanisms . 24
3.1 Molecular Structure and Reactivity of Phenols. 25
3.2 Formaldehyde-Waterand Formaldehyde-Alcohol Equilibria . 29
3.3 Phenol-Formaldehyde Reaction under Alkaline Conditions 31
3.3.1 Inorganic Catalysts and Tertiary Amines . . . . . . . . . 31
3.3.2 Ammonia, HMTA, and Amine-Catalyzed Reactions .... 34
3.3.3 Reaction Kinetics of the Base-Catalyzed Hydroxymethylation 36
3.3.4 Prepolymer Formation . . . . . . . . . . . . . . . . 40
3.3.5 Resol Crosslinking Reactions. Quinone Methides 42
3.4 Phenol-Formaldehyde Reactions under Acidic Conditions . 46
3.4.1 Strong Acids . . . . . . . . . . 46
3.4.2 Reaction Kinetics in Acidic Medium . . . . . . . . . . 48
VIII Table of Contents
3.4.3 Reaction under Weak Acidic Conditions. "High-Ortho" Novolak Resins 49
3.5 Novolak Crosslinking Reaction with HMTA 52
3.6 Reaction with Epoxide Resins . . . . . . . . . . 54
3.7 Reaction with Diisocyanates . . . . . . . . . . 55
3.8 Reaction with Urea, Melamine, and UF/MF-Resins 56
3.9 Reaction with Imide Precursors . . . . . . . 57
3.10 Statistical Approach and Computer Simulation . . 58
3.11 References . . . . . . . . . . . . . . . . . . 58
4 Structurally Uniform Oligomers (by Volker Böhmer) 62
4.1 Synthesis . . . . . . . . . 63
4.1.1 Principles, Protective Groups . 63
4.1.2 Linear Oligomers . . . . . . 65
4.1.3 Cyclic Compounds, Calixarenes 67
4.1.4 Chemical Modifications 69
4.2 Properties . . . . 73
4.2.1 Physical Properties . . . 73
4.2.2 Acidity. . . . . . . . 74
4.2.3 Complexation of Cations . 76
4.2.4 Kinetic Studies . . . . . 77
4.2.5 Crystal Structure . . . . 80
4.2.6 Conformation in Solution. 85
4.3 References . . . 88
5 Resin Production . 91
5.1 Novolak Resins . 93
5.2 Resols . . . . . 95
5.3 High-Ortho Resins . 97
5.3.1 Novolak . . . . . 97
5.3.2 Liquid Resol . . . 98
5.4 In Situ Dispersions 98
5.4.1 Aqueous Dispersions . 99
5.4.2 Solid Resols . . . 99
5.5 Dust Explosions . . 100
5.6 Spray Dried Resins 101
5.7 References . . . . 101
6 Toxicology and Environmental Protection 103
6.1 Toxicological Behavior of Phenols . . . 104
6.2 Toxicological Behavior of Formaldehyde 104
6.3 Environmental Protection and Regulation . 106
6.4 Waste Waterand Exhaust Air Treatment Processes 108
6.4.1 Microbial Transformation and Degradation . . . 108
6.4.2 Chemical Oxidation and Resinification Reactions 109
6.4.3 Thermal and Catalytic Incineration 110
6.4.4 Extraction Processes and Recovery. 111
6.4.5 Activated Carbon Process. 112
6.4.6 Gas Scrubbing Processes . . . . . 112
Table of Contents IX
6.5 Smoke and Gas Evolution from the Combustion of Phenolics 113
6.6 References . . . . 116
7 Analytical Methods 118
7.1 Monomers . . 118
7.1.1 Phenols ... 118
7.1.2 Formaldehyde. 119
7.2 Polymers . . . 119
7. 2.1 Infrared Spectroscopy 119
7.2.2 Nuclear Magnetic Resonance Spectroscopy 120
7. 2.3 Electron Spectroscopy . . . . . . . . . 123
7. 2.4 Mass Spectrometry . . . . . . . . . . 124
7. 2.5 High Performance Liquid Chromatography 124
7.2.6 Paper and Thin Layer Chromatography 128
7.2.7 Gas Chromatography ..... 128
7.2.8 Gel Permeation Chromatography 130
7.2.9 Thermogravimetrie Analysis. . . 130
7.2.10 Differential Thermal Analysis . . 130
7. 2.11 Differential Scanning Calorimetry 130
7.2.12 Dynamic Mechanical Analysis. 131
7.2.13 TorsionalBraid Analysis . . 131
7.3 X-Ray Diffraction Analysis . 132
7.4 Other Characterization . . 132
7.4.1 Thermodynamic Properties 132
7.4.2 Solution Properties . 133
7.4.3 Dipole Moments .. 133
7.5 Resin Macrostructure 134
7.5.1 Nitrogen and Water . 134
7.5.2 Resin Properties and Quality Control 135
7.6 Structural Analysis of Cured Resins . 137
7.7 References . . . . . . . . . . . . 137
8 Degradation of Phenolic Resins by Heat, Oxygen, and High-Energy
Radiation ..... . 140
8.1 Thermal Degradation . . . . . . . . 140
8.2 Oxidation Reactions . . . . . . . . . 143
8.3 Degradation by High-Energy Radiation 144
8.4 References . . . . . . . . . . . . 146
9 Modified and Thennai-Resistant Resins 147
9.1 Etherification Reactions 148
9.2 Esterification Reactions 149
9.2.1 Boron-Modified Resins. 149
9.2.2 Silicon-Modified Resins 150
9.2.3 Phosphorus-Modified Resins 151
9.3 Heavy Metal-Modified Resins . 151
9.4 Nitrogen-Modified Resins 152
9.5 Sulfur-Modified Resins . . . . 152
X Table of Contents
906 Others 0 0 0 0 0 0 0 0 0 0 0 0 0 0 153
907 References 0 0 0 0 0 0 0 0 0 0 0 0 154
10 High Technology and New Applications 156
10.1 Carbon and Graphite Materials 156
0 0
1002 Phenolic Resirr - Fiber Composites 160
1003 Reaction Injection Molding 0 164
10.4 Phenolic Fibers 165
0
1005 Photo Resists 0 0 0 0 166
1006 Carbonless Paper 0 0 168
1007 Ion Exchange Resins 0 169
1008 Interpenetrating Polymer Networks and Polymer Blends 171
1009 Enhanced Oil Recovery 0 0 172
10.10 References 0 0 0 0 0 0 0 172
11 Composite Wood Materials 175
11.1 Wood 0 0 0 0 0 0 0 0 0 175
11.2 Adhesives and Wood Gluing 176
11.3 Physical Properties of Composite Wood Materials 177
11.4 Partide Boards 0 0 0 0 0 0 0 0 0 177
11.401 W ood Chips, Resins, and Additives 179
11.402 Production of Partide Boards 0 0 0 182
11.403 Properties of Partide Boards 0 0 0 183
11.5 Wafer Board and Oriented Strand Board 185
11.6 Plywood 0 0 0 0 0 0 0 0 0 0 0 0 186
11.6.1 Resins, Additives, and Formulations 187
110602 Production of Plywood 0 0 0 0 188
11.603 Compressed Laminated Wood 0 0 0 189
110 7 Fiber Boards 0 0 0 0 0 0 0 0 0 0 190
11.7.1 Wood Fibers, Resins, and Additives 190
11.702 Production of Fiber Boards 0 191
11.8 Structural Wood Gluing 192
11.8.1 Resorcinol Adhesives 0 192
1109 References 0 0 0 0 0 0 193
12 Molding Compounds 196
0 0
1201 Standardization and Minimum Properties 0 199
1202 Composition of Molding Compounds 200
1202.1 Resins 0 0 0 0 0 0 0 0 0 0 0 0 0 0 200
120202 Fillers, Reinforcements, and Additives 201
1203 Production of Molding Compounds 204
12.4 Thermoset Flow 0 0 0 0 0 0 0 0 205
1205 Manufacturing of Molded Parts 0 207
1206 Selected Properties 0 0 0 0 0 0 0 209
1207 References 0 0 0 0 0 0 0 0 0 0 211
13 Heat and Sound Insolation Materials 213
13.1 Inorganic Fiber Insulating Materials 213
1301.1 Inorganic Fibers and Fiber Production 215
Table of Contents XI
13.1.2 Resins and Formu1ation 217
13.1.3 Properties of Fiber Mats 218
13.2 Phenolic Resin Foam 219
13.2.1 Resins . . . . . . . 220
13.2.2 Foaming Equipment . 221
13.2.3 Foam Properties. . . 222
13.3 Bonded Textile Felts . 226
13.4 References . . . . . 228
14 lndustrial Laminatesand Paper Impregnation 230
14.1 E1ectrica1 Laminates . . . . . . . 230
14.1.1 Materials . . . . . . . . . . . . 233
14.1.2 Production of Electrical Laminates. 235
14.2 Laminated Tubesand Rods .... 237
14.3 Cotton Fabric Reinforced Laminates . 238
14.4 Decorative Laminates 238
14.5 Filters . . . . . . 241
14.6 Battery Separators . 242
14.7 References . . . . 243
15 Coatings . . . . . 244
15.1 Automotive Coatings 245
15.1.1 Water-Borne Coatings and Electrodeposition 246
15.2 Coatings for Metal Containers 247
15.3 Marine Paints . 249
15.3.1 Shop Primers . . . . . . . . 250
15.3.2 WashPrimers . . . . . . . . 250
15.3.3 Oil-Modified Phenolic Resin Paints 251
15.4 Printing Inks . . . . . . . . . 251
15.4.1 Rosin-Modified Phenolic Resins . 252
15.5 Other Applications 253
15.6 References . . 254
16 Foundry Resins 256
16.1 Mold- and Core-Making Processes . 256
16.1.1 lnorganic Binders . . . . . . . 256
16.1.2 Organic Binders ....... . 257
16.1.3 Requirements of Foundry Sands. 257
16.2 Shell Molding Process 259
16.3 Hot-Box Process 261
16.4 No-Bake Process 263
16.5 Cold-Box Process 265
16.6 SOrProcess 266
16.7 Ingot Mold Hot Tops 266
16.8 References . . . . 267
17 Abrasive Materials . . 269
17.1 Grinding Wheels . . 269
17.1.1 Composition of Grinding Wheels 270
XII Table of Contents
17 .1.2 Manufacturing of Grinding Wheels 273
17.2 Coated Abrasives . . . . . . . 275
17 .2.1 Composition of Coated Abrasives 276
17.2.2 Coating Process . 277
17 .2.3 Abrasive Papers . . . . . 278
17.2.4 Abrasive Tissues. . . . . 279
17.2.5 Vulcanized Fiber Abrasives 279
17.3 References . . . . . . . 280
18 Friction Materials . . . . 281
18.1 Formulation of Friction Materials 282
18.2 References . . . . . . . . . . 286
19 Phenolic Resins in Rubbers and Adhesives 288
19.1 Mechanisms of Rubber Vulcanization with Phenolic Resins 288
19.2 Thermosetting Alloy Adhesives . . . 290
19.2.1 Vinyl-Phenolic Structural Adhesives . 290
19.2.2 Nitrile-Phenolic Structural Adhesives . 291
19.3 Phenolic Resins in Contact Adhesives 292
19.3.1 Chloroprene-Pheno1ic Contact Adhesives 292
19.3.2 Nitri1e-Phenolic Contact Adhesives. . . 295
19.4 Phenolic Resins in Pressure-Sensitive Adhesives 295
19.5 Rubber-Reinforcing Resins . . . . . . 296
19.6 Resorcinol-Formaldehyde Latex Systems 297
19.7 References . . . . . 297
20 Phenolic Antioxidaufs 299
20.1 References . . . . . 301
21 Other Applications . . 303
21.1 Refractory Linings and Taphole Mixes 303
21.2 Pheno1ics for Chemical Equipment . 303
21.3 Socket Putties . 304
21.4 Brush Putties . . . 304
21.5 Synthanes . . . . 304
21.6 Concrete Additives 305
21.7 Casting Resins 305
21.8 References 306
Subject Index . . . . 307
