《POLYMER PROCESSES》

Ⅰ．Introduction to Free Radical Polymerization．＆By John H．Baxendale1

Evidence for Existence of Radicals2

Analysis2

Paramagnetism3

Spectroscopy4

Products of Chemical Reactions5

Reactive Intermediates6

Chain Reactions7

Methods of Formation of Free Radicals8

Thermal Bond Fission8

Decomposition by Absorption of Radiation12

Oxidation or Reduction by Single-Electron Steps15

Basic Reactions of Free Radicals20

Combination of Radicals21

Oxidation and Raduction22

Atom Abstraction23

Radical Addition Reactions25

Ⅱ．Polymerizations in Bulk．＆By C．E．Schildknecht31

Laboratory Polymerizations35

Bulk Polymerization of Styrene41

Industrial Polymerizations of Styrene43

Other Homopolymerizations in Bulk46

Copolymerization in Bulk48

Cast Polymerizations53

Monomer-Polymer Slurries and Doughs(Dental Plastics)58

Heterogeneous Bulk Polymerizations62

Proliferous Polymerizations(Popcorn or Cauliflower Polymers)65

Prospects67

Ⅲ．Polymerizations in Suspension．＆By Ernst Trommsdorff and C．E．Schild-knecht69

History of Pearl or Bead Polymerization71

The Aqueous Phase and Suspending Agents72

The Mouomer Phase82

Polymerization Conditions85

Aftertreatment of the Pearls89

Products with Special Properties91

Examples of Pearl Polymerization Processes91

Difficulties in Pearl Polymerization94

Polymerization Kinetics97

Commercial Products from Pearl Polymerization102

Dispersion Polymerization(Stable Suspensions)105

Ⅳ．Polymerizations in Emulsion．＆By H．Leverne Williams111

Mechanism of Emulsion Polymerization113

Micelles113

Solubilization115

Initiation115

Propagation117

Copolymerization118

Termination119

Kinetics of Emulsion Polymerization120

Polymerization Variables121

Monomers121

Aqueous Phase136

Catalyst-Activator Systems141

Modifiers or Chain Transfer Agents147

Stopping,Stabilizing,Stripping and Finishing152

Agitation and Heat Transfer154

Temperature155

Polymerization Equipment156

Laboratory Equipment156

Pilot Plant Equipment158

Plant Equipment161

Control of Copolymerization Reactions163

Temperature163

Conversion163

Polymer Structures and Molecular Weight164

Examples of Butadiene-Styrene Copolymerization165

Examples of Butadiene-Acrylonitrile Copolymerization171

Ⅴ．Polymerizations in Solution．＆By C．E．Schildknecht175

Solyent Reactivity176

Induced Peroxide Decomposition176

Chain Transfer177

Applications of Chain Transfer180

Other Types of Solvent Reactivity181

Homogeneous Polymerizations183

Maleic Anhydride Copolymerization185

Styrenation185

Lubricant Additives187

Vinyl Acetate and Other Polymers188

Polymerization from Precipitating Solvents(Precipitation Poly-merization)190

Polymerizations in Aqueous Solution191

Non-Electrolytes192

Electrolytes193

Acrylonitri1e Polymerization194

Ⅵ．Ionic Polymerizations．＆By C．E．Schildknecht199

Cationic Polymerizations201

Monomer Reactivity in Cationic Polymerization203

Polymerization of Isobutylene208

Preparation of Butyl Rubbers212

Other Cationic Polymerizations217

Anionic Polymerizations220

Polymerization of Butadiene with Alkali Metal Catalysts226

Ionic Polymerization of Non-Olefinic Compounds230

Ⅶ．Polyamides and Polyesters．＆By D．G．Bannermau and E．E．Magat235

Linear and Three-Dimensional Polymers235

Condensation and Addition Polymers235

History236

Nomenclature238

Polymer Preparation239

Polyamides239

Linear Polyesters254

Polymer Properties266

Relations between Chemical Structure and Physical Properties of Some Linear Polymers266

Properties of 6,6-Nylon285

Properties of Polyethylene Terephthalate287

Polymer Applications291

Fibers291

Films292

Molded Plastics293

Ⅷ．Condensations with Formaldehyde．＆By T．J．Suen295

Introduction295

Functionality of Reactants295

Forms of Formaldehyde Available297

Equipment298

Scope of This Work299

Basic Reactions Involved300

Reactions of Formaldehyde with Phenol,Urea or Melamine300

Preparation of Intermediates305

Factors Influencing the Course and Speed of Reaction306

Nature of Reactants306

Mole Ratio of Reactants307

Catalyst310

Temperature316

Reaction Medium318

Control of the Extent of Reaction318

Free Formaldehyde Content319

Solubility Characteristics320

Refractive Index322

Viscosity323

Melting Point325

Stabilizing the Finished Products326

Formulation of Resins for Specific Applications328

Molding328

Laminating332

Bonding332

Casting336

Chemical Modifications-Water-Soluble Products338

Low Molecular Weight Products338

Introduction of Hydrophilic Groups340

Ion Exchange Resins344

Chemical Modifications-Oil-Soluble Products345

Alkyl-or Aryl-Substituted Reactants345

Formation of Ethers346

Condensation with Esters349

Ⅸ．Cellulose and Cellulose Derivatives．＆By B．G．Ranby and S．A．Rydholm351

Historical Survey351

Classification351

Cellulose-The Raw Material352

Occurrence and Importance352

Chemical Constitution353

Physical Properties356

Chemical Grade Celluloses366

Chemistry of Cellulose Derivatives372

Addition Compounds372

Reaction Mechanisms of Esterification and Etherification379

Distribution of Substitnents386

Technology of Cellulose Derivatives394

General Considerations394

Nitrate-Permutoid Esterification in Acid Medium397

Acetate-Heterogeneous Esterification in Acid Medium401

Carboxymethyl Ether-Permutoid Etherification in Alkaline Medium406

Xanthate-Permutoid Esterfication in Alkaline Medium412

Properties of Cellulose Derivatives417

Influence of the Cellulose Chain417

Influence of the Substituents421

Ⅹ．Epoxy Resins．＆By Salyatore S．Stivala429

Preparation of Epoxy Resins430

Raw Materials430

Chemistry431

Resins from Bisphenol A and Epichlorohydrin432

Resins from Other Intermediates435

Curing of Epoxy Resins439

Organic Amines439

Amine Salts of Fatty Acids443

Acid Curing Agents444

Polysulfides448

Polyamide Curing449

Aldehyde-Condensation Resins450

Miscellaneous Curing Agents452

Applications of Epoxy Resins454

Adhesives454

Finishes457

Casting and Potting(Electrical Applications)462

Laminates467

Foams471

Stabilizers473

Latest Developments473

Ⅺ．Polysulfide Polymers．＆By E．M．Fettes and J．S．Jorczak475

Preparation476

Raw Materials476

Plant Polymerization477

Secondary Treatments478

Polymer Properties479

Crude or Bulk Rubbers481

Compounding483

Applications488

Aqueous Dispersions of Polysulfide Polymers490

Liquid Polysulfide Polymers492

Compounding493

Applications496

Ⅻ．New Adhesives．＆By W．J．Powers499

Epoxy Adhesives502

Modified Epoxies506

Rubber-Resin Adhesives509

Isocyanate Adhesives514

Copolymers of Methacrylic Acid and Miscellaneous Adhesives517

Pressure-Sensitive Adhesives522

ⅩⅢ．Stabilization of Polymers．＆By C．E．Schildknecht525

Cellulose and Its Derivatives529

Stabillzation of Rubbers532

Folyethylenes535

Polystyrenes537

Acrylic Polymers539

Polyesters and Polyamides540

Vinyl Chloride Polymers542

Vinylidene Chloride and Miscellaneous Polymers548

ⅩⅣ．Paste Techniques．＆By W．D．Todd551

General Characteristics of Pastes551

Vinyl Pastes．Types and Advantages552

History of Vinyl Pastes554

General Principles of Plastisols and Organosols556

Raw Materials558

Resins558

Plasticizers559

Stabilizers563

Thinners567

Fillers567

Pigments568

Miscellaneous Ingredients569

Methods of Paste Preparation570

Mixing and Grinding570

Deaeration of Pastes576

Flushing578

Fusion578

Laboratory Preparations of Pastes582

Compounding for Specific Properties584

Flow Properties585

Formulation of Economical Pastes595

Physical Properties of the Paste Plastics595

Chemical Properties of the Paste Plastics599

Processing and Applications600

Spread Coating600

Dip Coating609

Low Pressure Molding614

Expanded Vinyl Pastes(Sponge and Foam)617

Miscellaneous Processing Techniques622

ⅩⅤ．Latex Techniques．＆By G．J．Antlfinger and N．H．Sherwood625

Plastomeric Latices626

Elastomeric Latices627

Polymer Properties629

Heat and Light Resistance629

Oil Resistance630

Grease Resistance630

Water Resistance630

Compounding Aqueous Dispersions635

Film Formation636

Electrolyte,Solvent and pH Effects640

Compounding Procedures for Latices641

Pigmentation649

Thickening654

Colors658

Vulcanization658

Plasticization663

Applications of Aqueous Polymer Dispersions665

Paper665

Textiles668

Leather Finishing669

Dipped Goods670

Foam Sponge672

Adhesives674

Latex Paints674

Latex Handling678

ⅩⅥ．Compounding and Processing Rubbers and Resins．＆By G．S．Carvin679

General Compounding Ingredients680

Plasticizers680

Stabilizers682

Fillers683

Colorants684

Lubricants685

Curing Agents686

Miscellaneous Ingredients687

General Processing Methods688

Compression Molding688

Injection Molding689

Jet Molding689

Transfer Molding689

Extrusion690

Vulcanizing690

Vacuum Forming and Blow Molding691

Film Casting692

Spread Coating693

Dip Coating693

Block Skiving693

Calendering693

Planishing697

Embossing698

Printing699

Hot Joining and Welding699

General Compounding Methods700

Mills700

Internal Mixers702

Grinders and Granulators703

Compounding and Processing Synthetic Rubbers703

Butadiene-Styrene Copolymers(GR-S)709

Butadiene-Acrylonitrile Copolymers712

Isobutylene-Isoprene Copolymers719

Polysulfide Polymers722

Chloroprene Polymers722

Polyacrylic Ester Rubbers724

Fluorocarbon Rubbers726

Silicone Polymers726

Urethane Polymers727

Compounding and Processing Synthetic Resins728

Polyvinyl Chloride and Copolymers729

Rigid PVC Plastics739

Vinylidene Chloride Polymers740

Vinyl Acetate Polymers741

Polyvinyl Acetal Resins741

Polyvinyl Alcohols742

Polyethylenes742

Styrene Molding Polymers744

Ethyl Cellulose747

Cellulose Acetate747

Other Cellulose Esters748

Cellulose Nitrate749

Polyamides(Nylons)751

Polychlorotrifluoroethylene753

Polytetrafluoroethylene(Teflon and Fluon)753

Methyl Methacrylate Polymers758

New Ether Polymers759

ⅩⅦ．Polymer Reinforcement(Polyester,Epoxy,Silicone and Phenolic Resins)＆By H．L．Gerhart and E．W．Moffett761

Resins763

Polyfunctional Unsaturated Esters763

Unsaturated Polyesters766

Epoxy Resins782

Silicone and Phenolic Resins785

Resin Reinforcement786

Paper Laminates789

Glass Fibers795

Other Fabric Fillers807

Granular Fillers809

Pigments812

Summary of Strength Properties814

Fabrication Techniques815

Rod Shapes817

Zero Pressure Molding817

Bag Molding819

Matched Die Molding823

Continuous Laminating829

Pipe and Tubing830

Paste Molding833

Thermoelastic Forming834

Prospects835

ⅩⅧ．Spinning and Drawing Fibers．＆By J．L．Riley837

Spinning Processes840

Melt Spinning840

Solution Spinning842

Dry Spinning843

Wet Spinning844

Chemical Solutions845

Drawing Processes845

Drawing Unplasticized Yarn845

Drawing Plasticized Yarn847

Drawing Combined with Wet Spinning847

Molecular Aspects of Synthetic Fiber Processes848

Spinning848

Drawing850

Heat Treatiug851

Viscose Rayon Manufacture851

Dissolving851

Dearating851

Filtration852

Spinning852

Stretching854

Purification854

Yarn Handling855

Drying857

Cellulose Acetate Yarn Manufacture858

Dissolving858

Filtration858

Spinning859

Textile Operations860

Nylon Yarn Manufacture861

Polymerization861

Melt Spinning863

Drawing864

Heat Treating865

Recent Developments in Melt Spinning866

Recent Developments in Solution Spinning870

Acrylic Fibers870

Other Polymers873

Appendix879

Index883