ISBN: 3-540-65517-4
TITLE: Phenolic Resins
AUTHOR: Gardziella, A.; Pilato, L.A.; Knop, A.
TOC:

Abbreviations XXI 
Conversion Factors XXV 
Part A Chemistry/Production 1 
Chapter 1 Raw Materials 3 
1.1 Phenols 3 
1.1.1 Physical Properties of Phenol 4 
1.1.2 Supply and Use of Phenol 4 
1.1.3 Phenol Production Processes 5 
1.1.3.1 Cumene Oxidation (Hock Process) 5 
1.1.3.2 Toluene Oxidation Process 8 
1.1.3.3 Nitrous Oxide Oxidation of Benzene 9 
1.1.3.4 Other Synthesis Processes 9 
1.1.4 Alkylphenols 9 
1.1.4.1 Methylphenols 10 
1.1.4.2 Higher Alkylphenols 11 
1.1.5 Phenols from Coal and Mineral Oil 12 
1.1.6 Resorcinol 12 
1.1.7 Bisphenol-A 13 
1.2 Aldehydes 14 
1.2.1 Formaldehyde 14 
1.2.2 Production and Economics of Formaldehyde 16 
1.2.3 Paraformaldehyde 20 
1.2.4 Trioxane and Cyclic Formals 20 
1.2.5 Hexamethylenetetramine 21 
1.2.6 Other Aldehydes 21 
References 22 
Chapter 2 Phenolic Resins: Chemistry, Reactions, Mechanism 24 
2.1 Introduction 24 
2.2 Chemistry 24 
2.2.1 Resole 25 
2.2.1.1 Methylol Phenol(s) 25 
2.2.1.2 Oligomerization 27 
2.2.2 Novolak 36 
2.2.2.1 Bisphenol F 36 
2.2.2.2 Oligomerization 39 
2.2.2.2.1 Random 39 
2.2.2.2.2 High Ortho 46 
2.2.2.2.3 Modified Novolaks 48 
Bismethylol Para Substituted Phenols 48  Diethers 49 
 Dialcohols 49  Diolefins 50  Enzymes 50 
2.3 Reactions 51 
2.3.1 Functional Group Appendage to Phenolics 51 
2.3.1.1 Epoxy 51 
2.3.1.2 Allyl, Benzyl Group 55 
2.3.1.3 Cyanate Ester 56 
2.3.2 Ring Formation with Phenolic 57 
2.3.2.1 Benzoxazine 57 
2.3.3 Alkylation 60 
2.3.3.1 Friedel-Crafts 60 
2.3.3.2 Hydroxymethylation 60 
2.3.4 Miscellaneous 60 
2.3.4.1 Polyimide 60 
2.3.5 Natural Products 61 
2.4 Mechanism 61 
2.4.1 Cure 61 
2.4.1.1 Resole 62 
2.4.1.1.1 Thermal/Viscoelastic Analyses 62 
2.4.1.1.2 NMR Analyses 64 
2.4.1.2 Novolak 66 
2.4.1.3 Non-Hexa Cure 72 
2.4.1.4 Level of Cure 74 
2.4.2 Toughness/Alloys/IPN 75 
2.4.3 Hazardous Occurrences 77 
2.5 Summary/Trends 78 
References 79 
Chapter 3 Production of Phenolic Resins 83 
3.1 Production of Novolak 87 
3.2 Production of Resole 89 
3.3 Continuous Process 89 
References 90 
Chapter 4 Structure (Methods of Analysis) 91 
4.1 Introduction 91 
4.2 Structural Characteristics 91 
4.2.1 Hydrodynamic Volume Characterization 91 
4.2.1.1 Chromatography 92 
4.2.2 MALDI 92 
4.2.3 Compositional Structure 96 
4.2.3.1 Oligomer, Uncured Resin 96 
4.2.3.2 Cured Resin 96 
4.3 Solution Properties 97 
4.3.1 Novolaks 97 
4.3.2 Resoles 97 
4.3.3 Amine Catalyzed Resoles 98 
4.3.4 "All ortho" Novolaks 101 
4.4 Complexation 101 
4.4.1 "All ortho" Novolaks 101 
4.4.2 Ethyl Acetate Appendage 101 
4.4.3 Trioxyethylene Ether Appendage 102 
4.5 Mechanical Properties 103 
4.6 Fire Properties 104 
4.7 Summary/Trends 105 
References 106 
Part B Applications of Phenolic Resins 107 
Chapter 5 Thermosets: Overview, Definitions, and Comparisons 109 
References 120 
Chapter 6 Economic Significance of Phenolic Resins, 
Survey of Applications, and Six Bonding Functions 122 
6.1 Permanent Bonding 126 
6.1.1 Wood Composites 127 
6.1.1.1 Introduction 127 
6.1.1.2 Wood Structure/Surface 128 
6.1.1.3 Wood Sources 129 
6.1.1.4 Wood Composite Materials 130 
6.1.1.4.1 Wood Panel and Engineered Lumber Products 130 
6.1.1.4.2 Adhesives 130 
Phenolic Resins 131  Panels 131  Plywood 131 
 Resins, Additives, and Formulations 133  Production 
of Plywood 134  Co-Reaction of PF with UF 136 
 Color Improvement 137  Oriented Strand Board 
(OSB)/Waferboard 137  Core and Surface Resins 138 
 Resin Distribution by Imaging 140  MDI 141 
 Particleboard 141  Classification of PB 141  Emission 
Studies 142  Medium Density Fiberboard (MDF) 142 
 Hardboard 142 
6.1.1.4.3 Engineered Lumber Products 143 
Laminated Veneer Lumber (LVL) 143  Parallel Strand 
Lumber (Parallam) 143  Parallam Features 145 
6.1.1.5 New Process and Equipment Developments 
in Panel Manufacture 145 
6.1.1.5.1 Steam Injection Pressing (SIP) 145 
6.1.1.5.2 Wider Presses 146 
6.1.1.5.3 Increased Length  OSB Flakes 146 
6.1.1.5.4 Uniform Mats 146 
6.1.1.6 Natural Resins 146 
6.1.1.6.1 Introduction 146 
6.1.1.6.2 Lignin 147 
6.1.1.6.3 Tannin 148 
6.1.1.7 Non-Wood Materials 149 
6.1.1.8 Structural Wood Gluing 149 
6.1.1.8.1 Introduction 149 
6.1.1.8.2 Resorcinol Adhesives 150 
6.1.1.8.3 New Areas 151 
FRP Glulam Adhesive 151  Coupling Agent 152 
6.1.1.9 Summary/Future Directions 152 
6.1.2 Insulation 153 
6.1.2.1 Inorganic Fibers 153 
6.1.2.1.1 Introduction 153 
6.1.2.1.2 Types of Inorganic Fibers 154 
6.1.2.1.3 Resins for Inorganic Fibers 156 
6.1.2.1.4 Resin Formulation 157 
6.1.2.2 Phenolic Foam 158 
6.1.2.2.1 Introduction 158 
6.1.2.2.2 Resins 159 
6.1.2.2.3 Catalysts 160 
6.1.2.2.4 Blowing Agents 160 
6.1.2.2.5 Surfactants 161 
6.1.2.2.6 Wetting Agents 162 
6.1.2.2.7 Fillers 162 
6.1.2.2.8 Foam Stabilizers 162 
6.1.2.2.9 Foam Applications 162 
Thermal Insulation 162  Low Density Foam (< 50 kg/m^3) 162 
 Corrosion 163  Closed Cell 163  Medium to High Density 
Foam 163  Floral Foam 163  Orthopedic Foam 164 
 Mine/Tunnel Foam 164  Hybrid Phenolic Foams 165 
 Polyurethane 165  Urea Formaldehyde 165  Furfuryl 
Alcohol 165 
6.1.2.2.10 Foaming Equipment 165 
Batch 166  Continuous 166 
6.1.2.2.11 Properties of Various Phenolic Foam Products 166 
6.1.2.2.12 Foam Testing 166 
Fire Conditions 166  Thermal Conductivity 168 
6.1.2.2.13 Aerogels 168 
6.1.2.2.14 Summary/Trends 169 
6.1.2.3 Phenolic Resin-Bonded Textile Felts (DIN 61210) 170 
6.1.2.3.1 Introduction (Textile Recycling, Raw Materials, 
Applications) 170 
6.1.2.3.2 Definitions 170 
6.1.2.3.3 Composition of Textile Felts 171 
6.1.2.3.4 Types of Resins for Textile Felts 172 
6.1.2.3.5 Manufacturing Processes 176 
6.1.2.3.6 Properties and Applications 179 
6.1.2.3.7 Property and Quality Testing 180 
6.1.2.3.8 Recycling 184 
6.1.3 Phenolic Molding Compounds 187 
6.1.3.1 Introduction: Economic Aspects 187 
6.1.3.2 Composition of Phenolic Molding Compounds 
(Resins, Fillers, and Reinforcing Agents) 188 
6.1.3.3 Phenolic Molding Compound Standardization 
(Current Status) 194 
6.1.3.4 Production of Molding Compounds 197 
6.1.3.5 Processing of Molding Compounds 199 
6.1.3.6 Test Methods (Application of ISO Standards) 203 
6.1.3.6.1 Bulk Density (ISO 60) 205 
6.1.3.6.2 Process Shrinkage (ISO 2577) 205 
6.1.3.6.3 Tensile Strength (ISO 527) 205 
6.1.3.6.4 Bending Strength (ISO 178) 205 
6.1.3.6.5 Charpy Impact Resistance (ISO 179/1eU) 
and Charpy Notched Impact Strength (ISO 179/1eA) 206 
6.1.3.6.6 Heat Distortion Temperature (ISO 75) 206 
6.1.3.6.7 Maximum Application Temperature 
(IEC 60216, Part 1) 206 
6.1.3.6.8 Flammability Test (UL 94) 207 
6.1.3.6.9 BH Incandescent Rod Flammability Method 
(IEC 60707) 207 
6.1.3.6.10 Water Absorption (ISO 62) 207 
6.1.3.6.11 Specific Surface Resistance (IEC 60093) 207 
6.1.3.6.12 Specific Volume Resistance (IEC 60093) 208 
6.1.3.6.13 Dielectric Loss Factor and Dielectric Number 
(IEC 60250) 208 
6.1.3.6.14 Dielectric Strength (IEC 60243, Part 1) 208 
6.1.3.6.15 Tracking Resistance (CTI and PTI Comparative 
Tracking Index, IEC 60112) 209 
6.1.3.7 Flow Behavior of Phenolic Molding Compounds 209 
6.1.3.8 Application of Phenolic Molding Compounds 212 
6.1.3.9 Standardized and Non-Standardized Molding 
Compounds (as Examples for Applications) 220 
6.1.3.10 Properties of Phenolic Molding Compounds 
Compared to Those of Other Materials 224 
6.1.3.11 Phenolic Novolaks and Epoxidized Phenolic Novolaks 
for Production of Epoxy Molding Compounds 230 
6.1.4 Impregnation of Paper and Fabric (Overview) 231 
6.1.4.1 Molded Laminates (Introduction) 232 
6.1.4.2 Molded Laminates (Survey of Technologies 
and Diversification) 234 
6.1.4.3 Economic Considerations and Background 
(Electrical Laminates and Printed Circuit Boards) 237 
6.1.4.4 Standardization of Molded Laminates 244 
6.1.4.5 Raw Materials and Impregnation 248 
6.1.4.6 Fabric Laminates 250 
6.1.4.7 Applications of Paper- and Fabric-Based 
Laminates 251 
6.1.4.8 Industrial Filter Inserts 251 
6.1.4.9 Miscellaneous Impregnation Applications 254 
6.1.5 High Performance and Advanced Composites 259 
6.1.5.1 Introduction 259 
6.1.5.2 Composite Market Segments 260 
6.1.5.3 Fiber Reinforced Plastics 263 
6.1.5.4 Phenolic Resin Developments 263 
6.1.5.5 Fiber Developments 264 
6.1.5.6 Composite Fabrication Processes 264 
6.1.5.6.1 Impregnation 265 
Prepreg 265  Cargo Liner 266  Ballistics 266  Carbon-Carbon 
Composites 267  Honeycomb Core Sandwich Construction 268 
6.1.5.6.2 Filament Winding 272 
6.1.5.6.3 Pultrusion 275 
6.1.5.6.4 Sheet Molding Compound 279 
6.1.5.6.5 Resin Transfer Molding 280 
6.1.5.6.6 Hand Lay Up 281 
6.1.5.7 Summary/Trends 281 
6.1.6 Miscellaneous 282 
6.1.6.1 Chemically Resistant Putties and Chemical 
Equipment Construction 282 
6.1.6.2 Lampbase Cements ("Socket Putties") 285 
6.1.6.3 Various Applications (Brush Cements, Casting Resins, 
and Concrete Flow Promoters) 287 
6.1.6.4 Phenolic Resin Fibers 288 
6.2 Temporary Bonding 291 
6.2.1 Foundry 292 
6.2.1.1 Introduction (Economic and Technical Survey) 292 
6.2.1.2 Hot Curing Processes 300 
6.2.1.3 The Shell Molding Process 300 
6.2.1.3.1 Sand Conditioning 301 
Hot Coating 301  Warm Coating 301 
6.2.1.3.2 Fabrication of Cores and Shells 301 
6.2.1.4 The Hot Box Process 302 
6.2.1.5 The Warm Box Process 304 
6.2.1.6 Cold Curing with Direct Addition of a Curing Agent 
(No Bake Process) 305 
6.2.1.6.1 Acid Curing 305 
6.2.1.6.2 No Bake Curing with Added Esters 307 
6.2.1.6.3 No Bake Process with Isocyanate Curing 307 
6.2.1.7 Gas Curing Processes Using Phenolic Resin Binders 308 
6.2.1.7.1 The Polyurethane Cold Box Process 309 
6.2.1.7.2 The Methyl Formate Process 311 
6.2.1.7.3 The CO_2-Resole Process 312 
6.2.1.7.4 The Acetal Process 312 
6.2.1.7.5 Other Gassing Processes 313 
6.2.1.8 General Remarks on Core/Mold Fabrication 
Processes Using Phenolic Resins 313 
6.2.2 Abrasives 314 
6.2.2.1 Introduction (Grinding, Abrasives) 314 
6.2.2.2 Economical Significance 315 
6.2.2.3 Grinding Wheels (Classification, Definitions) 317 
6.2.2.4 Grinding Wheel Design, Bonded Abrasives 
(Composition and Stresses) 319 
6.2.2.5 Liquid and Powdered Binders (Phenolic Resins) 323 
6.2.2.6 Cold Pressed Cutting and Roughing Wheels 328 
6.2.2.7 Production and Use of Glass Fabric Inserts 333 
6.2.2.8 Binders for High Wet Strength Grinding Wheels 
and Segments 336 
6.2.2.9 Hot Pressed, Highly Compacted Grinding Wheels 
(HP Wheels) 337 
6.2.2.10 Diamond Wheels 339 
6.2.2.11 Phenolic Resins as Binders for Coated Abrasives 340 
6.2.3 Friction Linings 353 
6.2.3.1 Introduction (General Information) 353 
6.2.3.2 Demands on Friction Linings 355 
6.2.3.3 Composition of Friction Linings 358 
6.2.3.4 Phenolic Resins and Properties of Friction Linings 361 
6.2.3.5 Manufacture of Friction Linings 365 
6.2.3.5.1 Process 1 (Dry Mixes for Hot Pressing 
or Warm Shaping with Subsequent Oven Curing) 365 
6.2.3.5.2 Process 2 (Wet Mixes for the Calender and Extrusion 
Processes) 366 
6.2.3.5.3 Process 3 (Impregnation of Fiber Textiles 
and Yarns) 367 
6.2.4 Auxiliaries for Petroleum and Natural Gas Production 
(Proppant Sands and Tensides) 370 
6.3 Complementary Bonding 373 
6.3.1 Phenolic Resins for Coatings and Surface 
Protection 374 
6.3.1.1 Introduction: History and Possible Applications 374 
6.3.1.2 Phenolic Resins as Binders in Coatings 
(Types of Resins and Modifications) 375 
6.3.1.3 Phenolic Resin Coatings Composition 377 
6.3.1.4 Packaging Coatings (Protective Interior Coatings) 377 
6.3.1.5 Anticorrosion Primers 380 
6.3.1.6 Electrically Insulating Coatings 383 
6.3.1.7 Miscellaneous Coatings Applications 
(Printing Inks, Alkyd Coatings, Photosensitive 
Coatings, Powder Coatings) 384 
6.3.1.8 Photoresist/Imaging 385 
6.3.1.8.1 Introduction 385 
6.3.1.8.2 Photoresist 386 
Positive Resists 388  Negative Resists 388  Cresol Novolak 
Microstructure 389  Molecular Weight and Molecular Weight 
Distribution 390  Cresol Novolak Preparation 391 
 Chemically Amplified Resists (CAR) 395 
6.3.1.8.3 Summary/Trends 397 
6.3.2 Phenolic Resins as Additives in the Rubber 
Industry 398 
6.3.2.1 Vulcanization Resins 399 
6.3.2.2 Tackifying Resins: Resins Used to Increase the Tack 
of Rubber Mixes 401 
6.3.2.3 Reinforcing Resins: Phenolic Resins Used 
for Reinforcement of Rubber Mixes 403 
6.3.3 Binders for the Adhesives Industry 405 
6.3.3.1 Polychloroprene-Based Adhesives 406 
6.3.3.2 Nitrile Rubber Adhesives 408 
6.3.3.3 Polyurethane-Based Contact Adhesives 409 
6.3.3.4 Rubber/Metal Bonding 410 
6.3.3.5 Friction Lining Adhesives 412 
6.3.3.6 Other Applications of Phenolic Resins in Adhesives 
Formulations and Sealants 414 
6.3.3.6.1 Metal Bonding 414 
6.3.3.6.2 Cladding Adhesives 414 
6.3.3.6.3 Natural Rubber-Based Bonding Adhesives 414 
6.3.3.6.4 Hot Melts 415 
6.3.3.6.5 Gaskets 415 
6.3.3.6.6 Sealants 415 
6.4 Intermediate and Carbon-Forming Bonding 416 
6.4.1 Pyrolysis of Phenolics 417 
6.4.2 Phenolic Resins as Binders for Refractories 425 
6.4.2.1 Definitions 425 
6.4.2.2 Economic Importance and Applications 427 
6.4.2.3 Environmental Impact in Use of Phenolic Resins 430 
6.4.2.4 Shaped Products 432 
6.4.2.5 Manufacture of Bricks 434 
6.4.2.6 Isostatically Pressed Products for Continuous 
Casting 438 
6.4.2.7 Slide Gates, Graphite Crucibles, Insulating Plates 441 
6.4.2.8 Unshaped Refractory Mixes 442 
6.4.2.9 Impregnation of Refractories 442 
6.4.3 Carbon and Graphite Materials 444 
6.4.3.1 Introduction (General Information) 444 
6.4.3.2 Phenolic Resins as Binders for Carbon and Graphite 
Engineering Materials (Including CFC) 446 
6.4.3.3 Phenolic Resins as Impregnating Agents 
for Porous Carbon or Graphite Articles 450 
6.4.3.4 Electrode Production 450 
6.4.4 Glassy Carbon (Polymeric Carbon) 452 
6.5 The Chemically Reactive Bonding Function 455 
6.5.1 Summary: Epoxidation, Alkoxylation, Polyurethane 455 
6.5.2 Alkylphenolic Resins as Dye Developers for 
Carbonless Copy Paper 456 
6.5.2.1 Thermography 459 
6.5.3 Antioxidants/Stabilizers 460 
6.5.3.1 Introduction 460 
6.5.3.2 Types of Antioxidants/Stabilizers 460 
6.5.3.2.1 Natural Antioxidants 460 
6.5.3.2.2 Synthetic Antioxidants 460 
6.5.3.3 Classification of Antioxidants/Stabilizers 461 
6.5.3.3.1 Primary Antioxidants 461 
6.5.3.3.2 Secondary Antioxidants 461 
6.5.3.4 Mechanism of Oxidation 461 
6.5.3.5 Effect of Antioxidants/Stabilizers 462 
6.5.3.5.1 Hindered Phenols and Secondary Aromatic 
Amines 462 
6.5.3.5.2 Trivalent Phosphorus Compounds 462 
6.5.3.5.3 Hindered Amines (HALS) 462 
6.5.3.6 Market Areas 463 
6.5.3.6.1 Food/Beverages 463 
6.5.3.6.2 Petroleum Products 464 
Fuels 464  Lubricating Oils 464 
6.5.3.6.3 Rubber Compounds 464 
6.5.3.6.4 Polymeric Materials 464 
6.5.3.7 New Developments 466 
6.5.3.7.1 Polymer Bound 466 
6.5.3.7.2 Benzotriazole Types 466 
6.5.3.7.3 Triazine 467 
6.5.3.7.4 Lactone/Hydroxylamine 467 
6.5.3.8 Summary/Trends 467 
References 468 
Chapter 7 Chemical, Physical and Application Technology 
Parameters of Phenolic Resins 488 
7.1 Introduction (Purpose and Objective) 488 
7.2 Standard Chemical and Physical Tests 490 
7.3 Description of Physical and Chemical Test Methods 
(ISO 10082) and Their Significance [1, 2] 491 
7.3.1 ISO 3146, Melting Range, Melting Behavior 492 
7.3.2 ISO 8620, Screen Analysis with the Air Jet Screen 
and Particle Size Analysis as Specified by ISO 13320 
(Laser Method) 492 
7.3.3 ISO 60, Bulk Density 494 
7.3.4 ISO 2811 and ISO 3675, Determination of Density 495 
7.3.5 ISO 2555, ISO 3219, and ISO 12058, Determination 
of Viscosity 495 
7.3.6 ISO 8975, Determination of pH 496 
7.3.7 ISO 9944, Determination of Electrical Conductivity 497 
7.3.8 ISO 8989, Water Miscibility 497 
7.3.9 ISO 8819, Determination of the Flow Distance 497 
7.3.10 ISO 8987, ISO 9396, and ISO 11409, Measurement 
of the Curing Characteristics 498 
7.3.11 ISO 9771, Acid Reactivity of Liquid Phenolic Resins 500 
7.3.12 ISO 8618, Determination of Nonvolatile 
Components 500 
7.3.13 ISO 8974, Residual Phenol, Gas Chromatographic 
Determination 501 
7.3.13.1 DIN 16916-02-L 1 and DIN 38409-16, 
Conventional Methods for Determination 
of Residual Phenol 501 
7.3.14 ISO 11402, Determination of Free Formaldehyde 
in Phenolic Resins and Co-Condensates 502 
7.3.15 ISO 8988, Hexamethylene Tetramine (HMTA) 
7.4 Miscellaneous Chemical Test Methods Used 
for Analysis of Phenolic Resins 504 
7.4.1 ISO 11401, Liquid Chromatography for Separation 
of Phenolic Resins 504 
7.4.2 Thin-Layer Chromatography 
(Company-Specific Method) 505 
7.5 Application Technology Testing 507 
7.5.1 Refractories 509 
7.5.2 Foundry Binders 509 
7.5.3 Abrasives (Grinding Wheels, Abrasive Shapes, 
and Coated Abrasives) 510 
7.5.4 Friction Linings 510 
7.5.5 Impregnating Resins for Industrial and Paper Base 
Electrical Laminates 510 
7.5.6 Resins for the Coatings Industry 511 
7.5.7 Resins for the Adhesives Area 512 
7.5.8 Resins for the Rubber Industry 512 
7.5.9 Resins for Textile Felt Production and Related 
Applications 512 
7.5.10 Plywood and Resorcinol Resin Adhesives 512 
7.5.11 Resins for Floral Foam 512 
References 513 
Chapter 8 Industrial Safety and Ecological Questions 
(Raw Materials, Recycling, Environment) 514 
8.1 Toxicological Properties, Hazards Labeling [25] 515 
8.2 Workplace, Exhaust Air, Low-Monomer Resins 516 
8.3 Flue Gas Treatment 520 
8.4 Analytical Determinations at the Workplace 
and in Flue Gas 522 
8.4.1 Example of a Measurement Procedure 523 
8.5 Waste, Recycling 524 
8.6 Renewable Raw Materials (Furfuryl Alcohol, Lignin, 
Tannin) 527 
References 529 
Chapter 9 Conclusion: Guidelines for Future Developments 
of Phenolic Resins and Related Technologies 532 
Subject Index 535 
END
