A. 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

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under §54 of the German Copyright Law where copies are made for other than private use, a fee is payable to "Verwertungsgesellschaft Wort", Munich.

© by Springer-Verlag Berlin Heidelberg 1985 Originally published by Springer-Verlag Berlin Heidelberg New York Tokyo in 1985 Softcoverreprint ofthe bardeover Istedition 1985

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2154/3020-543210

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, auto­motive, 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

Units

1 Introduction . 1.1 Origin ... 1.2 Commercial Development of Phenolic Resins 1.3 References . .

2 Raw Materials . . . . . . 2.1 Phenols . . . . . . . . . 2.1.1 Physical Properties of Phenol 2.1.2 Supply and U se of Phenol . 2.1.3 2.1.4 2.1.5 2.1.6 2.1.7 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 2.3

3 3.1 3.2 3.3 3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 3.4 3.4.1 3.4.2

Phenol Production Processes Cresols and Xylenols - Synthesis Methods Alkylphenols . . . . . . . . . Phenols from Coal and Petroleum Other Phenolic Compounds . . . Aldehydes ......... . Formaldehyde, Properties, and Processing. Paraformaldehyde . . . . . . . Trioxane and Cyclic Formals . . Hexamethylenetetramine, HMT A Furfural .... Other Aldehydes References . . .

Reaction Mechanisms . Molecular Structure and Reactivity of Phenols. Formaldehyde-Waterand Formaldehyde-Alcohol Equilibria . Phenol-Formaldehyde Reaction under Alkaline Conditions Inorganic Catalysts and Tertiary Amines . . . . . . . . . Ammonia, HMTA, and Amine-Catalyzed Reactions .... Reaction Kinetics of the Base-Catalyzed Hydroxymethylation Prepolymer Formation . . . . . . . . . . . . . . . . Resol Crosslinking Reactions. Quinone Methides Phenol-Formaldehyde Reactions under Acidic Conditions . Strong Acids . . . . . . . . . . Reaction Kinetics in Acidic Medium . . . . . . . . . .

. XIII

.XV

3 4

5 5 5 6 7 9

10 11 13 14 14 18 19 20 20 21 22

24 25 29 31 31 34 36 40 42 46 46 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 6.1 Toxicological Behavior of Phenols . . . 6.2 Toxicological Behavior of Formaldehyde 6.3 Environmental Protection and Regulation . 6.4 Waste Waterand Exhaust Air Treatment Processes 6.4.1 Microbial Transformation and Degradation . . . 6.4.2 Chemical Oxidation and Resinification Reactions 6.4.3 Thermal and Catalytic Incineration 6.4.4 Extraction Processes and Recovery. 6.4.5 Activated Carbon Process. 6.4.6 Gas Scrubbing Processes . . . . .

103 104 104 106 108 108 109 110 111 112 112

Table of Contents IX

6.5 Smoke and Gas Evolution from the Combustion of Phenolics 113 6.6 References . . . . 116

7 Analytical Methods 7.1 Monomers . . 7.1.1 Phenols ... 7.1.2 Formaldehyde. 7.2 Polymers . . . 7 .2.1 Infrared Spectroscopy 7.2.2 Nuclear Magnetic Resonance Spectroscopy 7 .2.3 Electron Spectroscopy . . . . . . . . . 7 .2.4 Mass Spectrometry . . . . . . . . . . 7 .2.5 High Performance Liquid Chromatography 7.2.6 Paper and Thin Layer Chromatography 7.2.7 Gas Chromatography ..... 7.2.8 Gel Permeation Chromatography 7.2.9 Thermogravimetrie Analysis. . . 7.2.10 Differential Thermal Analysis . . 7 .2.11 Differential Scanning Calorimetry 7.2.12 Dynamic Mechanical Analysis. 7.2.13 TorsionalBraid Analysis . . 7.3 X-Ray Diffraction Analysis . 7.4 Other Characterization . . 7.4.1 Thermodynamic Properties 7.4.2 Solution Properties . 7.4.3 Dipole Moments .. 7.5 Resin Macrostructure 7.5.1 Nitrogen and Water . 7.5.2 Resin Properties and Quality Control 7.6 Structural Analysis of Cured Resins . 7.7 References . . . . . . . . . . . .

8

8.1 8.2 8.3 8.4

9 9.1 9.2 9.2.1 9.2.2 9.2.3 9.3 9.4 9.5

Degradation of Phenolic Resins by Heat, Oxygen, and High-Energy Radiation ..... . Thermal Degradation . . . . . . . . Oxidation Reactions . . . . . . . . . Degradation by High-Energy Radiation References . . . . . . . . . . . .

Modified and Thennai-Resistant Resins Etherification Reactions Esterification Reactions Boron-Modified Resins. Silicon-Modified Resins Phosphorus-Modified Resins Heavy Metal-Modified Resins . Nitrogen-Modified Resins Sulfur-Modified Resins . . . .

118 118 118 119 119 119 120 123 124 124 128 128 130 130 130 130 131 131 132 132 132 133 133 134 134 135 137 137

140 140 143 144 146

147 148 149 149 150 151 151 152 152

X

906 Others 0 0 0 0 0 0 0 0 0 0 0 0 0 0 907 References 0 0 0 0 0 0 0 0 0 0 0 0

10 High Technology and New Applications 10.1 Carbon and Graphite Materials 0 0

1002 Phenolic Resirr - Fiber Composites 1003 Reaction Injection Molding 0 10.4 Phenolic Fibers 0

1005 Photo Resists 0 0 0 0 1006 Carbonless Paper 0 0 1007 Ion Exchange Resins 0 1008 Interpenetrating Polymer Networks and Polymer Blends 1009 Enhanced Oil Recovery 0 0 10.10 References 0 0 0 0 0 0 0

11 Composite Wood Materials 11.1 Wood 0 0 0 0 0 0 0 0 0 11.2 Adhesives and Wood Gluing 11.3 Physical Properties of Composite Wood Materials 11.4 Partide Boards 0 0 0 0 0 0 0 0 0 11.401 W ood Chips, Resins, and Additives 11.402 Production of Partide Boards 0 0 0 11.403 Properties of Partide Boards 0 0 0 11.5 Wafer Board and Oriented Strand Board 11.6 Plywood 0 0 0 0 0 0 0 0 0 0 0 0 11.6.1 Resins, Additives, and Formulations 110602 Production of Plywood 0 0 0 0 11.603 Compressed Laminated Wood 0 0 0 110 7 Fiber Boards 0 0 0 0 0 0 0 0 0 0 11.7.1 Wood Fibers, Resins, and Additives 11.702 Production of Fiber Boards 0 11.8 Structural Wood Gluing 11.8.1 Resorcinol Adhesives 0 1109 References 0 0 0 0 0 0

12 Molding Compounds 0 0

1201 Standardization and Minimum Properties 0 1202 Composition of Molding Compounds 1202.1 Resins 0 0 0 0 0 0 0 0 0 0 0 0 0 0 120202 Fillers, Reinforcements, and Additives 1203 Production of Molding Compounds 12.4 Thermoset Flow 0 0 0 0 0 0 0 0 1205 Manufacturing of Molded Parts 0 1206 Selected Properties 0 0 0 0 0 0 0 1207 References 0 0 0 0 0 0 0 0 0 0

13 Heat and Sound Insolation Materials 13.1 Inorganic Fiber Insulating Materials 1301.1 Inorganic Fibers and Fiber Production

Table of Contents

153 154

156 156 160 164 165 166 168 169 171 172 172

175 175 176 177 177 179 182 183 185 186 187 188 189 190 190 191 192 192 193

196 199 200 200 201 204 205 207 209 211

213 213 215

Table of Contents

13.1.2 Resins and Formu1ation 13.1.3 Properties of Fiber Mats 13.2 Phenolic Resin Foam 13.2.1 Resins . . . . . . . 13.2.2 Foaming Equipment . 13.2.3 Foam Properties. . . 13.3 Bonded Textile Felts . 13.4 References . . . . .

14 lndustrial Laminatesand Paper Impregnation 14.1 E1ectrica1 Laminates . . . . . . . 14.1.1 Materials . . . . . . . . . . . . 14.1.2 Production of Electrical Laminates. 14.2 Laminated Tubesand Rods .... 14.3 Cotton Fabric Reinforced Laminates . 14.4 Decorative Laminates 14.5 Filters . . . . . . 14.6 Battery Separators . 14.7 References . . . .

15 Coatings . . . . . 15.1 Automotive Coatings 15.1.1 Water-Borne Coatings and Electrodeposition 15.2 Coatings for Metal Containers 15.3 Marine Paints . 15.3.1 Shop Primers . . . . . . . . 15.3.2 WashPrimers . . . . . . . . 15.3.3 Oil-Modified Phenolic Resin Paints 15.4 Printing Inks . . . . . . . . . 15.4.1 Rosin-Modified Phenolic Resins . 15.5 Other Applications 15.6 References . .

16 Foundry Resins 16.1 Mold- and Core-Making Processes . 16.1.1 lnorganic Binders . . . . . . . 16.1.2 Organic Binders ....... . 16.1.3 Requirements of Foundry Sands. 16.2 Shell Molding Process 16.3 Hot-Box Process 16.4 No-Bake Process 16.5 Cold-Box Process 16.6 SOrProcess 16.7 Ingot Mold Hot Tops 16.8 References . . . .

17 Abrasive Materials . . 17.1 Grinding Wheels . . 17.1.1 Composition of Grinding Wheels

XI

217 218 219 220 221 222 226 228

230 230 233 235 237 238 238 241 242 243

244 245 246 247 249 250 250 251 251 252 253 254

256 256 256 257 257 259 261 263 265 266 266 267

269 269 270

XII

17 .1.2 Manufacturing of Grinding Wheels 17.2 Coated Abrasives . . . . . . . 17 .2.1 Composition of Coated Abrasives 17.2.2 Coating Process . 17 .2.3 Abrasive Papers . . . . . 17.2.4 Abrasive Tissues. . . . . 17.2.5 Vulcanized Fiber Abrasives 17.3 References . . . . . . .

18 Friction Materials . . . . 18.1 Formulation of Friction Materials 18.2 References . . . . . . . . . .

19 Phenolic Resins in Rubbers and Adhesives 19.1 Mechanisms of Rubber Vulcanization with Phenolic Resins 19.2 Thermosetting Alloy Adhesives . . . 19.2.1 Vinyl-Phenolic Structural Adhesives . 19.2.2 Nitrile-Phenolic Structural Adhesives . 19.3 Phenolic Resins in Contact Adhesives 19.3.1 Chloroprene-Pheno1ic Contact Adhesives 19.3.2 Nitri1e-Phenolic Contact Adhesives. . . 19.4 Phenolic Resins in Pressure-Sensitive Adhesives 19.5 Rubber-Reinforcing Resins . . . . . . 19.6 Resorcinol-Formaldehyde Latex Systems 19.7 References . . . . .

20 Phenolic Antioxidaufs 20.1 References . . . . .

21 Other Applications . . 21.1 Refractory Linings and Taphole Mixes 21.2 Pheno1ics for Chemical Equipment . 21.3 Socket Putties . 21.4 Brush Putties . . . 21.5 Synthanes . . . . 21.6 Concrete Additives 21.7 Casting Resins 21.8 References

Subject Index . . . .

Table of Contents

273 275 276 277 278 279 279 280

281 282 286

288 288 290 290 291 292 292 295 295 296 297 297

299 301

303 303 303 304 304 304 305 305 306

307

Abbreviations

ASTM BHMP BP BR CHP COD CP CR DIN DMA DMF DPM DSC DTA EPA ESCA F FA FAO FDA FDMS FTIR GC GPC HPL HPLC HMP HMTA IB IE IPN IR LCso MAK MAS MF MOE

American Society of Testing and Materials Bis(hydroxymethyl)phenol, dimethylphenol Boiling point Butyl ruhher Cumene hydroperoxide Chemical oxygen demand Cross polarization Chloroprene ruhher Deutsche Industrie Normen Dynamic mechanical analysis Dimethylformamide Diphenylmethane Differential scanning calorimetry Differential thermal analysis Environmental Protection Agency Electron spectroscopy for chemical analysis Formaldehyde Furfuryl alcohol Food and Agriculture Organization F ood and Drug Administration Field desorption mass spectrometry Fourier transform infrared spectroscopy Gas chromatography Gel permeability chromatography High-pressure Iaminate High-performance liquid chromatography Hydroxymethylphenol Hexamethylenetetramine Interna} band ( = tensile strength vertical to the surface) Ion exchange resin Interpenetrating polymer network Polyisobutylene ruhher Medium Iethai concentration Maximum workplace exposure, 8 h Magie angle spinning Melamine-formaldehyde resin Modulus of elasticity

XIV

MP MW MWD NBR NMR OSHA p PB pbw PF PPO PS PVAc PVB PVF Py QM RH SEM SG TBA TBBA TEM TGA THMP TKN TLC TTT UF UMP vc XPS

Melting point Molecular weight Molecular weight distribution Nitrile butadiene rubber Nuclear magnetic resonance spectroscopy Occupational Health and Safety Administration Phenol Partide board Parts by weight Phenol-formaldehyde resin Polyphenylene oxide Patent specification Polyvinyl acetate Polyvinyl butyral Polyvinyl formal Pyridine Quinone methide Relative hurnidity Scanning electron microscopy Specific gravity Torsional braid analysis Tetrabromobisphenol A Transmission electron microscopy Thermogravimetrie analysis Tris(hydroxymethyl)phenol, Trimethylolphenol Total Kjeldahl nitrogen Thin layer chromatography Time temperature transformation Urea-formaldehyde resin Urea-melamine-phenol resin Volatiles content X-ray photoelectron spectroscopy

Abbreviations

Units

Force Mechanical tension

Pressure

Temperature Dynamic viscosity Heat quantity Thermal conductivity

Length

Area

Mass Density

lkp =9.80665N~lON

1 kpjcm2 = 0.0981 Njmm2 ~0.1 Njmm2

1 N/mm2 = 145 psi 1 at = 1 kpjcm2 =0.980665bar~1 bar 1 Pa = 10- 5 bar °F = °C ·1.8+32 1 cP = 1 mPa · s 1 kcal = 4.187 kJ 1 W /Km = 0.86 kcal/m h oc 1 W/Km = 0.579BTU/fth op 1 W/Km = 6.95 BTU injft2 h 1 mm = 0.0394 in 1m = 3.2808 ft lmm2

1m2

1 kg 1 gjcm 3

= 0.0016 sq in = 10.764 sq ft = 2.2046lb = 62.4llbjft3